Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/38—Separation; Purification; Stabilisation; Use of additives
  • C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C19/00—Acyclic saturated compounds containing halogen atoms
  • C07C19/01—Acyclic saturated compounds containing halogen atoms containing chlorine

Definitions

• the present invention pertains to azeotropic or azeotrope-like compositions of 1,1,1,3,3-pentachloropropane (HCC-240fa or 240fa) and hydrogen fluoride (HF).
• HCC-240fa or 240fa 1,1,1,3,3-pentachloropropane
• HF hydrogen fluoride
• Chlorofluorocarbon (CFC) based chemicals have been widely use in industry in a variety of different applications including as refrigerants, aerosol propellants, blowing agents and solvents, among others.
• CFCs are suspected of depleting the Earth's ozone layer.
• more environmentally friendly substitutes have been introduced as replacements for CFCs.
• 1,1,1,3,3-pentafluoropropane (HFC-245fa) is recognized as having favorable physical properties for certain industrial applications, such as foam blowing agents and solvents, and therefore is consider to be a good substitute for the CFCs previously used for these applications.
• hydro fluorocarbons including HFC-245fa
• hydrofluorocarbons including HFC-245fa
• hydrofluorocarbons including HFC-245fa
• the compound l-chloro-3,3,3-trifluoropropene also known as HCFO-1233zd or simply 1233zd, is a candidate for replacing HFC-245fa in some applications, including uses as blowing agents and solvents. 1233zd has a Z-isomer and an E-isomer.
• pure 1233zd (E), pure 1233zd (Z), or certain mixtures of the two isomers may be suitable for particular applications as refrigerants, propellants, blowing agents, solvents, or for other uses.
• the compound 1,1,1,2,3-pentachloropropane (240fa) is a reactant useful in the production of both 245fa and 1233zd.
• Processes for making these compounds are well known in the art. See for example, U.S. Patent Nos. 5,763,706 and 6,844,475. See also, U.S. Patent Publication No. 2011-0201853, which provides an integrated process and methods of producing 1233zd (E).
• This intermediate once formed, may thereafter be separated into its component parts, for example, by extraction or distillation techniques.
• HCC-240fa has a boiling point of about 178.5°C
• HF has a boiling point of about 20°C at standard atmospheric pressure.
• These azeotropic or azeotrope-like compositions find use not only as reactor feeds in the production of 245fa and 1233zd, but they are additionally useful as solvent compositions useful for removing surface oxidation from metals.
• the present invention is directed to azeotropic or azeotrope-like mixtures of 1,1,1,3,3-pentachloropropane (240fa) and hydrogen fluoride. Such compositions are useful as an intermediate in the production of HFC-245fa and HCFO-1233zd.
• the composition comprises effective amounts of 1,1,1, 3,3-pentachloro-propane (240fa) and hydrogen fluoride (HF).
• the azeotropic or azeotrope-like composition of the invention consists essentially of from about 90 to about 97 weight percent hydrogen fluoride and from about 10 to about 3 weight percent 1,1,1,3,3-pentachloropropane (240fa), which composition has a boiling point of about 24°C to about 60°C at pressure of about 17.8 psia to pressure of about 55.4 psia.
• the composition consists of hydrogen fluoride and 1,1,1,3,3-pentachloropropane (240fa).
• the composition comprises from about 99 to about 1 weight percent HF.
• the composition comprises from about 40 weight percent to about 97 weight percent HF.
• the composition comprises from about 60 to about 3 weight percent 240fa.
• the composition comprises from about 90 weight percent to about 95 weight percent 240fa.
• the composition comprises from about 10 weight percent to about 5 weight percent 240fa.
• the composition has a boiling point of about from 24°C to about 60°C at a pressure from about 17.8 psia to about 55.4 psia.
• the invention is directed to an azeotropic or azeotrope-like composition having about 92 + 2 weight percent HF and about 8 + 2 weight percent 240fa has a boiling point of about 24°C at 17.8 psia.
• Another aspect of the present invention is directed to a method of forming an azeotropic or azeotrope-like composition which comprises blending hydrogen fluoride and 1,1,1,3,3-pentachloropropane (240fa), which composition has a boiling point of about 24°C to about 60°C at pressure of about 17.8 psia to pressure of about 55.4 psia.
• 240fa 1,1,1,3,3-pentachloropropane
• the composition consists essentially of from about 90 to about 97 weight percent hydrogen fluoride and from about 10 to about 3 weight percent 1,1,1,3,3-pentachloropropane (240fa).
• the composition consists of hydrogen fluoride and 1,1,1,3,3-pentachloropropane (240fa).
• the composition consists essentially of about 92 + 2 weight percent HF and about 8 + 2 weight percent 240fa and has a boiling point of about 24°C at 17.8 psia.
• Another aspect of the present invention is directed to a method of forming a heterogeneous azeotropic or azeotrope-like composition which comprises blending from about 0.2 to about 97 weight percent hydrogen fluoride and from about 99.8 to about 3 weight percent 1,1,1,3,3-pentachloropropane (240fa), which composition has a boiling point of about from 24°C to about 60°C at pressure of about from 17.8 psia to about 55.4 psia.
• the composition comprises from about 99 to about 1 weight percent HF.
• the composition comprises from about 40 weight percent to about 97 weight percent HF.
• the composition comprises from about from about 90 to about 97 weight percent HF.
• the composition comprises from about 60 to about 3 weight percent 240fa.
• the composition comprises from about 90 weight percent to about 95 weight percent 240fa.
• the composition comprises from about 10 weight percent to about 3 weight percent 240fa.
• the composition has a boiling point of about from 24°C to about 60°C at a pressure from about 17.8 psia to about 55.4 psia.
• Another aspect of the present invention is directed to a method of separating 240fa from the azeotropic like mixture of 240fa and HF comprising the step of extracting the HF from the mixture.
• the extraction of HF is accomplished using water or other aqueous solution.
• the extraction of HF is accomplished using sulfuric acid. In certain embodiments of this method, the extraction of HF is accomplished by distillation.
• the distillation comprises extractive distillation.
• the distillation comprises pressure swing distillation.
• Figure 1 shows a plot of the vapor pressures of the mixtures formed in Example 1 and Example 2 as measured at 30°C and 60°C.
• the present invention provides a heterogeneous azeotropic composition consisting essentially of 1,1,1,1,3-pentachloropropane (240fa) and hydrogen fluoride (HF).
• the invention further provides an azeotropic or azeotrope-like composition which consists essentially of from about 90 to about 97 weight percent hydrogen fluoride and from about 10 to about 3 weight percent 1,1,1,3,3-pentachloropropane (240fa), which composition has a boiling point of about 24°C to about 60°C at pressure of about 17.8 psia to pressure of about 55.4 psia.
• azeotropic or azeotrope-like composition which consists essentially of from about 90 to about 97 weight percent hydrogen fluoride and from about 10 to about 3 weight percent 1,1,1,3,3-pentachloropropane (240fa), which composition has a boiling point of about 24°C to about 60°C at pressure of about 17.8 psia to pressure of about 55.4 psia.
• the invention also provides a method of forming a heterogeneous azeotropic or azeotrope-like composition which consists essentially of blending from about 0.2 to about 97 weight percent hydrogen fluoride and from about 99.8 to about 3 weight percent 1,1,1,3,3-pentachloropropane (240fa), which composition has a boiling point of about - from 24°C to about 60°C at pressure of about from 17.8 psia to about 55.4 psia.
• 1,1,1,3,3-pentachloropropane (240fa) and HF were added to a vessel, it was observed that 240fa forms an azeotropic or azeotrope-like mixture with HF.
• the unreacted 240fa/HF intermediate was found in the vapor space of the vessel.
• thermodynamic state of a fluid is defined by its pressure, temperature, liquid composition and vapor composition.
• the liquid composition and vapor phase are essentially equal at a given temperature and pressure. In practical terms this means that the components cannot be separated during a phase change.
• an azeotrope is a liquid mixture that exhibits a maximum or minimum boiling point relative to the boiling points of surrounding mixture compositions.
• An azeotrope or an azeotrope-like composition is an admixture of two or more different components which, when in liquid form under given pressure, will boil at a substantially constant temperature, which temperature may be higher or lower than the boiling temperatures of the components and which will provide a vapor composition essentially identical to the liquid composition undergoing boiling.
• azeotropic compositions are defined to include azeotrope-like compositions, which means, a composition that behaves like an azeotrope, i.e., has constant-boiling characteristics or a tendency not to fractionate upon boiling or evaporation.
• azeotrope-like compositions which means, a composition that behaves like an azeotrope, i.e., has constant-boiling characteristics or a tendency not to fractionate upon boiling or evaporation.
• the composition of the vapor formed during boiling or evaporation is the same as or substantially the same as the original liquid composition.
• the liquid composition if it changes at all, changes only to a minimal or negligible extent. This is in contrast with non-azeotrope-like compositions in which during boiling or evaporation, the liquid composition changes to a substantial degree.
• the essential features of an azeotrope or an azeotrope-like composition are that at a given pressure, the boiling point of the liquid composition is fixed and that the composition of the vapor above the boiling composition is essentially that of the boiling liquid composition, i.e., essentially no fractionation of the components of the liquid composition takes place. Both the boiling point and the weight percentages of each component of the azeotropic composition may change when the azeotrope or azeotrope-like liquid composition is subjected to boiling at different pressures.
• an azeotrope or an azeotrope-like composition may be defined in terms of the relationship that exists between its components or in terms of the compositional ranges of the components or in terms of exact weight percentages of each component of the composition characterized by a fixed boiling point at a specified pressure.
• the present invention provides a composition which comprises effective amounts of hydrogen fluoride and 240fa to form an azeotropic or azeotrope-like composition.
• effective amount is meant an amount of each component which, when combined with the other component, results in the formation of an azeotrope or azeotrope-like mixture.
• inventive compositions preferably are binary azeotropes which consist essentially of combinations of only hydrogen fluoride with 240fa.
• the inventive composition contains from about 99 to about 1 weight percent HF, preferably from about 1 weight percent to about 99 weight percent and most preferably from about 40 weight percent to about 97 weight percent. In the preferred embodiment, the inventive composition contains from about 60 to about 3 weight percent 240fa preferably from about 90 weight percent to about 95 weight percent and most preferably from about 10 weight percent to about 5 weight percent.
• the composition of the present invention has a boiling point of about from 24°C to about 60°C at a pressure from about 17.8 psia to about 55.4 psia.
• An azeotropic or azeotrope- like composition having about 92 + 2 weight percent HF and about 8 + 2 weight percent 240fa has been found to boil at about 24°C and 17.8 psia.
• Binary compositions containing solely 1,1,1,3,3-pentachloropropane (240fa) and HF are blended to form a heterogeneous azeotrope mixtures at different compositions.
• the vapor pressures of the mixtures are measured at about 29.9°C, 30°C and 60°C and the following results are noticed.
• Tables 1 and 2 show the vapor pressure measurement of 240fa and HF as a function of composition of weight percent HF at constant temperatures of about 29.9°C, 30°C and 60°C.
• variation of the amount of HF in the composition shows no significant (+/- 0.3 psia or less) change in pressure at 30°C, and similarly no significant change in pressure (+/- 0.8 psia) at 60°C, supporting the azeotrope-like nature of the composition over this range of HF in the composition.
• the azeotropic composition of the 240fa/HF mixture is also verified by Vapor- Liquid -Liquid Equilibrium (VLLE) experiment.

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• 2012
  • 2012-02-23 US US13/402,983 patent/US8999909B2/en active Active
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