Azeotropic or azeotrope-like compositions of 3,3,3, - trifluoropropyne (TFPY) and hydrogen fluoride (HF)

Abstract

To provide an azeotropic mixture and a method for reducing 2333 - trifluoropropyne (TFPY) which is an impurity in the production of 333 - tetrafluoropropene (HFO - 1234yf).SOLUTION: A heterogeneous azeotrope or azeotrope-like composition comprising TFPY and hydrogen fluoride (HF), wherein the composition may comprise from about 71. 5wt.% to about 98. 8wt.% TFPY and from about 1. 2wt.% to about 28. 5wt.% hydrogen fluoride, and wherein the composition has a boiling point from about - 10.0 °C. to about 25.0 °C. at a pressure from about 61psia to about 171psia. This azeotrope or azeotrope-like composition can be used to separate TFPY as an impurity from 2-chloro - 333 - trifluoropropene (1233xf), 2-chloro - 1112 - tetrafluoropropane (HCFC - 244bb), or HFO - 1234yf compositions.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE

[0001] This disclosure relates to azeotrope or azeotrope-like compositions, particularly azeotrope or azeotrope-like compositions comprising effective amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF). [Background technology]

[0002]

[0002] Hydrofluoroolefins (HFOs), such as tetrafluoropropenes, including 2,3,3,3-tetrafluoropropene (HFO-1234yf), are known to be effective refrigerants, heat transfer media, propellants, foaming agents, blowing agents, gaseous dielectrics, sterilant carriers, polymerization media, particle removal fluids, carrier fluids, buffing agents, displacement desiccants, and power cycle working fluids. Unlike chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), both of which can damage the Earth's ozone layer, HFOs do not pose a threat to the ozone layer. HFO-1234yf has also been shown to be a low-toxicity, low-global-warming-potential compound, and therefore may meet the increasingly stringent requirements for refrigerants in mobile air conditioning systems. Therefore, compositions containing HFO-1234yf are among the materials being developed for use in many of the aforementioned applications.

[0003] One method for producing HFO-1234yf uses 1,1,2,3-tetrachloropropene (HCFC-1230xa) as a starting material. The method involves the following three steps: Step (1) 1230xa + 3HF → 2-chloro-3,3,3-trifluoropropene (1233xf) + 3HCl in a gas-phase reactor loaded with a solid catalyst; Step (2) 1233xf + HF → 2-chloro-1,1,1,2-tetrafluoropropane (244bb) in a liquid-phase reactor loaded with a liquid catalyst, and Step (3) 244bb-->1234yf+HCl in a gas phase reactor or in the liquid phase.

[0004] During the above processes, 3,3,3-trifluoropropyne (TFPY) is sometimes produced and / or otherwise present as an impurity, which is undesirable, and therefore methods for reducing the presence of TFPY, as well as other impurities, are desirable. Summary of the Invention

[0005]

[0005] The present disclosure provides azeotrope or azeotrope-like compositions of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF).

[0006] It is well recognized in the art that the formation of azeotropes is impossible to predict, and the present inventors have unexpectedly discovered that 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) form azeotropes or azeotrope-like compositions, and in particular, form heterogeneous azeotropes or azeotrope-like compositions.

[0006]

[0007] The present disclosure provides compositions comprising an azeotrope or azeotrope-like composition consisting essentially of effective amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF), preferably the azeotrope or azeotrope-like composition having a boiling point of about −10.0° C. to about 25.0° C. at a pressure of about 61 psia to about 171 psia.

[0007]

[0008] The azeotrope or azeotrope-like composition may be from about 71.5 wt.% to about 98.8 wt.% % 3,3,3-trifluoropropyne (TFPY) and about 1.2 wt.% to about 28.5 wt.% hydrogen fluoride, or may consist essentially of about 83.1 wt.% to about 98.8 wt.% 3,3,3-trifluoropropyne (TFPY) and about 1.2 wt.% to about 16.9 wt.% hydrogen fluoride, wherein the azeotrope or azeotrope-like composition has a boiling point of about -10.0°C to about 25.0°C at a pressure of about 61 psia to about 171 psia.

[0008]

[0009] The present disclosure also provides a method of forming an azeotrope or azeotrope-like composition, the method comprising combining 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) to form an azeotrope or azeotrope-like composition consisting essentially of effective amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF), the azeotrope or azeotrope-like composition having a boiling point of about −10.0° C. to about 25.0° C. at a pressure of about 61 psia to about 171 psia.

[0009]

[0010] The present disclosure further provides a method for separating 3,3,3-trifluoropropyne (TFPY) as an impurity from a composition comprising 3,3,3-trifluoropropyne (TFPY) as a primary compound and 3,3,3-trifluoropropyne (TFPY) as an impurity, the method comprising the steps of providing a composition comprising 3,3,3-trifluoropropyne (TFPY) as a primary compound and 3,3,3-trifluoropropyne (TFPY) as an impurity; varying the relative amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) and subjecting the composition to conditions effective to form an azeotrope or azeotrope-like composition consisting essentially of or consisting of effective amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF); and separating the azeotrope or azeotrope-like composition from the composition comprising the primary compound. The primary compound may be selected from the group consisting of 2-chloro-3,3,3-trifluoropropene (1233xf), 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), and 2,3,3,3-tetrafluoropropene (HFO-1234yf), or may be selected from the group consisting of 1,1,1,2,3-pentafluoropropane (HFC-245eb) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), or may be selected from the group consisting of 1,3,3,3-tetrafluoropropene (HFO-1234ze) and 1,1,1,3,3-pentafluoropropane (HFC-245fa). The separation step may include at least one of phase separation, distillation, and fractionation.

[0010]

[0011] In the above method, varying the relative amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) may involve adding 3,3,3-trifluoropropyne (TFPY) to the composition, adding hydrogen fluoride (HF) to the composition, or adding both 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) to the composition. [Brief explanation of the drawings]

[0011] [Figure 1]

[0012] 1 is a graph showing a plot of gas pressure of mixtures formed according to Example 1 measured at −10° C. and 25° C. DETAILED DESCRIPTION OF THE INVENTION

[0012]

[0013] It has been discovered that 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) form heterogeneous azeotropes and azeotrope-like compositions or mixtures, and the present disclosure provides heterogeneous azeotropes or azeotrope-like compositions comprising 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF). The azeotrope or azeotrope-like composition may consist essentially of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF), or the azeotrope or azeotrope-like composition may consist essentially of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF). , 3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF).

[0013]

[0014] The present inventors have experimentally found that 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) form azeotropes or azeotrope-like compositions.

[0014]

[0015] A heterogeneous azeotrope consists of two liquid phases and one vapor phase, all in equilibrium. At a given temperature and pressure, the composition of each of the two liquid phases and the composition of the vapor phase remain constant. When a heterogeneous azeotrope is formed, at a constant pressure, the boiling point of the heterogeneous azeotrope is lower than that of the lower-boiling component (a "minimum-boiling azeotrope").

[0015]

[0016] An "azeotrope" (or "azeotropic") composition is a unique combination of two or more components. Azeotropes can be either homogeneous (having one liquid phase) or heterogeneous (having two liquid phases). Azeotrope compositions can be characterized in various ways. For example, at a given pressure, an azeotrope composition boils at a characteristic temperature that is either above the higher-boiling component (maximum-boiling azeotrope) or below the lower-boiling component (minimum-boiling azeotrope). However, in the case of heterogeneous azeotropes, the boiling point of the azeotrope is always below the boiling point of the lower-boiling component. At this characteristic temperature, a homogeneous azeotrope has the same composition in both the vapor and liquid phases. In the case of heterogeneous azeotropes, the composition of each of the two liquid phases and the vapor phase remains constant during boiling. Azeotrope compositions do not fractionate upon boiling or evaporation. Therefore, the components of an azeotrope composition cannot separate during a phase transition.

[0016]

[0017] Homogeneous azeotrope compositions are also characterized by the fact that the boiling point pressure of the liquid phase is the same as the dew point pressure of the vapor phase at a particular azeotrope temperature. The behavior of azeotrope compositions contrasts with non-azeotrope compositions, in which the liquid composition changes to a significant degree during boiling or evaporation.

[0017]

[0018] However, those skilled in the art will understand that at different pressures, both the composition and boiling point of an azeotrope composition will vary to some extent. Therefore, depending on temperature and / or pressure, an azeotrope composition may have a variable composition. Therefore, those skilled in the art will understand that a composition range, rather than a fixed composition, can be used to define an azeotrope composition. Furthermore, an azeotrope can be defined in terms of the exact weight percentage of each component of the composition, characterized by a fixed boiling point at a particular pressure.

[0018]

[0019] An "azeotrope-like" composition is a composition of two or more components that behaves substantially as an azeotrope composition. Thus, for purposes of this disclosure, an azeotrope-like composition is a combination of two or more different components that, in the case of a homogeneous azeotrope, when in liquid form at a given pressure, boils at a substantially constant temperature and yields a gas composition substantially identical to the liquid composition undergoing boiling. In the case of a heterogeneous azeotrope, two liquid phases are formed at a given pressure, overlain by a gas composition. Each of the two liquid phases and the gas phase remain substantially constant upon boiling.

[0019]

[0020] For purposes of this disclosure, an azeotrope-like composition is a composition or range of compositions that boils at a temperature range of about -10°C to 25°C and a pressure of about 61 psia to about 171 psia.

[0020]

[0021] Azeotrope or azeotrope-like compositions can be identified using several different methods.

[0022] For purposes of this disclosure, an azeotrope or azeotrope-like composition is an azeotrope-like mixture. (Walas, Phase Equilibria in Chemical Engineering, Butterworth-Heinemann, 1985, pp. 533-544) The ebullometer is designed to provide a highly accurate measurement of the boiling point of a liquid by measuring the temperature of vapor-liquid equilibrium.

[0021]

[0023] The boiling points of each of the components alone are measured at a constant pressure. As those skilled in the art will understand, in a binary azeotrope or azeotrope-like composition, the boiling point of one of the components of the composition is first measured. Then, the second component of the composition is added in various amounts, and the boiling points of each of the resulting compositions are measured using an ebullometer at the constant pressure. In the case of a ternary azeotrope, the initial composition comprises a binary mixture, and the third component is added in various amounts. The boiling points of each of the resulting ternary compositions are measured using an ebullometer at the constant pressure.

[0022]

[0024] The measured boiling points are plotted against the composition of the tested composition, e.g., for binary azeotropes, the amount of the second component added to the composition (expressed as either weight % or mole %). The presence of an azeotrope composition can be identified by the observation of a maximum or minimum boiling point above or below the boiling point of either of the components alone.

[0023]

[0025] As one skilled in the art will understand, the identification of an azeotrope or azeotrope-like composition is made by comparing the boiling point change of the composition upon addition of a second component to the boiling point of the first component, and therefore the system does not need to be calibrated to the reported boiling point of a particular component in order to measure the boiling point change.

[0024]

[0026] As previously discussed, at the maximum or minimum boiling point, the composition of the vapor phase is the same as the composition of the liquid phase. Thus, an azeotrope-like composition is a composition of components that results in a substantially constant minimum or maximum boiling point, i.e., a boiling point of about -10°C to about 25°C, at a pressure of about 61 psia to about 171 psia, and at that substantially constant boiling point, the composition of the vapor phase is substantially the same as the composition of the liquid phase.

[0025]

[0027] The present disclosure provides an azeotrope or azeotrope-like composition comprising effective amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) to form an azeotrope or azeotrope-like composition. As used herein, the term "effective amount" refers to the amount of each component that, when combined with the other component, results in the formation of an azeotrope or azeotrope-like composition.

[0026]

[0028] The azeotrope or azeotrope-like composition may consist essentially of, or may consist of, a combination of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF).

[0027]

[0029] As used herein, the term "consisting essentially of" with respect to components of an azeotrope or azeotrope-like composition or mixture means that the composition contains the indicated components in an azeotropic or azeotrope-like ratio, and may contain additional components, provided that the additional components do not form a new azeotrope or azeotrope-like system. For example, an azeotrope mixture consisting essentially of two compounds is an azeotrope mixture that forms a binary azeotrope, optionally including one or more additional components, provided that the additional components do not render the mixture non-azeotropic and do not form azeotropes with either or both of the compounds (e.g., do not form ternary or higher azeotropes).

[0028]

[0030] The present disclosure provides a method for treating a cancer cell comprising administering to a patient a composition comprising an effective amount of 3,3,3-trifluoropropyne (TFPY) and fluorine. Also provided is a method for forming an azeotrope or azeotrope-like composition by mixing, combining, or blending 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF). Any of a variety of methods known in the art for combining two or more components to form a composition may be used in this method. For example, 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) may be mixed, blended, or otherwise combined by hand and / or machine as part of a batch or continuous reaction and / or process, or by a combination of two or more such steps. The components may be provided in the required amounts, for example, by weighing and then combining the amounts.

[0029]

[0031] The azeotrope or azeotrope-like composition has a boiling point of about −10° C. to about 25° C. at a pressure of about 61 psia to about 171 psia and consists essentially of, or consists of, about 71.5 wt.% to about 98.8 wt.% 3,3,3-trifluoropropyne (TFPY) and about 1.2 wt.% to about 28.5 wt.% hydrogen fluoride (HF).

[0030]

[0032] The azeotrope or azeotrope-like composition having a boiling point of about −10.0° C. to about 25.0° C. at a pressure of about 61 psia to about 171 psia may consist essentially of, or may consist of, about 71.5 wt.% to about 98.8 wt.% 3,3,3-trifluoropropyne (TFPY) and about 1.2 wt.% to about 28.5 wt.% hydrogen fluoride, or may consist essentially of, or may consist of, about 83.1 wt.% to about 98.8 wt.% 3,3,3-trifluoropropyne (TFPY) and about 1.2 wt.% to about 16.9 wt.% hydrogen fluoride (HF), or within any range defined between any two of the foregoing values.

[0031]

[0033] The present disclosure also provides compositions comprising azeotropes or azeotrope-like compositions, such as compositions comprising at least about 14 wt.% azeotrope or azeotrope-like compositions, or at least about 21 wt.% azeotrope or azeotrope-like compositions, or at least about 25 wt.% azeotrope or azeotrope-like compositions, or at least about 70 wt.% azeotrope or azeotrope-like compositions, or at least about 90 wt.% azeotrope or azeotrope-like compositions, or at least 95 wt.% azeotrope or azeotrope-like compositions, or 99 wt.% azeotrope or azeotrope-like compositions.

[0032]

[0034] Disclosed herein are azeotrope or azeotrope-like compositions comprising, consisting essentially of, or consisting of effective amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF), including 2-chloro-3,3,3-trifluoropropene (1233xf), 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), and 2,3,3,3-tetrafluoropropene (HFO-1234yf); Or it can be used to separate 3,3,3-trifluoropropyne (TFPY) as an impurity from other compositions, such as a composition of 1,1,1,2,3-pentafluoropropane (HFC-245eb) and 2,3,3,3-tetrafluoropropene (HFO-1234yf); or a composition of 1,3,3,3-tetrafluoropropene (HFO-1234ze) and 1,1,1,3,3-pentafluoropropane (HFC-245fa).

[0033]

[0035] The preparation of an azeotropic or azeotrope-like composition comprising, consisting essentially of, or consisting of effective amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) enables separation techniques, such as azeotropic distillation, to be used to remove 3,3,3-trifluoropropyne (TFPY) as an impurity from other compositions.

[0034]

[0036] In particular, azeotropes or azeotropes comprising, consisting essentially of, or consisting of effective amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) A mixture-like composition may be formed from a composition comprising one or both of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF), along with one or more other chemical compounds other than 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF), such as, for example, 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb). Following formation of the azeotrope or azeotrope-like composition, the azeotrope or azeotrope-like composition may be separated from the other chemical compounds by a suitable method, such as distillation, phase separation, or fractionation. This procedure may be used to separate 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) from other compounds such as those mentioned above (selected from the group consisting of 2-chloro-3,3,3-trifluoropropene (1233xf), 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), and 2,3,3,3-tetrafluoropropene (HFO-1234yf), or selected from the group consisting of 1,1,1,2,3-pentafluoropropane (HFC-245eb) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), or selected from the group consisting of 1,3,3,3-tetrafluoropropene (HFO-1234ze) and 1,1,1,3,3-pentafluoropropane (HFC-245fa).

[0035]

[0037] In one example, the disclosure provides a method for separating 3,3,3-trifluoropropyne (TFPY) as an impurity from a crude primary composition of 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) containing 3,3,3-trifluoropropyne (TFPY), the method comprising the steps of providing a primary composition of crude 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) and 3,3,3-trifluoropropyne (TFPY) as an impurity; The present invention provides a method comprising the steps of: varying the relative amounts of 3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) and subjecting a primary composition to conditions effective to form a secondary composition that is an azeotrope or azeotrope-like composition consisting essentially of or consisting of effective amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF); and separating the secondary composition from the primary composition by a separation technique, such as phase separation, distillation, or fractionation. The secondary composition may then be subjected to further separation or purification steps to obtain purified 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb). Varying the relative amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) may involve adding 3,3,3-trifluoropropyne (TFPY) to the composition, adding hydrogen fluoride (HF) to the composition, or adding both 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) to the composition.

[0036]

[0038] In another example, a composition may be provided that includes one of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) together with at least one additional compound, to which a sufficient amount of the other of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) is added, and the composition is subjected to conditions effective to form a composition that is an azeotrope or azeotrope-like composition consisting essentially of or consisting of effective amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF), and then the azeotrope or azeotrope-like composition is separated from the additional compound by a separation technique such as, for example, phase separation, distillation, or fractionation.

[0037]

[0039] The following non-limiting examples serve to illustrate the present invention. [Example]

[0038] Example 1 - Vapor-Liquid Equilibrium (VLE) Study

[0040] 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) only Binary compositions containing were blended to form azeotropic mixtures of various weight percent. The gas pressures of these mixtures were measured at -10°C and 25°C. The results were as follows:

[0039]

[0041] PTX measurements of 3,3,3-trifluoropropyne (TFPY) at -10°C and 25°C showed that 3,3,3-trifluoropropyne (TFPY) formed a minimum-boiling azeotrope with hydrogen fluoride (HF). The azeotropic composition was approximately 4 to 5 wt.% hydrogen fluoride (HF). Vapor-liquid equilibrium (VLE) measurements were performed on this system. The gas composition of the system was verified and was consistent with the PTX measurements. This system is considered heterogeneous. The azeotrope composition was only 4 to 5 wt.% hydrogen fluoride (HF) based on the weight of the azeotrope composition. Table 1 below shows the PTX phase equilibrium and gas pressure measurements for 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) at constant temperatures of -10°C and 25°C, depending on the composition with various weight percentages of hydrogen fluoride (HF). The data show that when the gas pressure of a mixture of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) is higher than the gas pressure of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) alone, the mixture is azeotropic or azeotrope-like. The data in Table 1 are presented in graph form in Figure 1.

[0040] [Table 1]

[0041]

[0042] The azeotrope composition is about 4 wt.% at T=-10°C and T=25°C. Example 2 - Gas Sample Studies

[0043] A mixture of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) was prepared with 64.5 wt.% 3,3,3-trifluoropropyne (TFPY) and 35.5 wt.% hydrogen fluoride (HF). Gas samples were collected at -10°C and 25°C. The gas composition was about 4 to about 5 wt.% HF. The results are shown below in Table 2. .

[0042] [Table 2]

[0043]

[0044] The results are consistent with the PTX measurements in Example 1. Example 3 - Separation of 3,3,3-trifluoropropyne (TFPY) as an impurity

[0045] In this example, a composition is provided that contains a primary compound, such as 2-chloro-3,3,3-trifluoropropene (1233xf), 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), or 2,3,3,3-tetrafluoropropene (HFO-1234yf), along with 3,3,3-trifluoropropyne (TFPY) as an impurity. An effective amount of hydrogen fluoride (HF) is added to the composition, and the composition is subjected to conditions effective to form an azeotrope or azeotrope-like composition consisting essentially of or consisting of effective amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF). The azeotrope or azeotrope-like composition is then separated from the composition containing the primary compound by separation techniques such as phase separation, distillation, and / or fractionation.

[0044] Example 4 - Separation of 3,3,3-trifluoropropyne (TFPY) as an impurity

[0046] In this example, a composition is provided that contains a primary compound, such as 2-chloro-3,3,3-trifluoropropene (1233xf), 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), or 2,3,3,3-tetrafluoropropene (HFO-1234yf), along with hydrogen fluoride (HF) and 3,3,3-trifluoropropyne (TFPY) as impurities. An effective amount of 3,3,3-trifluoropropyne (TFPY) is added to the composition, and the composition is subjected to conditions effective to form an azeotrope or azeotrope-like composition consisting essentially of or consisting of effective amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF). The azeotrope or azeotrope-like composition is then separated from the composition containing the primary compound by separation techniques such as phase separation, distillation, and / or fractionation.

[0045] Aspects

[0047] Embodiment 1 is a composition comprising an azeotrope or azeotrope-like composition consisting essentially of effective amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF).

[0046]

[0048] Example 2 is the composition of Example 1, wherein the azeotrope or azeotrope-like composition consists essentially of about 71.5 wt.% to about 98.8 wt.% 3,3,3-trifluoropropyne (TFPY) and about 1.2 wt.% to about 28.5 wt.% hydrogen fluoride.

[0047]

[0049] Embodiment 3 is the composition of Embodiment 1, wherein the azeotrope or azeotrope-like composition consists essentially of about 83.1 wt.% to about 98.8 wt.% 3,3,3-trifluoropropyne (TFPY) and about 1.2 wt.% to about 16.9 wt.% hydrogen fluoride (HF). .

[0048]

[0050] Embodiment 4 is the composition of any of Embodiments 1-3, wherein the azeotrope or azeotrope-like composition has a boiling point of from about -10.0°C to about 25.0°C at a pressure of from about 61 psia to about 171 psia.

[0049]

[0051] Example 5 is the composition of any of Examples 1-4, wherein the azeotrope or azeotrope-like composition consists essentially of or consists of at least about 15 wt.% azeotrope or azeotrope-like composition.

[0050]

[0052] Example 6 is the composition of any of Examples 1-4, wherein the azeotrope or azeotrope-like composition consists essentially of or consists of at least about 50 wt.% azeotrope or azeotrope-like composition.

[0051]

[0053] Example 7 is the composition of any of Examples 1-4, wherein the azeotrope or azeotrope-like composition consists essentially of or consists of at least about 70 wt.% azeotrope or azeotrope-like composition.

[0052]

[0054] Example 8 is the composition of any of Examples 1-4, wherein the azeotrope or azeotrope-like composition consists essentially of, or consists of, at least about 90 wt.% of the azeotrope or azeotrope-like composition.

[0053]

[0055] A ninth aspect is a method of forming an azeotrope or azeotrope-like composition, comprising combining 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) to form an azeotrope or azeotrope-like composition consisting essentially of effective amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF), the azeotrope or azeotrope-like composition having a boiling point of about −10.0° C. to about 25.0° C. at a pressure of about 61 psia to about 171 psia.

[0054]

[0056] Example 10 is the method of Example 9, wherein the combining step comprises combining about 71.5 wt.% to about 98.8 wt.% 3,3,3-trifluoropropyne (TFPY) and about 1.2 wt.% to about 28.5 wt.% hydrogen fluoride (HF).

[0055]

[0057] Example 11 is the method of Example 9, wherein the combining step includes combining about 83.1 wt.% to about 98.8 wt.% 3,3,3-trifluoropropyne (TFPY) and about 1.2 wt.% to about 16.9 wt.% hydrogen fluoride (HF).

[0056]

[0058] Aspect 12 is a method for separating 3,3,3-trifluoropropyne (TFPY) as an impurity from a composition comprising a primary compound and 3,3,3-trifluoropropyne (TFPY) as an impurity, the method comprising: providing a composition comprising 3,3,3-trifluoropropyne (TFPY) as a primary compound and 3,3,3-trifluoropropyne (TFPY) as an impurity; subjecting the composition to conditions effective to vary the relative amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) and to form an azeotrope or azeotrope-like composition consisting essentially of, or consisting of, effective amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF); and separating the azeotrope or azeotrope-like composition from the composition comprising the primary compound.

[0057]

[0059] Example 13 is the method of Example 12, wherein varying the relative amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) comprises adding 3,3,3-trifluoropropyne (TFPY) to the composition.

[0058]

[0060] Example 14 is the method of Example 13, wherein varying the relative amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) comprises adding hydrogen fluoride (HF) to the composition.

[0059]

[0061] Example 15 is the method of Example 14, wherein varying the relative amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) comprises adding both 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) to the composition.

[0060]

[0062] Example 16 is the method of example 12, wherein the primary compound is selected from the group consisting of 2-chloro-3,3,3-trifluoropropene (1233xf), 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), and 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0061]

[0063] Example 17 is the method of example 12, wherein the separating step comprises at least one of phase separation, distillation, and fractionation.

[0064] As used herein, the phrase "within any range defined as between any two of the above values" literally means that any range may be selected from any two of the values ​​listed before such phrase, regardless of whether the values ​​are the lower or higher of the enumeration. For example, a pair of values ​​may be selected from two lower values, two higher values, or a lower and a higher value.

[0062]

[0065] As used herein, the singular forms "a," "an," and "the" include the plural unless the context clearly dictates otherwise. Furthermore, when an amount, concentration, or other value or parameter is given as either a range, a preferred range, or a list of upper and lower preferred values, this should be understood to specifically disclose all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether the ranges are separately disclosed. When a range of numerical values ​​is recited herein, unless otherwise specified, the range is intended to include its endpoints, and all integers and fractions within the range. It is not intended that the scope of the present disclosure be limited to the specific values ​​recited when defining a range.

[0063]

[0066] As used herein, the phrase "within any range defined as between any two of the above values" literally means that any range may be selected from any two of the values ​​listed before such phrase, regardless of whether the values ​​are the lower or higher of the enumeration. For example, a pair of values ​​may be selected from two lower values, two higher values, or a lower and a higher value.

[0064]

[0067] It should be understood that the foregoing specification is only illustrative of the present disclosure. Various alternatives and modifications may be devised by those skilled in the art without departing from the disclosure. Accordingly, the present disclosure is intended to embrace all such alternatives, modifications, and variations that fall within the scope of the appended claims.

Claims

1. A composition comprising an azeotrope or azeotrope-like composition consisting essentially of effective amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF).

2. 3. The composition of claim 1 or 2, wherein the azeotrope or azeotrope-like composition has a boiling point of from about -10.0°C to about 25.0°C at a pressure of from about 61 psia to about 171 psia.

3. 2. The composition of claim 1, wherein the azeotrope or azeotrope-like composition consists essentially of about 71.5 wt.% to about 98.8 wt.% 3,3,3-trifluoropropyne (TFPY) and about 1.2 wt.% to about 28.5 wt.% hydrogen fluoride (HF).

4. 4. The composition of any of claims 1 to 3, wherein the azeotrope or azeotrope-like composition consists essentially of about 83.1 wt.% to about 98.8 wt.% 3,3,3-trifluoropropyne (TFPY) and about 1.2 wt.% to about 16.9 wt.% hydrogen fluoride (HF).

5. 1. A method for forming an azeotrope or azeotrope-like composition, comprising combining 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) to form an azeotrope or azeotrope-like composition consisting essentially of effective amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF), the azeotrope or azeotrope-like composition having a boiling point of about -10.0°C to about 25.0°C at a pressure of about 61 psia to about 171 psia.

6. 6. The method of claim 5, wherein the combining step comprises combining about 71.5 wt.% to about 98.8 wt.% 3,3,3-trifluoropropyne (TFPY) and about 1.2 wt.% to about 28.5 wt.% hydrogen fluoride, or wherein the combining step comprises combining about 83.1 wt.% to about 98.8 wt.% 3,3,3-trifluoropropyne (TFPY) and about 1.2 wt.% to about 16.9 wt.% hydrogen fluoride (HF).

7. A method for separating 3,3,3-trifluoropropyne (TFPY) as an impurity from a composition containing a primary compound and 3,3,3-trifluoropropyne (TFPY) as an impurity, comprising: providing a composition comprising a primary compound and 3,3,3-trifluoropropyne (TFPY) as an impurity; Varying the relative amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) and subjecting the composition to conditions effective to form an azeotrope or azeotrope-like composition consisting essentially of or consisting of effective amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF); separating the azeotrope or azeotrope-like composition from the composition comprising the primary compound; A method comprising:

8. Varying the relative amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) comprises adding 3,3,3-trifluoropropyne (TFPY) to the composition; or Varying the relative amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) comprises adding hydrogen fluoride (HF) to the composition; or Varying the relative amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) may result in the composition containing 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF). adding both hydrogen fluoride (HF) and The method of claim 8.

9. 9. The method of claim 7 or 8, wherein the primary compound is selected from the group consisting of 2-chloro-3,3,3-trifluoropropene (1233xf), 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), and 2,3,3,3-tetrafluoropropene (HFO-1234yf), or selected from the group consisting of 1,1,1,2,3-pentafluoropropane (HFC-245eb) and 2,3,3,3-tetrafluoropropene (HFO-1234yf).

10. 9. The method of claim 7 or 8, wherein the primary compound is selected from the group consisting of 1,3,3,3-tetrafluoropropene (HFO-1234ze) and 1,1,1,3,3-pentafluoropropane (HFC-245fa).

11. 11. The method of any of claims 7 to 10, wherein the separation step comprises at least one of phase separation, distillation, and fractionation.

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