Non-catalytic vapor phase hydrofluorination process for making HCFO-1233XF and HCFO-1232XF from HCO-1230xa

Abstract

Processes for producing at least one of 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) or 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf) from 1,1,2,3-tetrachloro-1-propene (HCO-1230xa), in the absence of a catalyst, are provided.

Description

NON-CATALYTIC VAPOR PHASE HYDROFLUORINATION PROCESS FOR MAKING HCFO-1233XF AND HCFO-1232XF FROM HCO-1230XACROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority of U.S. Provisional Application 63 / 668,931 filed July 9, 2024, the disclosure of which is incorporated herein by reference it its entirety.BACKGROUND

[0002] The fluorocarbon industry has been working for the past few decades to find replacement refrigerants for the ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) 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 HFC refrigerants, HFC-134a and HFC-125 being the most widely used at this time, have zero ozone depletion potential (ODP) and thus are not affected by the current regulatory phase-out as a result of the Montreal Protocol. In addition to ozone depleting concerns, global warming is another environmental concern in many of these applications. HFC refrigerants such as HFC-134a and HFC-125 respectively have global warming potentials (GWP) of 1,300 and 3,170 according to the UN's IPCC Fifth Assessment Report (AR5).

[0003] This regulatory landscape is continuously evolving, taking into consideration properties beyond just ODP and GWP. More particularly, there is a need for refrigerant compositions that not only meet low ODP standards and have low global warming potentials, but that also exhibit low or no flammability, provide superior performance in a variety of applications and which meet the standards of evolving regulations.

[0004] There is a need in this art for new refrigerants that meet evolving regulations as well as provide heat transfer and refrigerant characteristics that meetor exceed the effectiveness of conventional refrigerants, often referred to a next generation refrigerant (NGR) molecules.

[0005] Some fluoropropenes, such as 1 ,1 -difluoropropene (HFO-1252zc, CF2=CHCH3), are such potential new refrigerants. Chlorofluoroolefins, such as 2- chloro-3,3,3-trifluoropropene (HCFO-1233xf) and 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf) are useful intermediates for the production of HFO-1252zc, as well as for other fluoropropenes such as 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0006] Some processes to produce HCFO-1233xf and / or HCFO-1232xf from 1 ,1 , 2, 3-tetrachloro-1 -propene (HCO-1230xa) involve using a metal oxide catalyst, such as a chromium oxide catalyst. Although chromium oxide catalysts are highly efficient, they are expensive, have limited availability, and can be toxic to the environment. Therefore, a need exists for alternative approaches that are more cost effective and much more environmentally friendly. The present invention provides an innovative process of converting HCO-1230xa to at least one or both of HCFO- 1233xf and HCFO-1232xf without the use of a catalyst.SUMMARY

[0007] The present invention relates to processes for producing HCFO-1233xf and / or HCFO-1232xf from HCO-1230xa in the absence of a catalyst.

[0008] In one aspect, the present invention relates to a process of producing at least one of 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf) and 2-chloro-3,3,3- trifluoropropene (HCFO-1233xf). The process comprises contacting 1 , 1 ,2,3- tetrachloro-1-propene (HCO-1230xa) and hydrogen fluoride (HF) in the vapor phase, in the absence of a catalyst, at an elevated temperature to form at least one of HCFO-1233xf and HCFO-1232xf.

[0009] In one aspect, the present invention relates to a composition comprising: (i) HCFO-1233xf and at least one additional compound selected from the group consisting of HCO-1230xa, C4H6CIF, HCFO-1232 isomers, HCFO-1231 isomers and CO-1110; (ii) HCFO-1232xf and at least one additional compound selected from the group consisting of HCO-1230xa, C4H6CIF, HCFO-1232 isomers, HCFO-1231 isomers and CO-1110; or (iii) HCFO-1233xf, HCFO-1232xf and at least oneadditional compound selected from the group consisting of HCO-1230xa, C4H6CIF, HCFO-1232 isomers, HCFO-1231 isomers and CO-1110.

[0010] In one aspect, the present invention relates to a vapor phase process of producing 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf). The process comprises contacting 1 ,1 , 2, 3-tetrachloro-1 -propene (HCO-1230xa) and HF at temperatures between about 200°C and about 400°C, in the absence of a catalyst, at an HF:HCO- 1230xa mole ratio of between about 10:1 and about 15:1 , and more preferably between about 10:1 and about 40:1 , and preferably with a contact time of between about 5 seconds and about 60 seconds.

[0011] In one aspect, the present invention relates to a vapor phase process of producing 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf). The process comprises contacting 1 ,1 ,2,3-tetrachloro-1-propene and HF at temperatures between about 160°C and 300°C, in the absence of a catalyst, at an HF:HCO-1230xa mole ratio of between about 1 :1 and about 30:1 , and more preferably between about 5:1 and 25:1 , and preferably with a contact time of between about 5 seconds and about 60 seconds

[0012] In one aspect, the present invention relates to a vapor phase process of coproducing 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) and 2,3-dichloro-3,3- difluoropropene (HCFO-1232xf). The process comprises contacting 1 , 1 ,2,3- tetrachloro-1-propene and HF at temperatures between about 200°C and 400°C, in the absence of a catalyst, at an HF:HCO-1230xa mole ratio of between about 5:1 and about 50:1 , and more preferably between about 10:1 and about 40:1 , and preferably with a contact time of between about 5 seconds and about 60 seconds.

[0013] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Fig. 1 illustrates a system according to one embodiment of the present invention.DETAILED DESCRIPTION

[0015] The foregoing summary and the following detailed description and drawings are exemplary and explanatory only and are not restrictive of the invention, as defined in the appended claims. Other features and benefits of any one or more of the embodiments will be apparent from the following detailed description, drawings and from the claims.

[0016] Before addressing details of embodiments described herein, certain terms are defined or clarified as follows.

[0017] Reactors suitable for either liquid phase reactions or for vapor phase reactions can be used. In the vapor phase, a heated reactor is used and the reactor is provided with suitable heat control. A number of reactor configurations are possible including packed bed tube or column reactors, optionally containing suitable inert packing such as Monel™ or Hastelloy™ nickel alloy turnings or wool, or other material inert to halogenated species. E.g., HCI and HF which allows efficient mixing of starting materials.

[0018] Reactor configurations whether containing the suitable packing or free of any packing can be operated in batch, semi-batch or continuous modes. In addition to the reactors disclosed herein, preheaters and vaporizers, heat exchangers, feed and effluent lines, units associated with mass transfer, contacting vessels (premixers), distillation columns, and valving associated with reactors, heat exchangers, vessels, columns, and units that are used in the processes of various embodiments disclosed herein should be constructed of materials resistant to corrosion.

[0019] 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 process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but mayinclude other elements not expressly listed or inherent to such 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 is true (or present).

[0020] 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.”

[0021] 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.

[0022] 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.”

[0023] 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.

[0024] 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 rangesformed 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.

[0025] Reactors suitable catalyst free reaction include packed bed tube or column reactors, operated in batch, semi-batch or continuous modes.. In addition the reactors disclosed herein, preheaters and vaporizers, heat exchangers, feed and effluent lines, units associated with mass transfer, contacting vessels (pre-mixers), distillation columns, and valving associated with reactors, heat exchangers, vessels, columns, and units that are used in the processes of various embodiments disclosed herein should be constructed of materials resistant to corrosion. For example, 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 other hydroreactors, 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™ nickelcopper alloys, Hastelloy™ nickel-based alloys and, Inconel™ nickel-chromium alloys, and copper-clad steel. In certain embodiments disclosed herein, the reaction can be conducted in the presence of a suitable packing such as Monel™ or Hastelloy™ nickel alloy turnings or wool, or other material inert to HCI and HF which allows efficient mixing of starting materials.

[0026] 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 response factors either calculated or measured. See https: / / www.chromatographytoday.com / news / gc-mdgc / 32 / breaking-news / what-is-a- response-factor / 31169.

[0027] As used herein, the term “about” is meant to account for variations due to experimental error (e.g., plus or minus approximately 10% of the indicated value-±1%, ± 2%, ± 3, ... ±10%, or between ±1% of a stated value and ±10% of the stated value and all ranges therebetween). For example, about 160°C could equal 160°C ±1% of 160°C= 160°C+1.6°C=161.6°C, or 160°C-1.6°C=t 158.4°C. All temperature values described herein can be modified by the term “about,” whether or not the term is explicitly used, unless explicitly stated otherwise.

[0028] Compounds referred to in this disclosure may be referred to by code, based on fluorochemical naming convention, chemical structure and / or chemical name. For convenience and reference, selected compounds with codes, structures and chemical names are provided in Table 1.Table 1

[0029] The present invention relates to processes for producing HCFO-1233xf and / or HCFO-1232xf from HCO-1230xa in the absence of a catalyst.

[0030] Certain embodiments of the invention disclosed herein relate to vapor phase processes for converting HCO-1230xa by hydrofluorination to at least one of HCFO-1233xf and HCFO-1232xf without a catalyst.

[0031] In some embodiments, vapor phase catalyst free processes of the present invention convert HCO-1230xa by hydrofluorination to HCFO-1233xf.

[0032] In some embodiments, the temperature for the vapor phase non-catalytic hydrofluorination of HCO-1230xa to produce HCFO-1233xf ranges from about 200°C to about 400°C, preferably from about 250°C to about 350°C.

[0033] In certain catalyst-free vapor phase embodiments, particularly where the target compound to be formed is HCFO-1233xf, contact of HCO-1230xa and HF is conducted in a reactor or reaction zone heated to or maintained at a temperature selected from one of about 195°C, about 200°C, about 205°C, about 210°C, about 215°C, about 220°C, about 225°C, about 230°C, about 235°C, about 240°C, about245°C, about 250°C, about 255°C, about 260°C, about 265°C, about 270°C, about 275°C, about 280°C, about 285°C, about 290°C, about 295°C, about 300°C, about305°C, about 310°C, about 315°C, about 320°C, about 325°C, about 330°C, about335°C, about 340°C, about 345°C, about 350°C, about 355°C, about 360°C, about365°C, about 370°C, about 375°C, about 380°C, about 385°C, about 390°C, about395°C, or about 400°C, and all values and ranges within and between about 195°C and about 400°C.

[0034] In some embodiments, the HF:organic mole ratio, and more particularly HF:HCO-1230xa ratio, for the vapor phase non-catalytic hydrofluorination of HCO- 1230xa to produce HCFO-1233xf is greater than about 10:1 and less than about 45:1, preferably between about 15:1 and about 40:1, and more preferably between about 20:1 and about 35:1.

[0035] In certain catalyst-free, vapor phase embodiments, contact of HCO-1230xa and HF to produce HCFO-1233xf is conducted at an HF:organic mole ratio between > 10:1 and <45:1, inclusive of all values, endpoints, and fractions therebetween, including, but not limited to, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1, 21:1, 22:1, 23:1, 24:1, 25:1, 30:1, 35:1, 40:1, or 45:1; or fractional values including but not limited to 10.5:1, 11.5:1, 12.5:1, 13.5:1, 14.5:1, 15.5:1,20.5:1, about21.1:1, 21.2:1, 21.3:1, 21.4:1, 21.5:1, 21.6:1, 21.7:1, 21.8:1, 21.9:1, 22.1:1, 22.2:1, 22.3:1, 22.4:1, 22.5:1, 22.6:1, 22.7:1, 22.8:1, 22.9:1, 24.5:1, 25.5:1, 26.5:1, 30.5:1, 34.5:1, about 35.5:1, 39.5:1, 40.5:1, or 44:5:1.

[0036] In some embodiments, the reaction pressure for the vapor phase non- catalytic hydrofluorination of HCO-1230xa to produce HCFO-1233xf is subatmospheric, including but not limited to between about 0 psig and about 100 psig.

[0037] In some embodiments, the conversion of HCO-1230xa by vapor phase non-catalytic hydrofluorination to HCFO-1233xf is about 2% to about 20%.

[0038] Suitable contact times range from about 5 seconds to about 60 seconds, and in some embodiments, about 10 seconds to about 40 seconds.

[0039] One embodiment of the invention disclosed herein relates to a vapor phase process of producing HCFO-1233xf by contacting HCO-1230xa and HF attemperatures between about 200°C and 400°C, in the absence of catalyst, at an HF:HCO-1230xa mole ratio of greater than about 10:1 and less than about 45:1 preferably between about 10:1 and about 40:1 , and preferably with a contact time of between about 5 seconds and about 60 seconds.

[0040] One embodiment of the invention disclosed herein relates to a vapor phase process of producing HCFO-1233xf by contacting HCO-1230xa and HF at temperatures between about 200°C and 400°C, in the absence of catalyst, at an HF:HCO-1230xa mole ratio of greater than about 10:1 and less than about 45:1 , preferably between about 10:1 and about 40:1, and at a pressure between about 0 psig and about 100 psig, and preferably with a contact time of between about 5 seconds and about 60 seconds.

[0041] One embodiment of the invention disclosed herein relates to a vapor phase process of producing HCFO-1233xf by contacting HCO-1230xa and HF at temperatures between about 200°C and 400°C, in the absence of catalyst, at an HF:HCO-1230xa mole ratio of greater than about 10:1 and less than about 45:1 , preferably between about 10:1 and about 40:1, and at a pressure between about 0 psig and about 100 psig, wherein the amount of HCFO-1233xf produced ranges between about 15% and about 100%, and preferably with a contact time of between about 5 seconds and about 60 seconds.

[0042] In some embodiments, vapor phase catalyst free processes of the present invention convert HCO-1230xa by hydrofluorination to HCFO-1232xf.

[0043] In some embodiments, the temperature for the vapor phase non-catalytic hydrofluorination of HCO-1230xa to produce HCFO-1232xf ranges from about 160°C to about 300°C.

[0044] In certain catalyst-free vapor phase embodiments, particularly where the target compound to be formed is HCFO-1232xf, contact of HCO-1230xa and HF is conducted in a reactor or reaction zone heated to or maintained at a temperature selected from one of about 155°C, about 160°C, about 165°C, about 170°C, about 175°C, about 180°C, about 185°C, about 190°C, about 195°C, about 200°C, about 205°C, about 210°C, about 215°C, about 220°C, about 225°C, about 230°C, about 235°C, about 240°C, about 245°C, about 250°C, about 255°C, about 260°C, about 265°C, about 270°C, about 275°C, about 280°C, about 285°C, about 290°C, about295°C, or about 300°C, and all values and ranges within and between about 155°C and about 300°C.

[0045] In some embodiments, the HF:organic mole ratio, and more particularly HF:HCO-1230xa ratio, for the vapor phase non-catalytic hydrofluorination of HCO- 1230xa to produce HCFO-1232xf is about 1:1 to about 30:1 , preferably between about 5:1 and 25:1.

[0046] In certain catalyst-free, vapor phase embodiments, contact of HCO-1230xa and HF to produce HCFO-1232xf is conducted at an HF:organic mole ratio between > 1:1 and < 30:1, inclusive of all values, endpoints, and fractions therebetween, including, but not limited to, 1:1, 2:1 , 3:1, 4:1, 5:1 , 6:1 , 7:1 , 8:1 , 9:1, 10:1 , 11:1, 12:1, 13:1, 14:1, 15:1 , 16:1 , 17:1, 18:1, 19:1, 20:1 , 21 :1 , 22:1 , 23:1, 24:1 , 25:1, or 30:1; or fractional values including but not limited to 1.5:1 , 2.5:1 , 3.5:1 , 4.5:1, 5.5:1 , 6.5:1 , 7.5:1 , 8.5:1, 9.5:1, 10.5:1 , 11.5:1, 12.5:1 , 13.5:1 , 14.5:1 , 15.5:1, 20.5:1 , about 21.1 :1, 21.2:1, 21.3:1 , 21.4:1 , 21.5:1 , 21.6:1, 21.7:1 , 21.8:1 , 21.9:1, 22.1:1, 22.2:1 , 22.3:1, 22.4:1, 22.5:1 , 22.6:1 , 22.7:1 , 22.8:1, 22.9:1 , 24.5:1 , 25.5:1, 26.5:1, 27.5:1 , 28.5:1, or 29.5:1.

[0047] In some embodiments, the reaction pressure for the vapor phase non- catalytic hydrofluorination of HCO-1230xa to produce HCFO-1232xf is subatmospheric, including but not limited to between about 0 psig and about 100 psig.

[0048] In some embodiments, the conversion of HCO-1230xa by vapor phase non-catalytic hydrofluorination to HCFO-1232xf is about 50% or greater.

[0049] Suitable contact times range from about 5 seconds to about 60 seconds, and in some embodiments, about 10 seconds to about 40 seconds.

[0050] One embodiment of the invention disclosed herein relates to a vapor phase process of producing HCFO-1232xf by contacting HCO-1230xa and HF at temperatures between about 160°C and 300°C, in the absence of catalyst, at an HF:HCO-1230xa mole ratio of greater than about 1 :1 and less than about 30:1, preferably between about 5:1 and about 25:1 , and preferably with a contact time of between about 5 seconds and about 60 seconds.

[0051] One embodiment of the invention disclosed herein relates to a vapor phase process of producing HCFO-1232xf by contacting HCO-1230xa and HF at temperatures between about 160°C and 300°C, in the absence of catalyst, at an HF:HCO-1230xa mole ratio of greater than about 1 :1 and less than about 30:1, preferably between about 5:1 and about 25:1 , and at a pressure of about 0 psig and about 100 psig, and preferably with a contact time of between about 5 seconds and about 60 seconds.

[0052] One embodiment of the invention disclosed herein relates to a vapor phase process of producing HCFO-1232xf by contacting HCO-1230xa and HF at temperatures between about 160°C and 300°C, in the absence of catalyst, at an HF:HCO-1230xa mole ratio of greater than about 1 :1 and less than about 30:1, preferably between about 5:1 and about 25:1 , and at a pressure of about 0 psig and about 100 psig, wherein the amount of HCFO-1232xf produced ranges between about 15% and about 100%, and preferably with a contact time of between about 5 seconds and about 60 seconds.

[0053] In some embodiments, the present invention relates vapor phase catalyst free processes for hydrofluorination of HCO-1230xa to co-produce HCFO-1233xf and HCFO-1232xf.

[0054] In some embodiments, the temperature for the vapor phase non-catalytic hydrofluorination of HCO-1230xa to co-produce HCFO-1232xf and HCFO-1233xf ranges from about 200°C to about 400°C, preferably from about 250°C to about 350°C.

[0055] In certain catalyst-free vapor phase embodiments, particularly where the target compound to be formed is HCFO-1232xf, contact of HCO-1230xa and HF is conducted in a reactor or reaction zone heated to or maintained at a temperature between about 200°C and about 400°C.

[0056] In some embodiments, the HF:organic mole ratio, and more particularly HF:HCO-1230xa ratio, for the vapor phase non-catalytic hydrofluorination of HCO- 1230xa to co-produce HCFO-1232xf and HCFO-1233xf is about 5:1 to about 50:1 , preferably between about 10:1 and about 40:1.

[0057] In some embodiments, the reaction pressure for the vapor phase non- catalytic hydrofluorination of HCO-1230xa to co-produce HCFO-1232xf and HCFO- 1233xf is subatmospheric, including but not limited to between about 0 psig and about 100 psig, preferably between about 10 psig and about 80 psig.

[0058] In some embodiments, conversion of HCO-1230xa by vapor phase non- catalytic hydrofluorination to HCFO-1232xf and HCFO-1233xf co-produced is about 90% or greater.

[0059] Suitable contact times range from about 5 to about 60 seconds, and in some embodiments, about 10 to about 40 seconds.

[0060] One embodiment of the invention disclosed herein relates to a vapor phase process of co-producing HCFO-1232xf and HCFO-1233xf by contacting HCO- 1230xa and HF at temperatures between about 200°C and 400°C, in the absence of catalyst, at an HF:HCO-1230xa mole ratio of between about 5:1 to about 50:1, preferably between about 10:1 and about 40:1, and preferably with a contact time of between about 5 seconds to about 60 seconds.

[0061] One embodiment of the invention disclosed herein relates to a vapor phase process of co-producing HCFO-1232xf and HCFO-1233xf by contacting HCO- 1230xa and HF at temperatures between about 200°C and 400°C, in the absence of catalyst, at an HF:HCO-1230xa mole ratio of between about 5:1 to about 50:1, preferably between about 10:1 and about 40:1, and at a pressure of about 0 psig and about 100 psig, preferably between about 10 psig and about 80 psig, and preferably with a contact time of between about 5 seconds to about 60 seconds.

[0062] One embodiment of the invention disclosed herein relates to a vapor phase process of co-producing HCFO-1232xf and HCFO-1233xf by contacting HCO- 1230xa and HF at temperatures between about 200°C and 400°C, in the absence of catalyst, at an HF:HCO-1230xa mole ratio of between about 5:1 to about 50:1, preferably between about 10:1 and about 40:1, and at a pressure of about 0 psig and about 100 psig, preferably between about 10 psig and about 80 psig, and preferably with a contact time of between about 5 seconds to about 60 seconds, with a conversion of about 90% or greater.

[0063] In certain catalyst-free, vapor phase embodiments, contact of HCO-1230xa and HF to produce at least one of HCFO-1232xf and HCFO-1233xf (i.e., either to produce HCFO-1232xf, to produce HCFO-1233xf, and / or co-produce HCFO-1232xf and HCFO-1233xf) is conducted at temperatures between two of: a. about 175°C (which is equal to 175°C ± 1 % ± 2%, ± 3%, ± 4%, ±5%, ± 6%, ±7%, ± 8%, ±9% or ± 10% of 175°C), b. about 400°C (which is equal to 400°C ± 1 % ± 2%, ± 3%, ± 4%, ±5%, ± 6%, ±7%, ± 8%, ±9% or ± 10% of 400°C), c. about 325°C (which is equal to 325°C ± 1 % ± 2%, ± 3%, ± 4%, ±5%, ± 6%, ±7%, ± 8%, ±9% or ± 10% of 325°C), d. about 200°C (which is equal to 200°C ± 1 % ± 2%, ± 3%, ± 4%, ±5%, ± 6%, ±7%, ± 8%, ±9% or ± 10% of 200°C), e. about 300°C (which is equal to 300°C ± 1% ± 2%, ± 3%, ± 4%, ±5%, ± 6%, ±7%, ± 8%, ±9% or ± 10% of 300°C), f. about 320°C (which is equal to 300°C ± 1% ± 2%, ± 3%, ± 4%, ±5%, ± 6%, ±7%, ± 8%, ±9% or ± 10% of 320°C), g. about 150°C (which is equal to 150°C ± 1 % ± 2%, ± 3%, ± 4%, ±5%, ± 6%, ±7%, ± 8%, ±9% or ± 10% of 150°C), h. about 250°C (which is equal to 250°C ± 1 % ± 2%, ± 3%, ± 4%, ±5%, ± 6%, ±7%, ± 8%, ±9% or ± 10% of 250°C), i. about 160°C (which is equal to 160°C ± 1 % ± 2%, ± 3%, ± 4%, ±5%, ± 6%, ±7%, ± 8%, ±9% or ± 10% of 160°C), and j. about 240°C (which is equal to 240°C ± 1 % ± 2%, ± 3%, ± 4%, ±5%, ± 6%, ±7%, ± 8%, ±9% or ± 10% of 240°C), such as, but not limited to, between “a” and “b,” “b” and “d,” “c” and “g,” “e” and “I,” or between “b” and “i.”

[0064] Referring to Fig. 1 , there is shown an embodiment of the process and system 100 according to the present invention for the conversion HCO-1230xa. The HCO-1230xa feed flows from line 102 and is conveyed by pump 104 to and through optional vaporizer 110 in which the organic feed is heated to about 200°C, along with an HF feed, in the presence of an inert gas (e.g., nitrogen). The mixture isdischarged from the vaporizer 110 through line 114 to optional mixer 116 (or instead of mixer 116, the organic feed and HF lines can be connected through valving directly to the reactor 120 and combined therein). The combined 1230xa / HF feed is fed into a heated, catalyst free reactor 120 (optionally containing a suitable inert packing) using any system suitable for heating, controlling and regulating temperatures ranging from between about room temperature and 700°C, at a temperature suitable for the hydrofluorination of HCO-1230xa. The product mixture from reactor 120 is discharged through line 124 or optionally transferred through line 124 into and through a treating system 130, e.g., scrubbers (via scrubbing fluid 132), distillation columns (not shown), etc. to purify and recover at least one of HCFO- 1232xf or HCFO-1233xf in line 134.

[0065] One embodiment disclosed herein relates to compositions which comprise, consist essentially of or consist of HCFO-1233xf and at least one additional compound selected from HCO-1230xa, C4H6CIF, HCFO-1232 isomers, HCFO-1231 (trichlorofluoropropene, C3H2CI3F) isomers and CO-1110 (tetrachloroethylene, CCI2=CCI2), wherein the total amount of the additional compounds is greater than 0 and less than about 1 wt.%, or greater than 0 and less than about 0.5 wt.%, or greater than 0 and less than 0.4 wt.%, or greater than 0 and less than 0.3 wt.%, or greater than 0 and less than 0.2 wt.% or greater than 0 and less than 0.1 wt.% based on the total composition.

[0066] One embodiment disclosed herein relates to compositions which comprise, consist essentially of or consist of HCFO-1232xf and at least one additional member selected from HCO-1230xa, C4H6CIF, HCFO-1232 isomers, HCFO-1231 isomers and CO-1110, wherein the total amount of the additional members is greater than 0 and less than about 1 wt.%, or greater than 0 and less than about 0.5 wt.%, or greater than 0 and less than 0.4 wt.%, or greater than 0 and less than 0.3 wt.%, or greater than 0 and less than 0.2 wt.% or greater than 0 and less than 0.1 wt.% based on the total composition.

[0067] One embodiment disclosed herein relates to compositions which comprise, consist essentially of or consist of HCFO-1232xf and HCFO-1233xf. In some embodiments, the amount of HCFO-1232xf is about 70 wt.% or greater and theamount of HCFO-1233xf is about 30 wt.% or less, based on the total amount of the composition.

[0068] One embodiment disclosed herein relates to compositions which comprise, consist essentially of or consist of HCFO-1233xf, HCFO-1232xf and at least one additional compound selected from HCO-1230xa, C4H6CIF, HCFO-1232 isomers, HCFO-1231 isomers and CO-1110, wherein the total amount of the additional compounds is greater than 0 and less than about 1 wt.%, or greater than 0 and less than about 0.5 wt.%, or greater than 0 and less than 0.4 wt.%, or greater than 0 and less than 0.3 wt.%, or greater than 0 and less than 0.2 wt.% or greater than 0 and less than 0.1 wt.% based on the total composition. In some embodiments, the amount of HCFO-1232xf is about 70 wt.% or greater and the amount of HCFO- 1233xf is about 30 wt.% or less, based on the total amount of the composition.

[0069] Among the additional compounds, HCFO-1231 isomers may include, for example, HCFO-1231xf, HCFO-1231xb, HCFO-1231xa and HCFO-1231ya, and / or HCFO-1231xb. HCFO-1231xb, when present, may be E-HFCO-1231xb, Z-HFCO- 1231xb, or a combination of both E and Z isomers.

[0070] 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.

[0071] 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.EXAMPLESExample 1 : Hyrofluorination of HCO-1230xa to HCFO-1233xf and HCFO-1232xf without a catalyst

[0072] An empty 12-inches long Monel (0.5” OD and 0.43” ID) tube was used as a reactor with a 10-inch heating zone. The HCO-1230xa-HF reaction was testedat / under the conditions provided in Table 2. HCO-1230xa was fed by a pump and passed through a vaporizer at 200°C with N2 and was then mixed with HF, and the mixture flowed through the reactor. The reactor effluent was analyzed by a GC-MS- FID. The analysis shows that HCFO-1233xf and HCFO-1232xf were co-produced at high concentrations at various conditions. All of the tests were done at atmospheric pressure. The test conditions are provided in Table 2 and the product analysis is provided in Table 3.Table 2: Example 1 Reaction ConditionsTable 3: Example 1 GC analysis of product streamTable 3 Example 1 GC analysis of product stream (Continued)Example 2: Hydrofluorination of HCO-1230xa to HCFO-1233xf and HCFO-1232xf without a catalyst

[0073] An empty 12-inches long Monel (0.5 0.5” OD and 0.43” ID) tube was used as a reactor with a 10-inch heating zone. The test conditions are provided in Table 2 and the product analysis is provided in Table 3

[0074] An empty 12-inches long Monel (0.5” OD and 0.43” ID) tube with a 10-inch heating zone was used as a reactor. The HCO-1230xa-HF reaction was tested at / under the conditions provided in Table 2. HCO-1230xa was fed by a pump and passed through a vaporizer at 200°C with N2 and was then mixed with HF, and the mixture flowed through the reactor. The reactor effluent was analyzed by a GC-MS- FID. The analysis shows that HCFO-1233xf and HCFO-1232xf were co-produced at high concentrations at various conditions. All of the tests were done at atmospheric pressure and with longer contact times compared to Example 1. The test conditions are provided in Table 4 and the product analysis is provided in Table 5. Comparing similar conditions in Examples 1 and 2 shows that the longer contact time in Example 2 longer contact time increased HCFO-1232xf selectivity.Table 4: Example 2 Reaction ConditionsTable 5: Example 2 GC analysis of product streamTable 5: Example 2 GC analysis of product stream (continued)OTHER EMBODIMENTS

[0075] Embodiment 1. A process of producing at least one of 2,3-dichloro-3,3- difluoropropene (HCFO-1232xf) and 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) comprising: contacting 1,1, 2, 3- tetrachloro- 1 -propene (HCO-1230xa) and hydrogen fluoride (HF) in the vapor phase, in the absence of a catalyst, at an elevated temperature to form at least one of HCFO-1233xf and HCFO-1232xf.

[0076] Embodiment 2. The process of claim 1 , wherein the HCO-1230xa is converted to at least one of HCFO-1233xf and HCFO-1232xf by hydrofluorination with the HF.

[0077] Embodiment 3. The process of any of claims 1 to 2, wherein conversion of HCO-1230xa to HCFO-1233xf is about 2 to about 20.

[0078] Embodiment 4. The process of claim 3, wherein the elevated temperature is from about 200°C to about 400°C, preferably from about 250°C to about 350°C.

[0079] Embodiment 5. The process of any of claims 3 to 4, wherein the HF to HCO-1230xa mole ratio is between about 10:1 and about 45:1.

[0080] Embodiment 6. The process of any of claims 3 to 5, wherein a contact time for the process is between about 5 seconds to about 60 seconds.

[0081] Embodiment 7. The process of any of claims 1 to 2, wherein conversion of HCO-1230xa to HCFO-1232xf is about 50 or greater.

[0082] Embodiment 8. The process of claim 7, wherein the elevated temperature is from about 160°C to about 300°C.

[0083] Embodiment 9. The process of any of claims 7 to 8, wherein the HF to HCO-1230xa mole ratio is between about 1 :1 and about 30:1.

[0084] Embodiment 10. The process of any of claims 7 to 9, wherein a contact time for the process is between about 5 seconds to about 60 seconds.

[0085] Embodiment 11. The process of any of claims 1 to 2, wherein conversion of HCO-1230xa to HCFO-1233xf and HCFO-1232xf is about 90 or greater.

[0086] Embodiment 12. The process of claim 11 , wherein the elevated temperature is from about 200°C to 400°C.

[0087] Embodiment 13. The process of any of claims 11 to 12, wherein the HF to HCO-1230xa mole ratio is between about 5:1 and about 50:1.

[0088] Embodiment 14. The process of any of claims 11 to 13, wherein a contact time for the process is between about 5 seconds to about 60 seconds.

[0089] Embodiment 15. A composition formed by the process of any of claims 1 to 14.

[0090] Embodiment 16. The composition of claim 15, (i) wherein the composition comprises HCFO-1233xf and at least one additional compound selected from the group consisting of HCO-1230xa, C4H6CIF, HCFO-1232 isomers, HCFO-1231 isomers and CO-1110; (ii) wherein the composition comprises HCFO-1232xf and at least one additional compound selected from the group consisting of HCO-1230xa, C4H6CIF, HCFO-1232 isomers, HCFO-1231 isomers and CO-1110; or (iii) wherein the composition comprises HCFO-1233xf, HCFO-1232xf and at least one additional compound selected from the group consisting of HCO-1230xa, C4H6CIF, HCFO- 1232 isomers, HCFO-1231 isomers and CO-1110.

[0091] Embodiment 17. A composition comprising: (i) HCFO-1233xf and at least one additional compound selected from the group consisting of HCO-1230xa, C4H6CIF, HCFO-1232 isomers, HCFO-1231 isomers and CO-1110; (ii) HCFO-1232xf and at least one additional compound selected from the group consisting of HCO- 1230xa, C4H6CIF, HCFO-1232 isomers, HCFO-1231 isomers and CO-1110; or (iii) HCFO-1233xf, HCFO-1232xf and at least one additional compound selected from the group consisting of HCO-1230xa, C4H6CIF, HCFO-1232 isomers, HCFO-1231 isomers and CO-1110.

[0092] Embodiment 18. The composition of any of claims 16 to 17, wherein the total amount of the additional compounds is greater than 0 and less than about 1 wt., based on the total composition.

[0093] Embodiment 19. The composition of any of claims 16 to 17, wherein the composition (iii) comprises about 70 wt. or greater of HCFO-1232xf and about 30 wt. or less of HCFO-1233xf, based on the total amount of the composition.

[0094] Embodiment 20. A vapor phase process of producing 2-chloro-3,3,3- trifluoropropene (HCFO-1233xf), the process comprising contacting 1 ,1 , 2, 3-tetrachloro-1-propene (HCO-1230xa) and HF at temperatures between about 200°C and about 400°C, in the absence of a catalyst, at an HF:HCO-1230xa mole ratio of between about 10:1 and about 15:1 , and more preferably between about 10:1 and about 40:1 , and preferably with a contact time of between about 5 seconds and about 60 seconds.

[0095] Embodiment 21. A vapor phase process of producing 2,3-dichloro-3,3- difluoropropene (HCFO-1232xf), the process comprising contacting 1, 1,2,3- tetrachloro-1-propene and HF at temperatures between about 160°C and 300°C, in the absence of a catalyst, at an HF:HCO-1230xa mole ratio of between about 1:1 and about 30:1, and more preferably between about 5:1 and 25:1, and preferably with a contact time of between about 5 seconds and about 60 seconds.

[0096] Embodiment 22. A vapor phase process of co-producing 2-chloro-3,3,3- trifluoropropene (HCFO-1233xf) and 2,3-dichloro-3,3-difluoropropene (HCFO- 1232xf), the process comprising contacting 1,1,2,3-tetrachloro-1-propene and HF at temperatures between about 200°C and 400°C, in the absence of a catalyst, at an HF:HCO-1230xa mole ratio of between about 5:1 and about 50:1, and more preferably between about 10:1 and about 40:1, and preferably with a contact time of between about 5 seconds and about 60 seconds.

[0097] Although certain aspects, embodiments and principals have been described above, it is understood that this description is made only way of example and not as limitation of the scope of the invention or appended claims. The foregoing various aspects, embodiments and principals can be used alone and in combinations with each other.

Claims

CLAIMSWhat is claimed is:

1. A process of producing at least one of 2,3-dichloro-3,3-difluoropropene (HCFO- 1232xf) and 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) comprising: contacting 1,1 , 2, 3-tetrachloro-1 -propene (HCO-1230xa) and hydrogen fluoride (HF) in the vapor phase, in the absence of a catalyst, at an elevated temperature to form at least one of HCFO-1233xf and HCFO-1232xf.

2. The process of claim 1, wherein the HCO-1230xa is converted to at least one of HCFO-1233xf and HCFO-1232xf by hydrofluorination with the HF.

3. The process of any of claims 1 to 2, wherein conversion of HCO-1230xa to HCFO-1233xf is about 2 to about 20.

4. The process of claim 3, wherein the elevated temperature is from about 200°C to about 400°C, preferably from about 250°C to about 350°C.

5. The process of any of claims 3 to 4, wherein the HF to HCO-1230xa mole ratio is between about 10:1 and about 45:1.

6. The process of any of claims 3 to 5, wherein a contact time for the process is between about 5 seconds to about 60 seconds.

7. The process of any of claims 1 to 2, wherein conversion of HCO-1230xa to HCFO-1232xf is about 50 or greater.

8. The process of claim 7, wherein the elevated temperature is from about 160°C to about 300°C.

9. The process of any of claims 7 to 8, wherein the HF to HCO-1230xa mole ratio is between about 1:1 and about 30:1.

10. The process of any of claims 7 to 9, wherein a contact time for the process is between about 5 seconds to about 60 seconds.

11. The process of any of claims 1 to 2, wherein conversion of HCO-1230xa to HCFO-1233xf and HCFO-1232xf is about 90 or greater.

12. The process of claim 11 , wherein the elevated temperature is from about 200°C to 400°C.

13. The process of any of claims 11 to 12, wherein the HF to HCO-1230xa mole ratio is between about 5:1 and about 50:1.

14. The process of any of claims 11 to 13, wherein a contact time for the process is between about 5 seconds to about 60 seconds.

15. A composition formed by the process of any of claims 1 to 14.

16. The composition of claim 15,(i) wherein the composition comprises HCFO-1233xf and at least one additional compound selected from the group consisting of HCO-1230xa, C4H6CIF, HCFO-1232 isomers, HCFO-1231 isomers and CO-1110,(ii) wherein the composition comprises HCFO-1232xf and at least one additional compound selected from the group consisting of HCO-1230xa, C4H6CIF, HCFO-1232 isomers, HCFO-1231 isomers and CO-1110, or(iii) wherein the composition comprises HCFO-1233xf, HCFO-1232xf and at least one additional compound selected from the group consisting of HCO-1230xa, C4H6CIF, HCFO-1232 isomers, HCFO-1231 isomers and CO-1110.

17. A composition comprising:(i) HCFO-1233xf and at least one additional compound selected from the group consisting of HCO-1230xa, C4H6CIF, HCFO-1232 isomers, HCFO- 1231 isomers and CO-1110,(ii) HCFO-1232xf and at least one additional compound selected from the group consisting of HCO-1230xa, C4H6CIF, HCFO-1232 isomers, HCFO- 1231 isomers and CO-1110, or(iii) HCFO-1233xf, HCFO-1232xf and at least one additional compound selected from the group consisting of HCO-1230xa, C4H6CIF, HCFO-1232 isomers, HCFO-1231 isomers and CO-1110.

18. The composition of any of claims 16 to 17, wherein the total amount of the additional compounds is greater than 0 and less than about 1 wt., based on the total composition.

19. The composition of any of claims 16 to 17, wherein the composition (iii) comprises about 70 wt. or greater of HCFO-1232xf and about 30 wt. or less of HCFO-1233xf, based on the total amount of the composition.

20. A vapor phase process of producing 2-chloro-3,3,3-trifluoropropene (HCFO- 1233xf), the process comprising contacting 1 ,1 ,2,3-tetrachloro-1-propene (HCO-1230xa) and HF at temperatures between about 200°C and about 400°C, in the absence of a catalyst, at an HF:HCO-1230xa mole ratio of between about 10:1 and about 15:1 , and more preferably between about 10: 1 and about 40:1 , and preferably with a contact time of between about 5 seconds and about 60 seconds.21 . A vapor phase process of producing 2,3-dichloro-3,3-difluoropropene (HCFO- 1232xf), the process comprising contacting 1 ,1 ,2,3-tetrachloro-1-propene and HF at temperatures between about 160°C and 300°C, in the absence of a catalyst, at an HF:HCO-1230xa mole ratio of between about 1 :1 and about 30:1 , and more preferably between about 5:1 and 25:1 , and preferably with a contact time of between about 5 seconds and about 60 seconds.

22. A vapor phase process of co-producing 2-chloro-3,3,3-trifluoropropene (HCFO- 1233xf) and 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf), the process comprising contacting 1 ,1 ,2,3-tetrachloro-1-propene and HF at temperatures between about 200°C and 400°C, in the absence of a catalyst, at an HF:HCO- 1230xa mole ratio of between about 5:1 and about 50:1 , and more preferably between about 10: 1 and about 40:1 , and preferably with a contact time of between about 5 seconds and about 60 seconds.

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