Process to produce 1,2-difluoroethylene (HFO-1132) from 1,2‑dichloro-1,2-difluoroethane (HCFC-132)

Abstract

A process includes contacting 1,2-dichloro-1,2-difluoroethane (HCFC-132) with an activated zinc powder in the presence of a catalyst and a solvent and producing a product mixture comprising E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132). In some embodiments, the catalyst includes tetrabutylammonium bromide. In some embodiments, the catalyst includes zinc chloride. In some embodiments, the catalyst includes zinc acetate.

Description

TS0071-W001TITLE OF THE INVENTIONPROCESS TO PRODUCE 1 ,2-DIFLUOROETHYLENE (HFO-1132) FROM 1 ,2-DICHLORO-l ,2-DIFLUOROETHANE (HCFC-132)CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Application No. 63 / 698,123, filed on September 24, 2024, the disclosure of which is herein incorporated by reference in its entirety.FIELD

[0002] The present disclosure relates to processes of producing olefins and produced compositions thereof. More specifically, the present disclosure relates to processes of producing 1 ,2-difluoroethylene (CHF=CHF; HFO-1132) and produced compositions of HFO-1132.BACKGROUND

[0003] Hydrofluoroolefins (HFOs) having low ozone depletion potential (ODP) and low global warming potential (GWP) have been replacing saturated CFCs (chlorofluorocarbons), HCFCs (hydrochlorofluorocarbons), and HFCs (hydrofluorocarbons) in a variety of applications for several years because saturated hydrohalocarbons tend to have high GWP values. For example, HFC-32 (CH2F2), HFC-125 (C2HF5), and HFC-134a (CH2FCF3) have GWPs of 675, 3500, and 1430, respectively. As a result, low ODP and low GWP materials continue to be of interest for uses, such as, for example, as next generation refrigerants (NGRs), solvents, foam expansion agents, cleaning agents, aerosol propellants, dielectrics, fire extinguishants, and power cycle working fluids.

[0004] To meet these increasing demands, existing and new haloolefins continue to be developed, evaluated, and produced with more efficient processes. One such candidate is E-1 ,2-difluoroethylene (E-CHF=CHF; HFO-E-1132), for example, which is suitable as a blending component given its environmentally friendly decomposition profile in the atmosphere.TS0071-W001

[0005] Current processing generally favors the production of the Z-isomer (Z-1 ,2- difluoroethylene; Z-CHF=CHF; HFO-Z-1132) of 1,2-difluoroethylene, which requires significant amounts to be isomerized to the E-isomer.

[0006] Thus, the need for new processes to produce HFO-E-1132 remains.SUMMARY

[0007] In an example embodiment, a process comprises contacting 1 ,2-dichloro-1.2-difluoroethane (HCFC-132) with an activated zinc powder in the presence of a catalyst and a solvent; and producing a product mixture comprising HFO-E-1132 and HFO-Z-1132.

[0008] In another example embodiment, a product mixture is formed by any of the processes disclosed herein.

[0009] Other features and advantages of the present disclosure will be apparent from the following more detailed description, taken in conjunction with the accompanying drawing which illustrates, by way of example, the principles of this disclosure.BRIEF DESCRIPTION OF THE DRAWINGS

[0010] The Figure shows profiles of reaction pressure as a function of reaction time.DETAILED DESCRIPTION

[0011] A process produces HFO-1132 in high selectivity from a composition including 1 ,2-dichloro-1 ,2-difluoroethane (HCFC-132).

[0012] As used herein, the terms “1 ,2-difluoroethylene”, “CHF=CHF”, “HFO-1132”, “E / Z-1 ,2-difluoroethylene”, “E / Z-CHF=CHF”, and “HFO-E / Z-1132” refer to any enantiomeric mixture, including racemic mixtures, of E-1 ,2-difluoroethylene and Z-1.2-difluoroethylene.

[0013] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having”, or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus thatTS0071-W001 comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus. Further, unless expressly stated to the contrary, “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

[0014] The transitional phrase “consisting of” excludes any element, step, or ingredient not specified. If in the claim such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase “consists of’ appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.

[0015] The transitional phrase “consisting essentially of’ is used to define a composition, method that includes materials, steps, features, components, or elements, in addition to those literally disclosed provided that these additional included materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention, especially the mode of action to achieve the desired result of any of the processes of the present invention. The term “consisting essentially of” occupies a middle ground between “comprising” and “consisting of”.

[0016] Where applicants have defined an invention or a portion thereof with an open-ended term such as “comprising”, it should be readily understood that (unless otherwise stated) the description should be interpreted to also include such an invention using the terms “consisting essentially of’ or “consisting of”.

[0017] Also, use of “a” or “an” are employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

[0018] Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers andTS0071-W001 fractions within the range. It is not intended that the scope of the disclosure be limited to the specific values recited when defining a range. Moreover, all ranges set forth herein are intended to include not only the particular ranges specifically described, but also any combination of values therein, including the minimum and maximum values recited.

[0019] When an amount, concentration, or other value or parameter is given as either a range, preferred range, or a list of upper preferable values and / or lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.

[0020] As used herein GC / FID peak area correlates to the amount of a compound present as a proportion of the total area of all detected peaks. FID area% can be converted to mol% using a response factor either calculated or measured.

[0021] As used herein the term “about” in certain embodiments can be quantified to mean ± 1%, ± 2%, ± 3% and up to and including ±10% of the stated value, and all whole numbers and fractions therebetween.TABLE OF COMPOUNDS

[0022] By way of example, mention is made of the following compounds:TS0071-W001

[0023] Some of the compounds present in the compositions of the present disclosure identified in the Table of Compounds may exist as different configurational isomers or stereoisomers. The present disclosure is intended to include all single configurational isomers, single stereoisomers or any combination or mixture thereof, unless otherwise specified as the Z-isomer or the E-isomer. For instance, HFO-1132 is meant to represent the cis-isomer Z, trans-isomer E, or any combination or mixture of both isomers in any ratio. Similarly, 1 -chloro- 1,2-difluoroethylene (HFO-1122a) exists as a Z-isomer, an E-isomer, or any combination or mixture of both isomers in any ratio. Single isomers or multiple isomers of the same compound may be used in any proportion.

[0024] In some embodiments, a process includes contacting a hydrohaloalkane, and more particularly a chlorofluoroethane, a bromofluoroethane or an iodofluoroethane, with a metal in the presence of a catalyst to produce a product mixture comprising HFO-E-1132 and HFO-Z-1132. In some embodiments, the chlorofluoroethane is, for example, HCFC-132 or HCFC-133. In some embodiments, the bromofluoroethane is, for example, HBFC-132B, HBFC-132B1 or HBFC-133bB. In some embodiments, the iodofluoroethane is, for example, HIFC-1321 or HIFC- 133bl. In a preferred embodiment, the starting hydrohaloalkane is a chlorofluoroethane, and more preferably HCFC-132.

[0025] In some embodiments, a process includes contacting HCFC-132 with a metal in the presence of a catalyst to produce a product mixture comprising HFO-E- 1132 and HFO-Z-1132. Preferably, the reaction is conducted in the liquid phase. In some embodiments, the process of the present invention comprises contacting HCFC-132 with a metal in the presence of a catalyst and a solvent to produce a product mixture comprising HFO-E-1132 and HFO-Z-1132.TS0071-W001

[0026] In certain embodiments, the HCFC-132 feed composition comprises, consists essentially of or consists of HCFC-132 as the main component, preferably present in amounts of about 99 wt.% or greater, based on the total amount of the composition, and one or more additional compounds selected from 1 , 2- difluoroethane (HFC-152, CH2FCH2F), 1-chloro-1 , 2-difluoroethane (HCFC-142a, CH2FCHCIF), 1 ,1-dichloro-1 , 2-difluoroethane (HCFC-132c, CH2FCCI2F), 1 ,2- dichloro-1 , 1-difluoroethane (HCFC-132b, CH2CICCIF2), 1 , 1 ,2-trichloro-1 , 2- difluoroethane (HCFC-122a, CHCIFCCI2F) and 1 ,1 , 2, 2-tetrachloro-1 , 2-difluoroethane (CFC-112, CCI2FCCI2F), wherein the total amount of additional compounds is less than about 1 wt.%, or less than about 0.9 wt.%, or less than about 0.8 wt.%, or less than about 0.7 wt.%, or less than about 0.6 wt.%, or less than about 0.5 wt.%, or less than about 0.4 wt.%, or less than about 0.3 wt.%, or less than about 0.2 wt.%, or less than about 0.1 wt.%, based on the total amount of the composition.

[0027] In some embodiments, the metal is a reactive metal. As used herein, reactive metal refers to reactive metals such as magnesium turnings, activated zinc powder, aluminum, and a powder of any of the following metals: magnesium, calcium, titanium, iron, cobalt, nickel, copper, zinc, indium, and combinations thereof. Magnesium turnings are pieces of magnesium which are cut to produce small pieces with higher surface areas and generally low amounts of surface oxides (which reduce reactivity). In some embodiments, the reactive metal powders of magnesium, calcium, titanium, iron, cobalt, nickel, copper, zinc and indium are Rieke metals, which are prepared by a specific procedure which produces high surface area metal powders which are very reactive in reactions such as those of the present invention. Without wishing to be bound by any particular theory, Rieke metals are thought to be highly reactive because they have high surface areas and lack passivating surface oxides.

[0028] In some embodiments, the metal is selected from zinc, magnesium, cadmium, and combinations thereof. In one embodiment, the metal is zinc. In one embodiment, the metal is zinc powder. In some embodiment, the metal is activated zinc powder.

[0029] In some embodiments, the metal is activated by an acid, and more particularly is activated by contact with an acid before used for reaction withTS0071-W001HCFC-132. In some embodiments, the zinc is activated by an acid, such as HCI. In some embodiments, the zinc powder is activated by aqueous hydrochloric acid and dried. In some embodiments, the activation is carried out by washing zinc powder with aqueous hydrochloric acid having a concentration of about 1 wt% to about 5 wt%. In some embodiments, the activation also includes washing the zinc powder with water and acetone prior to the drying. In some embodiments, the drying occurs under nitrogen (N2). In some embodiments, the drying includes vacuum drying. In certain embodiments disclosed herein, zinc powder is activated with HCI (e.g., aqueous or in an alcohol) and is then used to convert HCFC-132 to HFO-E-1132 and HFO-Z-1132.

[0030] As noted above, in some embodiments, the method of the present invention comprises contacting an HCFC-132 feed with a metal, preferably a reactive metal such as zinc, in the presence of a catalyst and in the presence of a solvent. In some embodiments, the solvent is a polar protic solvent or polar aprotic solvent. In some embodiments, the solvent is selected from alcohol, amide, pyridine and ether. In certain embodiments disclosed herein, the solvent comprises an alcohol selected from methanol, ethanol, propanol, isopropanol and ethylene glycol. In some embodiments, the solvent is dried methanol. In some embodiments, the solvent comprises an amide selected from dimethylformamide (DMF), N-methylpyrrolidone (NMP), and dimethylacetamide (DMAC).

[0031] In some embodiments, the catalyst is selected from zinc salt, ammonium salt and phosphonium salt. In some embodiments, the catalyst comprises a zinc salt selected from zinc acetate and zinc chloride. In some embodiments, the catalyst comprises an ammonium salt, such as tetrabutylammonium bromide (TBAB).

[0032] In some embodiments, the mole ratio of organic (e.g., HCFC-132) to metal is from about 1:1 to about 1:3, preferably about 1:2, or preferably about 1:1.2. In some embodiments, the mole ratio of organic (e.g., HCFC-132) to catalyst is from about 1:1 to about 1 :3, preferably about 1:2, or preferably about 1 :1.2. In some embodiments, the mole ratio of metal to catalyst is from about 1 :1 to about 1:3, preferably about 1:2, or preferably about 1:1.2.

[0033] In some embodiments, the method of the present invention comprises introducing the HCFC-132, the metal, the catalyst, and the solvent to a reactor andTS0071-W001 then sealing the reactor. The reactor may operate in batch, semi-batch, continuous or semi-continuous modes. In some embodiments, the reactor is an autoclave.

[0034] In some embodiments, the method further comprises an optional step of cooling the reactor to a reduced temperature. In some embodiments, the method further comprises removing the air or inert gases from the reactor by vacuum.

[0035] In some embodiments, an appropriate temperature for the cooling may include, but is not limited to, 0°C to -60°C, alternatively -20°C to -60°C, alternatively -30°C to -50°C, alternatively -35°C to -45°C, alternatively about -40°C, or any value, range, or sub-range therebetween.

[0036] According to the present invention, the method further comprises heating the reaction mixture to a reaction temperature and preferably agitating the reaction mixture in the reactor for a reaction time to effect dehydrohalogenation of the HCFC- 132 to HFO-E-1132 and HFO-Z-1132.

[0037] In some embodiments, an appropriate reaction temperature may include, but is not limited to, about 100°C to about 140°C, alternatively about 105°C to about 135°C, alternatively about 110°C to about 130°C, alternatively about 115°C to about 125°C, alternatively about 120°C, or any value, range, or sub-range therebetween.

[0038] In some embodiments, an appropriate reaction time may include, but is not limited to, about 1 to about 24 hours, alternatively about 5 to about 15 hours, alternatively about 8 to about 12 hours, alternatively about 9 to about 11 hours, alternatively about 10 hours, or any value, range, or sub-range therebetween.

[0039] In some embodiments, the reaction begins at a reaction pressure of about 0 psig, and the reaction pressure in the sealed reactor is measured to monitor the progress of the reaction. In some embodiments, the pressure in the sealed reactor increases over time, which is indicative of the progress of the reaction. In some embodiments, the reaction is run until a predetermined reaction pressure is reached. An appropriate reaction pressure at which to stop the reaction may include, but is not limited to, about 500 psig to about 1000 psig, at least about 500 psig, at least about 600 psig, at least about 700 psig, at least about 800 psig, at least about 900 psig, or any value, range, or sub-range therebetween. In some embodiments, the reactionTS0071-W001 pressure is measured during the producing to monitor progression of the dehydrohalogenation reaction.

[0040] In some embodiments, the catalyst, the reaction temperature, the reaction time, and / or the reaction pressure is / are selected to provide a product mixture having a high yield of HFO-1132 and a low weight ratio of HFO-Z-1132 to HFO-E-1132 (Z / E ratio).

[0041] In some embodiments, the high yield of HFO-1132 in the product mixture is at least about 45 mol%, alternatively at least about 60 mol%, alternatively at least about 80 mol%, alternatively at least about 90 mol%, or any value, range, or subrange therebetween.

[0042] In some embodiments, the low Z / E ratio of HFO-1132 in the product mixture is about 1.5:1 or less, alternatively about 1.4:1 or less, alternatively about 1.3:1 or less, alternatively about 1.2:1 or less, alternatively about 1.1:1 or less, alternatively about 1:1 or less, alternatively about 0.9:1 or less, alternatively about 0.8:1 or less, alternatively about 0.7:1 or less, or any value, range, or sub-range therebetween.

[0043] In some embodiments, the dehydrohalogenation reaction occurs in the liquid phase. In some embodiments, the dehydrohalogenation reaction produces a vapor phase.

[0044] In some embodiments, the present invention relates to liquid phase reaction of HCFC-132 and zinc at a temperature between about 100°C and about 140°C, preferably from about 110°C to about 130°C, in the presence of a catalyst preferably selected from a zinc salt (e.g., ZnCh or zinc acetate), ammonium salt (e.g., tetrabutylammonium bromide) or phosphonium salt, and in the presence of a solvent preferably selected from alcohol, amide, pyridine and ether, and more preferably an alcohol solvent such as methanol. In some embodiments, the zinc used for this reaction has been activated by an acid, for example zinc powder which has been activated with HCI (e.g., aqueous or in an alcohol). Preferably, a molar ratio of HCFC-132:metal for the liquid phase conversion of HCFC-132 is in the range of about 1:1 to about 1:3, preferably about 1:2, or preferably about 1:1.2.TS0071-W001

[0045] In some embodiments, the present invention is directed to a composition comprising HFO-E-1132, HFO-Z-1132 and one or more additional compounds selected from ethane, ethylene, fluoroacetylene (fluoroethyne), HCFC-132, HCFC- 142a, HFC-152, HCFO-1122a, HCFO-1131a, HCFO-E-1131, HCFO-Z-1131 , HFO- 1141, and HFO-1252zc.

[0046] In some embodiments, the present invention is directed to a composition comprising HFO-E-1132, HFO-Z-1132 and one or more additional compounds selected from ethane, fluoroacetylene (fluoroethyne), HCFC-132, HCFC-142a, HFC- 152, HCFO-1122a, HCFO-1131a, HCFO-E-1131 , HCFO-Z-1131 , HFO-1141, and HFO-1252zc.

[0047] In some embodiments, the present invention is directed to a composition comprising HFO-E-1132, HFO-Z-1132 and one or more additional compounds selected from ethane, ethylene, HCFC-132, HCFC-142a, HFC-152, HCFO-1122a, HCFO-1131a, HCFO-E-1131, HCFO-Z-1131 , HFO-1141, and HFO-1252zc.

[0048] In some embodiments, the present invention is directed to a composition comprising HFO-E-1132, HFO-Z-1132 and one or more additional compounds selected from ethane, fluoroacetylene (fluoroethyne), HCFC-132, HCFC-142a, HFC- 152, HCFO-1131a, HCFO-E-1131, HCFO-Z-1131 and HFO-1141.

[0049] In one embodiment, the total amount of the additional compounds is greater than 0 and less than about 1 wt%, or less than about 0.5 wt%, or less than about 0.4 wt%, or less than about 0.3 wt%, or less than about 0.2 wt% or less than about 0.1 wt% based on the total composition. In one embodiment, the total amount of the additional compounds is about 0.1 wt% based on the total composition. In some embodiments, the total amount of the additional compounds is less than about 1000 ppm, less than about 500 ppm, less than about 400 ppm, less than about 300 ppm, less than about 200 ppm, less than about 100 ppm, less than about 50 ppm, less than about 10 ppm, less than about 5 ppm, or any value, range, or sub-range therebetween, based on the total composition.

[0050] The product mixture may be treated by a purification process to remove one or more impurities. Appropriate purification processes may include, but are not limited to, a simple distillation, a fractional distillation, an extractive distillation, or a solvent scrubbing.TS0071-W001

[0051] In the present invention, reactors, distillation columns, and their associated feed lines, effluent lines, and associated units used in applying the processes of this invention should be constructed of materials resistant to hydrogen fluoride and hydrogen chloride. Typical materials of construction, well-known to the fluorination art, include stainless steels, in particular of the austenitic type, the well-known high nickel alloys, such as Monel™ nickel-copper alloys, Hastelloy™ nickel-based alloys and, Inconel™ nickel-chromium alloys, and copper-clad steel.

[0052] Without further elaboration, it is believed that one skilled in the art can, using the description herein, utilize the present invention to its fullest extent. The following specific embodiments are, therefore, to be construed as merely illustrative, and do not constrain the remainder of the disclosure in any way whatsoever.

[0053] The invention will be described in greater detail below by way of specific examples. The following examples are offered for illustrative purposes and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of non-critical parameters which can be changed or modified to yield essentially the same results.EXAMPLES

[0054] As shown in the Examples, three different catalysts were used under the same reaction conditions. Of the three catalysts, zinc chloride provided the lowest Z / E ratio in the vapor phase but also the lowest yield. TBAB provided the highest yield in the vapor phase but also the highest Z / E ratio. Zinc acetate provided an intermediate yield and Z / E ratio in the vapor phase.Example 1 : Dehydrohalogenation reaction of HCFC-132 with Zinc to form HFO-E / Z-1132 with TBAB as catalyst

[0055] 0.9 g Zn powder, which had been previously activated by aqueous HCI and dried under N2, was added into an autoclave together with 1.7 g HCFC-132, 0.3 g tetrabutylammonium bromide (TBAB), and 4 g dried methanol. After the autoclave was sealed, it was chilled to -40°C, and then a full vacuum was pulled to remove air. The reaction mixture was then heated to 120°C with agitation and agitated at 120°C for 10 hours. The pressure of the autoclave increased over the time, which indicated the progress of reaction. After the reaction mixture was cooled to room temperature,TS0071-W001 the vapor phase of the reactor was blown into a 75-mL cylinder and was analyzed by gas chromatography-mass spectrometry with a flame ionization detector (GC-MS- FID). The results are provided in Table 1.Table 1

[0056] As shown in Table 1 , the major detected products were 47.8 area% HFO-Z- 1132 and 31 .7 area% HFO-E-1132 for a Z / E ratio of 1.51 :1. Significant minor amounts of methanol (12.2 area%), HCFC-132 (4.5 area%), and HCFO-1122a (1.5 area%) were detected in the product along with a number of other additional compounds in lesser amounts. After adjusting for the detected methanol, the yield of HFO-1132 was about 90.6 mol%.

[0057] The pressure profile of this reaction is shown in the Figure, with the pressure 10 increasing over time and not quite reaching 500 psig by 10 hours.Example 2: Dehydrohalogenation reaction of HCFC-132 with Zinc to form HFO-E / Z-1132 with ZnCh as catalyst

[0058] 0.88 g Zn powder, which had been previously activated by aqueous HCI and dried under N2, was added into an autoclave together with 2.1 g HCFC-132, 0.3 g zinc chloride (ZnCh), and 3.8 g dried methanol. After the autoclave was sealed, it was chilled to -40°C, and then a full vacuum was pulled to remove air. The reaction mixture was then heated to 120°C with agitation and agitated at 120°C for 10 hours. The pressure of the autoclave increased over the time, which indicated the progressTS0071-W001 of reaction. After the reaction mixture was cooled to room temperature, the vapor phase of the reactor was blown into a 75-mL cylinder and was analyzed by GC-MS- FID. The results are provided in Table 2.Table 2

[0059] As shown in Table 2, the major detected products were 39.3 area% HFO- E-1132 and 26.3 area% HFO-Z-1132 for a Z / E ratio of 0.67:1. Significant minor amounts of methanol (14.0 area%) and HCFC-132 (17.6 area%) were detected in the product along with a number of other additional compounds in lesser amounts. After adjusting for the detected methanol, the yield of HFO-1132 was about 76.3 mol%.

[0060] The pressure profile of this reaction is shown in the Figure, with the pressure 20 increasing over time and reaching about 725 psig by 10 hours.Example 3: Dehydrohalogenation reaction of HCFC-132 with Zinc to form HFO-E / Z-1132 with zinc acetate as catalyst

[0061] 0.82 g Zn powder, which had been previously activated by aqueous HCI and dried under N2, was added into an autoclave together with 2.1 g HCFC-132, 0.31 g zinc acetate (Zn(CHsCOO)2), and 4.08 g dried methanol. After the autoclave was sealed, it was chilled to -40°C, and then a full vacuum was pulled to remove air. The reaction mixture was then heated to 120°C with agitation and agitated at 120°C for 10 hours. The pressure of the autoclave increased over the time, which indicatedTS0071-W001 the progress of reaction. After the reaction mixture was cooled to room temperature, the vapor phase of the reactor was blown into a 75-mL cylinder and was analyzed by gas chromatography-mass spectrometry with a flame ionization detector (GC-MS- FID). The results are provided in Table 3.Table 3

[0062] As shown in Table 3, the major detected products were 26.1 area% H FOE-1132 and 23.2 area% HFO-Z-1132 for a Z / E ratio of 0.89:1. Significant amounts of methanol (36.8 area%), HCFC-132 (10.9 area%), and methyl acetate (2.5 area%) were detected in the product along with a number of other additional compounds in lesser amounts. After adjusting for the detected methanol and methyl acetate, the yield of HFO-1132 was about 81.2 mol%.

[0063] The pressure profile of this reaction is shown in the Figure, with the pressure 30 increasing over time and exceeding 500 psig by 10 hours.OTHER EMBODIMENTS

[0064] Embodiment 1. A process comprising: contacting 1 ,2-dichloro-1 ,2- difluoroethane (HCFC-132) with a reactive metal in the presence of a catalyst and a solvent; and producing a product mixture comprising E-1 ,2-difluoroethylene (HFO-E- 1132) and Z-1,2-difluoroethylene (HFO-Z-1132).TS0071-W001

[0065] Embodiment 2. The process of Embodiment 1 , wherein the reactive metal is selected from the group consisting of magnesium, calcium, titanium, iron, cobalt, nickel, copper, zinc, indium, and combinations thereof.

[0066] Embodiment 3. The process of any of Embodiments 1 to 2, wherein the reactive metal comprises zinc, preferably zinc powder.

[0067] Embodiment 4. The process of any of Embodiments 1 to 3, wherein the metal is activated by an acid.

[0068] Embodiment 5. The process of any of Embodiments 1 to 4, wherein the reactive metal comprises activated zinc powder.

[0069] Embodiment 6. The process of Embodiment 5, wherein the activated zinc powder is activated by aqueous hydrogen chloride.

[0070] Embodiment 7. The process of any of Embodiments 1 to 6, wherein the solvent is selected from the group consisting of methanol, ethanol, propanol, isopropanol and ethylene glycol, preferably wherein the solvent comprises methanol, more preferably dried methanol.

[0071] Embodiment 8. The process of any of Embodiments 1 to 7, wherein the catalyst is selected from the group consisting of zinc salt, ammonium salt and phosphonium salt.

[0072] Embodiment 9. The process of any of Embodiments 1 to 8, wherein the catalyst comprises tetrabutylammonium bromide.

[0073] Embodiment 10. The process of any of Embodiments 1 to 8, wherein the catalyst comprises zinc chloride.

[0074] Embodiment 11. The process of any of Embodiments 1 to 8, wherein the catalyst comprises zinc acetate.

[0075] Embodiment 12. The process of any of Embodiments 1 to 11 , wherein the producing occurs at a temperature in the range of about 100°C to about 140°C, preferably about 110°C to about 130°C, more preferably about 120°C.

[0076] Embodiment 13. The process of any of Embodiments 1 to 12, wherein the producing occurs for a time in the range of about 8 hours to about 12 hours.TS0071-W001

[0077] Embodiment 14. The process of any of Embodiments 1 to 13, wherein a molar ratio of the HCFC-132 to reactive metal is from about 1 :1 to about 1:3, preferably about 1:2, or preferably about 1:1.2.

[0078] Embodiment 15. The process of any of Embodiments 1 to 14, wherein a molar ratio of the HCFC-132 to catalyst is from about 1 :1 to about 1:3, preferably about 1 :2, or preferably about 1:1.2.

[0079] Embodiment 16. The process of any of Embodiments 1 to 15, wherein a molar ratio of the reactive metal to catalyst is from about 1 :1 to about 1:3, preferably about 1 :2, or preferably about 1:1.2.

[0080] Embodiment 17. The process of any of Embodiments 1 to 16, wherein a yield of a combined amount of the HFO-E-1132 and the HFO-Z-1132 in the product mixture is at least 75 mol%.

[0081] Embodiment 18. The process of any of Embodiments 1 to 17, wherein an E / Z molar ratio of the HFO-Z-1132 to the HFO-E-1132 in the product mixture is about 1.5:1 or less.

[0082] Embodiment 19. The process of any of Embodiments 1 to 18, wherein the producing occurs in a sealed reactor.

[0083] Embodiment 20. The process of Embodiment 19, further comprising cooling the sealed reactor to a temperature of about -20°C to about -60°C prior to the producing.

[0084] Embodiment 21. The process of any of Embodiments 19 to 20, further comprising removing air from the sealed reactor under vacuum prior to the producing.

[0085] Embodiment 22. The process of any of Embodiments 1 to 21 , wherein the producing occurs in a liquid phase.

[0086] Embodiment 23. The process of any of Embodiments 1 to 22, wherein the product mixture includes at least one additional compound selected from ethane, ethylene, fluoroacetylene, HCFC-132, HCFC-142a, HFC-152, HCFO-1122a, HCFO- 1131a, HCFO-E-1131 , HCFO-Z-1131, HFO-1141 , and HFO-1252zc.TS0071-W001

[0087] Embodiment 24. The process of any of Embodiments 1 to 23, further comprising treating the product mixture to reduce an amount of at least one additional compound in the product mixture.

[0088] Embodiment 25. A composition formed by the process of any of Embodiments 1 to 24.

[0089] Embodiment 26. A composition comprising HFO-E-1132, HFO-Z-1132 and one or more additional compounds selected from the group consisting of ethane, ethylene, fluoroacetylene (fluoroethyne), HCFC-132, HCFC-142a, HFC-152, HCFO- 1122a, HCFO-1131a, HCFO-E-1131 , HCFO-Z-1131, HFO-1141, and HFO-1252zc.

[0090] Embodiment 27. The composition of Embodiment 26, wherein the one or more additional compounds are selected from the group consisting of ethane, fluoroacetylene (fluoroethyne), HCFC-132, HCFC-142a, HFC-152, HCFO-1122a, HCFO-1131a, HCFO-E-1131, HCFO-Z-1131 , HFO-1141, and HFO-1252zc.

[0091] Embodiment 28. The composition of any of Embodiments 26 to 27, wherein the one or more additional compounds are selected from the group consisting of ethane, fluoroacetylene (fluoroethyne), HCFC-132, HCFC-142a, HFC- 152, HCFO-1131a, HCFO-E-1131, HCFO-Z-1131 and HFO-1141.

[0092] Embodiment 29. A composition comprising HFO-E-1132, HFO-Z-1132 and one or more additional compounds selected from the group consisting of ethane, ethylene, HCFC-132, HCFC-142a, HFC-152, HCFO-1122a, HCFO-1131a, HCFO-E- 1131, HCFO-Z-1131 , HFO-1141 , and HFO-1252zc.

[0093] Embodiment 30. The composition according to any of Embodiments 26 to 29, wherein a total amount of the one or more additional compounds is greater than 0 wt% and less than about 1 wt%, preferably less than about 0.5 wt%, more preferably less than about 0.2 wt%, most preferably less than about 0.1 wt%.

[0094] While this specification contains many specific implementation details, these should not be construed as limitations on the scope of any inventions or of what may be claimed, but rather as descriptions of features specific to particular implementations of particular inventions. Certain features that are described in this specification in the context of separate implementations can also be implemented in combination in a single implementation. Conversely, various features that areTS0071-W001 described in the context of a single implementation can also be implemented in multiple implementations separately or in any suitable sub-combination. Moreover, although features may be described above as acting in certain combinations and even initially claimed as such, one or more features from a claimed combination can in some cases be excised from the combination, and the claimed combination may be directed to a sub-combination or variation of a sub-combination.

[0095] Similarly, while operations are depicted in a particular order, this should not be understood as requiring that such operations be performed in the particular order shown or in sequential order, or that all illustrated operations be performed, to achieve desirable results. In certain circumstances, multitasking and parallel processing may be advantageous. Moreover, the separation of various system components in the implementations described above should not be understood as requiring such separation in all implementations, and it should be understood that the described program components and systems can generally be integrated together in a single software product or packaged into multiple software products.

[0096] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which example embodiments belong. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

[0097] While the disclosure has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made, and equivalents may be substituted for elements thereof without departing from the scope of the disclosure. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the disclosure without departing from the essential scope thereof. While various aspects and embodiments have been disclosed herein, other aspects and embodiments will be apparent to those skilled in the art. The various aspects and embodiments disclosed herein are for purposes of illustration and are not intended to be limiting, with the true scope and spirit being indicated by the following claims.

Claims

TS0071-W001CLAIMSWhat is claimed is:

1. A process comprising: contacting 1 ,2-dichloro-1,2-difluoroethane (HCFC-132) with a reactive metal in the presence of a catalyst and a solvent; and producing a product mixture comprising E-1,2-difluoroethylene (HFO-E- 1132) and Z-1 ,2-difluoroethylene (HFO-Z-1132).

2. The process of claim 1, wherein the reactive metal is selected from the group consisting of magnesium, calcium, titanium, iron, cobalt, nickel, copper, zinc, indium, and combinations thereof.

3. The process of any of claims 1 to 2, wherein the reactive metal comprises zinc, preferably zinc powder.

4. The process of any of claims 1 to 3, wherein the metal is activated by an acid.

5. The process of any of claims 1 to 4, wherein the reactive metal comprises activated zinc powder.

6. The process of claim 5, wherein the activated zinc powder is activated by aqueous hydrogen chloride.

7. The process of any of claims 1 to 6, wherein the solvent is selected from the group consisting of methanol, ethanol, propanol, isopropanol and ethylene glycol, preferably wherein the solvent comprises methanol, more preferably dried methanol.

8. The process of any of claims 1 to 7, wherein the catalyst is selected from the group consisting of zinc salt, ammonium salt and phosphonium salt.

9. The process of any of claims 1 to 8, wherein the catalyst comprises tetrabutylammonium bromide.

10. The process of any of claims 1 to 8, wherein the catalyst comprises zinc chloride.

11. The process of any of claims 1 to 8, wherein the catalyst comprises zinc acetate.TS0071-W00112. The process of any of claims 1 to 11, wherein the producing occurs at a temperature in the range of about 100°C to about 140°C, preferably about 110°C to about 130°C, more preferably about 120°C.

13. The process of any of claims 1 to 12, wherein a molar ratio of the HCFC-132 to reactive metal is from about 1 :1 to about 1 :3, preferably about 1 :2, or preferably about 1 :1.2.

14. The process of any of claims 1 to 13, wherein a molar ratio of the HCFC-132 to catalyst is from about 1 :1 to about 1:3, preferably about 1:2, or preferably about 1:1.2.

15. The process of any of claims 1 to 14, wherein a molar ratio of the reactive metal to catalyst is from about 1 :1 to about 1 :3, preferably about 1:2, or preferably about 1 :1.2.

16. The process of any of claims 1 to 15, wherein a yield of a combined amount of the HFO-E-1132 and the HFO-Z-1132 in the product mixture is at least 75 mol%.

17. The process of any of claims 1 to 16, wherein an E / Z molar ratio of the HFO-Z- 1132 to the HFO-E-1132 in the product mixture is about 1.5:1 or less.

18. The process of any of claims 1 to 17, further comprising removing air from the sealed reactor under vacuum prior to the producing.

19. The process of any of claims 1 to 18, wherein the producing occurs in a liquid phase.

20. The process of any of claims 1 to 19, wherein the product mixture includes at least one additional compound selected from ethane, ethylene, fluoroacetylene, HCFC-132, HCFC-142a, HFC-152, HCFO-1122a, HCFO-1131a, HCFO-E- 1131 , HCFO-Z-1131, HFO-1141, and HFO-1252zc.

21. The process of any of claims 1 to 20, further comprising treating the product mixture to reduce an amount of at least one additional compound in the product mixture.

22. A composition formed by the process of any of claims 1 to 21.TS0071-W00123. A composition comprising HFO-E-1132, HFO-Z-1132 and one or more additional compounds selected from the group consisting of ethane, ethylene, fluoroacetylene (fluoroethyne), HCFC-132, HCFC-142a, HFC-152, HCFO- 1122a, HCFO-1131a, HCFO-E-1131, HCFO-Z-1131 , HFO-1141 , and HFO- 1252zc.

24. The composition of claim 23, wherein the one or more additional compounds are selected from the group consisting of ethane, fluoroacetylene (fluoroethyne), HCFC-132, HCFC-142a, HFC-152, HCFO-1122a, HCFO-1131a, HCFO-E-1131 , HCFO-Z-1131, HFO-1141, and HFO-1252zc.

25. The composition of any of claims 23 to 24, wherein the one or more additional compounds are selected from the group consisting of ethane, fluoroacetylene (fluoroethyne), HCFC-132, HCFC-142a, HFC-152, HCFO-1131a, HCFO-E- 1131 , HCFO-Z-1131 and HFO-1141.

26. A composition comprising HFO-E-1132, HFO-Z-1132 and one or more additional compounds selected from the group consisting of ethane, ethylene, HCFC-132, HCFC-142a, HFC-152, HCFO-1122a, HCFO-1131a, HCFO-E- 1131 , HCFO-Z-1131, HFO-1141, and HFO-1252zc.

27. The composition according to any of claims 23 to 26, wherein a total amount of the one or more additional compounds is greater than 0 wt% and less than about 1 wt%, preferably less than about 0.5 wt%, more preferably less than about 0.2 wt%, most preferably less than about 0.1 wt%.

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