1,1-Difluoropropene (HFO-1252zc), its composition, and process for producing intermediates

Abstract

This specification provides processes for producing difluoroolefins, particularly difluoropropenes such as 1,1-difluoropropene, as well as intermediates, compositions, and uses thereof.

Description

Technical Field

[0001] (Cross-Reference to Related Applications) This application claims the benefit of priority from U.S. Provisional Application No. 63 / 527,096 filed on July 17, 2023, and U.S. Provisional Application No. 63 / 565,026 filed on March 14, 2024, the disclosures of each of which are hereby incorporated by reference in their entireties into the present specification.

[0002] (Field of the Invention) The present invention relates to difluoroolefins, particularly difluoropropenes, intermediates thereof, processes for producing compositions, and uses thereof. Background Art

[0003] Over the past several decades, the fluorocarbon industry has been committed to finding alternative refrigerants to ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), which are being phased out as a result of the Montreal Protocol. The solution for many applications has been the commercialization of hydrofluorocarbon (HFC) compounds for use as refrigerants, solvents, fire extinguishing agents, blowing agents, and propellants. These new compounds, such as the most widely used HFC refrigerants at present, HFC-134a and HFC-125, have zero ozone depletion potential (ODP), so they are not affected by current regulations that mandate phasing-out as a result of the Montreal Protocol. In addition to the problem of ozone depletion, another environmental concern for many of these applications is global warming. According to the IPCC Fifth Assessment Report (AR5) of the United Nations, HFC refrigerants such as HFC-134a and HFC-125 have a global warming potential (GWP) of 1,300 and 3,170, respectively. Prior Art Literature Patent Literature

[0004] [Patent Document 1] U.S. Provisional Application No. 63 / 527,096 [Patent Document 2] U.S. Provisional Application No. 63 / 565,026 [Overview of the project] [Problems that the invention aims to solve]

[0005] This regulatory environment is constantly evolving, and properties other than ODP and GWP are now being considered. More specifically, there is a need for refrigerant compositions that not only meet low ODP standards and have a low global warming potential, but also exhibit low flammability or no flammability at all, provide excellent performance in a variety of applications, and meet evolving regulatory standards.

[0006] In this technological field, there is a need for new refrigerants that meet evolving regulations and provide heat transfer and cooling properties that meet or exceed the effectiveness of conventional refrigerants.

[0007] Some fluoropropenes, such as 1,1-difluoropropene (HFO-1252zc), are such potential new refrigerants. There is an ongoing need for effective and efficient processes for preparing 1,1-difluoropropene (HFO-1252zc) and its intermediates and compositions. [Means for solving the problem]

[0008] The present invention relates to a process for producing 1,1-difluoropropene (HFO-1252zc, CF2=CHCH3) from 1,1,1,3-tetrachloropropane (HCC-250fb, C3H4Cl4), and to the composition thereof.

[0009] One embodiment of the present invention disclosed herein relates to a process for converting HCC-250fb to HFO-1252zc via one or more intermediates, including but not limited to 1,3-dichloro-1,1-difluoropropane (HCFC-252fc, C3H4Cl2F2), 1-chloro-1,1-difluoropropane (HCFC-262fc, CH3CH2CCIF2), and 3-chloro-3,3-difluoro-1-propene (HCFO-1242zf, C3H3ClF2).

[0010] In one embodiment, the conversion of HCC-250fb to HFO-1252zc proceeds via the intermediate HCFC-252fc.

[0011] In one embodiment, the conversion of HCC-250fb to HFO-1252zc proceeds via the intermediate HCFC-262fc.

[0012] In one embodiment, the conversion of HCC-250fb to HFO-1252zc proceeds via intermediates HCFC-252fc and HCFC-262fc.

[0013] One embodiment of the present invention disclosed herein relates to a process for converting HCC-250fb to HCFC-262fc via the intermediate HCFC-252fc.

[0014] One embodiment of the present invention disclosed herein relates to a process for converting HCFC-252fc to HFO-1252zc via the intermediate HCFC-262fc.

[0015] One embodiment of the present invention disclosed herein relates to a process for converting HCFC-252fc to HCFC-262fc.

[0016] One embodiment of the present invention disclosed herein relates to a process for converting HCFC-262fc to HFO-1252zc.

[0017] One embodiment of the present invention disclosed herein relates to a process for converting HCC-250fb to HCFC-252fc by contacting HCC-250fb with hydrogen fluoride to form HCFC-252fc, preferably in the presence of a catalyst and preferably in a liquid phase.

[0018] In one embodiment, the present invention provides a process for converting HCC-250fb to HFO-1252zc, comprising: contacting HCC-250fb with hydrogen fluoride in the presence of a catalyst to form HCFC-252fc; contacting HCFC-252fc with hydrogen in the presence or absence of a catalyst to form HCFC-262fc; and dehydrohalogenating HCFC-262fc in the presence or absence of a catalyst to form HFO-1252zc.

[0019] In one embodiment, the present invention provides a process for converting HCC-250fb to HCFC-262fc, comprising: contacting HCC-250fb with hydrogen fluoride in the presence of a catalyst to form HCFC-252fc; and contacting HCFC-252fc with hydrogen in the presence or absence of a catalyst to form HCFC-262fc.

[0020] In one embodiment, the present invention provides a process for converting HCFC-252fc to HFO-1252zc, comprising: contacting HCFC-252fc with hydrogen in the presence or absence of a catalyst to form HCFC-262fc; and dehydrohalogenating (dehydrochlorinating) HCFC-262fc in the presence of a catalyst to form HFO-1252zc.

[0021] In one embodiment, the present invention provides a process for converting HCFC-252fc to HCFC-262fc by contacting HCFC-252fc with hydrogen in either a liquid phase or a gas phase, in the presence or absence of a catalyst, to form HCFC-262fc.

[0022] In one embodiment, the present invention provides a process for converting HCFC-262fc to HFO-1252zc by dehydrohalogenating (dehydrochlorinating) HCFC-262fc to form HFO-1252zc in either a liquid phase or a gas phase, in the presence or absence of a catalyst.

[0023] In one embodiment, the conversion of HCC-250fb to HFO-1252zc proceeds via the intermediate HCFO-1242zf.

[0024] In one embodiment, the conversion of HCC-250fb to HFO-1252zc proceeds via the intermediates HCFO-1242zf and HCFC-262fc.

[0025] One embodiment of the invention disclosed herein relates to a process for converting HCC-250fb to HCFC-262fc via the intermediate HCFO-1242zf.

[0026] One embodiment of the invention disclosed herein relates to a process for converting HCFO-1242zf to HFO-1252zc via the intermediate HCFC-262fc.

[0027] One embodiment of the invention disclosed herein relates to a process for converting HCFO-1242zf to HCFC-262fc.

[0028] One embodiment of the invention disclosed herein relates to a process for converting HCFO-1242zf to HFO-1252zc.

[0029] In one embodiment, the present invention provides a process for converting HCC-250fb to HFO-1252zc by contacting HCC-250fb with hydrogen fluoride in the presence or absence of a catalyst to form HCFO-1242zf, contacting HCFO-1242zf with hydrogen in the presence of a catalyst to form HCFC-262fc, and dehydrochlorinating (dehydrohalogenating) HCFC-262fc in the presence or absence of a catalyst to form HFO-1252zc.

[0030] In one embodiment, the present invention provides a process for converting HCC-250fb to HCFC-262fc by contacting HCC-250fb with hydrogen fluoride in or without a catalyst to form HCFO-1242zf, and then contacting HCFO-1242zf with hydrogen in the presence of a catalyst to form HCFC-262fc.

[0031] In one embodiment, the present invention provides a process for converting HCFO-1242zf to HFO-1252zc by contacting HCFO-1242zf with hydrogen in the presence of a catalyst to form HCFC-262fc, and then dehydrochlorinating (dehydrohalogenating) HCFC-262fc in the presence or absence of the catalyst to form HFO-1252zc.

[0032] In one embodiment, the present invention provides a process for converting HCFO-1242zf to HCFC-262fc by contacting HCFO-1242zf with hydrogen in the presence of a catalyst in either the liquid phase or the gas phase to form HCFC-262fc.

[0033] In one embodiment, the present invention provides a process for converting HCC-250fb to HCFC-252fc by contacting HCC-250fb with hydrogen fluoride in a liquid phase in the presence of a catalyst.

[0034] In one embodiment, the present invention provides a process for converting HCC-250fb to HCFO-1242zf by contacting HCC-250fb with hydrogen fluoride in the gas phase, in the absence or presence of a catalyst.

[0035] In one embodiment, the present invention provides a process for converting HCC-250fb to HFO-1243zf by contacting HCC-250fb with hydrogen fluoride in the gas phase, in the absence or presence of a catalyst.

[0036] In one embodiment, the present invention provides a process for converting HCC-250fb to HFO-1252zc by contacting HCC-250fb with hydrogen fluoride in or without a catalyst to form HCFO-1242zf, and then dechlorinating HCFO-1242zf with zinc in or without a catalyst to form HFO-1252zc.

[0037] In one embodiment, the conversion of HCC-250fb to HFO-1252zc proceeds by first contacting HCC-250fb with hydrogen fluoride in or without a catalyst to form either HCFC-252fc or HCFO-1242zf, then contacting HCFC-252fc or HCFO-1242zf with hydrogen in or without a catalyst to form HCFC-262fc, or contacting HCFO-1242zf with zinc in or without a catalyst to form HFO-1252zc. In one embodiment, if HCFC-262fc is formed, the method further includes dehalogenating (dehydrochlorinating) HCFC-262fc in or without a catalyst to form HFO-1252zc. In one embodiment, the intermediate formed from the hydrofluorination of HCC-250fb is preferably HCFC-252fc. In another embodiment, the intermediate formed from the hydrofluorication of HCC-250fb is preferably HCFO-1242zf.

[0038] In one embodiment disclosed herein, HFO-1252zc is prepared according to the following reaction scheme A. Process 1A: CCl3CH2CH2Cl(HCC-250fb)+HF→CClF2CH2CH2Cl(HCFC-252fc)+HCl Process 2A: CClF2CH2CH2Cl(HCFC-252fc)+H2→CClF2CH2CH3(HCFC-262fc)+HCl Process 3A: CClF2CH2CH3(HCFC-262fc)→CF2=CHCH3(HFO-1252zc)+HCl or in solution CClF2CH2CH3(HCFC-262fc)+strong base→CF2=CHCH3(HFO-1252zc)

[0039] In some embodiments, steps 1A, 2A, and 3A include an integration process for producing HFO-1252zc. In some embodiments, the integration process further includes a separation step or process for recovering a desired intermediate (e.g., HCFC-252fc and HCFC-262fc) and the desired reaction product, HFO-1252zc.

[0040] In some embodiments, step 1A may be omitted to use HCFC-252fc as a starting material to prepare HCFC-262fc according to step 2A, and / or HFO-1252zc according to steps 2A and 3A.

[0041] In some embodiments, steps 1A and 2A may be omitted in order to prepare HFO-1252zc using HCFC-262fc as the starting material.

[0042] In some embodiments, the present invention relates to a process for preparing HCFC-262fc according to (i) steps 1A and 2A, or (ii) step 2A.

[0043] In one embodiment disclosed herein, HFO-1252zc is prepared according to the following reaction scheme B. Process 1B: CCl3CH2CH2Cl(HCC-250fb)+HF→CClF2CH=CH2(HCFO-1242zf)+HCl or CClF2CH2CH2Cl(HCFC-252fc) + caustic agent → CClF2CH=CH2(HCFO-1242zf) + H2O + salt Process 2B: CClF2CH=CH2(HCFO-1242zf)+H2→CClF2CH2CH3(HCFC-262fc) Process 3B: CClF2CH2CH3(HCFC-262fc)→CF2=CHCH3(HFO-1252zc)+HCl or in solvent CClF2CH2CH3(HCFC-262fc)+strong base→CF2=CHCH3(HFO-1252zc)

[0044] In some embodiments, steps 1B, 2B, and 3B include an integration process for producing HFO-1252zc. In some embodiments, the integration process further includes a separation step or process for recovering a desired intermediate (e.g., HCFO-1242zf and HCFC-262fc) and the desired reaction product, HFO-1252zc.

[0045] In some embodiments, step 1B may be omitted to use HFO-1243zf as a starting material to prepare HCFC-262fc according to step 2B, and / or HFO-1252zc according to steps 2B and 3B.

[0046] In some embodiments, steps 1B and 2B may be omitted in order to prepare HFO-1252zc using HCFC-262fc as the starting material.

[0047] In some embodiments, the present invention relates to a process for preparing HCFC-262fc according to (i) steps 1B and 2B, or (ii) step 2B.

[0048] In one embodiment disclosed herein, HFO-1252zc is prepared according to the following reaction scheme C. Process 1C: CCl3CH2CH2Cl(HCC-250fb)+HF→CClF2CH=CH2(HCFO-1242zf)+HCl or CClF2CH2CH2Cl(HCFC-252fc) + caustic agent → CClF2CH=CH2(HCFO-1242zf) + H2O + salt Process 2C: CClF2CH=CH2(HCFO-1242zf)+Zn→CF2=CHCH3(HFO-1252zc)+ZnCl2

[0049] In some embodiments, steps 1C and 2C include an integration process for producing HFO-1252zc. In some embodiments, the integration process further includes a separation step or process for recovering a desired intermediate (e.g., HCFO-1242zf) and the desired reaction product, HFO-1252zc.

[0050] In some embodiments, the present invention relates to a process for preparing HFO-1252zc from HCFO-1242zf according to step 2C.

[0051] In one embodiment, HFO-1252zc can be prepared by integrating one or more of the above steps as follows (reaction scheme D). Process 1D: CCl3CH2CH2Cl(HCC-250fb)+HF→CClF2CH2CH2Cl(HCFC-252fc)+HCl Process 2D: CClF2CH2CH2Cl(HCFC-252fc) + caustic agent → CClF2CH=CH2(HCFO-1242zf) + H2O + salt Process 3D: CClF2CH=CH2(HCFO-1242zf)+Zn→CF2=CHCH3(HFO-1252zc)+ZnCl2 or CClF2CH=CH2(HCFO-1242zf)+H2→CClF2CH2CH3(HCFC-262fc)→CF2=CHCH3(HFO-1252zc)+HCl or In bases / solvents CClF2CH=CH2(HCFO-1242zf)+H2→CClF2CH2CH3(HCFC-262fc)→CF2=CHCH3(HFO-1252zc)

[0052] In some embodiments disclosed herein, such as reaction schemes B and C, the HCC-250fb feed is first vaporized before hydrofluorication, and the hydrofluorication reaction is carried out in the gas phase. In other embodiments, such as reaction scheme A, the hydrofluorication of HCC-250fb is carried out in the liquid phase.

[0053] In one embodiment disclosed herein, HCFC-252fc is converted to HCFC-262fc by hydrogenation in either the liquid or gas phase.

[0054] In one embodiment disclosed herein, HCFO-1242zf is converted to HCFC-262fc by hydrogenation in either the liquid or gas phase.

[0055] In one embodiment disclosed herein, HCFC-262fc is converted to HFO-1252zc by dehydrochlorination in the gas phase, with or without a catalyst.

[0056] In one embodiment disclosed herein, HCFC-262fc is converted to HFO-1252zc by dehydrochlorination in the liquid phase, with or without a catalyst.

[0057] In one embodiment disclosed herein, HCFO-1242zf is converted to HFO-1252zc by contacting zinc in a liquid phase.

[0058] Some embodiments of the present invention disclosed herein relate to compositions comprising, essentially comprising, or consisting of HCFC-262fc and one or more compounds selected from HCC-250fb, HCFC-252fc, HCFO-1242zf, HFC-263fb, HCFC-272fb, and HFO-1252zf. In some embodiments, HCFC-262fc constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, including all integers and ranges in between.

[0059] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HCFC-262fc and one or more additional compounds selected from HCC-250fb, HCFC-252fc, HFC-263fb, HCFC-262fa, and HCFC-272fb. In some embodiments, HCFC-262fc constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, including all integers and ranges in between.

[0060] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HCFC-262fc and one or more additional compounds selected from HCC-250fb, HCFO-1242zf, HFC-263fb, HFO-1252zf, and HCFC-272fb. In some embodiments, HCFC-262fc constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, including all integers and ranges in between.

[0061] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HCC-250fb and HCFO-1242zf. In some embodiments, HCFO-1242zf constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, and includes all integers and ranges in between.

[0062] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HCFC-262fc and one or more additional compounds selected from propane, propylene, HCFC-252dc, HCFC-262db, HFC-272fb, HCFO-1232xf, HCFO-1242zf, HFO-1243zf, E-HCFO-1251zd, Z-HCFO-1251zd, HFO-1252zf, E-HFO-1261ze, Z-HFO-1261ze, HCFO-1242 isomers, and HCO-1260. In some embodiments, HCFC-262fc constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, including all integers and ranges in between.

[0063] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HCFC-262fc and one or more additional compounds selected from propane, propylene, HCFC-252dc, HCFC-262db, HFC-272fb, HCFO-1232xf, HCFO-1242zf, HFO-1243zf, E-HCFO-1251zd, Z-HCFO-1251zd, HFO-1252zf, E-HFO-1261ze, Z-HFO-1261ze, and HCO-1260. In some embodiments, HCFC-262fc constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, including all integers and ranges in between.

[0064] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HCFC-262fc and one or more additional compounds selected from propane, propylene, HCFC-252dc, HCFC-262db, HCFO-1232xf, HCFO-1242zf, HFO-1243zf, E-HCFO-1251zd, Z-HCFO-1251zd, HFO-1252zf, E-HFO-1261ze, Z-HFO-1261ze, and HCFO-1242 isomers. In some embodiments, HCFC-262fc constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, including all integers and ranges in between.

[0065] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HCFC-262fc and one or more additional compounds selected from HCFC-262db, HCFO-1232xf, HCFO-1242zf, HFO-1243zf, E-HCFO-1251zd, Z-HCFO-1251zd, HFO-1252zf, and E-HFO-1261ze. In some embodiments, HCFC-262fc constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, including all integers and ranges in between.

[0066] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HCFC-262fc and one or more additional compounds selected from ethane, HFC-152a, HFC-253db, HCFO-1232 isomer, HCFO-1242 isomer, HCFO-1242zf, HFO-1243zf, and HFO-1252zc. In some embodiments, HCFC-262fc constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, including all integers and ranges in between.

[0067] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HCFC-262fc and one or more additional compounds selected from propane, propylene, E-HFO-1261ze, Z-HFO-1261ze, HFO-1252zc, HFC-272fb, E-HCFO-1251zd, Z-HCFO-1251zd, HCFC-262db, HCFC-252dc, HCO-1250, HCC-260, HFO-1243zf, HCFO-1242zf, HCFO-1242 isomer, HCFO-1232 isomer, and HCFC-252 isomer. In some embodiments, HCFC-262fc constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, including all integers and ranges in between.

[0068] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HCFC-262fc, HCFO-1242zf, and one or more additional compounds selected from propane, propylene, E-HFO-1261ze, Z-HFO-1261ze, HFO-1252zc, HFC-272fb, E-HCFO-1251zd, Z-HCFO-1251zd, HCFC-262db, HCFC-252dc, HCO-1250, HCC-260, HFO-1243zf, HCFO-1242 isomer, HCFO-1232 isomer, and HCFC-252 isomer. In some embodiments, HCFC-262fc constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, including all integers and ranges in between.

[0069] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HCFC-262fc, HFC-272fb, and one or more additional compounds selected from propane, propylene, E-HFO-1261ze, Z-HFO-1261ze, HFO-1252zc, E-HCFO-1251zd, Z-HCFO-1251zd, HCFC-262db, HCFC-252dc, HCO-1250, HCC-260, HFO-1243zf, HCFO-1242zf, HCFO-1242 isomer, HCFO-1232 isomer, and HCFC-252 isomer. In some embodiments, HCFC-262fc constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, including all integers and ranges in between.

[0070] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HCFO-1242zf and one or more additional compounds selected from HCC-250fb, HCFC-253fb, HCFC-252fc, HCFC-251fb, HCFC-1243zf, HCFC-1241zf, and HCFC-1240za. In some embodiments, HCFO-1242zf constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, including all integers and ranges in between.

[0071] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HCFC-1243zf and one or more additional compounds selected from HCC-250fb, HCFC-253fb, HCFC-252fc, HCFC-251fb, HCFO-1242zf, HCFC-1241zf, and HCFC-1240za. In some embodiments, HCFO-1242zf constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, including all integers and ranges in between.

[0072] Some embodiments of the present invention disclosed herein relate to compositions comprising, essentially comprising, or consisting of HCFC-1252zc and one or more compounds selected from HCC-250fb, HCFC-252fc, HCFC-262fc, and HCFO-1242zf. In some embodiments, HCFC-1252zc constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, including all integers and ranges in between.

[0073] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HFO-1252zc, HCFC-262fc, HCC-250fb, and HCFC-252fc. In some embodiments, HCFC-1252zc constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, and includes all integers and ranges in between.

[0074] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HFO-1252zc, HCFC-262fc, HCC-250fb, and HCFO-1242zf. In some embodiments, HCFC-1252zc constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, and includes all integers and ranges in between.

[0075] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HFO-1252zc and one or more additional compounds selected from HCFC-262fc, HCC-250fb, HFC-263fb, HFO-1243zf, other 1252 isomers, ethane, ethylene, HFC-23, HCFC-22, HFO-1132a, propane, HFC-143a, HCFC-142b, HFO-1234yf, HFO-1234ze, HFO-1225zc, HCFO-1242zf, and HCFC-252fc. In some embodiments, HCFC-1252zc constitutes about 0.1% to about 99.9% by weight, or about 40% to about 99.9% by weight, or about 90% to about 99.9% by weight, and includes all integers and ranges in between, based on the total weight of the composition. In some embodiments, such compositions are formed by reaction scheme A or B.

[0076] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HFO-1252zc, HCC-250fb, and HCFO-1242zf. In some embodiments, HCFC-1252zc constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, and includes all integers and ranges in between.

[0077] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HFO-1252zc and one or more additional compounds selected from HCFC-262fc, HCC-250fb, HFC-263fb, HCFO-1242zf, HFO-1252zf, HFO-1243zf, and HCFC-252fc. In some embodiments, HCFC-1252zc constitutes about 0.1% to about 99.9% by weight, or about 40% to about 99.9% by weight, or about 90% to about 99.9% by weight, including all integers and ranges in between, based on the total weight of the composition. In some embodiments, such a composition is formed by reaction scheme C.

[0078] One embodiment of the present invention disclosed herein relates to a composition comprising, essentially consisting of, or further comprising one or more additional components comprising hydrofluorocarbons (HFCs), hydrochlorocarbons (HCCs), hydrofluorochlorocarbons (HCFCs), hydrofluoroolefins (HFOs), hydrochlorofluoroolefins (HCFOs), C2-C4 alkanes, C2-C4 alkenes, and t-butoxy-fluoropropene.

[0079] In preferred embodiments, the compositions according to the present invention do not contain or substantially contain any Group A fluorinated substances as defined herein.

[0080] In preferred embodiments, the decomposition products of the composition according to the present invention do not contain or substantially contain any Group A fluorinated substances as defined herein.

[0081] Some embodiments of the present invention disclosed herein relate to compositions comprising, essentially comprising, or consisting of HFO-1252zc and one or more additional components selected from HFCs, HCCs, HCFCs, HFOs, HCFOs, C2-C4 alkanes, C2-C4 alkenes, and t-butoxy-fluoropropenes. In some embodiments, such compositions are free of or substantially free of Group A fluorinated substances as defined herein, and / or the decomposition products of such compositions are free of or substantially free of Group A fluorinated substances.

[0082] Further embodiments of the present invention disclosed herein are compositions comprising, essentially comprising, or consisting of HFO-1252zc. In some embodiments, the composition further comprises at least one additional component or compound, the total amount of the additional component or compound being greater than 0 and less than about 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1%, as well as all values ​​and ranges in between.

[0083] Further embodiments of the present invention disclosed herein are compositions comprising, essentially comprising, or consisting of HFO-1252zc. In some embodiments, the composition further comprises at least one additional component or compound, the total amount of which is greater than 0 and about 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, less than 10%, greater than 0.001% and less than 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1%, and all values ​​and ranges between them.

[0084] One embodiment of the present invention disclosed herein is a composition comprising, essentially, or consisting of HFO-1252zc, wherein HFO-1252zc is present in amounts greater than about 20% by weight, greater than about 30% by weight, about 30% to about 99% by weight, about 40% to about 99% by weight, about 50% to about 99% by weight, less than 100% by weight, and greater than about 90% by weight, greater than about 95% by weight, greater than about 99% by weight, greater than about 99% by weight, greater than about 99.3% by weight, greater than about 99.5% by weight, greater than about 99.6% by weight, greater than 99.7% by weight, greater than about 99.8% by weight, or greater than about 99.9% by weight, and all values ​​and ranges in between.

[0085] In one embodiment, the liquid-phase hydrogenation of HCFC-252fc is carried out at a temperature of about 20°C to about 150°C, preferably about 30°C to about 100°C.

[0086] In one embodiment, the gas-phase hydrogenation of HCFC-252fc is carried out at a temperature of about 20°C to about 120°C, preferably about 30°C to about 80°C.

[0087] In one embodiment, the liquid-phase hydrogenation of HCFO-1242zf is carried out at a temperature of about 20°C to about 150°C, preferably about 30°C to about 100°C.

[0088] In one embodiment, the gas-phase hydrogenation of HCFO-1242zf is carried out at a temperature of about 20°C to about 120°C, preferably about 30°C to about 80°C.

[0089] In one embodiment, the gas-phase dehalogenation hydrogenation of HCFC-262fc is carried out at a temperature of about 400°C to about 800°C, preferably about 450°C to about 700°C.

[0090] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art in the field to which the present invention pertains. In the event of any conflict, including definitions, this specification shall prevail. Similar or equivalent methods and materials to those described herein may be used in carrying out or testing embodiments of the present invention, but preferred methods and materials are described below. Furthermore, the materials, methods, and examples are illustrative only and not intended to be limiting.

[0091] Various aspects and embodiments of the present invention can be used individually or in combination with each other. Other features and advantages of the present invention will become apparent from the following more detailed description, which is made in conjunction with the accompanying drawings illustrating the principles of the present invention as an example. [Brief explanation of the drawing]

[0092] The following detailed description of preferred embodiments of the present invention will be better understood in conjunction with the accompanying drawings. For the purpose of illustrating the present invention, currently preferred embodiments are shown in the drawings. However, it should be understood that the present invention is not limited to the exact arrangements and means shown. The drawings are as follows. [Figure 1] A system according to the first embodiment of the present invention is shown. [Figure 2] A system according to a second embodiment of the present invention is shown. [Figure 3] A system according to a third embodiment of the present invention is shown. [Modes for carrying out the invention]

[0093] The present invention provides a process for preparing 1,1-difluoropropene (HFO-1252zc) and its intermediates and compositions.

[0094] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” or any other variations thereof are intended to encompass non-exclusive inclusion. For example, a composition, process, method, article, or apparatus containing the elements listed is not necessarily limited to those elements alone, but may include other elements not expressly listed, or other elements inherent in such composition, process, method, article, or apparatus. Furthermore, unless expressly stated otherwise, “or” means an inclusive “or” and not an exclusive “or.” For example, condition A or B is satisfied by any one of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); and both A and B are true (or exist).

[0095] The transitional phrase "consisting of" excludes any unspecified elements, processes, or components. In patent claims, such a phrase closes the claim to materials other than those listed, with the exception of impurities normally associated with the materials. If the phrase "consisting of" appears in a clause of the body of a claim rather than immediately following the preamble, it limits the elements to those specified in that clause only, and does not exclude other elements from the claim as a whole.

[0096] The transitional phrase "essentially from" is used to define compositions and methods that include materials, processes, mechanisms, components, or elements in addition to those literally disclosed, provided that these additionally included materials, processes, mechanisms, components, or elements do not substantially affect the fundamental and novel features of the claimed invention, in particular the mechanism of operation for achieving any of the desired results of the processes of the invention. The term "essentially from" occupies an intermediate position between "includes" and "consists of".

[0097] If applicants define an invention or part thereof using non-limiting terms such as "includes," it should be readily understood that (unless otherwise specified) such descriptions should be interpreted to include inventions that essentially consist of or comprise the same term.

[0098] Furthermore, the use of "a" or "an" is used to describe the elements and components described herein. This is done solely for convenience and to give a general sense of the scope of the invention. This description should be interpreted as including one or at least one, and the singular form also includes the plural form unless it is evident that it has a different meaning.

[0099] Where a quantity, concentration, or other value or parameter is given as a range, a preferred range, or a list of preferred upper and / or preferred lower values, these shall be understood to specifically disclose all ranges formed by any pair of any upper or preferred upper range values ​​and any lower or preferred lower range values, regardless of whether the ranges are disclosed separately. Where numerical ranges are enumerated herein, unless otherwise indicated, these ranges are intended to encompass their endpoints and include all integers and fractions within that range.

[0100] Where used herein, the term "approximately" means to take into account variations due to experimental error (e.g., plus or minus approximately 10%, ±1%, ±2%, ±3%, ... ±10% of the indicated value). All measurements reported herein, unless otherwise specified, are understood to be modified by the term "approximately," whether or not the term is explicitly used.

[0101] The compounds referred to herein may be referred to by code based on fluorochemical nomenclature, chemical structure, and / or chemical name. For convenience and reference, selected compounds with codes, structures, and chemical names are provided in Table 1.

[0102] [Table 1]

[0103] Some of the compounds present in the compositions of the present invention may exist as different stereoisomers or stereoisomers. The present invention is intended to include all single stereoisomers, single stereoisomers, or any combination or mixture thereof. Single or multiple isomers of the same compound may be used in any proportion.

[0104] Embodiments of the present invention disclosed herein relate to a process for converting HCC-250fb to HFO-1252zc via intermediates, including but not limited to one or more of HCFC-252fc, HCFC-262fc, and HCFO-1242zf, and to a process for preparing the intermediates HCFC-252fc, HCFC-262fc, and HCFO-1242zf.

[0105] Reactors suitable for either liquid-phase or gas-phase reactions can be used. In the gas phase, heated reactors are used, and the reactors are equipped with appropriate thermal control. Numerous reactor configurations are possible, including packed-bed tube or column reactors operated in batch, semi-batch, or continuous mode. Liquid-phase reactors may be equipped with suitable agitators to increase fluid-to-fluid contact and can be operated similarly in batch, semi-batch, and continuous modes. In addition to the reactors disclosed herein, preheaters and vaporizers, heat exchangers, feed lines and discharge lines, units related to mass transfer, contact vessels (premixers), distillation columns, and valves related to reactors, heat exchangers, vessels, columns, and units used in the processes of the various embodiments disclosed herein should be constructed of corrosion-resistant materials.

[0106] Fluorination of HCC-250fb In some embodiments, HCC-250fb can be used to produce HCFC-252fc or HCFO-1242zf by hydrofluorication. The hydrofluorication reaction can be carried out in the liquid phase or the gas phase. In one embodiment, the reaction of HCC-250fb with HF may be carried out in the liquid phase to form HCFC-252fc. In another embodiment, the reaction of HCC-250fb with HF may be carried out in the gas phase to form HCFO-1242zf. In yet another embodiment, the reaction of HCC-250fb with HF may be carried out in the gas phase to form HFO-1243zf. In yet another embodiment, the reaction of HCC-250fb with HF may be carried out in the gas phase to co-produce HCFO-1242zf and HFO-1243zf.

[0107] In the liquid-phase embodiment of the present invention, the reaction of HCC-250fb with HF may be carried out in a liquid-phase reactor operating in batch, semi-batch, semi-continuous, or continuous mode. In batch mode, HCC-250fb and HF are combined in an autoclave or other suitable reaction vessel and heated to the desired temperature.

[0108] In one embodiment, the reaction is carried out in a semi-batch mode by supplying HCC-250fb to a liquid-phase reactor containing HF, or by supplying HF to a liquid-phase reactor containing HCC-250fb, or by supplying HCC-250fb to a liquid-phase reactor containing a mixture of HF and a reaction product formed by first heating HCC-250fb and HF, or by supplying HF to a liquid-phase reactor containing a mixture of HCC-250fb and a reaction product formed by reacting HF and HCC-250fb. In another embodiment of the liquid-phase process, HF and HCC-250fb can be pre-mixed and supplied to the reactor, or supplied simultaneously to the reactor in a desired stoichiometric ratio and mixed upstream of the catalyst bed. In one embodiment, the reactor contains a mixture of HF, HCC-250fb, and / or a reaction product formed by reacting HF and HCC-250fb.

[0109] The suitable temperature for the reaction of HF with HCC-250fb in a liquid-phase reactor is approximately 40°C to 250°C in one embodiment and approximately 50°C to 100°C in another embodiment. Higher temperatures typically result in a greater conversion rate of HCC-250fb.

[0110] In one embodiment, a preheater may be used to preheat HCC-250fb before introducing it into the liquid-phase reactor.

[0111] The appropriate molar ratio of the total amount of HF to HCC-250fb supplied to the liquid-phase reactor is, in one embodiment, at least stoichiometric, and in another embodiment, about 1:1 to about 100:1, or about 1:1 to about 30:1, or about 2:1 to about 30:1.

[0112] In liquid-phase processes, reactor pressure is not critical; in batch reactions, it is typically the spontaneous pressure of the system at the reaction temperature. The system pressure increases as hydrogen chloride is formed by the substitution of chlorine in HCC-250fb with fluorine derived from HF. In continuous processes, the reactor pressure can be set so that the low-boiling point products of the reaction are optionally discharged from the reactor through a packed column or condenser. This method leaves higher-boiling point intermediates in the reactor and removes volatile products. Typical reactor pressures range from approximately 20 psig (239 kPa) to approximately 1,000 psig (6,994 kPa).

[0113] The appropriate contact time is in the range of 2 minutes to 12 hours, and in some embodiments, it is in the range of 10 minutes to 6 hours.

[0114] In some embodiments, the reaction between HCC-250fb and HF to form HCFC-252fc is carried out in the absence of a catalyst.

[0115] In some embodiments, the reaction between HCC-250fb and HF to form HCFC-252fc is carried out in the presence of a catalyst. In some embodiments in which the reaction is carried out using a liquid-phase process, possible catalysts include, but are not limited to, Lewis acid catalysts, transition metal halides, transition metal oxides, group IVb metal halides, group Vb metal halides, or combinations thereof. Non-limiting examples of liquid-phase fluorination catalysts include antimony halides, tin halides, tantalum halides, titanium halides, niobium halides, zirconium halides, thallium halides, sodium halides, molybdenum halides, iron halides, chromium fluoride halides, chromium fluoride oxides, or combinations thereof. Specific non-limiting examples of liquid-phase fluorination catalysts include, but are not limited to, SbCl5, SbCl3, SbF3, SbF5, SbF4, SnCl4, TaCl5, MoCl6, TiCl4, TiCl5, FeCl3, NaCl5, NbF5, ZrCl4, fluorinated species of SbCl5, fluorinated species of SbCl3, fluorinated species of SnCl4, fluorinated species of TaCl5, fluorinated species of TiCl4, fluorinated species of NbCl5, fluorinated species of MoCl6, fluorinated species of FeCl3, and similar, as well as combinations of two or more of these. These catalysts can be readily regenerated by any means known in the art if they become inactivated.

[0116] Under these conditions, for example, a mixture of HF and HCC-250fb is converted by a catalytic liquid-phase fluorination process into a reaction mixture containing HCl and a composition containing HCFC-252fc. In one embodiment, the composition contains HCFC-252fc and one or more additional compounds selected from HCFC-253fb, HCFC-251fb, and HCC-250fb.

[0117] In another embodiment, the reaction between HF and HCC-250fb is carried out in the gas phase to form HCFO-1242zf. In one embodiment, this reaction between HF and HCC-250fb is carried out in the gas phase to co-produce HCFO-1242zf and HFO-1243zf. Typically, a heated reactor is used. Many reactor configurations are possible, including horizontal or vertical reactors, and the sequence of reactions between HCC-250fb and HF. In one embodiment of the present invention, HCC-250fb may first be vaporized and supplied to the reactor as a gas.

[0118] In another embodiment of the present invention, HCC-250fb may be brought into contact with HF in a pre-reactor before the reaction in the gas-phase reactor. In one embodiment, the pre-reactor may be empty. In another embodiment, the pre-reactor is filled with a suitable packing material such as a nickel-based alloy such as Hastelloy®, a nickel-chromium alloy (hereinafter, Inconel®) commercially available from Special Metals Corp. under the trademark Inconel®, or a nickel-copper alloy commercially available from Special Metals Corp. (New Hartford, NY) under the trademark Monel®, or other nickel alloy chips or wool, or other materials inert to HCl and HF that enable efficient mixing of HCC-250fb and HF vapor.

[0119] In some embodiments, an inert diluent gas is used as a carrier gas for HCC-250fb. In one embodiment, the carrier gas is selected and is nitrogen, argon, helium, or carbon dioxide. In some embodiments, the carrier gas is mixed with HCC-250fb and HF in a pre-reactor and vaporized.

[0120] In one embodiment, the appropriate temperature for the pre-reactor is about 20°C to about 375°C, and in another embodiment, it is about 50°C to about 310°C.

[0121] In one embodiment, the molar ratio of HF to HCC-250fb in the pre-reactor is about 50:1, based on the approximate stoichiometric ratio of HF to HCC-250fb. In another embodiment, the molar ratio of HF to HCC-250fb in the pre-reactor is about 1:1 to about 100:1, or about 1:1 to about 30:1, or about 2:1 to about 30:1, preferably about 3:1.

[0122] In one embodiment, HCC-250fb is optionally vaporized in the presence of HF and supplied together with HF to a pre-reactor or gas-phase reactor.

[0123] In some embodiments, the molar ratio of HF to HCC-250fb for the gas-phase reaction is about 1:1 to about 100:1, or about 1:1 to about 30:1, or about 2:1 to about 30:1, preferably about 3:1.

[0124] The appropriate temperature range for the gas-phase reaction is approximately 20°C to 375°C, and in another embodiment, approximately 50°C to 310°C.

[0125] The suitable reactor pressure for a gas-phase reactor may be about 1 to about 30 atmospheres. To facilitate the separation of HCl from other reaction products, a pressure of about 15 to about 25 atmospheres may be advantageously used, and the appropriate reaction time may vary from about 1 to about 120 seconds, preferably about 5 to about 60 seconds.

[0126] In one embodiment, the gas-phase fluorination of HCC-250fb to form HFCO-1242zf is carried out in the absence of a catalyst. For example, the hydrofluorination of HCC-250fb can be performed by thermal decomposition in the absence of a catalyst in the reactor.

[0127] In another embodiment, a catalyst is used in the reaction zone of a gas-phase reaction between HF and HCC-250fb for the formation of HCFO-1242zf. Fluorination catalysts that can be used in the gas-phase reaction include, but are not limited to, Lewis acid catalysts, transition metal halides, transition metal oxides (preferably partially fluorinated transition metal oxides), group IVb metal halides, group Vb metal halides, and catalytically active metal alloy fillers, such as aluminum oxide, nickel-containing alloys such as Hastelloy®, nickel-chromium-containing alloys commercially available from Special Metals Corp. under the trademark Inconel®, nickel-copper-containing alloys commercially available from Special Metals Corp. (New Hartford, NY) under the trademark Monel®, other nickel alloy chips, or zinc-containing alloys, or combinations thereof.

[0128] In one embodiment, the gas-phase reaction of HCC-250fb to HCFO-1242zf may be carried out in the presence of a chromium-based catalyst, a cobalt-based catalyst, a nickel-based catalyst, an aluminum-based catalyst, an iron-based catalyst, or a combination thereof. In one embodiment, the chromium-based catalyst is chromium oxide (e.g., Cr2O3). In one embodiment, the iron-based catalyst may be FeCl3 on carbon. In one embodiment, the aluminum-based catalyst may be Al2O3.

[0129] In some cases, the catalyst described above can be pretreated with HF. This pretreatment can be achieved, for example, by placing the catalyst in a suitable container and then passing HF over the catalyst. In one embodiment, such a container may be a reactor used to carry out the hydrogenation reaction. In one embodiment, the pretreatment time is about 15 to about 300 minutes, and the pretreatment temperature is about 200°C to about 450°C.

[0130] In some embodiments, under these conditions, for example, a mixture of HF and HCC-250fb is converted by a gas-phase fluorination process into a reaction mixture comprising HCl and one or more additional compounds selected from HCFO-1242zf and HCFC-253fb, HCFC-252fc, HCFC-251fb, HCC-250fb, HFO-1243zf, HCFO-1241zf and HCO-1240za. In some embodiments, HCFO-1242zf constitutes about 0.1% to about 99.9% by weight, or about 40% to about 99.9% by weight, or about 90% to about 99.9% by weight, including all integers and ranges in between, based on the total weight of the composition.

[0131] In some embodiments, under these conditions, for example, a mixture of HF and HCC-250fb is converted by a catalytic gas-phase fluorination process into a reaction mixture comprising HCl and a composition comprising HCFO-1242zf, HFO-1243zf, and optionally one or more additional compounds selected from HCFC-253fb, HCFC-252fc, HCFC-251fb, HCC-250fb, HCFO-1241zf, and HCO-1240za.

[0132] In another embodiment, the reaction between HF and HCC-250fb is carried out in the gas phase to form HFO-1243zf. Typically, a heated reactor is used. Many reactor configurations are possible, including horizontal or vertical reactors, and the sequence of reactions between HCC-250fb and HF. In one embodiment of the present invention, HCC-250fb may first be vaporized and supplied to the reactor as a gas.

[0133] In another embodiment of the present invention, HCC-250fb may be brought into contact with HF in a pre-reactor before the reaction in the gas-phase reactor. In one embodiment, the pre-reactor may be empty. In another embodiment, the pre-reactor is filled with a suitable packing material such as a nickel-based alloy such as Hastelloy®, a nickel-chromium alloy (hereinafter, Inconel®) commercially available from Special Metals Corp. under the trademark Inconel®, or a nickel-copper alloy commercially available from Special Metals Corp. (New Hartford, NY) under the trademark Monel®, or other nickel alloy chips or wool, or other materials inert to HCl and HF that enable efficient mixing of HCC-250fb and HF vapor.

[0134] In some embodiments, an inert diluent gas is used as the carrier gas for HCC-250fb. In one embodiment, the carrier gas is selected and is nitrogen, argon, helium, or carbon dioxide. In some embodiments, the carrier gas is mixed with HCC-250fb and HF in a pre-reactor.

[0135] In one embodiment, the appropriate temperature for the pre-reactor is about 20°C to about 375°C, and in another embodiment, it is about 50°C to about 310°C.

[0136] In one embodiment, the molar ratio of HF to HCC-250fb in the pre-reactor is about 50:1, based on the approximate stoichiometric ratio of HF to HCC-250fb. In another embodiment, the molar ratio of HF to HCC-250fb in the pre-reactor is about 1:1 to about 100:1, or about 1:1 to about 30:1, or about 2:1 to about 30:1, preferably about 10.2:1 to 26.4:1.

[0137] In one embodiment, HCC-250fb is optionally vaporized in the presence of HF and supplied together with HF to a pre-reactor or gas-phase reactor.

[0138] The molar ratio of HF to the total amount of HCC-250fb for the gas-phase reaction is, in one embodiment, from the approximate stoichiometric ratio of HF to HCC-250fb to about 50:1, and in another embodiment, it is about 1:1 to about 100:1, or about 1:1 to about 30:1, or about 2:1 to about 30:1, preferably about 10.2:1 to 26.4:1.

[0139] The appropriate temperature range for the gas-phase reaction is approximately 20°C to 375°C, and in another embodiment, approximately 50°C to 310°C.

[0140] The suitable reactor pressure for a gas-phase reactor may be about 1 to about 30 atmospheres. To facilitate the separation of HCl from other reaction products, a pressure of about 15 to about 25 atmospheres may be advantageously used, and the appropriate reaction time may vary from about 1 to about 120 seconds, preferably about 5 to about 60 seconds.

[0141] In one embodiment, the gas-phase fluorination of HCC-250fb to form HFO-1243zf is carried out in the absence of a catalyst. For example, the hydrofluorination of HCC-250fb can be performed by thermal decomposition in the absence of a catalyst in the reactor.

[0142] In another embodiment, a catalyst is used in the reaction zone of a gas-phase reaction between HF and HCC-250fb for the formation of HFO-1243zf. Fluorination catalysts that can be used in the gas-phase reaction include, but are not limited to, Lewis acid catalysts, transition metal halides, transition metal oxides (preferably partially fluorinated transition metal oxides), Group IVb metal halides, Group Vb metal halides, and metal alloy fillers, such as aluminum oxide, nickel-containing alloys such as Hastelloy®, nickel-chromium-containing alloys commercially available from Special Metals Corp. under the trademark Inconel®, nickel-copper-containing alloys commercially available from Special Metals Corp. (New Hartford, NY) under the trademark Monel®, other nickel alloy chips, or zinc-containing alloys, or combinations thereof.

[0143] In one embodiment, the gas-phase reaction of HCC-250fb to HFO-1243zf may be carried out in the presence of a chromium-based catalyst, a cobalt-based catalyst, a nickel-based catalyst, an aluminum-based catalyst, an iron-based catalyst, or a combination thereof. In one embodiment, the chromium-based catalyst is chromium oxide (e.g., Cr2O3). In one embodiment, the iron-based catalyst may be FeCl3 on carbon. In one embodiment, the aluminum-based catalyst may be Al2O3.

[0144] Depending on the circumstances, the catalyst may be pre-treated with HF or activated by acid treatment. This pre-treatment can be achieved, for example, by placing the catalyst in a suitable container and then passing HF or acid over the catalyst. In one embodiment, such a container may be a reactor used to carry out a hydrofluorication reaction. If the metal alloy packing of the reactor is catalytically active, it can be activated by passing HF or acid over the surface of the metal alloy packing. In one embodiment, the pre-treatment time is about 15 to about 300 minutes, and the pre-treatment temperature is about 200°C to about 450°C.

[0145] In some embodiments, under these conditions, for example, a mixture of HF and HCC-250fb is converted by a gas-phase fluorination process into a reaction mixture comprising HCl and one or more additional compounds selected from HCFC-253fb, HCFC-252fc, HCFC-251fb, HCC-250fb, HCFO-1242zf, HCFO-1241zf, and HCO-1240za. In some embodiments, HFO-1243zf constitutes about 0.1% to about 99.9% by weight, or about 40% to about 99.9% by weight, or about 90% to about 99.9% by weight, including all integers and ranges in between, based on the total weight of the composition.

[0146] In some embodiments, under these conditions, for example, a mixture of HF and HCC-250fb is converted by a gas-phase fluorination process into a reaction mixture comprising HCl and a composition containing HFO-1243zf and one or more additional compounds selected from HCFC-253fb, HCFC-252fc, HCFC-251fb, and HCC-250fb.

[0147] Hydrogenation of HCFC-252fc In some embodiments, HCFC-262fc can be produced by hydrogenation using HCFC-252fc. The hydrogenation reaction of HCFC-252fc can be carried out in the liquid phase or the gas phase. In one embodiment, HCFC-252fc is produced by the liquid-phase hydrogenation of HCC-250fb described above.

[0148] In the liquid-phase embodiments of the present invention, the reaction of HCFC-252fc with H2 may be carried out in a liquid-phase reactor operating in batch, semi-batch, semi-continuous, or continuous mode. In batch mode, HCFC-252fc and H2 are combined in an autoclave or other suitable reaction vessel and heated to a desired temperature.

[0149] In one embodiment, the reaction is carried out in a semi-batch mode by supplying HCFC-252fc to a liquid-phase reactor containing H2, or by supplying H2 to a liquid-phase reactor containing HCFC-252fc, or by supplying HCFC-252fc to a liquid-phase reactor containing a mixture of H2 and a reaction product formed by first heating HCFC-252fc and H2, or by supplying H2 to a liquid-phase reactor containing a mixture of HCFC-252fc and a reaction product formed by reacting H2 and HCFC-252fc. In another embodiment of the liquid-phase process, H2 and HCFC-252fc can be pre-mixed and supplied to the reactor, or supplied simultaneously to the reactor in a desired stoichiometric ratio and mixed upstream of the catalyst bed. In one embodiment, the reactor contains a mixture of H2, HCFC-252fc, and / or a reaction product formed by reacting H2 and HCFC-252fc.

[0150] A suitable molar ratio of H2 to HCFC-252fc supplied to the liquid-phase reactor is, in one embodiment, at least stoichiometric, and in another embodiment, about 0.5:1 to about 100:1, or about 5:1 to about 100:1, or about 8:1 to about 50:1, or about 0.5 to about 30:1, or about 1:1 to about 30:1, or about 2:1 to about 30:1.

[0151] In liquid-phase processes, reactor pressure is not critical; in batch reactions, it is typically the spontaneous pressure of the system at the reaction temperature. In continuous processes, the reactor pressure can be set so that low-boiling point products of the reaction are optionally discharged from the reactor through a packed column or condenser. In this way, higher-boiling point intermediates remain in the reactor, and volatile products are removed. Typical reactor pressures range from approximately 20 psig (239 kPa) to approximately 1,000 psig (6,994 kPa).

[0152] In one embodiment, a catalyst is used in the reaction zone for the liquid-phase reaction between H2 and HCFC-252dc. Possible hydrogenation catalysts include group VIII metals or ruthenium. In one embodiment, the metal is supported on a carrier, for example, Pd is supported on aluminum oxide, aluminum fluoride, or carbon. In another embodiment, the metal is supported on (e.g., Raney nickel). In one embodiment, the metal catalyst is supported on carbon, and the carbon carrier includes carbon, acid-washed carbon, activated carbon, or a carbonaceous material in a three-dimensional matrix. In one embodiment, the catalyst is Pd / carbon.

[0153] In one embodiment, the suitable temperature for catalytic hydrogenation of HCFC-252fc in a liquid-phase reactor is about 20°C to 150°C, or about 30°C to 100°C. Higher temperatures typically result in a greater conversion rate of HCFC-252fc.

[0154] In another embodiment, the hydrogenation of HCFC-262fc to form HCFC-252fc is non-catalytic, and the appropriate temperature is in the range of about 100°C to about 400°C, or in some embodiments, about 200°C or higher.

[0155] Under these conditions, for example, a mixture of H2 and HCFC-252fc is converted into a composition containing HCFC-262fc by a liquid-phase hydrogenation process. In some embodiments, the composition comprises HCFC-262fc and one or more additional compounds selected from HCC-250fb, HCFC-252fc, HFC-263fb, HCFC-262fa, and HCFC-272fb.

[0156] In another embodiment, the reaction between H2 and HCFC-252fc takes place in the gas phase. Typically, a heated reactor is used. Many reactor configurations are possible, including horizontal or vertical reactors, and the sequence of reactions between HCFC-252fc and H2. In one embodiment of the present invention, HCFC-252fc may first be vaporized and supplied to the reactor as a gas.

[0157] In another embodiment of the present invention, HCFC-252fc may be brought into contact with H2 in a pre-reactor before the reaction in the gas-phase reactor. In one embodiment, the pre-reactor may be empty. In another embodiment, the reactor is filled with a suitable packing material such as a nickel-copper alloy (hereinafter "Monel®") commercially available from Special Metals Corp. (New Hartford, New York) under the trademark Monel®, a nickel-based alloy (hereinafter "Hastelloy®") commercially available from Haynes International (Kokomo, Indiana) under the trademark Hastelloy®, or other nickel alloy chips or wool, or other inert material that allows for efficient mixing of HCFC-252fc with hydrogen gas.

[0158] In one embodiment, a suitable temperature for the preliminary reactor is approximately 20°C to approximately 120°C, preferably approximately 30°C to approximately 80°C.

[0159] In one embodiment, HCFC-252fc is optionally vaporized in the presence of hydrogen and supplied together with hydrogen to a pre-reactor or gas-phase reactor.

[0160] The appropriate temperature for the gas-phase reaction is approximately 20°C to 120°C, preferably approximately 30°C to 80°C.

[0161] The appropriate reactor pressure for a gas-phase reactor may be about 1 to about 30 atmospheres, and the appropriate reaction time may vary from about 1 to about 120 seconds, preferably about 5 to about 60 seconds.

[0162] The molar ratio of H2 to the total amount of HCFC-252fc for the gas-phase reaction is, in one embodiment, about 5:1 to about 100:1, or about 8:1 to about 50:1, or about 1:1 to about 30:1, or about 2:1 to about 30:1.

[0163] In one embodiment, a catalyst is used in the reaction zone for the gas-phase reaction between H2 and HCFC-252dc. Possible hydrogenation catalysts include group VIII metals or ruthenium. In one embodiment, the metal is supported on a carrier, for example, Pd is supported on aluminum oxide, aluminum fluoride, or carbon. In another embodiment, the metal is supported on (e.g., Raney nickel). In one embodiment, the metal catalyst is supported on carbon, and the carbon carrier includes carbon, acid-washed carbon, activated carbon, or a carbonaceous material in a three-dimensional matrix. In one embodiment, the catalyst is Pd / carbon.

[0164] Under these conditions, for example, a mixture of H2 and HCFC-252fc is converted by a gas-phase hydrogenation process into a composition comprising HCFC-262fc and one or more additional compounds selected from HCC-250fb, HFC-252fc, HFC-263fb, HCFC-262fa, and HCFC-272fb. In some embodiments, HCFC-262fc constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, including all integers and ranges in between.

[0165] Conversion of HCFC-252fc to HCFO-1242zf using caustic agents In some embodiments, HCFO-1242zf can be produced using HCFC-252fc by contacting HCFC-252fc with a caustic agent in an aqueous solvent at a temperature in the range of about 20°C to about 150°C, preferably about 30°C to about 100°C. In one embodiment, HCFC-252fc is produced by the liquid-phase hydrofluorication of HCC-250fb described above.

[0166] In some embodiments, the caustic agent contains a base that dissociates or reacts with water when placed in water. Examples include alkali metal oxides, alkali metal hydroxides, or alkali metal amides, such as sodium or potassium oxide, or sodium or potassium hydroxide, or sodium or potassium amide, or alkaline earth metal hydroxides, alkaline earth metal oxides or amides, alkali metal carbonates, alkali metal phosphates, or alkali metal carboxylates. Examples of caustic agents include, but are not limited to, NaOH, KOH, LiOH, CsOH, Ca(OH)2, Zn(OH)2, Na2CO3, K2CO3, K3PO4, Na3PO4, KF, or CsF. In some embodiments, the caustic agent is dissolved in an aqueous solution or present in an aqueous suspension. The caustic agent in the aqueous phase is present in an amount effective for dehalogenation and hydrogenation.

[0167] This reaction produces alkali metal halide salts such as lithium chloride, lithium bromide, lithium iodide, sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, and mixtures thereof. In some embodiments, the alkali metal halide salt is sodium chloride.

[0168] Under these conditions, for example, a mixture of HCFC-252fc is converted by a liquid-phase reaction in the presence of a caustic agent into a product mixture comprising water, a metal salt, and a composition containing HCFO-1242zf and one or more additional compounds selected from HCFC-253fb, HCFC-251fb, HCFC-252fc, and HCC-250fb. In some embodiments, HCFO-1242zf constitutes about 0.1% to about 99.9% by weight, or about 40% to about 99.9% by weight, or about 90% to about 99.9% by weight, including all integers and ranges in between, based on the total weight of the composition.

[0169] Hydrogenation of HCFO-1242zf In some embodiments, HCFO-1242zf can be used to produce HCFC-262fc by hydrogenation. The hydrogenation reaction of HCFC-252fc can be carried out in the liquid phase or the gas phase. In one embodiment, HCFO-1242zf is produced by the gas-phase hydrogenation of HCC-250fb described above.

[0170] In the liquid-phase embodiments of the present invention, the reaction of HCFO-1242zf with H2 may be carried out in a liquid-phase reactor operating in batch, semi-batch, semi-continuous, or continuous mode. In batch mode, HCFO-1242zf and H2 are combined in an autoclave or other suitable reaction vessel and heated to the desired temperature.

[0171] In one embodiment, the reaction is carried out in a semi-batch mode by supplying HCFO-1242zf to a liquid-phase reactor containing H2, or by supplying H2 to a liquid-phase reactor containing HCFO-1242zf, or by supplying HCFO-1242zf to a liquid-phase reactor containing a mixture of H2 and a reaction product formed by first heating HCFO-1242zf and H2, or by supplying H2 to a liquid-phase reactor containing a mixture of HCFO-1242zf and a reaction product formed by reacting H2 and HCFO-1242zf. In another embodiment of the liquid-phase process, H2 and HCFO-1242zf can be pre-mixed and supplied to the reactor, or supplied simultaneously to the reactor in a desired stoichiometric ratio and mixed upstream of the catalyst bed. In one embodiment, the reactor contains a mixture of H2, HCFO-1242zf, and / or a reaction product formed by reacting H2 and HCFO-1242zf.

[0172] The suitable temperature for the reaction of H2 with HCFO-1242zf in a liquid-phase reactor is approximately 280°C to 150°C in one embodiment and approximately 30°C to 100°C in another embodiment. Higher temperatures typically result in a greater conversion rate of HCFO-1242zf.

[0173] A preferred molar ratio of H2 to HCFO-1242zf supplied to the liquid-phase reactor is, in one embodiment, at least stoichiometric, and in another embodiment, about 1:1 to about 5:1, or about 1.2:1 to about 3:1.

[0174] In liquid-phase processes, reactor pressure is not critical; in batch reactions, it is typically the spontaneous pressure of the system at the reaction temperature. In continuous processes, the reactor pressure can be set so that low-boiling point products of the reaction are optionally discharged from the reactor through a packed column or condenser. In this way, higher-boiling point intermediates remain in the reactor, and volatile products are removed. Typical reactor pressures range from approximately 20 psig (239 kPa) to approximately 1,000 psig (6,994 kPa).

[0175] In some embodiments where the reaction is carried out using a liquid-phase process, the hydrogenation catalyst that may be used in the liquid phase comprises a group VIII metal or ruthenium. In one embodiment, the metal is supported on a carrier, for example, Pd is supported on aluminum oxide, aluminum fluoride, or carbon. In another embodiment, the metal is supported on (e.g., Raney nickel). In one embodiment, the metal catalyst is supported on carbon, and the carbon carrier comprises carbon, acid-washed carbon, activated carbon, or a carbonaceous material of a three-dimensional matrix. In one embodiment, the catalyst is Pd / carbon.

[0176] Under these conditions, for example, a mixture of H2 and HCFO-1242zf is converted by a liquid-phase hydrogenation process into a composition comprising HCFC-262fc and one or more additional compounds selected from HCC-250fb, HFC-263fb, HFC-272fb, HFO-1252zc, and HCFO-1242zf, in which case HCFC-262fc constitutes about 90% to 99.9% by weight based on the total weight of the composition.

[0177] In one embodiment, under these conditions, for example, a mixture of H2 and HCFO-1242zf is converted by a liquid-phase hydrogenation process into a composition comprising HCFC-262fc and one or more additional compounds selected from ethane, HFC-152a, HFC-253db, HCFO-1232 isomer, HCFO-1242 isomer, HCFO-1242zf, HFO-1243zf, and HFO-1252zc. In some embodiments, HCFC-262fc constitutes about 0.1% to about 99.9% by weight, or about 40% to about 99.9% by weight, or about 90% to about 99.9% by weight, including all integers and ranges in between, based on the total weight of the composition.

[0178] In some embodiments, the vapor portion of the composition produced by the liquid-phase hydrogenation of HCFO-1242zf comprises HCFC-262fc and one or more additional compounds selected from ethane, HFC-152a, HFC-253db, HCFO-1232 isomer, HCFO-1242 isomer, HCFO-1242zf, HFO-1243zf, and HFO-1252zc. In some embodiments, HCFC-262fc constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, including all integers and ranges in between, based on the total weight of the vapor portion of the composition.

[0179] In some embodiments, the liquid portion of the composition produced by the liquid-phase hydrogenation of HCFO-1242zf comprises HCFC-262fc and one or more additional compounds selected from HFC-253db, HCFO-1232 isomers, HCFO-1242 isomers, HCFO-1242zf, and HFO-1252zc. In some embodiments, HCFC-262fc constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, including all integers and ranges in between, based on the total weight of the liquid portion of the composition.

[0180] In one embodiment, under these conditions, for example, a mixture of H2 and HCFO-1242zf is converted by a liquid-phase hydrogenation process into a composition comprising HCFC-262fc and one or more additional compounds selected from HFC-253db, HCFO-1232 isomers, HCFO-1242zf, and HFO-1252zc. In some embodiments, HCFC-262fc constitutes about 0.1% to about 99.9% by weight, or about 40% to about 99.9% by weight, or about 90% to about 99.9% by weight, including all integers and ranges in between, based on the total weight of the composition.

[0181] In another embodiment, the reaction between H2 and HCFO-1242zf takes place in the gas phase. Typically, a heated reactor is used. Many reactor configurations are possible, including horizontal or vertical reactors, and the sequence of reactions between HCFO-1242zf and H2. In one embodiment of the present invention, HCFO-1242zf may first be vaporized and supplied to the reactor as a gas.

[0182] In another embodiment of the present invention, HCFO-1242zf may be brought into contact with H2 in a pre-reactor before the reaction in the gas-phase reactor. In one embodiment, the pre-reactor may be empty. In another embodiment, the reactor is filled with a suitable packing material such as a nickel-copper alloy (hereinafter "Monel®") commercially available from Special Metals Corp. (New Hartford, New York) under the trademark Monel®, a nickel-based alloy (hereinafter "Hastelloy®") commercially available from Haynes International (Kokomo, Indiana) under the trademark Hastelloy®, or other nickel alloy chips or wool, or other inert material that allows for efficient mixing of HCFO-1242zf with hydrogen gas.

[0183] In one embodiment, the appropriate temperature for the pre-reactor is about 20°C to about 120°C, and in another embodiment, it is about 30°C to about 80°C.

[0184] In one embodiment, the molar ratio of H2 to HCFO-1242zf in the pre-reactor is approximately 10:1, based on the approximate stoichiometric ratio of H2 to HCFO-1242zf. In another embodiment, the molar ratio of H2 to HCFO-1242zf in the pre-reactor is approximately 1:1 to approximately 5:1, or approximately 1.2:1 to approximately 3:1.

[0185] In one embodiment, HCFO-1242zf is optionally vaporized in the presence of hydrogen and supplied together with hydrogen to a pre-reactor or gas-phase reactor.

[0186] The appropriate temperature range for the gas-phase reaction is approximately 20°C to 120°C, and in another embodiment, approximately 30°C to 80°C.

[0187] The appropriate reactor pressure for a gas-phase reactor may be about 1 to about 30 atmospheres, and the appropriate reaction time may vary from about 1 to about 120 seconds, preferably about 5 to about 60 seconds.

[0188] The molar ratio of H2 to the total amount of HCFO-1242zf for the gas-phase reaction is, in one embodiment, from the approximate stoichiometric ratio of H2 to HCFO-1242zf to about 10:1, and in another embodiment, it is about 1:1 to about 5:1, or about 1.2:1 to about 4:1.

[0189] In one embodiment, a catalyst is used in the reaction zone for a gas-phase reaction between H2 and HCFO-1242zf. Hydrogenation catalysts that can be used in the gas-phase reaction include group VIII metals or ruthenium. In one embodiment, the metal is supported on a carrier, for example, Pd is supported on aluminum oxide, aluminum fluoride, or carbon. In another embodiment, the metal is supported on (e.g., Raney nickel). In one embodiment, the metal catalyst is supported on carbon, and the carbon carrier includes carbon, acid-washed carbon, activated carbon, or a carbonaceous material in a three-dimensional matrix. In one embodiment, the catalyst is Pd / carbon.

[0190] In one embodiment, under these conditions, for example, a mixture of H2 and HCFO-1242zf is converted by a gas-phase hydrogenation process into a composition comprising HCFC-262fc and one or more additional compounds selected from propane, propylene, E-HFO-1261ze, Z-HFO-1261ze, HFO-1252zc, HFC-272fb, E-HCFO-1251zd, Z-HCFO-1251zd, HCFC-262db, HCFC-252dc, HCO-1250, HCC-260, HFO-1243zf, HCFO-1242zf, HCFO-1242 isomer, HCFO-1232 isomer, and HCFC-252 isomer. In some embodiments, HCFC-262fc constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, including all integers and ranges in between.

[0191] In one embodiment, under these conditions, for example, a mixture of H2 and HCFO-1242zf is converted by a gas-phase hydrogenation process into a composition comprising HCFC-262fc and one or more compounds selected from HFO-1252zc, HCFC-262db, HFC-272fb, HFO-1243zf, and HCFO-1242zf. In some embodiments, HCFC-262fc constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, including all integers and ranges in between.

[0192] In one embodiment, under these conditions, for example, a mixture of H2 and HCFO-1242zf is converted by a gas-phase hydrogenation process into a composition comprising HCFC-262fc, HCFO-1242zf, and one or more additional compounds selected from propane, propylene, E-HFO-1261ze, Z-HFO-1261ze, HFO-1252zc, HFC-272fb, E-HCFO-1251zd, Z-HCFO-1251zd, HCFC-262db, HCFC-252dc, HCO-1250, HCC-260, HFO-1243zf, HCFO-1242 isomers, HCFO-1232 isomers, and HCFC-252 isomers. In some embodiments, HCFC-262fc constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, including all integers and ranges in between.

[0193] In one embodiment, under these conditions, for example, a mixture of H2 and HCFO-1242zf is converted by a gas-phase hydrogenation process into a composition comprising HCFC-262fc, HFC-272fb, and one or more additional compounds selected from propane, propylene, E-HFO-1261ze, Z-HFO-1261ze, HFO-1252zc, E-HCFO-1251zd, Z-HCFO-1251zd, HCFC-262db, HCFC-252dc, HCO-1250, HCC-260, HFO-1243zf, HCFO-1242zf, HCFO-1242 isomer, HCFO-1232 isomer, and HCFC-252 isomer. In some embodiments, HCFC-262fc constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, including all integers and ranges in between.

[0194] In one embodiment, under these conditions, for example, a mixture of H2 and HCFO-1242zf is converted by a gas-phase hydrogenation process into a composition comprising HCFC-262fc and one or more compounds selected from HCC-250fb, HFC-263fb, HFC-272fb, HFO-1252zc, and HCFO-1242zf. In some embodiments, HCFC-262fc constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, including all integers and ranges in between.

[0195] In one embodiment, under these conditions, for example, a mixture of H2 and HCFO-1242zf is converted by a gas-phase hydrogenation process into a composition comprising HCFC-262fc and one or more additional compounds selected from propane, propylene, HCFC-252dc, HCFC-262db, HFC-272fb, HCFO-1232xf, HCFO-1242zf, HFO-1243zf, E-HCFO-1251zd, Z-HCFO-1251zd, HFO-1252zf, E-HFO-1261ze, Z-HFO-1261ze, HCFO-1242 isomers, and HCO-1260. In some embodiments, HCFC-262fc constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, including all integers and ranges in between.

[0196] In one embodiment, under these conditions, for example, a mixture of H2 and HCFO-1242zf is converted by a gas-phase hydrogenation process into a composition comprising HCFC-262fc and one or more additional compounds selected from propane, propylene, HCFC-252dc, HCFC-262db, HFC-272fb, HCFO-1232xf, HCFO-1242zf, HFO-1243zf, E-HCFO-1251zd, Z-HCFO-1251zd, HFO-1252zf, E-HFO-1261ze, Z-HFO-1261ze, and HCO-1260. In some embodiments, HCFC-262fc constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, including all integers and ranges in between.

[0197] In one embodiment, under these conditions, for example, a mixture of H2 and HCFO-1242zf is converted by a gas-phase hydrogenation process into a composition comprising HCFC-262fc and one or more additional compounds selected from propane, propylene, HCFC-252dc, HCFC-262db, HCFO-1232xf, HCFO-1242zf, HFO-1243zf, E-HCFO-1251zd, Z-HCFO-1251zd, HFO-1252zf, E-HFO-1261ze, Z-HFO-1261ze, and HCFO-1242 isomers. In some embodiments, HCFC-262fc constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, including all integers and ranges in between.

[0198] In one embodiment, under these conditions, for example, a mixture of H2 and HCFO-1242zf is converted by a gas-phase hydrogenation process into a composition comprising HCFC-262fc and one or more additional compounds selected from HCFC-262db, HCFO-1232xf, HCFO-1242zf, HFO-1243zf, E-HCFO-1251zd, Z-HCFO-1251zd, HFO-1252zf, and E-HFO-1261ze. In some embodiments, HCFC-262fc constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, including all integers and ranges in between.

[0199] Dehydrochlorination of HCFC-262fc In some embodiments, HFO-1252zc can be produced using HCFC-262fc by dehalogenation hydrogenation, more specifically by dechlorination hydrogenation. In one embodiment, HCFC-262fc is produced by liquid-phase or gas-phase hydrogenation of HCFC-252fc, or by liquid-phase or gas-phase hydrogenation of HCFO-1242zf.

[0200] In some embodiments, the dehalogenation hydrogenation reaction of HCFC-262fc is preferably carried out in the gas phase. In one embodiment, the gas-phase dehydrochlorination of HCFC-262fc to produce HFO-1252zc is carried out in the presence of a catalyst. In one embodiment, the dehalogenation hydrogenation catalyst may be, but is not limited to, carbon and / or metal catalysts. In one embodiment, the catalyst may be selected from activated carbon, nickel catalysts, palladium catalysts, or any combination thereof. In one embodiment, the catalyst may be selected from Ni mesh, palladium carbon, palladium aluminum oxide, or a combination thereof. In one embodiment, the catalyst may be a metal alloy, for example, a nickel alloy such as Hastelloy®, a nickel-chromium alloy (hereinafter, Inconel®) commercially available from Special Metals Corp. under the trademark Inconel®, or a nickel-copper alloy commercially available from Special Metals Corp. (New Hartford, NY) under the trademark Monel®, or other nickel alloy chips or activated carbon.

[0201] In some embodiments of the present invention, catalytic dehalogenation of HCFC-262fc to form HFO-1252zc is carried out at temperatures in the range of about 400°C to about 800°C, preferably in the range of about 400°C to about 700°C, or preferably above about 400°C, all values ​​and ranges in between.

[0202] In one embodiment, HFO-1252zc is prepared by thermal dehydrochlorination (pyrolysis) of HCFC-262fc. In one embodiment, this reaction occurs in the absence of a catalyst. In one embodiment, HCFC-262fc is introduced into a reaction vessel that is maintained at a temperature high enough to influence the thermal dehydrochlorination of HCFC-262fc. In one embodiment, the temperature is high enough to carry out thermal dehydrochlorination of HCFC-262fc to a conversion rate of at least 10% with a contact time of about 10 seconds to about 30 minutes.

[0203] In some embodiments of the present invention, the non-catalytic dehalogenation of HCFC-262fc to form HFO-1252zc is carried out at temperatures in the range of about 400°C to about 800°C, preferably about 450°C to about 700°C, or preferably about 450°C or higher, all values ​​and ranges in between.

[0204] In one embodiment, the reactor is constructed from a corrosion-resistant material. In one embodiment, the reactor is filled with a suitable packing material such as a nickel-copper alloy (hereinafter referred to as "Monel®") commercially available from Special Metals Corp. (New Hartford, New York) under the trademark Monel®, a nickel-based alloy (hereinafter referred to as "Hastelloy®") commercially available from Haynes International (Kokomo, Indiana) under the trademark Hastelloy®, or other nickel alloy chips or wool, or other inert material.

[0205] The appropriate reactor pressure for a gas-phase reactor may be approximately 10 to 200 psig, and the appropriate reaction time may vary from 10 seconds to approximately 30 minutes.

[0206] In one embodiment, HCFC-262fc is preheated to a temperature of approximately 200°C in a vaporizer.

[0207] In some embodiments, an inert diluent gas is used as the carrier gas for HCFC-262fc. In one embodiment, the carrier gas is selected and is nitrogen, argon, helium, or carbon dioxide.

[0208] In other embodiments, the dehalogenation and hydrogenation reaction of HCFC-262fc is preferably carried out in the liquid phase. More specifically, the dehydrochlorination of HCFC-262fc is carried out using a strong base in a solvent such as an aqueous solvent or an organic solvent, in or without a catalyst.

[0209] Examples of bases include, but are not limited to, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate, sodium phosphate, potassium phosphate, or mixtures thereof. Some examples of strong bases include, but are not limited to, hydroxides, alkoxides, metal amides, metal hydrides, metal dialkylamides, and arylamines. Examples of alkoxides include lithium, sodium, and potassium salts of methyl, ethyl, and t-butyl oxides; examples of metal amides include sodium amide, potassium amide, and lithium amide; examples of metal hydrides include sodium hydride, potassium hydride, and lithium hydride; and examples of metal dialkylamides include lithium, sodium, and potassium salts of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, trimethylsilyl, and cyclohexyl-substituted amides.

[0210] In some embodiments, the base is selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate, sodium phosphate, potassium phosphate, potassium tert-butoxide, methyl, ethyl, and t-butyl oxides, and mixtures thereof.

[0211] In some embodiments, the base is an aqueous basic solution. As used herein, “basic aqueous solution” is a liquid (e.g., a solution, dispersion, emulsion, or suspension) that is primarily an aqueous liquid with a pH greater than 7.

[0212] In some embodiments, the basic aqueous solution contains a small amount of an organic liquid which may be miscible or immiscible with water. In some embodiments, the liquid medium in the basic aqueous solution is at least 90%, for example, at least 95%, at least 97%, at least 98%, at least 99%, at least 99.5%, or at least 99.9% water. In some embodiments, the water used in the aqueous basic solution is tap water. In some embodiments, the water used in the aqueous basic solution is deionized water or distilled water.

[0213] In some embodiments, examples of solvents include alkyl, dialkyl, and trialkyl linear or cyclic amines, N-methylpyrrolidine, N-methylpiperidine, sulfoxides, ethers, pyridine or alkyl-substituted pyridines, pyrazines or pyrimidines, alkyl and aromatic nitriles, hexamethylphosphoramides, alcohols, esters, and mixtures thereof. In one embodiment, the alcohol solvent is methanol. In one embodiment, the ester solvent is methyl formate. In one embodiment, the sulfoxide solvent is dimethyl sulfoxide. In one embodiment, the alkyl nitrile solvent is acetonitrile. In one embodiment, the aromatic nitrile solvent is benzonitrile. In another embodiment, the reaction solvent is selected from trialkylamines, N-methylpyrrolidine, N-methylpiperidine, pyridine, alkyl-substituted pyridines, dimethylformamide, pyrazines or pyrimidines, and mixtures thereof. In yet another embodiment, the reaction solvent is selected from dimethylformamide, tetrahydrofuran, pyridine, dimethylacetamide, 1,4-dioxane, N-methylpyrrolidone, diethyl ether, and mixtures thereof. In yet another embodiment, the reaction solvent is pyridine or alkyl-substituted pyridine, or a mixture thereof. In yet another embodiment, the reaction solvent is a mixture of pyridine or alkyl-substituted pyridine and dimethylformamide.

[0214] Under these conditions, for example, HCFC-262fc is converted by a liquid-phase or gas-phase dehalogenation hydrogenation process into a composition comprising HFO-1252zc and one or more additional compounds selected from HCFC-262fc, HCC-250fb, HFC-263fb, HFO-1243zf, other 1252 isomers, ethane, ethylene, HFC-23, HCFC-22, HFO-1132a, propane, HFC-143a, HCFC-142b, HFO-1234yf, HFO-1234ze, HFO-1225zc, HCFO-1242zf, HFO-1241zf, HFO-1240za, and HCFC-252fc. In some embodiments, HCFC-1252zc constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, and includes all integers and ranges in between.

[0215] Conversion of HCFO-1242zf to HFO-1252zc by reaction with Zn In some embodiments, the present invention provides a liquid-phase method for dechlorinating HCFO-1242zf formed by the gas-phase hydrofluorination of HCC-250fb described above. The dechlorination method includes contacting HCFO-1242zf with zinc.

[0216] The reaction of HCFO-1242zf with HF can be carried out in a liquid-phase reactor operating in batch, semi-batch, semi-continuous, or continuous mode. In batch mode, HCFO-1242zf and Zn are combined in an autoclave or other suitable reaction vessel and heated to the desired temperature.

[0217] In one embodiment, the reaction is carried out in a semi-batch mode by supplying HCFO-1242zf to a liquid-phase reactor containing Zn, or by supplying Zn to a liquid-phase reactor containing HCFO-1242zf, or by supplying HCFO-1242zf to a liquid-phase reactor containing a mixture of Zn and a reaction product formed by first heating HCFO-1242zf and Zn, or by supplying Zn to a liquid-phase reactor containing a mixture of HCFO-1242zf and a reaction product formed by reacting Zn and HCFO-1242zf. In another embodiment of the liquid-phase process, Zn and HCFO-1242zf can be pre-mixed and supplied to the reactor, or supplied simultaneously to the reactor in a desired stoichiometric ratio and mixed upstream of the catalyst bed. In one embodiment, the reactor contains a mixture of Zn, HCFO-1242zf, and / or a reaction product formed by reacting Zn and HCFO-1242zf.

[0218] The suitable temperature range for the reaction of Zn with HCFO-1242zf in a liquid-phase reactor is approximately 20°C to 150°C in one embodiment and approximately 30°C to 100°C in another embodiment. Higher temperatures typically result in a greater conversion rate of HCFO-1242zf.

[0219] The appropriate molar ratio of Zn to HCFO-1242zf supplied to the liquid-phase reactor is, in one embodiment, at least stoichiometric, and in another embodiment, about 1:1 to about 30:1, or about 2:1 to about 30:1.

[0220] In liquid-phase processes, reactor pressure is not critical; in batch reactions, it is typically the spontaneous pressure of the system at the reaction temperature. In continuous processes, the reactor pressure can be set so that low-boiling point products of the reaction are optionally discharged from the reactor through a packed column or condenser. In this way, higher-boiling point intermediates remain in the reactor, and volatile products are removed. Typical reactor pressures range from approximately 20 psig (239 kPa) to approximately 1,000 psig (6,994 kPa).

[0221] In some embodiments in which the reaction is carried out using a liquid-phase process, the reaction is carried out by reacting HCFO-1242zf with zinc in an organic solvent, in or without the presence of a catalyst.

[0222] Organic solvents include alcohols such as methanol, ethanol, and glycols; organic acids such as acetic acid, propionic acid, butyric acid, octanoic acid, phthalic acid, and benzoic acid; esters of organic acids such as methyl acetate, ethyl acetate, ethylene glycol diacetate, propylene glycol diacetate, dimethyl adipate, methyl benzoate, ethyl benzoate, dimethyl phthalate, diethyl phthalate, dioctyl phthalate, phenyl acetate, and tolyl acetate; hydrocarbons such as dodecane, hexadecane, benzene, naphthalene, and biphenyl; and esters of inorganic acids such as triphenyl. Examples include phosphates, tricresyl phosphates, dibutylphenyl phosphates, silicates such as tetramethyl orthosilicate and tetrabutyl silicate, ketones such as aromatic ethers such as diphenyl ether, ketones such as acetone, methyl ethyl ketone, dibutyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone, polar aprotic solvents such as acetonitrile, propionitrile, and N,N-dimethylformamide (DMF), and carboxylic acid anhydrides such as acetic anhydride and propionic anhydride, as well as mixtures thereof.

[0223] In some embodiments, suitable organic solvents include alkyl, dialkyl, and trialkyl linear or cyclic amines, N-methylpyrrolidine, N-methylpiperidine, sulfoxides, ethers, pyridine or alkyl-substituted pyridines, pyrazines or pyrimidines, alkyl and aromatic nitriles, hexamethylphosphoramides, alcohols, esters, and mixtures thereof. In one embodiment, the alcohol solvent is methanol. In one embodiment, the ester solvent is methyl formate. In one embodiment, the sulfoxide solvent is dimethyl sulfoxide. In one embodiment, the alkyl nitrile solvent is acetonitrile. In one embodiment, the aromatic nitrile solvent is benzonitrile. In another embodiment, the reaction solvent is selected from trialkylamines, N-methylpyrrolidine, N-methylpiperidine, pyridine, alkyl-substituted pyridines, dimethylformamide, pyrazines or pyrimidines, and mixtures thereof. In yet another embodiment, the reaction solvent is selected from dimethylformamide, tetrahydrofuran, pyridine, dimethylacetamide, 1,4-dioxane, N-methylpyrrolidone, diethyl ether, and mixtures thereof. In yet another embodiment, the reaction solvent is pyridine or alkyl-substituted pyridine, or a mixture thereof. In yet another embodiment, the reaction solvent is a mixture of pyridine or alkyl-substituted pyridine and dimethylformamide.

[0224] In some embodiments, the reaction is carried out by reacting HCFO-1242zf with zinc in an organic solvent in the absence of a catalyst.

[0225] In some embodiments, this is carried out by reacting HCFO-1242zf with zinc under reaction conditions, in an organic solvent, and in the presence of a catalyst. In some embodiments, the catalyst is a metal salt and / or a phase transfer catalyst. Examples of metal salts include, but are not limited to, zinc salts. Suitable zinc salts include zinc acetate, zinc bromide, zinc chloride, zinc citrate, zinc sulfate, and mixtures thereof. Suitable phase transfer catalysts include quaternary ammonium halides (e.g., tetrabutylammonium bromide, tetrabutylammonium hydrosulfate, triethylbenzylammonium chloride, dodecyltrimethylammonium chloride, and tricaprylylammonium chloride), quaternary phosphonium halides (e.g., triphenylmethylphosphonium bromide and tetraphenylphosphonium chloride), or cyclic polyether compounds known in the art as crown ethers (e.g., 18-crown-6 and 15-crown-5). In some embodiments, the catalyst is activated by acid treatment. This activation can be achieved, for example, by placing the catalyst in a suitable container and then passing HF or an acid over the catalyst. In one embodiment, such a container may be a reactor used to carry out a hydrofluorication reaction.

[0226] Under these conditions, for example, a mixture of Zn and HCFO-1242zf is converted by a liquid-phase dechlorination process into a composition comprising a reaction mixture containing zinc chloride (ZnCl2), HFO-1252zc, and one or more additional compounds selected from HCC-250fb, HFO-1252zc, HFO-1243zf, HCC-262fc, HCC-263fb, and HCFO-1242zf. In some embodiments, HCFC-1252zc constitutes about 0.1% to about 99.9% by weight, or about 40% to about 99.9% by weight, or about 90% to about 99.9% by weight, based on the total weight of the composition, and includes all integers and ranges in between.

[0227] Integration process In one embodiment disclosed herein, HFO-1252zc is prepared according to an integrated process including reaction scheme A. Process 1A: CCl3CH2CH2Cl(HCC-250fb)+HF→CClF2CH2CH2Cl(HCFC-252fc)+HCl Process 2A: CClF2CH2CH2Cl(HCFC-252fc)+H2→CClF2CH2CH3(HCFC-262fc)+HCl Process 3A: CClF2CH2CH3(HCFC-262fc)→CF2=CHCH3(HFO-1252zc)+HCl or in solution CClF2CH2CH3(HCFC-262fc)+strong base→CF2=CHCH3(HFO-1252zc) In the formula, step 1A is the liquid-phase hydrofluorination of HCC-250fb as described herein, step 2A is the liquid-phase or gas-phase hydrofluorination of HCFC-252fc as described herein, and step 3A is the gas-phase or liquid-phase dehalogenation hydrofluorination of HCFC-262fc as described herein.

[0228] In some embodiments, the integration process further includes separation and / or purification steps to recover the desired intermediates (e.g., HCFC-252fc and HCFC-262fc) and the desired reaction product, HFO-1252zc.

[0229] In some embodiments, HCFC-262fc is prepared from HCFC-252fc according to step 2A, where step 2A is liquid-phase or gas-phase hydrogenation of HCFC-252fc as described herein.

[0230] In some embodiments, HCFC-262fc is prepared from HCC-250fb according to integrated steps 1A and 2A, where step 1A is the liquid-phase hydrofluorination of HCC-250fb as described herein, and step 2A is the liquid-phase or gas-phase hydrofluorination of HCFC-252fc as described herein.

[0231] In some embodiments, HFO-1252zc is prepared from HCFC-252fc according to integrated steps 2A and 3A, where step 2A is liquid-phase or gas-phase hydrogenation of HCFC-252fc as described herein, and step 3A is gas-phase dehalogenation hydrogenation of HCFC-262fc as described herein.

[0232] In some embodiments, HFO-1252zc is prepared from HCFC-262fc according to step 3A, where step 3A is the gas-phase dehalogenation hydrogenation of HCFC-262fc as described herein.

[0233] In one embodiment disclosed herein, HFO-1252zc is prepared according to an integrated process including reaction scheme B. Process 1B: CCl3CH2CH2Cl(HCC-250fb)+HF→CClF2CH=CH2(HCFO-1242zf)+HCl Process 2B: CClF2CH=CH2(HCFO-1242zf)+H2→CClF2CH2CH3(HCFC-262fc) Process 3B: CClF2CH2CH3(HCFC-262fc)→CF2=CHCH3(HFO-1252zc)+HCl In the formula, step 1B is the gas-phase hydrofluorination of HCC-250fb as described herein, step 2B is the liquid-phase or gas-phase hydrogenation of HCFO-1242zf as described herein, and step 3B is the gas-phase dehalogenation hydrofluorination of HCFC-262fc as described herein.

[0234] In some embodiments, the integration process further includes separation and / or purification steps to recover the desired intermediates (e.g., HCFO-1242zf and HCFC-262fc) and the desired reaction product, HFO-1252zc.

[0235] In some embodiments, HCFC-262fc is prepared from HFO-1243zf according to step 2B, where step 2B is the liquid-phase or gas-phase hydrogenation of HCFO-1242zf as described herein.

[0236] In some embodiments, HFO-1252zc is prepared from HFO-1243zf according to steps 2B and 3B, where step 2B is liquid-phase or gas-phase hydrogenation of HCFO-1242zf as described herein, and step 3B is gas-phase dehalogenation hydrogenation of HCFC-262fc as described herein.

[0237] In some embodiments, HFO-1252zc is prepared from HCFC-262fc according to step 3B, where step 3B is the gas-phase dehalogenation hydrogenation of HCFC-262fc as described herein.

[0238] In some embodiments, HCFC-262fc is prepared from HCC-250fb according to steps 1B and 2B, where step 1B is the gas-phase hydrogenation of HCC-250fb as described herein, and step 2B is the liquid-phase or gas-phase hydrogenation of HCFO-1242zf as described herein.

[0239] In some embodiments, HCFC-262fc is prepared from HCFO-1242zf according to step 2B, where step 2B is liquid-phase or gas-phase hydrogenation of HCFO-1242zf as described herein.

[0240] In one embodiment disclosed herein, HFO-1252zc is prepared according to an integrated process comprising reaction scheme C. Process 1C: CCl3CH2CH2Cl(HCC-250fb)+HF→CClF2CH=CH2(HCFO-1242zf)+HCl Process 2C: CClF2CH=CH2(HCFO-1242zf)+Zn→CF2=CHCH3(HFO-1252zc)+ZnCl2 In the formula, step 1C is the gas-phase hydrofluorination of HCC-250fb as described herein, and step 2C is the liquid-phase dechlorination of HCFO-1242zf as described herein.

[0241] In some embodiments, the integration process further includes separation and / or purification steps to recover a desired intermediate (e.g., HCFO-1242zf) and a desired reaction product, HFO-1252zc.

[0242] In some embodiments, the present invention relates to a process for preparing HFO-1252zc from HCFO-1242zf according to step 2C, where step 2C is liquid-phase dechlorination of HCFO-1242zf as described herein.

[0243] In one embodiment disclosed herein, HFO-1252zc is prepared according to an integrated process comprising reaction scheme D. Process 1D: CCl3CH2CH2Cl(HCC-250fb)+HF→CClF2CH2CH2Cl(HCFC-252fc)+HCl Process 2D: CClF2CH2CH2Cl(HCFC-252fc) + caustic agent → CClF2CH=CH2(HCFO-1242zf) + H2O + salt Process 3D: CClF2CH=CH2(HCFO-1242zf)+Zn→CF2=CHCH3(HFO-1252zc)+ZnCl2 or CClF2CH=CH2(HCFO-1242zf)+H2→CClF2CH2CH3(HCFC-262fc)→CF2=CHCH3(HFO-1252zc)+HCl or In bases / solvents CClF2CH=CH2(HCFO-1242zf)+H2→CClF2CH2CH3(HCFC-262fc)→CF2=CHCH3(HFO-1252zc) In the formula, step 1D is the liquid-phase hydrofluorination of HCC-250fb as described herein, step 2D is the liquid-phase hydrochloride dechlorination of HCFC-252fc as described herein, and step 3D is any of the following: (i) a liquid-phase reaction of HCFO-1242zf with zinc, (ii) liquid-phase or gas-phase hydrogenation of HCFO-1242zf as described herein, followed by gas-phase hydrohalogenation of HCFC-262fc as described herein, or (iii) liquid-phase hydrochloride dechlorination of HCFC-262fc using a strong base as described herein.

[0244] In some embodiments, the integration process further includes separation and / or purification steps to recover the desired intermediates (e.g., HCFO-1242zf and HCFC-262fc) and the desired reaction product, HFO-1252zc.

[0245] composition One embodiment of the present invention disclosed herein relates to a composition comprising, essentially consisting of, or comprising HCFC-262fc and one or more compounds selected from HCC-250fb, HCFC-252fc, HCFO-1242zf, HFC-263fb, HCFC-272fb, and HFO-1252zf.

[0246] One embodiment of the present invention disclosed herein relates to a composition comprising, essentially consisting of, or comprising HFO-1252zc and one or more additional compounds selected from HCFC-262fc, HCC-250fb, HFC-263fb, HFO-1243zf, other HFO-1252 isomers, ethane, ethylene, HFC-23, HCFC-22, HFO-1132a, propane, HFC-143a, HCFC-142b, HFO-1234yf, HFO-1234ze, HFO-1225zc, HCFO-1242zf, HCFC-252fc, HFO-1252zf, HCFC-272fb, HFO-1241zf, HFO-1240za, HCFC-253fb, and HCFC-251fb.

[0247] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises (i) HCFC-262fc, (ii) at least one of HCC-250fb and HCFC-252fc, and (iii) one or more additional compounds selected from HFC-263fb and HCFC-272fb. In some embodiments, these compositions are formed by step 2A or by steps 1A and 2A.

[0248] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HCFC-262fc, HCC-250fb, and one or more additional compounds selected from HCFC-252fc, HFC-263fb, and HCFC-272fb. In some embodiments, these compositions are formed by step 2A or by steps 1A and 2A.

[0249] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HCFC-262fc, HCFC-252fc, and one or more additional compounds selected from HCC-250fb, HFC-263fb, and HCFC-272fb. In some embodiments, these compositions are formed by step 2A or by steps 1A and 2A.

[0250] One embodiment of the present invention disclosed herein relates to a composition comprising, essentially consisting of, or comprising HFO-1252zc and one or more additional compounds selected from HCFC-262fc, HCC-250fb, HFC-263fb, HFO-1243zf, other 1252 isomers, ethane, ethylene, HFC-23, HCFC-22, HFO-1132a, propane, HFC-143a, HCFC-142b, HFO-1234yf, HFO-1234ze, HFO-1225zc, HCFO-1242zf, and HCFC-252fc.

[0251] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises (i) HFO-1252zc, (ii) at least one of HCC-250fb, HCFC-252fc and HCFC-262fc, and (iii) one or more additional compounds selected from HFC-263fb, HFO-1243zf, other 1252 isomers, ethane, ethylene, HFC-23, HCFC-22, HFO-1132a, propane, HFC-143a, HCFC-142b, HFO-1234yf, HFO-1234ze, HFO-1225zc and HCFO-1242zf. In some embodiments, these compositions are formed by steps 1A-3A, or steps 2A-3A, or step 3A, or steps 1B-3B, or steps 2B-3B, or step 3B.

[0252] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HFO-1252zc, HCFC-262fc, and one or more additional compounds selected from HCC-250fb, HFC-263fb, HFO-1243zf, other 1252 isomers, ethane, ethylene, HFC-23, HCFC-22, HFO-1132a, propane, HFC-143a, HCFC-142b, HFO-1234yf, HFO-1234ze, HFO-1225zc, HCFO-1242zf, and HCFC-252fc. In some embodiments, these compositions are formed by steps 1A-3A, or steps 2A-3A, or step 3A, or steps 1B-3B, or steps 2B-3B, or step 3B.

[0253] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HFO-1252zc, HCFC-262fc, HCFC-252fc, and one or more additional compounds selected from HCC-250fb, HFC-263fb, HFO-1243zf, other 1252 isomers, ethane, ethylene, HFC-23, HCFC-22, HFO-1132a, propane, HFC-143a, HCFC-142b, HFO-1234yf, HFO-1234ze, HFO-1225zc, and HCFO-1242zf. In some embodiments, these compositions are formed by steps 1A-3A, or steps 2A-3A, or step 3A, or steps 1B-3B, or steps 2B-3B, or step 3B.

[0254] One embodiment of the present invention disclosed herein relates to a composition comprising, essentially consisting of, or comprising HCFC-262fc and one or more compounds selected from HCC-250fb, HCFO-1242zf, HFC-263fb, HCO-1252zf, and HCFC-272fb.

[0255] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises (i) HCFC-262fc, (ii) at least one of HCC-250fb and HCFO-1242zf, and (iii) one or more additional compounds selected from HFC-263fb, HFO-1252zf, and HCFC-272fb. In some embodiments, these compositions are formed by step 2B or by steps 1B and 2B.

[0256] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HCFC-262fc, HCC-250fb, and one or more additional compounds selected from HCFO-1242zf, HFC-263fb, HFO-1252zf, and HCFC-272fb. In some embodiments, these compositions are formed by step 2B or by steps 1B and 2B.

[0257] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HCFC-262fc, HCFO-1242zf, and one or more additional compounds selected from HCC-250fb, HFC-263fb, HFO-1252zf, and HCFC-272fb. In some embodiments, these compositions are formed by step 2B or by steps 1B and 2B.

[0258] Some embodiments of the present invention disclosed herein relate to compositions comprising, essentially consisting of, or comprising HCFC-262fc and one or more additional compounds selected from propane, propylene, HCFC-252dc, HCFC-262db, HFC-272fb, HCFO-1232xf, HCFO-1242zf, HFO-1243zf, E-HCFO-1251zd, Z-HCFO-1251zd, HFO-1252zf, E-HFO-1261ze, Z-HFO-1261ze, HCFO-1242 isomers, and HCO-1260. In some embodiments, these compositions are formed by step 2B or steps 1B and 2B.

[0259] Some embodiments of the present invention disclosed herein relate to compositions comprising, essentially consisting of, or comprising HCFC-262fc and one or more additional compounds selected from ethane, HFC-152a, HFC-253db, HCFO-1232 isomer, HCFO-1242 isomer, HCFO-1242zf, HFO-1243zf, and HFO-1252zc. In some embodiments, these compositions are formed by step 2B or steps 1B and 2B.

[0260] Certain embodiments of the invention disclosed herein relate to compositions comprising, consisting essentially of, or consisting of HCFC-262fc and one or more additional compounds selected from propane, propylene, E-HFO-1261ze, Z-HFO-1261ze, HFO-1252zc, HFC-272fb, E-HCFO-1251zd, Z-HCFO-1251zd, HCFC-262db, HCFC-252dc, HCO-1250, HCC-260, HFO-1243zf, HCFO-1242zf, HCFO-1242 isomers, HCFO-1232 isomers, and HCFC-252 isomers. In some embodiments, HCFC-262fc constitutes from about 0.1 wt% to about 99.9 wt%, or from about 40 wt% to about 99.9 wt%, or from about 90 wt% to about 99.9 wt%, based on the total weight of the composition, including all integers and ranges therebetween. In some embodiments, these compositions are formed by step 2B or steps 1B and 2B.

[0261] In one embodiment, the composition according to the invention comprises, consists essentially of, or consists of (i) HCFC-262fc, (ii) at least one of HFO-1252zc, HCFC-262db, HFC-272fb, HFO-1243zf and HCFO-1242zf, and (iii) one or more additional compounds selected from propane, propylene, E-HFO-1261ze, Z-HFO-1261ze, HFO-1252zc, HFC-272fb, E-HCFO-1251zd, Z-HCFO-1251zd, HCFC-262db, HCFC-252dc, HCO-1250, HCC-260, HFO-1243zf, HCFO-1242zf, HCFO-1242 isomers, HCFO-1232 isomers, and HFC-252 isomers. In some embodiments, these compositions are formed by step 2B or steps 1B and 2B.

[0262] In one embodiment, the composition according to the present invention comprises, consists essentially of, or consists of (i) HCFC-262fc, (ii) at least one selected from the group consisting of HFO-1243zf, HFO-1252zf and HCFO-1242zf, and (iii) one or more additional compounds selected from the group consisting of propane, propylene, HCFC-252dc, HCFC-262db, HFC-272fb, HCFO-1232xf, HCFO-1242zf, HFO-1243zf, E-HCFO-1251zd, Z-HCFO-1251zd, HFO-1252zf, E-HFO-1261ze, Z-HFO-1261ze and HCO-1260. In some embodiments, HCFC-262fc constitutes from about 0.1% by weight to about 99.9% by weight, or from about 40% by weight to about 99.9% by weight, or from about 90% by weight to about 99.9% by weight, based on the total weight of the composition, including all integers and ranges therebetween. In some embodiments, these compositions are formed by step 2B or steps 1B and 2B.

[0263] In one embodiment, the composition according to the present invention comprises, consists essentially of, or consists of (i) HCFC-262fc, (ii) at least one selected from the group consisting of HFO-1243zf, HFO-1252zf and HCFO-1242zf, and (iii) one or more additional compounds selected from the group consisting of propane, propylene, HCFC-252dc, HCFC-262db, HCFO-1232xf, HCFO-1242zf, HFO-1243zf, E-HCFO-1251zd, Z-HCFO-1251zd, HFO-1252zf, E-HFO-1261ze, Z-HFO-1261ze and isomers of HCFO-1242. In some embodiments, HCFC-262fc constitutes from about 0.1% by weight to about 99.9% by weight, or from about 40% by weight to about 99.9% by weight, or from about 90% by weight to about 99.9% by weight, based on the total weight of the composition, including all integers and ranges therebetween. In some embodiments, these compositions are formed by step 2B or steps 1B and 2B.

[0264] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises (i) HCFC-262fc, (ii) at least one of HFO-1243zf, HFO-1252zf, and HCFO-1242zf, and (iii) one or more additional compounds selected from HCFC-262db, HCFO-1232xf, HCFO-1242zf, HFO-1243zf, E-HCFO-1251zd, Z-HCFO-1251zd, HFO-1252zf, and E-HFO-1261ze. In some embodiments, HCFC-262fc constitutes about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, including all integers and ranges in between. In some embodiments, these compositions are formed by step 2B or by steps 1B and 2B.

[0265] One embodiment of the present invention disclosed herein relates to a composition comprising, essentially consisting of, or comprising HCFC-1252zc and one or more compounds selected from HCFC262fc, HCC-250fb, HFC-263fb, HCFO-1242zf, HFO-1252zf, HFO-1243zf, and HCFC-252fc.

[0266] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises (i) HFO-1252zc, (ii) at least one of HCC-250fb and HCFO-1242zf, and (iii) one or more additional compounds selected from HCFC-262fc, HFC-263fb, HFO-1252zf, HFO-1243zf and HCFC-252fc. In some embodiments, these compositions are formed by steps 1C-2C or step 2C.

[0267] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HFO-1252zc, HCFO-1242zf, and one or more additional compounds selected from HCFC-262fc, HCC-250fb, HFC-263fb, HFO-1252zf, HFO-1243zf, and HCFC-252fc. In some embodiments, these compositions are formed by steps 1C-2C or step 2C.

[0268] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HCFC-262fc, HCC-250fb, HCFO-1242zf, and one or more additional compounds selected from HCFC-252fc, HFC-263fb, HCFC-272fb, and HFO-1252zf.

[0269] One embodiment of the present invention disclosed herein relates to a composition comprising, essentially consisting of, or comprising HFO-1252zc, one or more of HCC-250fb, HCFC-252fc, HCFC-262fc and HCFO-1242zf, and one or more additional compounds selected from HFC-263fb, other 1252 isomers, ethane, ethylene, HFC-23, HCFC-22, HFO-1132a, propane, HFC-143a, HCFC-142b, HFO-1234yf, HFO-1234ze, HFO-1225zc and HCFO-1242zf.

[0270] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HFO-1252zc, HCFC-262fc, HCC-250fb, HCFC-252fc, and one or more additional compounds selected from HFC-263fb, HCFO-1242zf, HFO-1252zf, HFO-1243zf, and HCFC-252fc.

[0271] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HFO-1252zc, HCFC-262fc, HCC-250fb, HCFO-1242zf, and one or more additional compounds selected from HCFC-252fc, HFC-263fb, other 1252 isomers, ethane, ethylene, HFC-23, HCFC-22, HFO-1132a, propane, HFC-143a, HCFC-142b, HFO-1234yf, HFO-1234ze, HFO-1241zf, HFO-1240za, and HFO-1225zc.

[0272] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HFO-1252zc, HCC-250fb, HCFO-1242zf, and one or more additional compounds selected from HFC-263fb, other 1252 isomers, ethane, ethylene, HFC-23, HCFC-22, HFO-1132a, propane, HFC-143a, HCFC-142b, HFO-1234yf, HFO-1234ze, HFO-1241zf, HFO-1240za, and HFO-1225zc.

[0273] In one embodiment, the composition according to the present invention comprises HFO-1252zc, HFC-263fb, HCFC-262fc, E-HFO-1251zb, Z-HFO-1251zb, HCFC-272fb, methane, HFC-32, ethylene, ethane, HFO-1132a, HCC-40, HCFC-22, ethylene oxide, E-HFO-1261ze, HFO-1252 isomer, HFC-281fa, HCC-30, C4H3ClF4, C4H6F4(I), C4H6F4(II), and C6F 12 The material comprises, essentially consists of, or comprises one or more additional compounds selected from HFO-1252zc dimer (I) and HFO-1252zc dimer (II) (HFO-1252zc dimer). In some embodiments, the one or more additional compounds comprise at least HFO-1252zc dimer.

[0274] In one embodiment, the composition according to the present invention comprises HFO-1252zc, HFC-263fb, HCFC-262fc, E-HFO-1251zb, Z-HFO-1251zb, HCFC-272fb, methane, HFC-32, ethylene, ethane, HFO-1132a, HCC-40, HCFC-22, E-HFO-1261ze, HFO-1252 isomer, HFC-281fa, HCC-30, C4H3ClF4, C4H6F4(I), C4H6F4(II), and C6F 12 The material comprises, essentially consists of, or comprises one or more additional compounds selected from HFO-1252zc dimer (I) and HFO-1252zc dimer (II). In some embodiments, the one or more additional compounds comprise at least an HFO-1252zc dimer.

[0275] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HFO-1252zc and one or more additional compounds selected from HFC-263fb, HCFC-262fc, E-HFO-1251zb, Z-HFO-1251zb, HCFC-272fb, HFO-1252zc dimer (I), and HFO-1252zc dimer (II). In some embodiments, the one or more additional compounds comprise at least an HFO-1252zc dimer.

[0276] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HCFO-1242zf and one or more additional compounds selected from HCC-250fb, HCFC-253fb, HCFC-252fc, HCFC-251fb, HCFC-1243zf, HCFC-1241zf, and HCFC-1240za. In one embodiment, the additional compound HCFC-1243zf may constitute about 30% to about 60% by weight, or about 30% to about 50% by weight, or about 30% to about 45% by weight, based on the total weight of the composition.

[0277] In one embodiment, the composition according to the present invention comprises, essentially consists of, or comprises HCFC-1243zf and one or more additional compounds selected from HCC-250fb, HCFC-253fb, HCFC-252fc, HCFC-251fb, HCFO-1242zf, HCFC-1241zf, and HCFC-1240za.

[0278] One or more additional components of the compositions disclosed herein may be selected from one or more HFCs, HCCs, HCFCs, HFOs, HCFOs, C2-C4 alkanes, C2-C4 alkenes, and t-butoxy-fluoropropenes.

[0279] In any embodiment of the compositions disclosed herein, the total amount of the additional compound may be, for example, greater than 0 to about 15% by weight, expressed as a GC-FID peak area percentage of the total amount of the composition, and all values ​​and ranges in between. In any embodiment of the compositions disclosed herein, the total amount of the additional compound may be greater than 0 to less than one of the following percentage values: 0 to 15%, 14%, 13%, 12%, 11%, 10%, 9%, 9%, 7%, 6%, 5%, 4%, 3%, 2%, or 1%, and all values ​​and ranges in between.

[0280] In any embodiment of the compositions disclosed herein, the total amount of the additional compound may be greater than 0 to less than 0.1 percent, greater than 0 to less than 0.01 percent, greater than 0.0001 to less than 0.3 percent, greater than 0.0001 to less than 0.2 percent, greater than 0.0001 to less than 0.1 percent, greater than 0.0001 to less than 0.01 percent, or greater than 0.0001 to less than 0.001 percent, as well as all values ​​and ranges in between, based on the total amount of the composition.

[0281] In any of the embodiments of the compositions disclosed herein, each additional compound is added based on the total amount of the composition. a) Greater than 0 and less than 4 percent, b) more than 0 and less than 3 percent, c) more than 0 and less than 2 percent, d) more than 0 and less than 1 percent, e) more than 0 and less than 0.5 percent, f) more than 0 and less than 0.1 percent, g) more than 0 and less than 0.01 percent, h) more than 0 and less than 0.005 percent, i) more than 0.001 and less than 4 percent, j) more than 0.001 and less than 3 percent, k) more than 0.001 and less than 2 percent, l) more than 0.001 and less than 1 percent, m) more than 0.001 and less than 0.5 percent, n) more than 0.001 and less than 0.1 percent, o) more than 0.001 and less than 0.01 percent, or p) more than 0.001 and less than 0.005 percent, may be present in an amount, provided that the total amount of additional compounds is more than 0.0001 and less than 15%, more than 0.0001 and less than 10%, more than 0.0001 and less than 8%, more than 0.0001 and less than 7%, more than 0.0001 and less than 6%, more than 0.0001 and less than 5%, more than 0.0001 and less than 4%, more than 0.0001 and less than 3%, more than 0.0001 and less than 2%, more than 0.0001 and less than 1%, more than 0.0001 and less than 0.5%, or more than 0.0001 and less than 0.1%.

[0282] In preferred embodiments, compositions according to the present invention are free from or substantially free from Group A fluorinated substances. In one embodiment, as used herein, “Group A fluorinated substance” includes a substance that (i) contains at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (the carbon atom is not bonded to H / Cl / Br / I) and (ii) meets the criteria for persistence in soil / sediments and water. The criteria are set forth in Annex XIII (Section 1.1.1) of the European Union's REACH Regulation (https: / / reachonline.eu / reach / en / annex-xiii-1-1.1-1.1.1.html, accessed May 2, 2023), which is referenced in the Regulatory Report Annex XV dated March 22, 2023, and whose disclosures are incorporated into this document by reference (https: / / echa.europa.eu / documents / 10162 / f605d4b5-7c17-7414-8823-b49b9fd43aea, accessed May 2, 2023).

[0283] In another embodiment, as used herein, “Group A fluorinated substance” has a Henry’s Law constant of 250 Pa * m 3 The amount is less than or equal to / mol and contains any substance that includes at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (the carbon is not bonded to H / Cl / Br / I).

[0284] In the embodiments, TFA is an example of a Group A fluorinated substance, but is not limited to it.

[0285] With regard to the presence of Group A fluorinated substances in this composition, the term "not present" as used herein means that the amount of such substances in the composition is so low that it is undetectable, but not limited to 0%, when measured by gas chromatography with a flame ionization detector, gas chromatography with a mass detector by analysis of gas or liquid samples, and / or ion chromatography by analysis of water samples after bubbling a thermal fluid through water. Such methodologies are well known to those skilled in the art. With regard to the presence of Group A fluorinated substances in this composition, the phrase "substantially absent" as used herein means that the amount of such substances in the composition can be determined by gas chromatography (GC) techniques, such as gas chromatography with a flame ionization detector or electron capture detector, or GC coupled with a mass detector (gas chromatography / mass spectral (GC / MS) method), by ion chromatography (IC) or ion chromatography-mass spectrometry (IC-MS) techniques, or by high-performance liquid chromatography (HPLC) or high-performance liquid chromatography-mass spectrometry (high-performance liquid chromatography-mass spectrometry). This means that, when measured by spectrometry (HPLC-MS) techniques, the TFA standard is greater than 0% by weight and less than or equal to 5% by weight, greater than 0% by weight and less than or equal to 4% by weight, greater than 0% by weight and less than or equal to 3% by weight, greater than 0% by weight and less than or equal to 2% by weight, greater than 0% by weight and less than or equal to 1% by weight, and all values ​​and ranges in between. The TFA analytical standard can be used with either gas chromatography or ion chromatography and is available, for example, from Sigma Aldrich.

[0286] In preferred embodiments, the decomposition products of the composition according to the present invention are free from or substantially free from Group A fluorinated substances. With respect to the formation of Group A fluorinated substances as decomposition products of the composition, the term “free from” as used herein means that the theoretical molar yield of such substances in the air, soil / sediment and water environmental compartments generated during the tropospheric decomposition of the composition is sufficiently low to be undetectable, including but not limited to 0%, when measured by GC techniques, e.g., GC or GC / MS methods using flame ionization detectors or electron capture detectors, by IC or IC-MS techniques, or by HPLC or HPLC-MS techniques. With respect to the formation of Group A fluorinated substances by this composition, the phrase "substantially free" as used herein means that the theoretical molar yield of such substances in the air, soil / sediment, and water environmental compartments generated during the tropospheric decomposition of the composition is greater than 0% and 5% or less, greater than 0% and 4% or less, greater than 0% and 3% or less, greater than 0% and 2% or less, greater than 0% and 1% or less, and all values ​​and ranges in between, when measured by GC techniques, e.g., GC or GC / MS using a flame ionization detector or electron capture detector, by IC or IC-MS techniques, or by HPLC or HPLC-MS techniques.

[0287] Some embodiments of the present invention disclosed herein relate to compositions containing, essentially derived from, or comprising HFO-1252zc, and not containing or substantially containing Group A fluorinated substances. In some embodiments, the compositions of the present invention contain, essentially derived from, or comprising HFO-1252zc, and the decomposition products of such compositions are not containing or substantially containing Group A fluorinated substances as defined herein.

[0288] Some embodiments of the present invention disclosed herein relate to compositions comprising, essentially comprising, or consisting of HFO-1252zc and one or more additional components selected from HFCs, HCCs, HCFCs, HFOs, HCFOs, C2-C4 alkanes, C2-C4 alkenes, and t-butoxy-fluoropropenes. In some embodiments, such compositions are free of or substantially free of Group A fluorinated substances as defined herein, and / or the decomposition products of such compositions are free of or substantially free of Group A fluorinated substances.

[0289] Some embodiments of the present invention disclosed herein relate to blend compositions comprising, essentially comprising, or consisting of HFO-1252zc and one or more refrigerant compounds selected from HFCs, HCCs, HCFCs, HFOs, HFCOs, C2-C4 alkanes, C2-C4 alkenes, and t-butoxy-fluoropropenes. In some embodiments, such blend compositions are free of or substantially free of Group A fluorinated substances as defined herein, and / or the decomposition products of such blend compositions are free of or substantially free of Group A fluorinated substances.

[0290] In some embodiments, at least a portion of any of the compositions disclosed herein includes recycled materials.

[0291] Systems and Processes Figure 1 shows a first embodiment of the present invention for producing HCFC-262fc and / or HFO-1252zc according to one or more steps of reaction scheme A. Referring to Figure 1, one embodiment shows three reactors or reaction zones 50, 60, 70, and first and second separators (e.g., distillation columns) 80, 90. This process can be operated in batch mode, semi-continuously, or continuously. The starting feed comprises HCC-250fb, which is introduced into the first reactor 50 to be contacted with HF to produce the HCFC-252fc intermediate. In some embodiments, HF is stored in a pressurized vessel 30. In some embodiments, HCC-250fb and HF may be pre-mixed in a mixer 40 and fed into reactor 50. In some embodiments, HCC-250fb and HF may be simultaneously fed into and mixed in reactor 50 upstream of the catalyst bed.

[0292] Preferably, the first reactor 50 is configured for a liquid-phase hydrofluorication reaction. The first reactor 50 is heated to allow the reaction to proceed and produce a product mixture containing HCFC-252fc. The HCFC-252fc reactor product mixture is removed and preferably further processed to purify HCFC-252fc using conventional separation methods, such as recirculation of unreacted HCC-250fb and / or HF back to the first reactor 50, and removal of the by-product HCl. For example, in some embodiments, the HCFC-252fc reactor product mixture is supplied from the first reactor 50 to the first separator system 80 for recovery of HCFC-252fc (stream 10), separation and recirculation of unreacted HCC-250fb and optionally unreacted HF (stream 12), and removal of HCl (stream 14). Removal of unreacted HCC-250fb from the product mixture increases the relative concentration / amount of HCFC-252fc.

[0293] HCFC-252fc (flow 10) is then supplied to two reactors or reaction zones 60. The second reactor is preferably suited for the hydrogenation of HCFC-252fc, i.e., the conversion of HCFC-252fc to HCFC-262fc. The second reactor 60 may be configured for either a liquid-phase or gas-phase reaction. HCFC-252fc and H2 can be pre-mixed and supplied to the second reaction zone 60, or mixed in a reaction zone 60 upstream of the catalyst bed. In some embodiments, H2 is stored in a pressurized vessel 32. In some embodiments, a single pressurized vessel serves as a source for both HF and H2. The second reactor 60 is heated to allow the reaction to proceed and produce a mixture of second intermediate products containing HCFC-262fc. The product mixture is removed from the second reaction zone 60 and preferably further processed to purify HCFC-262fc using, for example, conventional separation methods, recirculation of unreacted HCFC-252fc to the second reactor 60, etc. For example, in some embodiments, the HCFC-262fc reactor product mixture is supplied from the second reactor 60 to the second separator system 90 for the recovery of HCFC-262fc (stream 16) and the separation and recirculation of unreacted HCFC-252fc and optionally unreacted hydrogen (stream 18). Removing unreacted HCFC-252fc from the product mixture increases the relative concentration / amount of HCFC-262fc.

[0294] The HCFC-262fc intermediate (flow 16) can then be converted to HFO-1252zc by dehalogenation in a third reaction zone or reactor 70. The third reactor 70 is preferably configured for a gas-phase reaction. HCFC-262fc is supplied to the third reaction zone 70 for dehydrochlorination. The third reactor 70 may be heated, and the reaction proceeds to produce a product mixture containing HFO-1252zc. The product mixture is removed from the third reactor 70 and preferably further processed to purify HFO-1252zc using, for example, conventional separation methods or recirculation of unreacted HCFC-262fc back into the third reactor 70. Removal of unreacted HCFC-262fc from the product mixture increases the relative concentration / amount of HFO-1252zc.

[0295] Figure 2 shows a first embodiment of the present invention for producing HCFC-262fc and / or HFO-1252zc according to one or more steps of reaction scheme B. Referring to Figure 2, in one embodiment, three reactors or reaction zones 150, 160, 170 and first and second separators (e.g., distillation columns) 180, 190 are shown. This process can be operated in batch mode, semi-continuously, or continuously. The starting feed comprises HCC-250fb, which is introduced into the first reactor 150 to be contacted with HF to produce the HCFO-1242zf intermediate. In some embodiments, HF is stored in a pressurized vessel 130. In some embodiments, HCC-250fb and HF may be pre-mixed in a mixer 140 and fed into reactor 150. In some embodiments, HCC-250fb and HF may be simultaneously fed into reactor 150 upstream of the catalyst bed and mixed. In some embodiments, the HCC-250fb feed is preferably first vaporized in a vaporizer 120, then mixed with HF in a mixer 140, and supplied to a first reaction zone 150 to contact the catalyst bed.

[0296] Preferably, the first reactor 150 is configured for a gas-phase hydrofluorication reaction. The first reactor 150 is heated to allow the reaction to proceed and produce a product mixture containing HCFO-1242zf. The HCFO-1242zf reactor product mixture is removed and preferably further processed to purify HCFO-1242zf using conventional separation methods, recirculation of unreacted HCC-250fb and / or HF to the first reactor 150, removal of the by-product HCl, etc. For example, in some embodiments, the HCFO-1242zf reactor product mixture is supplied from the first reactor 150 to the first separator system 180 for recovery of HCFO-1242zf (flow 110), separation and recirculation of unreacted HCC-250fb and optionally unreacted HF (flow 112), and removal of HCl (flow 114). Removing unreacted HCC-250fb from the product mixture increases the relative concentration / amount of HCFO-1242zf.

[0297] HCFO-1242zf (flow 110) is then supplied to a second reactor or reaction zone 160. The second reactor is preferably suited for the hydrogenation of HCFO-1242zf, i.e., the conversion of HCFO-1242zf to HCFC-262fc. The second reactor 160 may be configured for either a liquid-phase or gas-phase reaction. HCFO-1242zf and H2 can be pre-mixed and supplied to the second reaction zone 160, or mixed in a reaction zone 160 upstream of the catalyst bed. In some embodiments, H2 is stored in a pressurized vessel 132. In some embodiments, a single pressurized vessel serves as a source for both HF and H2. The second reactor 160 is heated to allow the reaction to proceed, producing a second intermediate product mixture containing HCFC-262fc. The product mixture is removed from the second reaction zone 160 and preferably further processed to purify HCFC-262fc using conventional separation methods, recirculation of unreacted HCFO-1242zf to the second reactor 60, for example. For example, in some embodiments, the HCFC-262fc reactor product mixture is fed from the second reactor 160 to the second separator system 190 for the recovery of HCFC-262fc (stream 116) and the separation and recirculation of unreacted HCFC-252fc and optionally unreacted hydrogen (stream 118). Removal of unreacted HCFO-1242zf from the product mixture increases the relative concentration / amount of HCFC-262fc.

[0298] The HCFC-262fc intermediate (flow 116) can then be converted to HFO-1252zc by dehalogenation in a third reaction zone or reactor 170. The third reactor 170 is preferably configured for a gas-phase reaction. HCFC-262fc is supplied to the third reaction zone 170 for dehydrochlorination. The third reactor 170 may be heated, and the reaction proceeds to produce a product mixture containing HFO-1252zc. The product mixture is removed from the third reactor 170 and preferably further processed to purify HFO-1252zc, for example, by conventional separation methods or by recirculation of unreacted HCFC-262fc back into the third reactor 170. Removal of unreacted HCFC-262fc from the product mixture increases the relative concentration / amount of HFO-1252zc.

[0299] Figure 3 shows a first embodiment of the present invention for producing HFO-1252zc according to one or more steps of reaction scheme C. Referring to Figure 3, in one embodiment, two reactors or reaction zones 250, 270 and a separator (e.g., a distillation column) 280 are shown. This process can be operated in batch mode, semi-continuously, or continuously. The starting feed comprises HCC-250fb, which is introduced into the first reactor 250 to be contacted with HF to produce the HCFO-1242zf intermediate. In some embodiments, HF is stored in a pressurized vessel 230. In some embodiments, HCC-250fb and HF may be pre-mixed in a mixer 240 and fed into reactor 250. In some embodiments, HCC-250fb and HF may be simultaneously fed into reactor 250 upstream of the catalyst bed and mixed. In some embodiments, the HCC-250fb feed is preferably first vaporized in a vaporizer 220, then mixed with HF in a mixer 240, and supplied to a first reaction zone 250 to contact the catalyst bed.

[0300] Preferably, the first reactor 250 is configured for a gas-phase hydrofluorination reaction. The first reactor 250 is heated to allow the reaction to proceed and produce a product mixture containing HCFO-1242zf. The HCFO-1242zf reactor product mixture is removed and preferably further processed to purify HCFO-1242zf using conventional separation methods, recirculation of unreacted HCC-250fb and / or HF to the first reactor 250, removal of the by-product HCl, etc. For example, in some embodiments, the HCFO-1242zf reactor product mixture is supplied from the first reactor 250 to the first separator system 280 for recovery of HCFO-1242zf (flow 210), separation and recirculation of unreacted HCC-250fb and optionally unreacted HF (flow 212), and removal of HCl (flow 214). Removing unreacted HCC-250fb from the product mixture increases the relative concentration / amount of HCFO-1242zf.

[0301] HCFO-1242zf (flow 210) is then supplied to a second reactor or reaction zone 270. The second reactor 270 is preferably suitable for the dechlorination of HCFO-1242zf with zinc, i.e., for the conversion of HCFO-1242zf to HFO-1252zc. Zinc is supplied to the second reactor 270 from supply source 235. The second reactor 270 is preferably configured for a liquid-phase reaction. HCFO-1242zf and zinc can be pre-mixed and supplied to the second reaction zone 270, or mixed in a reaction zone 270 upstream of the catalyst bed. The second reactor 270 is heated to allow the reaction to proceed and produce a product mixture containing HFO-1252zc. The product mixture is removed from the second reactor 270 and preferably further processed to purify HFO-1252zc, for example, by conventional separation methods or by recirculating unreacted HCFO-1242zf back to the second reactor 270. Removing unreacted HCFO-1242zf from the product mixture increases the relative concentration / amount of HFO-1252zc.

[0302] One embodiment described herein relates to a system comprising a built-in supply source of HCC-250fb, a pressurized source vessel for hydrogen and / or hydrogen fluoride, one or more vaporizers, at least one mixer, at least first and second and optionally third series-arranged reactors each producing an intermediate product mixture, a furthest downstream reactor providing a final product mixture, and one or more separator systems. In some embodiments, the first reactor includes a flow-through bed of a fluorination catalyst. In some embodiments, the second reactor includes a flow-through bed of a hydrogenation catalyst. In some embodiments, each upstream reactor includes a discharge line for transporting the intermediate product mixture to its respective separator system for recovery of the desired intermediate product, and then transporting it to the respective downstream reactor.

[0303] Aspects of the present invention will be described with reference to the following examples. [Examples]

[0304] Example 1: Gas-phase hydrogenation of 252fc to 262fc Hydrogenation of 252fc to 262fc in the gas phase with 0.02% Pd / Al2O3: 5 mL of 0.02% Pd / Al2O3 was added to a 12-inch long, 1 / 2-inch outer diameter Monel reactor. The catalyst was treated with an H2 stream at 200°C for 1 hour. The reactor was then heated to 60°C. 252fc was supplied at a rate of 2 mL / hour, and H2 and N2 were supplied at 11 sccm and 10 sccm, respectively. The reactor effluent was analyzed by online GC-MS-FID. The analysis showed a conversion rate of over 30% to 262fc and an 85% selectivity to 263fb. 262fa (CHF2CH2CH2Cl) and 272fb (CHF2CH2CH3) were also found in the product.

[0305] Example 2: Thermal decomposition of 262 fc to 1252 zc in an empty gold-lined reaction tube HCFC-262fc was pumped into an empty, 10-inch long, 1 / 2-inch outer diameter, gold-lined tube reactor. The reaction test conditions are listed in Table 2 below. The reactor effluent was analyzed by online GC-MS-FID under each test condition. The analysis results are listed in Tables 2 and 3 below.

[0306] [Table 2-1]

[0307] [Table 2-2]

[0308] [Table 3]

[0309] Example 3: Thermal decomposition of 262 fc to 1252 zc in an empty Inconel 625 reaction tube HCFC-262fc was pumped into an empty 10-inch long, 1 / 2-inch outer diameter Inconel 625 tube reactor. The reaction test conditions are listed in Table 4 below. The reactor effluent was analyzed by online GC-MS-FID under each test condition. The analysis results are listed in Tables 4 and 5 below.

[0310] [Table 4]

[0311] [Table 5]

[0312] Example 4: Liquid-phase dehalogenation hydrogenation of 262fc to 1252zc A mixture of 262fc (6.2g, 63 mmol) and t-BuOK (7.1g, 6.3 mmol) in dry DMF (30 mL) is stirred at 0°C in a 100 mL flask equipped with an overhead condenser, and the reaction product is continuously removed from the reactor. The reaction is monitored using gas chromatography. After 1 hour, 1.3 g of the product CF2=CH-CH2 (conversion rate 30%, selectivity 86%) is collected in a dry eye trap.

[0313] Example 5: Gas-phase hydrofluorination of 250fb to 1242zf without the use of a catalyst. The fluorination of 250fb was carried out in an empty 10-inch Inconel (0.5-inch outer diameter) tube reactor. The reaction was carried out by supplying liquid 250fb to a heating chamber, where it was vaporized and mixed with HF and N2. The reaction mixture was then passed through the reactor under the conditions listed in Table 6 below. A portion of the reactor effluent was passed through a series of valves and analyzed by GCMS (Gas Chromatography and Mass Spectroscopy). The results are shown in Table 6 below.

[0314] [Table 6]

[0315] Example 6: Gas-phase hydrofluorination of 250fb to 1242zf and 1243zf Fluorination of 250 fb on metal packing: 6 cc of Monel packing was added to an Inconel (0.5 inch outer diameter) tube reactor. The reaction was carried out by supplying liquid 250 fb to a heating chamber, where it was vaporized and mixed with HF and N2. The reaction mixture was then passed through the reactor. The N2:HF:liquid feed ratio was 10.0:3.0:1. A portion of the reactor effluent was passed through a series of valves and analyzed by GCMS (Gas Chromatography and Mass Spectroscopy). The results are shown in Table 7 below.

[0316] [Table 7]

[0317] Example 7: Hydrogenation of 1242zf to 262fc in the gas phase with 0.02% Pd / Al2O3 Six ml of 0.02% Pd / Al2O3 was added to a 12-inch long, 1 / 2-inch outer diameter Monel reactor. The catalyst was treated with an H2 flow at 200°C for 1 hour. The reactor was then heated to 50°C. The supply of HFO-1243zf, H2, and N2 was controlled by a mass flow controller. The reaction test conditions are provided in Table 8. The reactor effluent was analyzed by online GC-MS-FID at the times shown in Table 8. The results of the analysis are provided in Tables 8-11, which show a high conversion rate of HCFO-1242zf to HCFC-262fc, with a selectivity of HCFC-262fc reaching 93%.

[0318] [Table 8]

[0319] [Table 9]

[0320] [Table 10]

[0321] [Table 11]

[0322] Example 8: Liquid-phase hydrogenation of 1242zf 0.25 g of 0.5% Pd / C was placed in a 10 mL Hastelloy C shaker tube. The shaker tube was then cooled to -30°C and evacuated. 5 g of HCFO-1242zf was added to the shaker tube and reheated to a temperature of 65°C. At 65°C, H2 was slowly added to a pressure of 300 psig. The pressure drop rapidly indicated that the reaction had occurred under these conditions. Further H2 was added until the reactor pressure no longer dropped. Both the gas and liquid phases of the reaction mixture were analyzed by GC-MS-FID, and the contents were identified in Tables 12 and 13.

[0323] [Table 12]

[0324] [Table 13]

[0325] Embodiment of the Claim Embodiment 1. A method comprising the step of contacting 1,3-dichloro-1,1-difluoropropane (HCFC-252fc) with hydrogen to form 1-chloro-1,1-difluoropropane (HCFC-262fc).

[0326] Embodiment 2. A method comprising the step of converting 1-chloro-1,1-difluoropropane (HCFC-262fc) to 1,1-difluoropropene (HFO-1252zc).

[0327] Embodiment 3. A method comprising: (i) contacting 1,1,1,3-tetrachloropropane (HCC-250fb) with hydrogen fluoride in a liquid-phase reaction to form 1,3-dichloro-1,1-difluoropropane (HCFC-252fc); and (ii) contacting HCFC-252fc with hydrogen to form 1-chloro-1,1-difluoropropane (HCFC-262fc).

[0328] Embodiment 4. A method comprising the steps of (i) contacting 1,3-dichloro-1,1-difluoropropane (HCFC-252fc) with hydrogen to form 1-chloro-1,1-difluoropropane (HCFC-262fc), and (ii) converting HCFC-262fc to 1,1-difluoropropene (HFO-1252zc).

[0329] Embodiment 5. A method comprising: (i) contacting 1,1,1,3-tetrachloropropane (HCC-250fb) with hydrogen fluoride in a liquid-phase reaction to form 1,3-dichloro-1,1-difluoropropane (HCFC-252fc); (ii) contacting HCFC-252fc with hydrogen to form 1-chloro-1,1-difluoropropane (HCFC-262fc); and (iii) converting HCFC-262fc to 1,1-difluoropropene (HFO-1252zc).

[0330] Embodiment 6. A method comprising the step of contacting 1,1,1,3-tetrachloropropane (HCC-250fb) with hydrogen fluoride in a gas-phase reaction in a reactor, either in the absence or in the presence of a catalyst, to form 3-chloro-3,3-difluoro-1-propene (HCFO-1242zf), wherein the catalyst, if present, is a metal alloy packing material in the reactor, and the metal alloy packing material has catalytic activity.

[0331] Embodiment 7. A method comprising the step of contacting 3-chloro-3,3-difluoro-1-propene (HCFO-1242zf) with hydrogen to form 1-chloro-1,1-difluoropropane (HCFC-262fc).

[0332] Embodiment 8. A method comprising: (i) contacting 1,1,1,3-tetrachloropropane (HCC-250fb) with hydrogen fluoride in a gas-phase reaction to form 3-chloro-3,3-difluoro-1-propene (HCFO-1242zf); and (ii) contacting HCFO-1242zf with hydrogen to form 1-chloro-1,1-difluoropropane (HCFC-262fc).

[0333] Embodiment 9. A method comprising: (i) contacting 1,3-dichloro-1,1-difluoropropane (HCFC-252fc) with a caustic agent in an aqueous solvent to form 3-chloro-3,3-difluoro-1-propene (HCFO-1242zf); and (ii) contacting HCFO-1242zf with hydrogen to form 1-chloro-1,1-difluoropropane (HCFC-262fc).

[0334] Embodiment 10. A method comprising the steps of (ii) contacting 3-chloro-3,3-difluoro-1-propene (HCFO-1242zf) with hydrogen to form 1-chloro-1,1-difluoropropane (HCFC-262fc), and (ii) converting HCFC-262fc to 1,1-difluoropropene (HFO-1252zc).

[0335] Embodiment 11. A method comprising: (i) contacting 1,1,1,3-tetrachloropropane (HCC-250fb) with hydrogen fluoride in a gas-phase reaction to form 3-chloro-3,3-difluoro-1-propene (HCFO-1242zf); (ii) contacting HCFO-1242zf with hydrogen to form 1-chloro-1,1-difluoropropane (HCFC-262fc); and (iii) converting HCFC-262fc to 1,1-difluoropropene (HFO-1252zc).

[0336] Embodiment 12. A method comprising: (i) contacting 1,3-dichloro-1,1-difluoropropane (HCFC-252fc) with a caustic agent in an aqueous solvent to form 3-chloro-3,3-difluoro-1-propene (HCFO-1242zf); (ii) contacting HCFO-1242zf with hydrogen to form 1-chloro-1,1-difluoropropane (HCFC-262fc); and (iii) converting HCFC-262fc to 1,1-difluoropropene (HFO-1252zc).

[0337] Embodiment 13. A method comprising: (i) contacting 1,1,1,3-tetrachloropropane (HCC-250fb) with hydrogen fluoride in a liquid-phase reaction to form 1,3-dichloro-1,1-difluoropropane (HCFC-252fc); (ii) contacting HCFC-252fc with a caustic agent in an aqueous solvent to form 3-chloro-3,3-difluoro-1-propene (HCFO-1242zf); (iii) contacting HCFO-1242zf with hydrogen to form 1-chloro-1,1-difluoropropane (HCFC-262fc); and (iv) converting HCFC-262fc to 1,1-difluoropropene (HFO-1252zc).

[0338] Embodiment 14. (i) A step of contacting 1,1,1,3-tetrachloropropane (HCC-250fb) with hydrogen fluoride in a gas-phase reaction to form 3-chloro-3,3-difluoro-1-propene (HCFO-1242zf), (ii) A method comprising the step of contacting HCFO-1242zf with zinc to form 1,1-difluoropropene (HFO-1252zc).

[0339] Embodiment 15. A method comprising: (i) contacting 1,3-dichloro-1,1-difluoropropane (HCFC-252fc) with a caustic agent in an aqueous solvent to form 3-chloro-3,3-difluoro-1-propene (HCFO-1242zf); and (ii) contacting HCFO-1242zf with zinc to form 1,1-difluoropropene (HFO-1252zc).

[0340] Embodiment 16. A method comprising: (i) contacting 1,1,1,3-tetrachloropropane (HCC-250fb) with hydrogen fluoride in a liquid-phase reaction to form 1,3-dichloro-1,1-difluoropropane (HCFC-252fc); (ii) contacting HCFC-252fc with a caustic agent in an aqueous solvent to form 3-chloro-3,3-difluoro-1-propene (HCFO-1242zf); and (iii) contacting HCFO-1242zf with zinc to form 1,1-difluoropropene (HFO-1252zc).

[0341] Embodiment 17. The method according to any one of Embodiments 1, 3, 4, and 5, wherein the step of contacting HCFC-252fc with hydrogen to form HCFC-262fc is performed in the gas phase.

[0342] Embodiment 18. The method according to any one of Embodiments 7 to 13, wherein the step of contacting HCFO-1242zf with hydrogen to form HCFC-262fc is performed in the gas phase.

[0343] Embodiment 19. The method according to any one of Embodiments 1, 3, 4, and 5, wherein the step of contacting HCFC-252fc with hydrogen to form HCFC-262fc is performed in a liquid phase.

[0344] Embodiment 20. The method according to any one of Embodiments 7 to 13, wherein the step of contacting HCFO-1242zf with hydrogen to form HCFC-262fc is performed in a liquid phase.

[0345] Embodiment 21. The method according to either Embodiment 19 or Embodiment 20, wherein the contact step is performed in the presence of a catalyst selected from the group consisting of Group VIII metals, Pd, Pt, Ni, Cu, and two or more combinations thereof, preferably Pd.

[0346] Embodiment 22. The method according to Embodiment 21, wherein the catalyst is either not supported or is supported.

[0347] Embodiment 23. The method according to Embodiment 22, wherein the carrier is a carbon or aluminum oxide carrier.

[0348] Embodiment 24. The method according to Embodiment 23, wherein the carbon support comprises one of carbon, acid-washed carbon, activated carbon, and a three-dimensional matrix carbonaceous material.

[0349] Embodiment 25. The method according to any one of Embodiments 21 to 24, wherein the amount of Pd catalyst is 0.5% to 0.01%, or the amount of Pd catalyst for the gas-phase reaction is 0.1% to 0.01%.

[0350] Embodiment 26. The method according to any one of Embodiments 21 to 25, wherein the catalyst is Pd / Al2O3 or Pd / C.

[0351] Embodiment 27. The method according to any one of Embodiments 2, 4, 5, and 10-13, wherein the conversion of HCFC-262fc to HFO-1252zc includes dehalogenation hydrogenation of HCFC-262fc.

[0352] Embodiment 28. The method according to Embodiment 27, wherein the conversion of HCFC-262fc to HFO-1252zc by dehalogenation hydrogenation of HCFC-262fc occurs in the gas phase or liquid phase using a strong base.

[0353] Embodiment 29. The method according to any one of Embodiments 6, 8, 11, and 14, wherein the step of contacting HCC-250fb with hydrogen fluoride to form HCFO-1242zf is performed in the absence of a catalyst.

[0354] Embodiment 30. The method according to any one of Embodiments 8, 11, and 14, wherein the step of contacting HCC-250fb with hydrogen fluoride is performed in the presence of a catalyst selected from the group consisting of Lewis acid catalysts, transition metal halides, transition metal oxides (preferably partially fluorinated transition metal oxides), group IVb metal halides, group Vb metal halides, and catalytically active metal alloy fillers.

[0355] Embodiment 31. The method according to any one of embodiments 3-5, 8-16, wherein a separate reactor is used for each of the reaction steps.

[0356] Embodiment 32. The method according to any one of Embodiments 9, 12, 13, 15, and 16, wherein the caustic agent is selected from the group consisting of alkali metal oxides, alkali metal hydroxides, alkali metal amides, alkaline earth metal hydroxides, alkaline earth metal oxides or amides, alkali metal carbonates, alkali metal phosphates, and alkali metal carboxylates.

[0357] Embodiment 33. The method according to any one of Embodiments 9, 12, 13, 15, 16, and 32, wherein the caustic agent is selected from the group consisting of NaOH, KOH, LiOH, CsOH, Ca(OH)2, Zn(OH)2, Na2CO3, K2CO3, K3PO4, Na3PO4, KF, and CsF.

[0358] Embodiment 34. The method according to any one of Embodiments 9, 12, 13, 15, 16, 32, and 33, wherein HCFC-252fc is in contact with the caustic agent at a temperature in the range of about 20°C to about 150°C, preferably about 30°C to about 100°C.

[0359] Embodiment 35. The method according to any one of Embodiments 2, 4, 5, 10-13, wherein the step of converting HCFC-262fc to HFO-1252zc includes contacting HCFC-262fc with a strong base in a solvent.

[0360] Embodiment 36. The method according to Embodiment 35, wherein the strong base is selected from the group consisting of hydroxides, alkoxides, metal amides, metal hydrides, metal dialkylamides, and arylamines.

[0361] Embodiment 37. The method according to any one of Embodiments 35 to 36, wherein the strong base is selected from the group consisting of alkoxides containing lithium, sodium, and potassium salts of methyl, ethyl, and t-butyl oxides; metal amides containing sodium amides, potassium amides, and lithium amides; metal hydrides containing sodium hydride, potassium hydride, and lithium hydride; and metal dialkylamides containing lithium, sodium, and potassium salts of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, trimethylsilyl, and cyclohexyl substituted amides.

[0362] Embodiment 38. The method according to any one of Embodiments 6, 8, 11, and 14, wherein HCC-250fb is contacted with hydrogen fluoride in the gas phase in the presence of a catalyst to co-produce 3,3,3-trifluoropropene (HFO-1243zf, CF3CH=CH2) and HCFO-1242zf.

[0363] Embodiment 39. The method according to Embodiment 38, wherein the catalyst is a metal surface.

[0364] Embodiment 40. The method according to Embodiment 39, wherein the metal surface is the surface of a metal alloy filler.

[0365] Embodiment 41. The method according to any one of Embodiments 38 to 40, wherein the catalyst is selected from the group consisting of Lewis acid catalysts, transition metal halides, transition metal oxides (preferably partially fluorinated transition metal oxides), group IVb metal halides, group Vb metal halides, chromium-based catalysts, cobalt-based catalysts, nickel-based catalysts, aluminum-based catalysts, iron-based catalysts, and combinations thereof.

[0366] Embodiment 42. A method comprising contacting 1,1,1,3-tetrachloropropane (HCC-250fb) with hydrogen fluoride in the gas phase, either in the absence or in the presence of a catalyst, to form 3,3,3-trifluoropropene (HFO-1243zf).

[0367] Embodiment 43. The method according to Embodiment 42, wherein the catalyst is selected from the group consisting of Lewis acid catalysts, transition metal halides, transition metal oxides (preferably partially fluorinated transition metal oxides), group IVb metal halides, group Vb metal halides, and metal alloy fillers.

[0368] Embodiment 44. The method according to Embodiment 43, wherein the catalyst is selected from the group consisting of chromium-based catalysts, cobalt-based catalysts, nickel-based catalysts, aluminum-based catalysts, iron-based catalysts, and combinations thereof.

[0369] Embodiment 45. A system comprising a built-in supply source of 1,1,1,3-tetrachloropropane (HCC-250fb), a pressurized source vessel of hydrogen and / or hydrogen fluoride, and at least first, second, and third reactors arranged in series, wherein the first and second reactors produce a first intermediate product mixture and a second intermediate product mixture, respectively, and the third reactor produces a final product mixture containing 1,1-difluoropropene (HFO-1252zc), the first reactor comprising a flow-through bed of fluorination catalyst, the second reactor comprising a flow-through bed of hydrogenation catalyst, and the third reactor configured for a gas-phase reaction that converts the hydrochlorofluorocarbon produced in the second reactor to HFO-1252zc.

[0370] Embodiment 46. The system according to Embodiment 45, wherein the first reactor is configured for a liquid-phase fluorination reaction that converts HCC-250fb to 1,3-dichloro-1,1-difluoropropane (HCFC-252fc).

[0371] Embodiment 47. The system according to any one of Embodiments 45 to 46, wherein the second reactor is configured for a liquid-phase or gas-phase hydrogenation reaction that converts HCFC-252fc to 1-chloro-1,1-difluoropropane (HCFC-262fc).

[0372] Embodiment 48. The system according to any one of Embodiments 45 to 47, wherein the first reactor is configured for a gas-phase fluorination reaction that converts HCC-250fb to 3-chloro-3,3-difluoro-1-propene (HCFO-1242zf).

[0373] Embodiment 49. The system according to any one of Embodiments 45 to 48, wherein the second reactor is configured for a liquid-phase or gas-phase hydrogenation reaction that converts HCFO-1242zf to hydrochlorofluorocarbon HCFC-262fc.

[0374] Embodiment 50. The system according to any one of embodiments 45 to 49, further comprising one or more separator systems.

[0375] Embodiment 51. The system according to Embodiment 50, further comprising a first discharge line configured to supply a first intermediate product mixture from a first reactor to a first separator system, wherein the first separator system is configured to recover the first intermediate product and transport the first intermediate product to a second reactor.

[0376] Embodiment 52. The system according to Embodiment 51, further comprising a second discharge line configured to supply a second intermediate product mixture from a second reactor to a second separator system, the second separator system configured to recover hydrochlorofluorocarbons and transport the hydrochlorofluorocarbons to a third reactor.

[0377] Embodiment 53. The system according to any one of Embodiments 45 to 52, further comprising a vaporizer and a mixer.

[0378] Embodiment 54. The system according to Embodiment 53, wherein the vaporizer and mixer are connected in series and are located downstream of the supply source and upstream of the first reactor.

[0379] Embodiment 55. The system according to any one of Embodiments 45 to 54, wherein the pressurized source of hydrogen fluoride is connected to the mixer.

[0380] Embodiment 56. The system according to any one of Embodiments 45 to 55, wherein the pressurized source of hydrogen fluoride is directly connected to the first reactor.

[0381] Embodiment 57. The system according to Embodiment 51, wherein unreacted HCFC-252fc from the first separator system is recycled to the first reactor.

[0382] Embodiment 58. The system according to Embodiment 52, wherein unreacted HCFC-262fc from the second separator system is recycled to the second reactor.

[0383] Embodiment 59. The system according to Embodiment 51, wherein unreacted HCFO-1242zf from the first separator system is recycled to the first reactor.

[0384] Embodiment 60. A system comprising a built-in supply source of 1,1,1,3-tetrachloropropane (HCC-250fb), a pressurized source vessel of hydrogen fluoride, and at least first and second reactors arranged in series, the first reactor producing a first intermediate product mixture containing hydrochlorofluoroolefin, and the second reactor producing a final product mixture containing 1,1-difluoropropene (HFO-1252zc), wherein the first reactor includes a flow-through bed of fluorination catalyst, and the second reactor is configured for a liquid-phase reaction to convert the hydrochlorofluoroolefin produced in the first reactor to HFO-1252zc.

[0385] Embodiment 61. The system according to Embodiment 60, wherein a first reactor is configured for a gas-phase fluorination reaction to convert HCC-250fb to hydrochlorofluoroolefin HCFO-1242zf, and a second reactor is configured for a liquid-phase conversion of the hydrochlorofluoroolefin to HFO-1252zc.

[0386] Embodiment 62. The system according to any one of embodiments 60 to 61, further comprising one or more separator systems.

[0387] Embodiment 63. The system according to Embodiment 62, further comprising a first discharge line configured to supply a first intermediate product mixture from a first reactor to a first separator system, wherein the first separator system is configured to recover hydrochlorofluoroolefins and transport the hydrochlorofluoroolefins to a second reactor.

[0388] Embodiment 64. The system according to any one of embodiments 60 to 63, further comprising a vaporizer and a mixer.

[0389] Embodiment 65. The system according to Embodiment 64, wherein the vaporizer and mixer are connected in series and are located downstream of the supply source and upstream of the first reactor.

[0390] Embodiment 66. The system according to any one of embodiments 60 to 65, wherein the pressurized source of hydrogen fluoride is connected to the mixer.

[0391] Embodiment 67. The system according to any one of embodiments 60 to 66, wherein the pressurized source of hydrogen fluoride is directly connected to the first reactor.

[0392] Embodiment 68. The system according to Embodiment 63, wherein unreacted HCFO-1242zf from the first separator system is recycled to the first reactor.

[0393] Embodiment 69. A process for producing HFO-1252zc, comprising using the system described in any of Embodiments 45 to 68.

[0394] Embodiment 70. A composition comprising, essentially consisting of, or comprising 1-chloro-1,1-difluoropropane (HCFC-262fc) and one or more additional compounds selected from the group consisting of propane, propylene, E-HFO-1261ze, Z-HFO-1261ze, HFO-1252zc, HFC-272fb, E-HCFO-1251zd, Z-HCFO-1251zd, HCFC-262db, HCFC-252dc, HCO-1250, HCC-260, HFO-1243zf, HCFO-1242zf, HCFO-1242 isomer, HCFO-1232 isomer, and HCFC-252 isomer.

[0395] Embodiment 71. The composition according to Embodiment 70, formed by the method of Embodiment 18.

[0396] Embodiment 72. A composition comprising, essentially consisting of, or comprising 1-chloro-1,1-difluoropropane (HCFC-262fc), 3-chloro-3,3-difluoro-1-propene (HCFO-1242zf), and one or more additional compounds selected from the group consisting of propane, propylene, E-HFO-1261ze, Z-HFO-1261ze, HFO-1252zc, HFC-272fb, E-HCFO-1251zd, Z-HCFO-1251zd, HCFC-262db, HCFC-252dc, HCO-1250, HCC-260, HFO-1243zf, HCFO-1242 isomer, HCFO-1232 isomer, and HCFC-252 isomer.

[0397] Embodiment 73. The composition according to Embodiment 72, formed by the method of Embodiment 18.

[0398] Embodiment 74. A composition comprising, essentially consisting of, or comprising 1-chloro-1,1-difluoropropane (HCFC-262fc), 1,1-difluoropropane (HFC-272fb), and one or more additional compounds selected from the group consisting of propane, propylene, E-HFO-1261ze, Z-HFO-1261ze, HFO-1252zc, E-HCFO-1251zd, Z-HCFO-1251zd, HCFC-262db, HCFC-252dc, HCO-1250, HCC-260, HFO-1243zf, HCFO-1242zf, HCFO-1242 isomer, HCFO-1232 isomer, and HCFC-252 isomer.

[0399] Embodiment 75. The composition according to Embodiment 74, formed by the method of Embodiment 18.

[0400] Embodiment 76. A composition comprising, essentially consisting of, or comprising 1-chloro-1,1-difluoropropane (HCFC-262fc) and one or more additional compounds selected from the group consisting of ethane, HFC-152a, HFC-253db, HCFO-1232 isomer, HCFO-1242 isomer, HCFO-1242zf, HFO-1243zf, and HFO-1252zc.

[0401] Embodiment 77. The composition according to Embodiment 76, formed by the method of Embodiment 20.

[0402] Embodiment 78. The composition according to either Embodiment 76 or 77, wherein the vapor portion of the composition comprises, essentially consists of, or consists of HCFC-262fc and one or more additional compounds selected from the group consisting of ethane, HFC-152a, HFC-253db, HCFO-1232 isomer, HCFO-1242 isomer, HCFO-1242zf, HFO-1243zf and HFO-1252zc, and the liquid portion of the composition comprises, essentially consists of, or consists of HCFC-262fc and one or more additional compounds selected from the group consisting of HFC-253db, HCFO-1232 isomer, HCFO-1242 isomer, HCFO-1242zf and HFO-1252zc.

[0403] Embodiment 79. A composition comprising, essentially consisting of, or comprising HCFO-1242zf and one or more additional compounds selected from the group consisting of HCC-250fb, HCFC-253fb, HCFC-252fc, HCFC-251fb, HCFC-1243zf, HCFC-1241zf, and HCFC-1240za.

[0404] Embodiment 80. A composition comprising, essentially consisting of, or comprising HCFC-1243zf and one or more additional compounds selected from the group consisting of HCC-250fb, HCFC-253fb, HCFC-252fc, HCFC-251fb, HCFO-1242zf, HCFC-1241zf, and HCFC-1240za.

[0405] Embodiment 81. A composition comprising, essentially consisting of, or comprising HFO-1252zc and one or more additional compounds selected from the group consisting of HCC-250fb, HCFC-252fc, HCFC-262fc, and HCFO-1242zf.

[0406] Embodiment 82. A composition comprising, essentially consisting of, or comprising HFO-1252zc and one or more additional compounds selected from the group consisting of HCFC-262fc, HCC-250fb, HFC-263fb, HFO-1243zf, other 1252 isomers, ethane, ethylene, HFC-23, HCFC-22, HFO-1132a, propane, HFC-143a, HCFC-142b, HFO-1234yf, HFO-1234ze, HFO-1225zc, HCFO-1242zf, and HCFC-252fc.

[0407] Embodiment 83. The composition according to Embodiment 82, wherein the composition is formed by any of the methods in Embodiments 2, 4, 5 and 10-13.

[0408] Embodiment 84. A composition comprising, essentially consisting of, or comprising (i) HFO-1252zc, (ii) at least one of HCC-250fb, HCFC-252fc and HCFC-262fc, and (iii) one or more additional compounds selected from the group consisting of HFC-263fb, HFO-1243zf, other 1252 isomers, ethane, ethylene, HFC-23, HCFC-22, HFO-1132a, propane, HFC-143a, HCFC-142b, HFO-1234yf, HFO-1234ze, HFO-1225zc and HCFO-1242zf.

[0409] Embodiment 85. The composition according to Embodiment 84, wherein the composition is formed by any of the methods in Embodiments 2, 4, 5 and 10-13.

[0410] Embodiment 86. A composition comprising, essentially consisting of, or comprising HFO-1252zc, HCFC-262fc, and one or more additional compounds selected from the group consisting of HCC-250fb, HFC-263fb, HFO-1243zf, other 1252 isomers, ethane, ethylene, HFC-23, HCFC-22, HFO-1132a, propane, HFC-143a, HCFC-142b, HFO-1234yf, HFO-1234ze, HFO-1225zc, HCFO-1242zf, and HCFC-252fc.

[0411] Embodiment 87. The composition according to Embodiment 86, wherein the composition is formed by any of the methods of Embodiments 2, 4, 5 and 10-13.

[0412] Embodiment 88. A composition comprising, essentially consisting of, or comprising HFO-1252zc, HCFC-262fc, HCFC-252fc, and one or more additional compounds selected from HCC-250fb, HFC-263fb, HFO-1243zf, other 1252 isomers, ethane, ethylene, HFC-23, HCFC-22, HFO-1132a, propane, HFC-143a, HCFC-142b, HFO-1234yf, HFO-1234ze, HFO-1225zc, and HCFO-1242zf.

[0413] Embodiment 89. The composition according to Embodiment 88, wherein the composition is formed by any of the methods in Embodiments 2, 4, 5 and 10-13.

[0414] Embodiment 90. A composition comprising, essentially consisting of, or comprising HFO-1252zc and one or more additional compounds selected from the group consisting of HCFC-262fc, HCC-250fb, HFC-263fb, HCFO-1242zf, HFO-1252zf, HFO-1243zf, and HCFC-252fc.

[0415] Embodiment 91. A composition comprising, essentially consisting of, or comprising (i) HFO-1252zc, (ii) at least one of HCC-250fb and HCFO-1242zf, and (iii) one or more additional compounds selected from HCFC-262fc, HFC-263fb, HFO-1252zf, HFO-1243zf and HCFC-252fc.

[0416] Embodiment 92. The composition according to Embodiment 90 or Embodiment 91, wherein the composition is formed by a step of contacting 3-chloro-3,3-difluoro-1-propene (HCFO-1242zf) with zinc to form a composition comprising, essentially consisting of, or comprising HFO-1252zc and one or more additional compounds.

[0417] Embodiment 93. The composition according to Embodiment 92, wherein the step of contacting HCFO-1242zf with zinc is performed in a liquid phase.

[0418] Embodiment 94. The composition according to Embodiment 93, wherein HCFO-1242zf reacts with zinc in an organic solvent.

[0419] Embodiment 95. The composition according to Embodiment 94, wherein the organic solvent is selected from the group consisting of alcohols, organic acids, polar aprotic solvents, carboxylic acid anhydrides, and mixtures thereof.

[0420] Embodiment 96. The composition according to any one of Embodiments 94 to 95, wherein the organic solvent is selected from the group consisting of acetic acid, N,N-dimethylformamide (DMF), acetic anhydride, and mixtures thereof.

[0421] Embodiment 97. The composition according to any one of Embodiments 94 to 96, wherein HCFO-1242zf reacts with zinc in an organic solvent in the presence of a catalyst.

[0422] Embodiment 98. The composition according to Embodiment 97, wherein the catalyst is selected from the group consisting of phase transfer catalysts, metal salts, and combinations thereof.

[0423] Embodiment 99. The composition according to Embodiment 98, wherein the metal salt is a zinc salt.

[0424] Embodiment 100. The composition according to Embodiment 99, wherein the zinc salt is selected from the group consisting of zinc acetate, zinc bromide, zinc chloride, zinc citrate, zinc sulfate, and mixtures thereof.

[0425] Embodiment 101. The composition according to Embodiment 98, wherein the phase transfer catalyst is selected from the group consisting of quaternary ammonium halides, quaternary phosphonium halides, and cyclic polyether compounds.

[0426] Embodiment 102. The composition according to any one of Embodiments 97 to 101, wherein the catalyst is activated by acid washing.

[0427] Embodiment 103. The composition according to any one of Embodiments 90-91 and 97-102, wherein zinc is activated by acid washing.

[0428] Embodiment 104. (i) HFO-1252zc and HFC-263fb, HCFC-262fc, E-HFO-1251zb, Z-HFO-1251zb, HCFC-272fb, methane, HFC-32, ethylene, ethane, HFO-1132a, HCC-40, HCFC-22, ethylene oxide, E-HFO-1261ze, HFO-1252 isomer, HFC-281fa, HCC-30, C4H3ClF4, C4H6F4(I), C4H6F4(II), C6F 12 A composition comprising, essentially consisting of, or comprising, one or more additional compounds selected from the group consisting of HFO-1252zc dimer (I) and HFO-1252zc dimer (II).

[0429] Embodiment 105. (i) HFO-1252zc and HFC-263fb, HCFC-262fc, E-HFO-1251zb, Z-HFO-1251zb, HCFC-272fb, methane, HFC-32, ethylene, ethane, HFO-1132a, HCC-40, HCFC-22, E-HFO-1261ze, HFO-1252 isomer, HFC-281fa, HCC-30, C4H3ClF4, C4H6F4(I), C4H6F4(II), C6F 12 A composition comprising, essentially consisting of, or comprising, one or more additional compounds selected from the group consisting of HFO-1252zc dimer (I) and HFO-1252zc dimer (II).

[0430] Embodiment 106. A composition comprising, essentially consisting of, or comprising HFO-1252zc and one or more additional compounds selected from the group consisting of HFC-263fb, HCFC-262fc, E-HFO-1251zb, Z-HFO-1251zb, HCFC-272fb, HFO-1252zc dimer (I), and HFO-1252zc dimer (II).

[0431] Embodiment 107. The composition according to any one of Embodiments 104 to 106, wherein one or more additional compounds comprise at least an HFO-1252zc dimer.

[0432] Embodiment 108. The composition according to any one of Embodiments 104 to 107, wherein the composition is formed by the method described in any one of Embodiments 2, 4, 5, 10 to 13, 27 and 28.

[0433] Embodiment 109. The composition according to any one of Embodiments 70 to 108, wherein the composition does not contain or substantially contains a group A fluorinated substance.

[0434] Embodiment 110. The composition according to any one of Embodiments 70 to 109, wherein the decomposition products of the composition do not contain or substantially contain Group A fluorinated substances.

[0435] While certain aspects, embodiments, and principles have been described above, it should be understood that this specification is for illustrative purposes only and does not limit the scope of the present invention or the appended claims. The various aspects, embodiments, and principles described above may be used individually or in combination with each other.

[0436] While the present invention has been described with reference to one or more embodiments, those skilled in the art will understand that various modifications can be made without departing from the scope of the invention, and that equivalents can be used in place of certain elements. Furthermore, many modifications can be made without departing from the essential scope of the invention to adapt specific situations or materials to the teachings of the invention. Therefore, the present invention is not limited to the specific embodiments disclosed as the best mode intended for carrying out the invention, but is intended to include all embodiments included within the appended claims. All numerical values ​​specified in the detailed description should be interpreted as both exact and approximate values ​​being explicitly specified.

Claims

1. A method comprising the step of contacting 1,3-dichloro-1,1-difluoropropane (HCFC-252fc) with hydrogen to form 1-chloro-1,1-difluoropropane (HCFC-262fc).

2. A method comprising the step of converting 1-chloro-1,1-difluoropropane (HCFC-262fc) to 1,1-difluoropropene (HFO-1252zc).

3. (i) A step of contacting 1,1,1,3-tetrachloropropane (HCC-250fb) with hydrogen fluoride in a liquid-phase reaction to form 1,3-dichloro-1,1-difluoropropane (HCFC-252fc), (ii) A step of contacting HCFC-252fc with hydrogen to form 1-chloro-1,1-difluoropropane (HCFC-262fc), Methods that include...

4. (i) A step of contacting 1,3-dichloro-1,1-difluoropropane (HCFC-252fc) with hydrogen to form 1-chloro-1,1-difluoropropane (HCFC-262fc), (ii) A step of converting HCFC-262fc to 1,1-difluoropropene (HFO-1252zc), Methods that include...

5. (i) A step of contacting 1,1,1,3-tetrachloropropane (HCC-250fb) with hydrogen fluoride in a liquid-phase reaction to form 1,3-dichloro-1,1-difluoropropane (HCFC-252fc), (ii) A step of contacting HCFC-252fc with hydrogen to form 1-chloro-1,1-difluoropropane (HCFC-262fc), (iii) A step of converting HCFC-262fc to 1,1-difluoropropene (HFO-1252zc), Methods that include...

6. A method comprising the step of contacting 1,1,1,3-tetrachloropropane (HCC-250fb) with hydrogen fluoride in a gas-phase reaction in a reactor, either in the absence or in the presence of a catalyst, to form 3-chloro-3,3-difluoro-1-propene (HCFO-1242zf), wherein, if present, the catalyst is a metal alloy packing material in the reactor, and the metal alloy packing material has catalytic activity.

7. A method comprising the step of contacting 3-chloro-3,3-difluoro-1-propene (HCFO-1242zf) with hydrogen to form 1-chloro-1,1-difluoropropane (HCFC-262fc).

8. (i) A step of contacting 1,1,1,3-tetrachloropropane (HCC-250fb) with hydrogen fluoride in a gas-phase reaction to form 3-chloro-3,3-difluoro-1-propene (HCFO-1242zf), (ii) A step of contacting HCFO-1242zf with hydrogen to form 1-chloro-1,1-difluoropropane (HCFC-262fc), Methods that include...

9. (i) A step of contacting 1,3-dichloro-1,1-difluoropropane (HCFC-252fc) with a caustic agent in an aqueous solvent to form 3-chloro-3,3-difluoro-1-propene (HCFO-1242zf), (ii) A step of contacting HCFO-1242zf with hydrogen to form 1-chloro-1,1-difluoropropane (HCFC-262fc), Methods that include...

10. (i) A step of contacting 3-chloro-3,3-difluoro-1-propene (HCFO-1242zf) with hydrogen to form 1-chloro-1,1-difluoropropane (HCFC-262fc), (ii) A step of converting HCFC-262fc to 1,1-difluoropropene (HFO-1252zc), Methods that include...

11. (i) A step of contacting 1,1,1,3-tetrachloropropane (HCC-250fb) with hydrogen fluoride in a gas-phase reaction to form 3-chloro-3,3-difluoro-1-propene (HCFO-1242zf), (ii) A step of contacting HCFO-1242zf with hydrogen to form 1-chloro-1,1-difluoropropane (HCFC-262fc), (iii) A step of converting HCFC-262fc to 1,1-difluoropropene (HFO-1252zc), Methods that include...

12. (i) A step of contacting 1,3-dichloro-1,1-difluoropropane (HCFC-252fc) with a caustic agent in an aqueous solvent to form 3-chloro-3,3-difluoro-1-propene (HCFO-1242zf), (ii) A step of contacting HCFO-1242zf with hydrogen to form 1-chloro-1,1-difluoropropane (HCFC-262fc), (iii) A step of converting HCFC-262fc to 1,1-difluoropropene (HFO-1252zc), Methods that include...

13. (i) A step of contacting 1,1,1,3-tetrachloropropane (HCC-250fb) with hydrogen fluoride in a liquid-phase reaction to form 1,3-dichloro-1,1-difluoropropane (HCFC-252fc), (ii) A step of contacting HCFC-252fc with a caustic agent in an aqueous solvent to form 3-chloro-3,3-difluoro-1-propene (HCFO-1242zf), (iii) A step of contacting HCFO-1242zf with hydrogen to form 1-chloro-1,1-difluoropropane (HCFC-262fc), (iv) A process to convert HCFC-262fc to 1,1-difluoropropene (HFO-1252zc), Methods that include...

14. (i) A step of contacting 1,1,1,3-tetrachloropropane (HCC-250fb) with hydrogen fluoride in a gas-phase reaction to form 3-chloro-3,3-difluoro-1-propene (HCFO-1242zf), (ii) A step of contacting HCFO-1242zf with zinc to form 1,1-difluoropropene (HFO-1252zc), Methods that include...

15. (i) A step of contacting 1,3-dichloro-1,1-difluoropropane (HCFC-252fc) with a caustic agent in an aqueous solvent to form 3-chloro-3,3-difluoro-1-propene (HCFO-1242zf), (ii) A step of contacting HCFO-1242zf with zinc to form 1,1-difluoropropene (HFO-1252zc), Methods that include...

16. (i) A step of contacting 1,1,1,3-tetrachloropropane (HCC-250fb) with hydrogen fluoride in a liquid-phase reaction to form 1,3-dichloro-1,1-difluoropropane (HCFC-252fc), (ii) A step of contacting HCFC-252fc with a caustic agent in an aqueous solvent to form 3-chloro-3,3-difluoro-1-propene (HCFO-1242zf), (iii) A step of contacting HCFO-1242zf with zinc to form 1,1-difluoropropene (HFO-1252zc), Methods that include...

17. The method according to any one of claims 1, 3, 4, and 5, wherein the step of contacting the HCFC-252fc with hydrogen to form HCFC-262fc is performed in the gas phase.

18. The method according to any one of claims 7 to 13, wherein the step of contacting HCFO-1242zf with hydrogen to form HCFC-262fc is performed in the gas phase.

19. The method according to any one of claims 1, 3, 4, and 5, wherein the step of contacting the HCFC-252fc with hydrogen to form HCFC-262fc is performed in a liquid phase.

20. The method according to any one of claims 7 to 13, wherein the step of contacting HCFO-1242zf with hydrogen to form HCFC-262fc is performed in a liquid phase.

21. The method according to claim 19 or claim 20, wherein the contact step is performed in the presence of a catalyst selected from the group consisting of Group VIII metals, Pd, Pt, Ni, Cu, and two or more combinations thereof, preferably Pd.

22. The method according to claim 21, wherein the catalyst is either not supported or is supported.

23. The method according to claim 22, wherein the carrier is a carbon or aluminum oxide carrier.

24. The method according to claim 23, wherein the carbon carrier comprises one of carbon, acid-washed carbon, activated carbon, and a three-dimensional matrix carbonaceous material.

25. The method according to any one of claims 21 to 24, wherein the amount of the Pd catalyst is 0.5% to 0.01%, or the amount of the Pd catalyst for the gas-phase reaction is 0.1% to 0.01%.

26. The catalyst is Pd / Al 2 O 3 The method according to any one of claims 21 to 25, wherein the ratio is Pd / C.

27. The method according to any one of claims 2, 4, 5, and 10 to 13, wherein the conversion of HCFC-262fc to HFO-1252zc includes dehalogenation hydrogenation of HCFC-262fc.

28. The method according to claim 27, wherein the conversion of HCFC-262fc to HFO-1252zc by dehalogenation hydrogenation of HCFC-262fc occurs in the gas phase or liquid phase using a strong base.

29. The method according to any one of claims 6, 8, 11, and 14, wherein the step of contacting HCC-250fb with hydrogen fluoride to form HCFO-1242zf is performed in the absence of a catalyst.

30. The method according to any one of claims 8, 11, and 14, wherein the step of contacting HCC-250fb with hydrogen fluoride is performed in the presence of a catalyst selected from the group consisting of Lewis acid catalysts, transition metal halides, transition metal oxides (preferably partially fluorinated transition metal oxides), group IVb metal halides, group Vb metal halides, and catalytically active metal alloy fillers.

31. The method according to any one of claims 3 to 5, 8 to 16, wherein a separate reactor is used for each of the reaction steps.

32. The method according to any one of claims 9, 12, 13, 15, and 16, wherein the caustic agent is selected from the group consisting of alkali metal oxides, alkali metal hydroxides, alkali metal amides, alkaline earth metal hydroxides, alkaline earth metal oxides or amides, alkali metal carbonates, alkali metal phosphates, and alkali metal carboxylates.

33. The caustic agent is selected from NaOH, KOH, LiOH, CsOH, Ca(OH) 2 , Zn(OH) 2 , Na 2 CO 3 , K 2 CO 3 , K 3 PO 4 , Na 3 PO 4 , KF, and CsF, according to any one of claims 9, 12, 13, 15, 16 and 32.

34. The method according to any one of claims 9, 12, 13, 15, 16, 32, and 33, wherein the HCFC-252fc is in contact with the caustic agent at a temperature in the range of about 20°C to about 150°C, preferably about 30°C to about 100°C.

35. The method according to any one of claims 2, 4, 5, 10 to 13, wherein the step of converting HCFC-262fc to HFO-1252zc includes contacting HCFC-262fc with a strong base in a solvent.

36. The method according to claim 35, wherein the strong base is selected from the group consisting of hydroxides, alkoxides, metal amides, metal hydrides, metal dialkylamides, and arylamines.

37. The method according to any one of claims 35 to 36, wherein the strong base is selected from the group consisting of alkoxides containing lithium, sodium, and potassium salts of methyl, ethyl, and t-butyl oxide; metal amides containing sodium amide, potassium amide, and lithium amide; metal hydrides containing sodium hydride, potassium hydride, and lithium hydride; and metal dialkylamides containing lithium, sodium, and potassium salts of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, trimethylsilyl, and cyclohexyl substituted amides.

38. The aforementioned HCC-250fb is brought into contact with hydrogen fluoride in the gas phase in the presence of a catalyst, and 3,3,3-trifluoropropene (HFO-1243zf, CF 3 CH=CH 2 The method according to any one of claims 6, 8, 11, and 14, wherein ) and HCFO-1242zf are co-produced.

39. The method according to claim 38, wherein the catalyst is a metal surface.

40. The method according to claim 39, wherein the metal surface is the surface of a metal alloy filler.

41. The method according to any one of claims 38 to 40, wherein the catalyst is selected from the group consisting of Lewis acid catalysts, transition metal halides, transition metal oxides (preferably partially fluorinated transition metal oxides), group IVb metal halides, group Vb metal halides, chromium-based catalysts, cobalt-based catalysts, nickel-based catalysts, aluminum-based catalysts, iron-based catalysts, and combinations thereof.

42. A method comprising contacting 1,1,1,3-tetrachloropropane (HCC-250fb) with hydrogen fluoride in the gas phase, either in the absence or in the presence of a catalyst, to form 3,3,3-trifluoropropene (HFO-1243zf).

43. The method according to claim 42, wherein the catalyst is selected from the group consisting of Lewis acid catalysts, transition metal halides, transition metal oxides (preferably partially fluorinated transition metal oxides), group IVb metal halides, group Vb metal halides, and metal alloy fillers.

44. The method according to claim 43, wherein the catalyst is selected from the group consisting of chromium-based catalysts, cobalt-based catalysts, nickel-based catalysts, aluminum-based catalysts, iron-based catalysts, and combinations thereof.

45. It is a system, A built-in supply source of 1,1,1,3-tetrachloropropane (HCC-250fb), A pressurized source container for hydrogen and / or hydrogen fluoride, A reactor comprising at least first, second, and third reactors arranged in series, wherein the first and second reactors produce a first intermediate product mixture and a second intermediate product mixture, respectively, and the third reactor produces a final product mixture containing 1,1-difluoropropene (HFO-1252zc), Includes, A system comprising: a first reactor including a flow-through bed of a fluorination catalyst; a second reactor including a flow-through bed of a hydrogenation catalyst; and a third reactor configured for a gas-phase reaction that converts the hydrochlorofluorocarbon produced in the second reactor into HFO-1252zc.

46. The system according to claim 45, wherein the first reactor is configured for a liquid-phase fluorination reaction that converts HCC-250fb to 1,3-dichloro-1,1-difluoropropane (HCFC-252fc).

47. The system according to any one of claims 45 to 46, wherein the second reactor is configured for a liquid-phase or gas-phase hydrogenation reaction that converts HCFC-252fc to 1-chloro-1,1-difluoropropane (HCFC-262fc).

48. The system according to any one of claims 45 to 47, wherein the first reactor is configured for a gas-phase fluorination reaction that converts HCC-250fb to 3-chloro-3,3-difluoro-1-propene (HCFO-1242zf).

49. The system according to any one of claims 45 to 48, wherein the second reactor is configured for a liquid-phase or gas-phase hydrogenation reaction that converts HCFO-1242zf to hydrochlorofluorocarbon HCFC-262fc.

50. The system according to any one of claims 45 to 49, further comprising one or more separator systems.

51. The system according to claim 50, further comprising a first discharge line configured to supply the first intermediate product mixture from a first reactor to a first separator system, wherein the first separator system is configured to recover the first intermediate product and transport the first intermediate product to a second reactor.

52. The system according to claim 51, further comprising a second discharge line configured to supply the second intermediate product mixture from the second reactor to a second separator system, the second separator system configured to recover hydrochlorofluorocarbons and transport the hydrochlorofluorocarbons to the third reactor.

53. The system according to any one of claims 45 to 52, further comprising a vaporizer and a mixer.

54. The system according to claim 53, wherein the vaporizer and the mixer are connected in series and are located downstream of the supply source and upstream of the first reactor.

55. The system according to any one of claims 45 to 54, wherein the pressurized source of the hydrogen fluoride is connected to the mixer.

56. The system according to any one of claims 45 to 55, wherein the pressurized source of hydrogen fluoride is directly connected to the first reactor.

57. The system according to claim 51, wherein unreacted HCFC-252fc from the first separator system is recycled to the first reactor.

58. The system according to claim 52, wherein unreacted HCFC-262fc from the second separator system is recycled to the second reactor.

59. The system according to claim 51, wherein unreacted HCFO-1242zf from the first separator system is recycled to the first reactor.

60. It is a system, A built-in supply source of 1,1,1,3-tetrachloropropane (HCC-250fb), A pressurized source container for hydrogen fluoride, A reactor comprising at least two reactors arranged in series, wherein the first reactor produces a first intermediate product mixture containing hydrochlorofluoroolefin, and the second reactor produces a final product mixture containing 1,1-difluoropropene (HFO-1252zc), Includes, The system comprises a first reactor containing a flow-through bed of a fluorination catalyst, and a second reactor configured for a liquid-phase reaction that converts the hydrochlorofluoroolefin produced in the first reactor into HFO-1252zc.

61. The system according to claim 60, wherein the first reactor is configured for a gas-phase fluorination reaction that converts HCC-250fb to hydrochlorofluoroolefin HCFO-1242zf, and the second reactor is configured for a liquid-phase conversion of hydrochlorofluoroolefin to HFO-1252zc.

62. The system according to any one of claims 60 to 61, further comprising one or more separator systems.

63. The system according to claim 62, further comprising a first discharge line configured to supply the first intermediate product mixture from the first reactor to a first separator system, wherein the first separator system is configured to recover hydrochlorofluoroolefins and transport the hydrochlorofluoroolefins to the second reactor.

64. The system according to any one of claims 60 to 63, further comprising a vaporizer and a mixer.

65. The system according to claim 64, wherein the vaporizer and the mixer are connected in series and are located downstream of the supply source and upstream of the first reactor.

66. The system according to any one of claims 60 to 65, wherein the pressurized source of the hydrogen fluoride is connected to the mixer.

67. The system according to any one of claims 60 to 66, wherein the pressurized source of hydrogen fluoride is directly connected to the first reactor.

68. The system according to claim 63, wherein unreacted HCFO-1242zf from the first separator system is recycled to the first reactor.

69. A process for generating HFO-1252zc, comprising using the system described in any one of claims 45 to 68.

70. 1-Chloro-1,1-difluoropropane (HCFC-262fc), Propane, propylene, one or more additional compounds selected from the group consisting of E-HFO-1261ze, Z-HFO-1261ze, HFO-1252zc, HFC-272fb, E-HCFO-1251zd, Z-HCFO-1251zd, HCFC-262db, HCFC-252dc, HCO-1250, HCC-260, HFO-1243zf, HCFO-1242zf, HCFO-1242 isomer, HCFO-1232 isomer and HCFC-252 isomer, A composition containing, essentially consisting of, or comprising.

71. The composition according to claim 70, formed by the method described in claim 18.

72. 1-Chloro-1,1-difluoropropane (HCFC-262fc), 3-chloro-3,3-difluoro-1-propene (HCFO-1242zf), Propane, propylene, one or more additional compounds selected from the group consisting of E-HFO-1261ze, Z-HFO-1261ze, HFO-1252zc, HFC-272fb, E-HCFO-1251zd, Z-HCFO-1251zd, HCFC-262db, HCFC-252dc, HCO-1250, HCC-260, HFO-1243zf, HCFO-1242 isomer, HCFO-1232 isomer and HCFC-252 isomer, A composition containing, essentially consisting of, or comprising.

73. The composition according to claim 72, formed by the method described in claim 18.

74. 1-Chloro-1,1-difluoropropane (HCFC-262fc), 1,1-Difluoropropane (HFC-272fb) and, Propane, propylene, one or more additional compounds selected from the group consisting of E-HFO-1261ze, Z-HFO-1261ze, HFO-1252zc, E-HCFO-1251zd, Z-HCFO-1251zd, HCFC-262db, HCFC-252dc, HCO-1250, HCC-260, HFO-1243zf, HCFO-1242zf, HCFO-1242 isomer, HCFO-1232 isomer and HCFC-252 isomer, A composition containing, essentially consisting of, or comprising.

75. The composition according to claim 74, formed by the method described in claim 18.

76. 1-Chloro-1,1-difluoropropane (HCFC-262fc), Ethane, one or more additional compounds selected from the group consisting of HFC-152a, HFC-253db, HCFO-1232 isomer, HCFO-1242 isomer, HCFO-1242zf, HFO-1243zf and HFO-1252zc, A composition containing, essentially consisting of, or comprising.

77. The composition according to claim 76, formed by the method described in claim 20.

78. The vapor portion of the above composition HCFC-262fc and, Ethane, one or more additional compounds selected from the group consisting of HFC-152a, HFC-253db, HCFO-1232 isomer, HCFO-1242 isomer, HCFO-1242zf, HFO-1243zf and HFO-1252zc, It includes, essentially consists of, or is composed of The liquid portion of the composition HCFC-262fc and, One or more additional compounds selected from the group consisting of HFC-253db, HCFO-1232 isomer, HCFO-1242 isomer, HCFO-1242zf, and HFO-1252zc, The composition according to either claim 76 or 77, which includes, essentially consists of, or comprises the following.

79. HCFO-1242zf and, One or more additional compounds selected from the group consisting of HCC-250fb, HCFC-253fb, HCFC-252fc, HCFC-251fb, HCFC-1243zf, HCFC-1241zf, and HCFC-1240za, A composition containing, essentially consisting of, or comprising.

80. HCFC-1243zf and, One or more additional compounds selected from the group consisting of HCC-250fb, HCFC-253fb, HCFC-252fc, HCFC-251fb, HCFO-1242zf, HCFC-1241zf, and HCFC-1240za, A composition containing, essentially consisting of, or comprising.

81. HFO-1252zc and, One or more additional compounds selected from the group consisting of HCC-250fb, HCFC-252fc, HCFC-262fc, and HCFO-1242zf, A composition containing, essentially consisting of, or comprising.

82. HFO-1252zc and, One or more additional compounds selected from the group consisting of HCFC-262fc, HCC-250fb, HFC-263fb, HFO-1243zf, 1252 other isomers, ethane, ethylene, HFC-23, HCFC-22, HFO-1132a, propane, HFC-143a, HCFC-142b, HFO-1234yf, HFO-1234ze, HFO-1225zc, HCFO-1242zf, and HCFC-252fc, A composition containing, essentially consisting of, or comprising.

83. The composition according to claim 82, wherein the composition is formed by the method described in any one of claims 2, 4, 5 and 10 to 13.

84. (i) HFO-1252zc and, (ii) At least one of HCC-250fb, HCFC-252fc, and HCFC-262fc, (iii) One or more additional compounds selected from the group consisting of HFC-263fb, HFO-1243zf, 1252 other isomers, ethane, ethylene, HFC-23, HCFC-22, HFO-1132a, propane, HFC-143a, HCFC-142b, HFO-1234yf, HFO-1234ze, HFO-1225zc and HCFO-1242zf, A composition containing, essentially consisting of, or comprising.

85. The composition according to claim 84, wherein the composition is formed by the method described in any one of claims 2, 4, 5 and 10 to 13.

86. HFO-1252zc and, HCFC-262fc and, One or more additional compounds selected from the group consisting of HCC-250fb, HFC-263fb, HFO-1243zf, 1252 other isomers, ethane, ethylene, HFC-23, HCFC-22, HFO-1132a, propane, HFC-143a, HCFC-142b, HFO-1234yf, HFO-1234ze, HFO-1225zc, HCFO-1242zf, and HCFC-252fc, A composition containing, essentially consisting of, or comprising.

87. The composition according to claim 86, wherein the composition is formed by the method described in any one of claims 2, 4, 5 and 10 to 13.

88. HFO-1252zc and, HCFC-262fc and, HCFC-252fc and, One or more additional compounds selected from HCC-250fb, HFC-263fb, HFO-1243zf, 1252 other isomers, ethane, ethylene, HFC-23, HCFC-22, HFO-1132a, propane, HFC-143a, HCFC-142b, HFO-1234yf, HFO-1234ze, HFO-1225zc and HCFO-1242zf, A composition containing, essentially consisting of, or comprising.

89. The composition according to claim 88, wherein the composition is formed by the method described in any one of claims 2, 4, 5 and 10 to 13.

90. A composition comprising, essentially consisting of, or comprising HFO-1252zc and one or more additional compounds selected from the group consisting of HCFC-262fc, HCC-250fb, HFC-263fb, HCFO-1242zf, HFO-1252zf, HFO-1243zf, and HCFC-252fc.

91. (i) HFO-1252zc and, (ii) At least one of HCC-250fb and HCFO-1242zf, (iii) One or more additional compounds selected from HCFC-262fc, HFC-263fb, HFO-1252zf, HFO-1243zf and HCFC-252fc, A composition containing, essentially consisting of, or comprising.

92. The composition according to claim 90 or 91, wherein the composition is formed by a step of contacting 3-chloro-3,3-difluoro-1-propene (HCFO-1242zf) with zinc to form a composition comprising, essentially consisting of, or comprising HFO-1252zc and one or more additional compounds.

93. The composition according to claim 92, wherein the step of contacting HCFO-1242zf with zinc is carried out in a liquid phase.

94. The composition according to claim 93, wherein HCFO-1242zf reacts with zinc in an organic solvent.

95. The composition according to claim 94, wherein the organic solvent is selected from the group consisting of alcohols, organic acids, polar aprotic solvents, carboxylic acid anhydrides, and mixtures thereof.

96. The composition according to any one of claims 94 to 95, wherein the organic solvent is selected from the group consisting of acetic acid, N,N-dimethylformamide (DMF), acetic anhydride, and mixtures thereof.

97. The composition according to any one of claims 94 to 96, wherein the HCFO-1242zf is reacted with zinc in an organic solvent in the presence of a catalyst.

98. The composition according to claim 97, wherein the catalyst is selected from the group consisting of phase transfer catalysts, metal salts, and combinations thereof.

99. The composition according to claim 98, wherein the metal salt is a zinc salt.

100. The composition according to claim 99, wherein the zinc salt is selected from the group consisting of zinc acetate, zinc bromide, zinc chloride, zinc citrate, zinc sulfate, and mixtures thereof.

101. The composition according to claim 98, wherein the interphase transfer catalyst is selected from the group consisting of quaternary ammonium halides, quaternary phosphonium halides, and cyclic polyether compounds.

102. The composition according to any one of claims 97 to 101, wherein the catalyst is activated by acid washing.

103. The composition according to any one of claims 90 to 91 and 97 to 102, wherein the zinc is activated by acid washing.

104. (i) HFO-1252zc and, HFC-263fb, HCFC-262fc, E-HFO-1251zb, Z-HFO-1251zb, HCFC-272fb, methane, HFC-32, ethylene, ethane, HFO-1132a, HCC-40, HCFC-22, ethylene oxide, E-HFO-1261ze, HFO-1252 isomer, HFC-281fa, HCC-30, C 4 H 3 CLF 4 , C 4 H 6 F 4 (I), C 4 H 6 F 4 (II), C 6 F 12 , one or more additional compounds selected from the group consisting of HFO-1252zc dimer (I) and HFO-1252zc dimer (II), A composition containing, essentially consisting of, or comprising.

105. (i) HFO-1252zc and, HFC-263fb, HCFC-262fc, E-HFO-1251zb, Z-HFO-1251zb, HCFC-272fb, methane, HFC-32, ethylene, ethane, HFO-1132a, HCC-40, HCFC-22, E-HFO-1261ze, HFO-1252 isomer, HFC-281fa, HCC-30, C 4 H 3 CLF 4 , C 4 H 6 F 4 (I), C 4 H 6 F 4 (II), C 6 F 12 , one or more additional compounds selected from the group consisting of HFO-1252zc dimer (I) and HFO-1252zc dimer (II), A composition containing, essentially consisting of, or comprising.

106. (i) HFO-1252zc and, One or more additional compounds selected from the group consisting of HFC-263fb, HCFC-262fc, E-HFO-1251zb, Z-HFO-1251zb, HCFC-272fb, HFO-1252zc dimer (I), and HFO-1252zc dimer (II), A composition containing, essentially consisting of, or comprising.

107. The composition according to any one of claims 104 to 106, wherein the one or more additional compounds comprise at least an HFO-1252zc dimer.

108. The composition according to any one of claims 104 to 107, wherein the composition is formed by the method described in any one of claims 2, 4, 5, 10 to 13, 27 and 28.

109. The composition according to any one of claims 70 to 108, wherein the composition does not contain or substantially contains a fluorinated substance of group A.

110. The composition according to any one of claims 70 to 109, wherein the decomposition products of the composition do not contain or substantially contain group A fluorinated substances.

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