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

Abstract

A heterogeneous azeotrope or azeotrope-like composition comprising 3, 3, 3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) may comprise from about 71.5 wt% to about 98.8 wt% of 3, 3, 3-trifluoropropyne (TFPY) and from about 1.2 wt% to about 28.5 wt% of hydrogen fluoride and have a boiling point of from about-10.0 DEG C to about 25.0 DEG C at a pressure of from about 61 psia to about 171 psia. The azeotrope or azeotrope-like composition may be used to separate 3, 3, 3-trifluoropropyne (TFPY) as an impurity from a composition of 2-chloro-3, 3, 3-trifluoropropene (1233xf), 2-chloro-1, 1, 1, 2-tetrafluoropropane (HCFC-244bb), or 2, 3, 3, 3-tetrafluoropropene (HFO-1234yf).

Description

[0001] The present application is a divisional application of the invention application with application number "202080091838.X" and invention name "Azeotrope or azeotrope-like composition of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF)". Technical Field

[0002] The present disclosure relates to azeotropes or azeotrope-like compositions, and in particular to azeotropes or azeotrope-like compositions comprising effective amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF). Background Art

[0003] 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, pesticide carriers, polymerization media, particle removal fluids, carrier fluids, polishing abrasives, displacement desiccants, and power cycle working fluids. Unlike chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), both of which can damage the Earth's ozone layer, HFOs pose no threat to the ozone layer. HFO-1234yf has also been shown to be a low global warming compound with low toxicity, and therefore can meet the increasingly stringent requirements for refrigerants in mobile air conditioners. Therefore, compositions containing HFO-1234yf are among the materials being developed for use in many of the above-mentioned applications.

[0004] A method for producing HFO-1234yf uses 1,1,2,3-tetrachloropropylene (HCFC-1230xa) as a starting material. The method comprises the following three steps:

[0005] Step (1) 1230xa+3HF→2-chloro-3,3,3-trifluoropropene (1233xf)+3HCl in a gas phase reactor equipped with a solid catalyst;

[0006] Step (2) 1233xf + HF → 2-chloro-1,1,1,2-tetrafluoropropane (244bb) in a liquid phase reactor containing a liquid catalyst; and

[0007] Step (3) 244bb→1234yf+HCl in a gas phase reactor or in a liquid phase.

[0008] During the above processes, 3,3,3-trifluoropropyne (TFPY) is sometimes produced and / or may otherwise be present as an impurity, which is undesirable, and thus methods of reducing the presence of TFPY as well as other impurities are desirable. Summary of the invention

[0009] The present disclosure provides azeotrope or azeotrope-like compositions of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF).

[0010] While it is recognized in the art that it is impossible to predict the formation of azeotropes, the present inventors have unexpectedly discovered that 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) form azeotrope or azeotrope-like compositions, and particularly form heterogeneous azeotrope or azeotrope-like compositions.

[0011] The present disclosure provides a composition comprising an azeotrope or azeotrope-like composition consisting essentially of effective amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF), 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.

[0012] The azeotrope or azeotrope-like composition can consist 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, or can 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.

[0013] The present disclosure also provides a method of forming an azeotrope or azeotrope-like composition, the method comprising the step of 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) and 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.

[0014] The present disclosure further provides a method for separating 3,3,3-trifluoropropyne (TFPY) as an impurity from a composition comprising a main compound and 3,3,3-trifluoropropyne (TFPY) as an impurity, the method comprising the steps of: providing a composition comprising the main 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 an effective amount of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF); and separating the azeotrope or azeotrope-like composition from the composition comprising the main compound. The main compound may be selected from 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 1,1,1,2,3-pentafluoropropane (HFC-245eb) and 2,3,3,3-tetrafluoropropene (HFO-1234yf); or selected from 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.

[0015] In the foregoing method, the step of varying the relative amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) may include 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 DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 is a graph of the vapor pressure of the mixture formed according to Example 1 measured at -10°C and 25°C. DETAILED DESCRIPTION

[0017] It has been found 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 of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF).

[0018] The present inventors have experimentally discovered that 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) form an azeotrope or azeotrope-like composition.

[0019] A heterozeotrope consists of two liquid phases and one vapor phase, all in equilibrium. For a heterozeotrope at a given temperature and pressure, the composition of each of the two liquid phases and the composition of the vapor phase remain constant. If a heterozeotrope is formed, then at constant pressure, the boiling point of the heterozeotrope will be lower than that of the lower boiling component ("minimum boiling azeotrope").

[0020] An "azeotrope" (or "azeotropic") composition is a unique combination of two or more components. Azeotropes can be homogeneous (having one liquid phase) or heterogeneous (having two liquid phases). Azeotropic compositions can be characterized in various ways. For example, at a given pressure, an azeotropic composition boils at a constant characteristic temperature, which is either higher than the higher boiling component (maximum boiling azeotrope) or lower than the lower boiling component (minimum boiling azeotrope). However, in the case of a heterogeneous azeotrope, the boiling point of the azeotrope will always be lower than the boiling point of the lower boiling component. At this characteristic temperature, a homogeneous azeotrope has the same composition in both the vapor phase and the liquid phase. In the case of a heterogeneous azeotrope, then at this characteristic temperature, the composition of each of the two liquid phases and the vapor phase will remain constant when boiling. Azeotropic compositions do not fractionate when boiling or evaporating. Therefore, the components of an azeotropic composition cannot be separated during a phase change.

[0021] A uniform azeotrope composition is also characterized in that at the characteristic azeotrope temperature, the bubble point pressure of the liquid phase is the same as the dew point pressure of the vapor phase. The behavior of an azeotrope composition is opposite to that of a non-azeotrope composition, wherein the liquid composition of the non-azeotrope composition changes to a significant degree during boiling or evaporation.

[0022] However, it will be appreciated by those of ordinary skill in the art that the composition and boiling point of an azeotrope composition will vary to some extent under different pressures. Thus, depending on the temperature and / or pressure, an azeotrope composition may have a variable composition. Thus, it will be appreciated by those of ordinary skill in the art that a composition range rather than a fixed composition may be used to define an azeotrope composition. In addition, an azeotrope may be defined by the precise weight percentages of each component of the composition characterized by a fixed boiling point at a specified pressure.

[0023] An "azeotrope-like" composition is a composition of two or more components that behaves essentially the same as an azeotrope composition. Thus, for purposes of this disclosure, an azeotrope-like composition is a combination of two or more different components that, when in liquid form at a given pressure in the case of a uniform azeotrope, will boil at a substantially constant temperature, and which will provide a vapor composition that is substantially the same as the liquid composition undergoing boiling. In the case of a non-uniform azeotrope, two liquid phases are formed at a given pressure that will be covered by a vapor composition. Each of the two liquid phases and the vapor phase will remain substantially constant when boiling.

[0024] For purposes of the present 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 at a pressure of about 61 psia to about 171 psia.

[0025] Azeotropes or azeotrope-like compositions can be identified using a number of different methods.

[0026] For purposes of the present disclosure, the azeotrope or azeotrope-like compositions are identified experimentally using an ebulliometer (Walas, Phase Equilibria in Chemical Engineering, Butterworth-Heinemann, 1985, 533-544). An ebulliometer is designed to provide an extremely accurate measurement of the boiling point of a liquid by measuring the vapor-liquid equilibrium temperature.

[0027] The boiling points of each component are measured individually at constant pressure. As will be appreciated by those skilled in the art, for binary azeotropes or azeotrope-like compositions, the boiling point of one component of the composition is initially measured. The second component of the composition is then added in varying amounts, and the boiling point of each resulting composition is measured at the constant pressure using an ebulliometer. In the case of a ternary azeotrope, the initial composition will comprise a binary blend, and the third component is added in varying amounts. The boiling point of each resulting ternary composition is measured at the constant pressure using an ebulliometer.

[0028] The measured boiling points are plotted against the composition of the composition tested, e.g., for a binary azeotrope, against the amount of the second component added to the composition (expressed as weight % or mole %). The presence of an azeotrope composition can be identified by observing a maximum or minimum boiling temperature that is higher or lower than the boiling point of any individual component.

[0029] As will be appreciated by those skilled in the art, identification of an azeotrope or azeotrope-like composition is made by comparing the change in boiling point of the composition relative to the boiling point of the first component when a second component is added to the first component. Thus, it is not necessary to calibrate the system to the reported boiling point of a specific component in order to measure the change in boiling point.

[0030] As previously stated, at the highest or lowest boiling point, the composition of the vapor phase will be the same as the composition of the liquid phase. Thus, the azeotrope-like composition is a composition of components that provides a substantially constant lowest or highest 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, at which substantially constant boiling point the composition of the vapor phase will be substantially the same as the composition of the liquid phase.

[0031] 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" is the amount of each component that, when combined with the other component, results in the formation of an azeotrope or azeotrope-like composition.

[0032] The azeotrope or azeotrope-like composition of the present invention can consist essentially of or consist of the combination of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF).

[0033] As used herein, with respect to the components of an azeotrope or azeotrope-like composition or mixture, the term "consisting essentially of" means that the composition comprises the indicated components in azeotropic or azeotrope-like ratios, and may include additional components, provided that the additional components do not form a new azeotrope or azeotrope-like system. For example, azeotropic mixtures consisting essentially of two compounds are those that form a binary azeotrope, which optionally may include one or more additional components, provided that the additional components do not render the mixture non-azeotropic and do not form an azeotrope with either or both of the compounds (e.g., do not form a ternary or higher azeotrope).

[0034] The present disclosure also provides a method for forming an azeotrope or azeotrope-like composition by mixing, combining, or blending an effective amount of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF). Any of the various methods known in the art for combining two or more components to form a composition can be used in the method of the present invention. For example, 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) can be mixed, blended, or otherwise combined as part of an intermittent or continuous reaction and / or process by hand and / or by a machine, or by a combination of two or more such steps. The components can be provided in the desired amounts, for example by weighing and then combining the amounts.

[0035] 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).

[0036] An 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 also consist essentially of, or 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 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.

[0037] The present disclosure also provides compositions comprising the azeotrope or azeotrope-like compositions. For example, compositions comprising at least about 14% by weight of the azeotrope or azeotrope-like compositions, or at least about 21% by weight of the azeotrope or azeotrope-like compositions, or at least about 25% by weight of the azeotrope or azeotrope-like compositions, or at least about 70% by weight of the azeotrope or azeotrope-like compositions, or at least about 90% by weight of the azeotrope or azeotrope-like compositions, or at least 95% by weight of the azeotrope or azeotrope-like compositions, 99% by weight of the azeotrope or azeotrope-like compositions are provided.

[0038] The azeotrope or azeotrope-like compositions disclosed herein comprising, consisting essentially of, or consisting of effective amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) can be used to separate 3,3,3-trifluoropropyne (TFPY) as an impurity from other compositions, such as compositions 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 1,1,1,2,3-pentafluoropropane (HFC-245eb) and 2,3,3,3-tetrafluoropropene (HFO-1234yf); or 1,3,3,3-tetrafluoropropene (HFO-1234ze) and 1,1,1,3,3-pentafluoropropane (HFC-245fa).

[0039] The preparation of azeotropic or azeotrope-like compositions comprising, consisting essentially of, or consisting of effective amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) allows separation techniques such as azeotropic distillation to be used to remove 3,3,3-trifluoropropyne (TFPY) as an impurity from other compositions.

[0040] In particular, an azeotrope or azeotrope-like composition comprising, consisting essentially of, or consisting of effective amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) can be formed from a composition comprising one or both of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) and one or more other compounds other than 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF), such as 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb). After the azeotrope or azeotrope-like composition is formed, the azeotrope or azeotrope-like composition can be separated from the other compounds by a suitable method, such as by distillation, phase separation, or fractional distillation. This process can be used to separate 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) from other compounds, such as those mentioned above (compounds selected from 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 1,1,1,2,3-pentafluoropropane (HFC-245eb) and 2,3,3,3-tetrafluoropropene (HFO-1234yf); or selected from 1,3,3,3-tetrafluoropropene (HFO-1234ze) and 1,1,1,3,3-pentafluoropropane (HFC-245fa)).

[0041] In one example, the present disclosure provides a method for separating 3,3,3-trifluoropropyne (TFPY) as an impurity from a primary crude 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), 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 primary composition to conditions effective to form a secondary composition, the secondary composition being 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 fractional distillation. Thereafter, the secondary composition may be subjected to further separation or purification steps to obtain purified 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb). The step of varying the relative amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) may comprise 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.

[0042] In another example, a composition can be provided, the composition comprising one of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF), and at least one additional compound. A sufficient amount of the other of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) is added to the composition, and the composition is subjected to conditions effective to form a composition that is an azeotrope or azeotrope-like composition, the 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 phase separation, distillation, or fractional distillation.

[0043] The following non-limiting examples serve to illustrate the invention.

[0044] Example

[0045] Example 1 - Vapor Liquid Equilibrium (VLE) Study

[0046] Binary compositions containing only 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) were blended to form azeotropic mixtures of varying weight percentages. The vapor pressures of these mixtures were measured at -10°C and 25°C. The results are as follows.

[0047] The PTX measurements of 3,3,3-trifluoropropyne (TFPY) at -10°C and 25°C show that 3,3,3-trifluoropropyne (TFPY) forms a minimum boiling azeotrope with hydrogen fluoride (HF). The azeotropic composition is about 4-about 5% by weight of hydrogen fluoride (HF). The system was subjected to a vapor-liquid equilibrium (VLE) measurement. The vapor composition of the system was verified, and it was consistent with the result of the PTX measurement. The system is considered to be a non-uniform system. Based on the weight of the azeotropic composition, the azeotropic composition is only 4-5% by weight of hydrogen fluoride (HF). Table 1 below shows the PTX phase equilibrium and vapor pressure measurements of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) at a constant temperature of -10°C and 25°C as a function of the composition with different weight percentages of hydrogen fluoride (HF). The data show that when the vapor pressure of a mixture of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) is higher than the vapor pressure of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) alone, the mixture is azeotropic or azeotrope-like. The data of Table 1 are shown in graphical form at Figure 1 middle.

[0048] Table 1

[0049] PTX of 3,3,3-trifluoropropyne (TFPY) / HF at -10°C and 25°C

[0050]

[0051]

[0052] At T = -10°C and T = 25°C, the azeotropic composition is about 4% by weight.

[0053] Example 2 - Vapor Sample Study

[0054] A mixture of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) was prepared having 64.5 wt% 3,3,3-trifluoropropyne (TFPY) and 35.5 wt% hydrogen fluoride (HF). Vapor samples were collected at -10°C and 25°C. The composition of the vapor was about 4 to about 5 wt% HF. The results are shown in Table 2 below.

[0055] Table 2

[0056] sample Sample weight Temperature(℃) Pressure (Psia) wt% HF VAP] 0.565 -10.09 58.28 4.2 VAP2 0.57 -10.09 58.24 4.05 VAP3 0.563 24.873 160.57 4.86 VAP4 0.564 24.873 160.53 5.01

[0057] The results are consistent with the PTX measurements in Example 1.

[0058] Example 3 - Separation of 3,3,3-trifluoropropyne (TFPY) as an impurity

[0059] In this embodiment, a composition is provided, which comprises a major 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), and 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, which consists essentially of or consists of an effective amount of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF). The azeotrope or azeotrope-like composition is then separated from the composition comprising the major compound by separation techniques such as phase separation, distillation and / or fractional distillation.

[0060] Example 4 - Separation of 3,3,3-trifluoropropyne (TFPY) as an impurity

[0061] In this embodiment, a composition is provided, which comprises a major 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), and 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, which consists essentially of or consists of an effective amount of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF). The azeotrope or azeotrope-like composition is then separated from the composition comprising the major compound by separation techniques such as phase separation, distillation and / or fractional distillation.

[0062] aspect

[0063] Aspect 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).

[0064] Aspect 2 is a composition according to aspect 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.

[0065] Aspect 3 is a composition according to aspect 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).

[0066] Aspect 4 is a composition according to any one of aspects 1-3, 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.

[0067] Aspect 5 is the composition of any one of aspects 1-4, wherein the azeotrope or azeotrope-like composition consists essentially of or consists of at least about 15 weight percent of the azeotrope or azeotrope-like composition.

[0068] Aspect 6 is the composition of any one of aspects 1-4, wherein the azeotrope or azeotrope-like composition consists essentially of or consists of at least about 50 weight percent of the azeotrope or azeotrope-like composition.

[0069] Aspect 7 is the composition of any one of aspects 1-4, wherein the azeotrope or azeotrope-like composition consists essentially of or consists of at least about 70 weight percent of the azeotrope or azeotrope-like composition.

[0070] Aspect 8 is the composition of any one of aspects 1-4, wherein the azeotrope or azeotrope-like composition consists essentially of or consists of at least about 90 weight percent of the azeotrope or azeotrope-like composition.

[0071] Aspect 9 is a method of forming an azeotrope or azeotrope-like composition comprising the step of 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) and 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.

[0072] Aspect 10 is a method according to aspect 9, wherein the combining step comprises combining about 71.5 wt % to about 98.8 wt % of 3,3,3-trifluoropropyne (TFPY) and about 1.2 wt % to about 28.5 wt % of hydrogen fluoride (HF).

[0073] Aspect 11 is a method according to aspect 9, wherein the combining step comprises combining about 83.1 wt % to about 98.8 wt % of 3,3,3-trifluoropropyne (TFPY) and about 1.2 wt % to about 16.9 wt % of hydrogen fluoride (HF).

[0074] Aspect 12 is a method for separating 3,3,3-trifluoropropyne (TFPY) as an impurity from a composition comprising a main compound and 3,3,3-trifluoropropyne (TFPY) as an impurity, the method comprising the steps of: providing a composition comprising the main compound and 3,3,3-trifluoropropyne (TFPY) as an impurity; changing 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 an effective amount of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF); and separating the azeotrope or azeotrope-like composition from the composition comprising the main compound.

[0075] Aspect 13 is a method according to aspect 12, wherein the step of changing the relative amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) comprises adding 3,3,3-trifluoropropyne (TFPY) to the composition.

[0076] Aspect 14 is a method according to aspect 13, wherein the step of changing the relative amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) comprises adding hydrogen fluoride (HF) to the composition.

[0077] Aspect 15 is a method according to aspect 14, wherein the step of changing 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.

[0078] Aspect 16 is a method according to aspect 12, wherein the main compound is selected from 2-chloro-3,3,3-trifluoropropene (1233xf), 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) and 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0079] Aspect 17 is a method according to aspect 12, wherein the separation step comprises at least one of phase separation, distillation and fractionation.

[0080] As used herein, the phrase "within any range defined between any two of the preceding values" literally means any range that can be selected from any two values ​​listed before such phrase, regardless of whether the values ​​are in the lower part of the list or in the upper part of the list. For example, a pair of values ​​can be selected from two lower values, two higher values, or one lower value and one higher value.

[0081] As used herein, the singular forms "a", "an" and "the" include plural forms unless the context clearly dictates otherwise. In addition, when an amount, concentration or other value or parameter is given as a range, a preferred range or a list of preferred upper values ​​and preferred lower values, this should be understood as specifically disclosing all ranges formed by any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether a range is disclosed individually. When a numerical range is cited herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within the range. When a range is defined, the disclosed range is not intended to be limited to the specific values ​​recited.

[0082] As used herein, the phrase "within any range defined between any two of the preceding values" literally means any range that can be selected from any two values ​​listed before such phrase, regardless of whether the values ​​are in the lower part of the list or in the upper part of the list. For example, a pair of values ​​can be selected from two lower values, two higher values, or one lower value and one higher value.

[0083] It should be understood that the foregoing description is only an illustration of the present disclosure. Those skilled in the art may come up with various substitutions and modifications without departing from the present disclosure. Therefore, the present disclosure is intended to cover all such substitutions, 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. The composition of claim 1 or claim 2, 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.

3. 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. The composition of any one 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. A method of forming an azeotrope or azeotrope-like composition comprising the step of 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) and 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. 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 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 comprising a main compound and 3,3,3-trifluoropropyne (TFPY) as an impurity, the method comprising the following steps: Providing a composition comprising the main 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 The azeotrope or azeotrope-like composition is separated from the composition comprising the principal compound.

8. The method of claim 8, wherein the step of 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 wherein the step of varying the relative amounts of 3,3,3-trifluoropropyne (TFPY) and hydrogen fluoride (HF) comprises adding hydrogen fluoride (HF) to the composition; or The step of 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.

9. The method according to claim 7 or claim 8, wherein the main compound is selected from 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 1,1,1,2,3-pentafluoropropane (HFC-245eb) and 2,3,3,3-tetrafluoropropene (HFO-1234yf).

10. The method according to claim 7 or claim 8, wherein the main compound is selected from 1,3,3,3-tetrafluoropropene (HFO-1234ze) and 1,1,1,3,3-pentafluoropropane (HFC-245fa).

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

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