Azeotropic composition containing hydrogen fluoride

Abstract

This application discloses azeotropic compositions and azeotropic-like compositions comprising hydrogen fluoride and a compound selected from 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd) and 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd).

Description

[Technical Field]

[0001] The present invention relates to azeotropic compositions and azeotropic-like compositions comprising hydrogen fluoride and a compound selected from 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd) and 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd). [Background technology]

[0002] Over the past several decades, many industries have been working to find alternatives to ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs). CFCs and HCFCs have been used in a wide range of applications, including aerosol propellants, refrigerants, cleaning agents, expanders for thermoplastics and thermosetting foams, heat transfer fluids, gaseous dielectrics, fire extinguishing and suppressing agents, power cycle working fluids, polymerization media, particulate control fluids, carrier fluids, buffing abrasives, and displacement drying agents. In the search for alternatives to these versatile compounds, many industries have turned their attention to the use of hydrofluorocarbons (HFCs) and hydrofluoroolefins (HFOs). [Overview of the project] [Means for solving the problem]

[0003] This application provides, in particular, a composition comprising i) hydrogen fluoride and ii) a compound selected from 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd) and 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd), wherein 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd) or 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd) is present in the composition in an amount effective for forming an azeotrope or azeotrope-like composition with hydrogen fluoride.

[0004] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art in which the present invention pertains. Methods and materials for use in the present invention are described herein, and other suitable methods and materials known in the art may also be used. The materials, methods, and examples are merely examples and are not intended to limit the invention. All publications, patent applications, patents, sequences, database entries, and other references referenced herein are incorporated herein by reference in their entirety. In the event of any conflict, including definitions, this specification shall prevail. [Brief explanation of the drawing]

[0005] [Figure 1] This is an exemplary vapor-liquid equilibrium plot illustrating the characteristics of a heterogeneous azeotropic mixture. [Modes for carrying out the invention]

[0006] New environmental regulations on refrigerants necessitate that the refrigeration and air conditioning industries seek new refrigerants with low global warming potential (GWP). There is a need for alternative refrigerants that are low GWP, low toxicity, low flammability or non-flammability, reasonably cost-effective, and offer superior refrigeration performance. Fluoroolefins meet these criteria.

[0007] While HFCs do not contribute to stratospheric ozone depletion, they are a cause for concern due to their "greenhouse effect" contribution; that is, they contribute to global warming. As a result of their contribution to global warming, HFCs are under scrutiny, and their widespread use may be restricted in the future. Therefore, there is a need for compositions that do not contribute to stratospheric ozone depletion and also have a low global warming potential (GWP). The formation of an azeotropic composition or azeotropic-like composition containing hydrogen fluoride and the compounds described herein (e.g., 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd) or 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd)) makes it possible to remove the compounds more easily and at a lower temperature from other high-boiling point byproducts formed during the synthesis of, for example, (E)-1,1,1,4,4,4-hexafluoro-2-butene, thereby improving the purification of the desired product with lower energy and cost. In addition, the azeotropic composition can be used in azeotropic distillation to remove hydrogen fluoride from higher-boiling point compounds that form an azeotropic mixture with hydrogen fluoride. The azeotropic compositions described herein are minimum-boiling point azeotropes, i.e., at a given pressure, the boiling point of the azeotrope is lower than the boiling point of each individual component. Therefore, these compositions may be useful for isolating azeotropic mixtures at lower temperatures compared to the individual components.

[0008] Exemplary processes for preparing (E)-1,1,1,4,4,4-hexafluoro-2-butene can be found, for example, in U.S. Patent No. 10,611,709 and No. 11,390,574, the disclosures of which are incorporated herein by reference in their entirety.

[0009] Definitions and Abbreviations 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 process, method, article, or apparatus containing a list of elements is not necessarily limited to those elements alone, and may also include other elements not expressly listed with or specific to such 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).

[0010] 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.

[0011] As used herein, the term "approximately" means to take into account variations due to experimental error (e.g., plus or minus approximately 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.

[0012] 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.

[0013] The Global Warming Potential (GWP) is an index used to estimate the relative contribution to global warming caused by one kilogram of atmospheric emissions of a particular greenhouse gas compared to one kilogram of carbon dioxide emissions. GWP can be calculated for various time periods and reflects the atmospheric lifetime impact of a given gas. A GWP over a 100-year period is a commonly referenced value.

[0014] As is recognized in the art, an azeotropic composition is a mixture of two or more different components that, when in liquid form, (1a) boil at a substantially constant temperature under a given constant pressure (this temperature may be higher or lower than the boiling temperatures of the individual components), or (1b) boil at a substantially constant pressure at a given constant temperature (this pressure may be higher or lower than the boiling pressures of the individual components), and (2) boil in a substantially constant composition (this phase composition is constant but not necessarily equal). (See, for example, MFDoherty and MFMalone, Conceptual Design of Distillation Systems, McGraw-Hill (New York), 2001, 185).

[0015] A homogeneous azeotropic mixture, in which a single gas phase is in equilibrium with a single liquid phase, possesses the properties (1a), (1b), and (2) described above, in addition to the property that the composition of each component is the same in each of the coexisting equilibrium phases. The general term "azeotrope" is a commonly used alternative name for a homogeneous azeotropic mixture.

[0016] A heterogeneous azeotropic mixture, in which a single gas phase is in equilibrium with two liquid phases, possesses the above characteristics (1a), (1b), and (2), and although constant, the three coexisting equilibrium phases each have different compositions (see, for example, MFDoherty and MFMalone, Conceptual Design of Distillation Systems, McGraw-Hill (New York), 2001, 352). In a heterogeneous azeotropic mixture, the overall composition of the liquid phase (i.e., the liquid phase composition obtained by combining the two equilibrium liquid phases) is identical to the composition of the equilibrium gas phase.

[0017] The properties of heterogeneous azeotropic mixtures are shown, for example, in Figure 1. As shown in Figure 1, at temperature T * T is the lowest temperature at which both the gas and liquid phases occur. * Below a certain temperature, depending on the composition, liquid phase α, liquid phase β, or both α and β exist. When the liquid composition is within the (α+β) region, the liquid composition separates into two distinct liquid phases whose composition is determined by the intersection of a solid line starting from points A and B and continuing toward the bottom of Figure 1, and a horizontal line at a specific temperature (Figure 1). * Above this temperature, in regions (α+v) and (β+v), a single liquid phase is in equilibrium with a gas phase, depending on the composition of the mixture, indicated by the intersection of the solid line enclosing region (α+v) or (β+v) and the horizontal line at a specific temperature. * Therefore, the three phases with different compositions, shown by A, B, and C in Figure 1, are in equilibrium with each other. (x1α) * and (x1β) * Any mixture having a liquid phase composition between (I) and (x1α) is shown in Figure 1. * and (x1β) * It separates into two liquid phases equal to (II) composition y1* is in the gas phase and in equilibrium, and (III) at the same temperature T * boils. Points A, B, and C in Figure 1 and temperature T * constitute three equilibrium phases of the heterogeneous azeotrope. At the azeotropic composition, the composition of the entire liquid phase is y1 * is equal to.

[0018] As used herein, an "azeotrope-like" composition refers to a composition that behaves like an azeotrope (i.e., has constant boiling characteristics or a tendency not to fractionate upon boiling or evaporation). Thus, during boiling or evaporation, the composition of the vapor and liquid changes minimally or negligibly, if at all. In contrast, the composition of the vapor and liquid of a non-azeotrope-like composition changes significantly during boiling or evaporation.

[0019] As used herein, the term "azeotrope-like" or "azeotrope-like behavior" refers to a composition that exhibits dew point pressure and bubble point pressure with virtually no pressure difference. In some embodiments, the difference between the dew point pressure and the bubble point pressure at a given temperature is 3% or less. In some embodiments, the difference between the bubble point pressure and the dew point pressure is 5% or less.

[0020] As used herein, the term "compound" is meant to include all stereoisomers, geometric isomers, tautomers, and isotopes of the indicated structure. A compound identified by name or structure as a particular tautomeric form herein is intended to include other tautomeric forms unless otherwise specified.

[0021] Chemical Substances, Abbreviations, and Acronyms 1335czd: 3-Chloro-1,1,4,4,4-pentafluorobut-1-ene 345lfd: 2,4-Dichloro-1,1,1,4,4-pentafluorobutane NRTL (Non-Random, Two-Liquid): Non-Random Two-Liquid psia (pounds per square inch absolute): pounds per square inch absolute VLE (vapor - liquid equilibrium): Vapor - liquid equilibrium

[0022] Composition This application provides a composition comprising i) hydrogen fluoride and ii) a compound selected from 2,4 - dichloro - 1,1,1,4,4 - pentafluorobutane (345lfd) and 3 - chloro - 1,1,4,4,4 - pentafluorobut - 1 - ene (1335czd), wherein 2,4 - dichloro - 1,1,1,4,4 - pentafluorobutane (345lfd) or 3 - chloro - 1,1,4,4,4 - pentafluorobut - 1 - ene (1335czd) is present in the composition in an amount effective to form an azeotropic composition or an azeotrope - like composition with hydrogen fluoride.

[0023] In some embodiments, the composition provided herein comprises hydrogen fluoride and 2,4 - dichloro - 1,1,1,4,4 - pentafluorobutane (345lfd), and 2,4 - dichloroloro - 1,1,1,4,4 - pentafluorobutane (345lfd) is present in the composition in an amount effective to form an azeotropic composition or an azeotrope - like composition with hydrogen fluoride.

[0024] In some embodiments, the composition comprises from about 83 to about 99.99 mole percent hydrogen fluoride, for example, from about 83 to about 99, from about 83 to about 95, from about 83 to about 90, from about 83 to about 85, from about 85 to about 99.99, from about 85 to about 99, from about 85 to about 95, from about 85 to about 90, from about 90 to about 99.99, from about 90 to about 99, from about 90 to about 95, from about 95 to about 99.99, from about 95 to about 99, or from about 99 to about 99.99 mole percent hydrogen fluoride.

[0025] In some embodiments, the composition comprises about 0.01 to about 17 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd), for example, about 0.01 to about 15, about 0.01 to about 10, about 0.01 to about 5, about 0.01 to about 1, about 1 to about 17, about 1 to about 15, about 1 to about 10, about 1 to about 5, about 5 to about 17, about 5 to about 15, about 5 to about 10, about 10 to about 17, about 10 to about 15, or about 15 to about 17 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd).

[0026] In some embodiments, the composition comprises about 83 to about 99.99 mole percent of hydrogen fluoride and about 0.01 to about 17 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd).

[0027] In some embodiments, the composition comprises about 88.7 to about 99.99 mole percent of hydrogen fluoride and about 0.01 to about 11.3 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd).

[0028] In some embodiments, compositions comprising 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd) are used at pressures of about 6 psia to about 360 psia, for example, about 6 psia to about 300 psia, about 6 psia to about 250 psia, about 6 psia to about 200 psia, about 6 psia to about 150 psia, about 6 psia to about 100 psia, about 6 psia to about 50 psia, and about 50 psia. ia~about 360psia, about 50psia~about 300psia, about 50psia~about 250psia, about 50psia~about 200psia, about 50psia~about 150psia, about 50psia~about 1 00psia, about 100psia to about 360psia, about 100psia to about 300psia, about 100psia to about 250psia, about 100psia to about 200psia, about 100psia to about 1 50psia, approximately 150psia to 360psia, approximately 150psia to 300psia, approximately 150psia to 250psia, approximately 150psia to 200psia, approximately 200psia to 360psia, approximately 200psia to 300psia, approximately 200psia to 250psia, approximately 250psia to 360psia, approximately 250psia to 300psia, or approximately 300psia At approximately 360 psia, it has a boiling point of approximately 0°C to approximately 130°C, for example, approximately 0°C to approximately 100°C, approximately 0°C to approximately 75°C, approximately 0°C to approximately 50°C, approximately 0°C to approximately 25°C, approximately 25°C to approximately 130°C, approximately 25°C to approximately 100°C, approximately 25°C to approximately 75°C, approximately 25°C to approximately 50°C, approximately 50°C to approximately 130°C, approximately 50°C to approximately 100°C, approximately 50°C to approximately 75°C, approximately 75°C to approximately 130°C, approximately 75°C to approximately 100°C, or approximately 100°C to approximately 130°C.

[0029] In some embodiments, the composition comprises hydrogen fluoride and 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd), wherein 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd) is present in the composition in an amount effective for forming an azeotrope composition with hydrogen fluoride.

[0030] In some embodiments, the composition comprises hydrogen fluoride and 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd), wherein 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd) is present in the composition in an amount effective for forming a homogeneous azeotropic composition with hydrogen fluoride.

[0031] In some embodiments, the composition comprises hydrogen fluoride and 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd), wherein 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd) is present in the composition in an amount effective for forming a heterogeneous azeotropic composition with hydrogen fluoride.

[0032] In some embodiments, the composition comprises hydrogen fluoride and 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd), wherein 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd) is present in the composition in an amount effective for forming an azeotrope or azeotrope-like composition with hydrogen fluoride.

[0033] In some embodiments, a composition comprising hydrogen fluoride and 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd) contains about 94 to about 75 mole percent of hydrogen fluoride, for example, about 94 to about 80, about 94 to about 85, about 94 to about 90, about 90 to about 75, about 90 to about 80, about 90 to about 85, about 85 to about 75, about 85 to about 80, or about 80 to about 75 mole percent of hydrogen fluoride.

[0034] In some embodiments, a composition comprising hydrogen fluoride and 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd) comprises about 6 to about 25 mole percent of 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd), for example, about 6 to about 20, about 6 to about 15, about 6 to about 10, about 10 to about 25, about 10 to about 20, about 10 to about 15, about 15 to about 25, about 15 to about 20, or about 20 to about 25 mole percent of 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd).

[0035] In some embodiments, a composition comprising hydrogen fluoride and 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd) contains about 94 to about 75 mole percent of hydrogen fluoride and about 6 to about 25 mole percent of 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd).

[0036] In some embodiments, a composition comprising hydrogen fluoride and 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd) is used at pressures of about 7 psia to about 299 psia, for example, about 7 psia to about 250 psia, about 7 psia to about 200 psia, about 7 psia to about 150 psia, about 7 psia to about 100 psia, about 7 psia to about 50 psia, about 50 psia to about 299 psia, about 50 psia to about 250 psia, about 50 psia to about 200 psia, about 50 psia to about 150 psia, about 50 psia to about 100 psia, about 100 psia to about 299 psia, about 100 psia to about 250 psia, and about 100 psia to about 200 psia. sia, at approximately 100 psia to 150 psia, approximately 150 psia to 299 psia, approximately 150 psia to 250 psia, approximately 150 psia to 200 psia, approximately 200 psia to 299 psia, approximately 200 psia to 250 psia, or approximately 250 psia to 299 psia, at approximately 0°C to 120°C, for example, approximately 0 It has boiling points of approximately 100°C, 0°C to 75°C, 0°C to 50°C, 0°C to 25°C, 25°C to 120°C, 25°C to 100°C, 25°C to 75°C, 25°C to 50°C, 50°C to 120°C, 50°C to 100°C, 50°C to 75°C, 75°C to 120°C, 75°C to 100°C, or 100°C to 120°C.

[0037] In some embodiments, the composition comprises hydrogen fluoride and 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd), wherein 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd) is present in the composition in an amount effective for forming an azeotrope composition with hydrogen fluoride.

[0038] In some embodiments, the composition comprises hydrogen fluoride and 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd), wherein 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd) is present in the composition in an amount effective for forming a homogeneous azeotrope composition with hydrogen fluoride.

[0039] In some embodiments, the composition comprises hydrogen fluoride and 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd), wherein 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd) is present in the composition in an amount effective for forming a heterogeneous azeotrope with hydrogen fluoride.

[0040] Therefore, these compositions may be useful for isolating azeotropic mixtures at lower temperatures compared to the individual components.

[0041] The formation of azeotropic or azeotropic compositions containing hydrogen fluoride and 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd), as described herein, and azeotropic or azeotropic compositions containing hydrogen fluoride and 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd), makes it possible to remove the compound more easily and at a lower temperature from other by-products formed in the synthesis of (E)-1,1,1,4,4,4-hexafluoro-2-butene, thereby improving the purification of the desired product with lower energy and cost. In addition, the azeotropic composition can be used in azeotropic distillation to remove hydrogen fluoride from higher boiling point compounds that form an azeotropic mixture with hydrogen fluoride.

[0042] The present invention provides a process for removing 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd) from a composition comprising (E)-1,1,1,4,4,4-hexafluoro-2-butene and 2,4-dichloro-1,1,1,4,4-pentafluorobutane, the process comprising forming an azeotropic composition or azeotropic-like composition of 2,4-dichloro-1,1,1,4,4-pentafluorobutane and HF, and removing the azeotropic composition or azeotropic-like composition from a composition comprising (E)-1,1,1,4,4,4-hexafluoro-2-butene and 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd), the process further comprising An azeotropic composition or azeotropic-like composition of 2,4-dichloro-1,1,1,4,4-pentafluorobutane and HF contains about 83 to about 99.99 mole percent of hydrogen fluoride and about 0.01 to about 17 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd).

[0043] A process for removing 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd) from a composition comprising (E)-1,1,1,4,4,4-hexafluoro-2-butene and 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd), the process comprising forming an azeotropic composition or azeotropic-like composition of 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd) and HF, and removing the azeotropic composition or azeotropic-like composition from a composition comprising (E)-1,1,1,4,4,4-hexafluoro-2-butene and 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd). An azeotropic composition or azeotropic-like composition of 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd) and HF contains about 94 to about 75 mole percent of hydrogen fluoride and about 6 to about 25 mole percent of 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd).

[0044] As described herein, 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd) and 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd) each form azeotropic mixtures with HF. These azeotropic mixtures allow HF to be separated from each of these individual compounds using azeotropic distillation. Furthermore, the formation of azeotropic mixtures makes it possible to separate other components from the reaction mixture containing HF and 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd) or 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd).

[0045] The present invention will be described in more detail by specific examples. The following examples are provided for illustrative purposes only and are not intended to limit the invention in any way. Those skilled in the art will readily recognize various non-essential parameters that can be changed or modified to obtain essentially the same results. [Examples]

[0046] Example 1. Gas-liquid equilibrium analysis The PTx method is a known method for experimentally measuring gas-liquid equilibrium (VLE) data of mixtures. Measurements can be performed either isothermally or isobarically. The isothermal method requires measuring the total pressure of a mixture of known compositions at a constant temperature. This method measures the total absolute pressure in a cell of known volume for various known compositions of two compounds at a constant temperature. The isobaric method requires measuring the temperature of a mixture of known compositions at a constant pressure. This method measures the temperature in a cell of known volume for various known compositions of two compounds at a constant pressure. The use of the PTx method is described in detail in "Phase Equilibrium in Process Design," Wiley-Interscience Publishers, 1970, by Harold R. Null, pp. 124–126, the disclosure of which is incorporated herein by reference in whole.

[0047] The measured data points can be converted into the equilibrium vapor-liquid compositions in a PTx cell to represent a non-ideal liquid-phase system by using activity coefficient models such as the non-random two-liquid (NRTL) equation. The use of activity coefficient equations such as the NRTL equation is described in detail in "The Properties of Gases and Liquids," 4th edition, published by McGraw Hill, by Reid, Prausnitz, and Poling, pp. 241-387, and in "Phase Equilibria in Chemical Engineering," published by Butterworth Publishers, 1985, by Stanley M. Walas, pp. 165-244, the disclosures of which are incorporated herein by reference in their entirety. While we do not wish to be bound by any theory or explanation, the NRTL equation, in conjunction with PTx cell data, is considered to adequately predict the gas-liquid phase equilibrium behavior of various compositions of the present invention, and the behavior of these mixtures in multi-stage separation apparatuses such as distillation columns.

[0048] In both homogeneous and heterogeneous azeotropic mixtures, the equilibrium gas phase composition and liquid phase composition (or overall liquid phase composition in the case of heterogeneous azeotropic mixtures) are equal. Therefore, the azeotropic composition can be determined over a range of temperatures or pressures by (1) measuring gas-liquid equilibrium data over the entire composition range, preferably at two or more temperatures or pressures; (2) fitting adjustable parameters of a gas-liquid equilibrium model, such as the Peng-Robinson equation of state and / or the NRTL equation, to the experimental data; and (3) calculating the gas-liquid equilibrium using the obtained model parameters to determine the point where the gas and liquid phase compositions are equal. The azeotropic compositions described in Table 1-2 and in each example were produced using this method. For mixtures forming heterogeneous azeotropes, unless otherwise specified, the described liquid phase composition is the overall liquid phase composition.

[0049] Example 2. Azeotropic composition of hydrogen fluoride and 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd) Table 1 summarizes the azeotropic temperature range from 0°C to 130°C for a mixture of hydrogen fluoride and 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd).

[0050] [Table 1]

[0051] Example 3. Azeotropic composition of hydrogen fluoride and 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd) Table 2 summarizes the azeotropic temperature range from 0°C to 120°C for a mixture of hydrogen fluoride and 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd).

[0052] [Table 2]

[0053] Embodiment In Embodiment 1, the present application provides a composition comprising i) hydrogen fluoride and ii) a compound selected from 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd) and 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd), wherein 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd) or 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd) is present in the composition in an amount effective for forming an azeotrope or azeotrope-like composition with hydrogen fluoride.

[0054] In Embodiment 2, the composition of Embodiment 1 comprises hydrogen fluoride and 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd), wherein 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd) is present in the composition in an amount effective for forming an azeotrope composition or azeotrope-like composition with hydrogen fluoride.

[0055] In Embodiment 3, the composition of Embodiment 2 comprises about 83 to about 99.99 mole percent of hydrogen fluoride and about 0.01 to about 17 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd).

[0056] In Embodiment 4, the composition of Embodiment 2 comprises about 83 to about 99 mole percent of hydrogen fluoride and about 1 to about 17 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd).

[0057] In Embodiment 5, the composition of Embodiment 2 comprises about 83 to about 95 mole percent of hydrogen fluoride and about 5 to about 17 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd).

[0058] In Embodiment 6, the composition of Embodiment 2 comprises about 83 to about 90 mole percent of hydrogen fluoride and about 10 to about 17 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd).

[0059] In Embodiment 7, the composition of Embodiment 2 comprises about 83 to about 85 mole percent of hydrogen fluoride and about 15 to about 17 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd).

[0060] In Embodiment 8, the composition of Embodiment 2 comprises about 85 to about 99.99 mole percent of hydrogen fluoride and about 0.01 to about 15 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd).

[0061] In Embodiment 9, the composition of Embodiment 2 comprises about 85 to about 99 mole percent of hydrogen fluoride and about 0.01 to about 15 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd).

[0062] In Embodiment 10, the composition of Embodiment 2 comprises about 85 to about 95 mole percent of hydrogen fluoride and about 0.01 to about 15 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd).

[0063] In Embodiment 11, the composition of Embodiment 2 comprises about 85 to about 90 mole percent of hydrogen fluoride and about 0.01 to about 15 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd).

[0064] In Embodiment 12, the composition of Embodiment 2 comprises about 90 to about 99.99 mole percent of hydrogen fluoride and about 0.01 to about 10 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd).

[0065] In Embodiment 13, the composition of Embodiment 2 comprises about 90 to about 99 mole percent of hydrogen fluoride and about 1 to about 10 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd).

[0066] In Embodiment 14, the composition of Embodiment 2 comprises about 90 to about 95 mole percent of hydrogen fluoride and about 5 to about 10 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd).

[0067] In Embodiment 15, the composition of Embodiment 2 comprises about 95 to about 99.99 mole percent of hydrogen fluoride and about 0.01 to about 5 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd).

[0068] In Embodiment 16, the composition of Embodiment 2 comprises about 95 to about 99 mole percent of hydrogen fluoride and about 1 to about 5 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd).

[0069] In Embodiment 17, the composition of Embodiment 2 comprises about 99 to about 99.99 mole percent of hydrogen fluoride and about 0.01 to about 1 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd).

[0070] In Embodiment 18, the composition of Embodiment 2 has a boiling point of about 0°C to about 130°C at a pressure of about 6 psia to about 360 psia.

[0071] In Embodiment 19, the composition of Embodiment 2 has a boiling point of about 0°C to about 130°C at a pressure of about 6 psia to about 360 psia.

[0072] In Embodiment 20, the composition of Embodiment 1 comprises hydrogen fluoride and 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd), wherein 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd) is present in the composition in an amount effective for forming an azeotrope or azeotrope-like composition with hydrogen fluoride.

[0073] In Embodiment 21, the composition of Embodiment 20 comprises about 94 to about 75 mole percent of hydrogen fluoride and about 6 to about 25 mole percent of 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd).

[0074] In Embodiment 22, the composition of Embodiment 21 comprises about 94 to about 80 mole percent of hydrogen fluoride and about 6 to about 20 mole percent of 3-chloro-1,1,4,4,4-pentafluorobutane-1-ene (1335czd).

[0075] In Embodiment 23, the composition of Embodiment 21 comprises about 94 to about 85 mole percent of hydrogen fluoride and about 6 to about 15 mole percent of 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd).

[0076] In Embodiment 24, the composition of Embodiment 21 comprises about 94 to about 90 mole percent of hydrogen fluoride and about 6 to about 10 mole percent of 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd).

[0077] In Embodiment 25, the composition of Embodiment 21 comprises about 90 to about 75 mole percent of hydrogen fluoride and about 10 to about 25 mole percent of 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd).

[0078] In Embodiment 26, the composition of Embodiment 21 comprises about 90 to about 80 mole percent of hydrogen fluoride and about 10 to about 20 mole percent of 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd).

[0079] In Embodiment 27, the composition of Embodiment 21 comprises about 90 to about 85 mole percent of hydrogen fluoride and about 10 to about 15 mole percent of 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd).

[0080] In Embodiment 28, the composition of Embodiment 21 comprises about 85 to about 75 mole percent of hydrogen fluoride and about 15 to about 25 mole percent of 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd).

[0081] In Embodiment 29, the composition of Embodiment 21 comprises about 85 to about 80 mole percent of hydrogen fluoride and about 15 to about 20 mole percent of 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd).

[0082] In Embodiment 30, the composition of Embodiment 21 comprises about 80 to about 75 mole percent of hydrogen fluoride and about 20 to about 25 mole percent of 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd).

[0083] In Embodiment 31, the composition of Embodiment 21 has a boiling point of about 0°C to about 120°C at a pressure of about 7 psia to about 299 psia.

[0084] In Embodiment 32, one of the compositions from Embodiments 1 to 31 is a homogeneous azeotrope composition or a homogeneous azeotrope-like composition.

[0085] In Embodiment 33, the composition according to any one of Embodiments 1 to 31 is a homogeneous azeotrope.

[0086] In Embodiment 34, the composition according to any one of Embodiments 1 to 31 is a heterogeneous azeotrope composition or a heterogeneous azeotrope-like composition.

[0087] In Embodiment 35, the composition according to any one of Embodiments 1 to 31 is a heterogeneous azeotrope.

[0088] In Embodiment 36, the composition according to any one of Embodiments 1 to 31 is an azeotrope-like composition.

[0089] Embodiment 37 provides a process for removing 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd) from a composition comprising (E)-1,1,1,4,4,4-hexafluoro-2-butene and 2,4-dichloro-1,1,1,4,4-pentafluorobutane, the process comprising forming an azeotropic composition or azeotropic-like composition of 2,4-dichloro-1,1,1,4,4-pentafluorobutane and HF, and removing the azeotropic composition or azeotropic-like composition from a composition comprising (E)-1,1,1,4,4,4-hexafluoro-2-butene and 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd).

[0090] In Embodiment 38, the process is as described in Embodiment 37, and the azeotropic composition or azeotropic-like composition of 2,4-dichloro-1,1,1,4,4-pentafluorobutane and HF is the composition described in any one of Embodiments 2 to 19.

[0091] Embodiment 39 provides a process for removing 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd) from a composition comprising (E)-1,1,1,4,4,4-hexafluoro-2-butene and 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd), the process comprising forming an azeotropic composition or azeotropic-like composition of 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd) and HF, and removing the azeotropic composition or azeotropic-like composition from a composition comprising (E)-1,1,1,4,4,4-hexafluoro-2-butene and 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd).

[0092] In Embodiment 40, the process is as described in Embodiment 39, and the azeotropic composition or azeotropic-like composition of 2,3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd) and HF is the composition described in any one of Embodiments 20 to 31.

[0093] While the present invention has been described in conjunction with its detailed description, it should be understood that the foregoing description is intended to illustrate, and not limit, the scope of the invention as defined by the appended claims. Other aspects, advantages, and modifications are within the scope of the following claims. It should be understood by those skilled in the art related to the invention that any feature described herein with respect to any particular aspect and / or embodiment of the invention can be combined with one or more other features of any other aspect and / or embodiment of the invention described herein, and can be modified as appropriate to ensure the suitability of the combination. Such combinations are considered to be part of the invention as contemplated by this disclosure.

Claims

1. i) Hydrogen fluoride and, ii) A compound selected from 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345 lfd) and 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335 czd), A composition comprising, A composition wherein the 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345 lfd) or the 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335 czd) is present in the composition in an amount effective for forming an azeotrope composition or azeotrope-like composition with the hydrogen fluoride.

2. The composition according to claim 1, wherein the composition comprises hydrogen fluoride and 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345 lfd).

3. The composition according to claim 2, wherein the composition comprises about 83 to about 99.99 mole percent of hydrogen fluoride and about 0.01 to about 17 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345 lfd).

4. The composition contains approximately 83 to approximately 99.99 mole percent of hydrogen fluoride, or approximately 83 to approximately 99 mole percent of hydrogen fluoride, or approximately 83 to approximately 95 mole percent of hydrogen fluoride, or approximately 83 to approximately 90 mole percent of hydrogen fluoride, or approximately 83 to approximately 85 mole percent of hydrogen fluoride, or approximately 85 to approximately 99.99 mole percent of hydrogen fluoride, or approximately 85 to approximately 99 mole percent of hydrogen fluoride, or approximately 85 to approximately 95 mole percent of hydrogen fluoride The composition according to claim 2 or 3, comprising hydrogen, or about 85 to about 90 mole percent of hydrogen fluoride, or about 90 to about 99.99 mole percent of hydrogen fluoride, or about 90 to about 99 mole percent of hydrogen fluoride, or about 90 to about 95 mole percent of hydrogen fluoride, or about 95 to about 99.99 mole percent of hydrogen fluoride, or about 95 to about 99 mole percent of hydrogen fluoride, or about 99 to about 99.99 mole percent of hydrogen fluoride.

5. The composition contains about 0.01 to about 17 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345 lfd), or about 0.01 to about 15 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345 lfd), or about 0.01 to about 10 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345 lfd), or about 0.01 to about 5 mole percent of 2,4-dichloro-1,1,1,4,4 -Pentafluorobutane (345 lfd), or about 0.01 to about 1 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345 lfd), or about 1 to about 17 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345 lfd), or about 1 to about 15 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345 lfd), or about 1 to about 10 mole percent of 2,4-dichloro-1,1 ,1,4,4-pentafluorobutane (345 lfd), or about 1 to about 5 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345 lfd), or about 5 to about 17 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345 lfd), or about 5 to about 15 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345 lfd), or about 5 to about 10 mole percent of 2,4-dichloro- The composition according to claim 2 or 3, comprising 1,1,1,4,4-pentafluorobutane (345lfd), or about 10 to about 17 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd), or about 10 to about 15 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd), or about 15 to about 17 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345lfd).

6. The composition according to claim 3, wherein the composition comprises about 88.7 to about 99.99 mole percent of hydrogen fluoride and about 0.01 to about 11.3 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345 lfd).

7. The composition according to claim 3, wherein the composition has a boiling point of about 0°C to about 130°C at a pressure of about 6 psia to about 360 psia.

8. The composition according to claim 3, wherein the 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345 lfd) is present in the composition in an amount effective for forming an azeotrope composition with the hydrogen fluoride.

9. The composition according to claim 8, wherein the 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345 lfd) is present in the composition in an amount effective for forming a homogeneous azeotrope composition with the hydrogen fluoride.

10. The composition according to claim 8, wherein the 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345 lfd) is present in the composition in an amount effective for forming a heterogeneous azeotrope with the hydrogen fluoride.

11. The composition according to claim 2, wherein the 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345 lfd) is present in the composition in an amount effective for forming an azeotrope-like composition with the hydrogen fluoride.

12. The composition according to claim 1, wherein the composition comprises hydrogen fluoride and 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd).

13. The composition according to claim 12, wherein the composition comprises about 94 to about 75 mole percent of hydrogen fluoride and about 6 to about 25 mole percent of 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd).

14. The composition according to claim 12 or 13, wherein the composition comprises about 94 to about 80 mole percent of hydrogen fluoride, or about 94 to about 85 mole percent of hydrogen fluoride, or about 94 to about 90 mole percent of hydrogen fluoride, or about 90 to about 75 mole percent of hydrogen fluoride, or about 90 to about 80 mole percent of hydrogen fluoride, or about 90 to about 85 mole percent of hydrogen fluoride, or about 85 to about 75 mole percent of hydrogen fluoride, or about 85 to about 80 mole percent of hydrogen fluoride, or about 80 to about 75 mole percent of hydrogen fluoride.

15. The composition contains about 6 to about 20 mole percent of 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd), or about 6 to about 15 mole percent of 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd), or about 6 to about 10 mole percent of 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd), or about 10 to about 25 mole percent of 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd), or about 10 to about 20 mole percent of 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd). The composition according to claim 12 or 13, comprising orobuta-1-ene (1335czd), or about 10 to about 15 mole percent of 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd), or about 15 to about 25 mole percent of 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd), or about 15 to about 20 mole percent of 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd), or about 20 to about 25 mole percent of 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd).

16. The composition according to claim 12, wherein the composition has a boiling point of about 0°C to about 120°C at a pressure of about 7 psia to about 299 psia.

17. The composition according to claim 12, wherein the 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd) is present in the composition in an amount that forms an azeotrope with hydrogen fluoride.

18. The composition according to claim 12, wherein the 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd) is present in the composition in an amount that forms a homogeneous azeotrope with hydrogen fluoride.

19. The composition according to claim 12, wherein the 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd) is present in the composition in an amount that forms a heterogeneous azeotrope with hydrogen fluoride.

20. The composition according to claim 12, wherein the 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd) is present in the composition in an amount that forms an azeotrope-like composition with hydrogen fluoride.

21. A process for removing 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345 lfd) from a composition comprising (E)-1,1,1,4,4,4-hexafluoro-2-butene and 2,4-dichloro-1,1,1,4,4-pentafluorobutane, comprising forming an azeotrope or azeotrope-like composition of 2,4-dichloro-1,1,1,4,4-pentafluorobutane and HF, and removing the azeotrope or azeotrope-like composition from the composition comprising (E)-1,1,1,4,4,4-hexafluoro-2-butene and 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345 lfd).

22. The process according to claim 21, wherein the azeotropic composition or azeotropic-like composition of 2,4-dichloro-1,1,1,4,4-pentafluorobutane and HF comprises about 83 to about 99.99 mole percent of hydrogen fluoride and about 0.01 to about 17 mole percent of 2,4-dichloro-1,1,1,4,4-pentafluorobutane (345 lfd).

23. A process for removing 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd) from a composition comprising (E)-1,1,1,4,4,4-hexafluoro-2-butene and 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd), the process comprising forming an azeotropic composition or azeotropic-like composition of 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd) and HF, and removing the azeotropic composition or azeotropic-like composition from the composition comprising (E)-1,1,1,4,4,4-hexafluoro-2-butene and 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd).

24. The process according to claim 23, wherein the azeotropic composition or azeotropic-like composition of 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd) and HF comprises about 94 to about 75 mole percent of hydrogen fluoride and about 6 to about 25 mole percent of 3-chloro-1,1,4,4,4-pentafluorobuta-1-ene (1335czd).

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