GB2546129A - Composition - Google Patents
Composition Download PDFInfo
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- GB2546129A GB2546129A GB1616785.0A GB201616785A GB2546129A GB 2546129 A GB2546129 A GB 2546129A GB 201616785 A GB201616785 A GB 201616785A GB 2546129 A GB2546129 A GB 2546129A
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- 239000000203 mixture Substances 0.000 title claims abstract description 171
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 claims abstract description 98
- 238000000034 method Methods 0.000 claims abstract description 39
- 238000004378 air conditioning Methods 0.000 claims abstract 4
- 238000005057 refrigeration Methods 0.000 claims abstract 3
- 238000001816 cooling Methods 0.000 claims abstract 2
- 238000010438 heat treatment Methods 0.000 claims abstract 2
- 238000000926 separation method Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims 6
- 229920001515 polyalkylene glycol Polymers 0.000 claims 4
- -1 polyol esters Chemical class 0.000 claims 4
- 239000000314 lubricant Substances 0.000 claims 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims 2
- 238000001704 evaporation Methods 0.000 claims 2
- 239000003063 flame retardant Substances 0.000 claims 2
- 239000005431 greenhouse gas Substances 0.000 claims 2
- 229920001289 polyvinyl ether Polymers 0.000 claims 2
- 239000003381 stabilizer Substances 0.000 claims 2
- QTHRIIFWIHUMFH-UHFFFAOYSA-N 3-chloropropyl dihydrogen phosphate Chemical compound OP(O)(=O)OCCCCl QTHRIIFWIHUMFH-UHFFFAOYSA-N 0.000 claims 1
- 239000004604 Blowing Agent Substances 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 239000005696 Diammonium phosphate Substances 0.000 claims 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical class O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- PQYJRMFWJJONBO-UHFFFAOYSA-N Tris(2,3-dibromopropyl) phosphate Chemical compound BrCC(Br)COP(=O)(OCC(Br)CBr)OCC(Br)CBr PQYJRMFWJJONBO-UHFFFAOYSA-N 0.000 claims 1
- 239000000443 aerosol Substances 0.000 claims 1
- 229910000410 antimony oxide Inorganic materials 0.000 claims 1
- 150000001491 aromatic compounds Chemical class 0.000 claims 1
- 150000001555 benzenes Chemical class 0.000 claims 1
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical class BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000002681 cryosurgery Methods 0.000 claims 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims 1
- 235000019838 diammonium phosphate Nutrition 0.000 claims 1
- 239000003989 dielectric material Substances 0.000 claims 1
- 150000001993 dienes Chemical group 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 claims 1
- 150000002118 epoxides Chemical class 0.000 claims 1
- 150000002334 glycols Chemical class 0.000 claims 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical class IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims 1
- 239000003589 local anesthetic agent Substances 0.000 claims 1
- 239000002480 mineral oil Substances 0.000 claims 1
- 235000010446 mineral oil Nutrition 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical class [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims 1
- 239000008188 pellet Substances 0.000 claims 1
- 150000002989 phenols Chemical class 0.000 claims 1
- 235000021317 phosphate Nutrition 0.000 claims 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 1
- 229920013639 polyalphaolefin Polymers 0.000 claims 1
- 229920005862 polyol Polymers 0.000 claims 1
- 229920000915 polyvinyl chloride Chemical class 0.000 claims 1
- 239000004800 polyvinyl chloride Chemical class 0.000 claims 1
- 238000010248 power generation Methods 0.000 claims 1
- 239000003380 propellant Substances 0.000 claims 1
- 238000009420 retrofitting Methods 0.000 claims 1
- 229920002545 silicone oil Polymers 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 230000001629 suppression Effects 0.000 claims 1
- VPAYJEUHKVESSD-UHFFFAOYSA-N trifluoroiodomethane Chemical compound FC(F)(F)I VPAYJEUHKVESSD-UHFFFAOYSA-N 0.000 claims 1
- DHNUXDYAOVSGII-UHFFFAOYSA-N tris(1,3-dichloropropyl) phosphate Chemical compound ClCCC(Cl)OP(=O)(OC(Cl)CCCl)OC(Cl)CCCl DHNUXDYAOVSGII-UHFFFAOYSA-N 0.000 claims 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 238000004140 cleaning Methods 0.000 abstract 1
- 238000000605 extraction Methods 0.000 abstract 1
- 238000009835 boiling Methods 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- OQISUJXQFPPARX-UHFFFAOYSA-N 2-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C(Cl)=C OQISUJXQFPPARX-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
- C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
- C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
- C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/122—Halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/126—Unsaturated fluorinated hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Azeotropic or near-azeotropic compositions comprising CH2CClCF3 (1233xf) and CF3CH2CF2H (245fa) and processes of separating and using such compositions e.g as a heat transfer composition. The composition may be used in a heat transfer device e.g. automotive air conditioning systems, chiller refrigeration systems. Also shown are methods of cooling, heating, extraction and cleaning using the composition.
Description
Composition
The present invention relates to azeotropic or near-azeotropic compositions comprising CF3CH2CF2H (245fa) and CF3CCICH2(1233xf) along with uses thereof of such compositions. 1.1.1.3.3- pentafluoropropane is also known as 245fa. Hereinafter, unless otherwise stated, 1.1.1.3.3- pentafluoropropane will be referred to as 245fa. 2-chloro-3,3,3-trifluoropropene is also known as 1233xf. Hereinafter, unless otherwise stated, 2-chloro-3,3,3-trifluoropropene will be referred to as 1233xf.
The listing or discussion of a prior-published document in this specification should not necessarily be taken as an acknowledgement that the document is part of the state of the art or is common general knowledge.
The present invention provides azeotropic or near-azeotropic compositions comprising 245fa and 1233xf.
Also provided by the invention is the use of such azeotropic or near-azeotropic compositions (e.g. as an intermediate) in the manufacture of one or more hydrofluoroolefins.
Further provided by the invention is the use of such azeotropic or near-azeotropic compositions (e.g., as an intermediate) in the manufacture of 2,3,3,3-tetrafluoropropene (1234yf) and/or 1,3,3,3-tetrafluoropropene (1234ze) and/or 2-chloro-3,3,3-trifluoropropene (1233xf).
Also provided is a process for the separation of an azeotropic or near-azeotropic composition of the invention.
Compositions of the Invention
In a first aspect, the invention provides an azeotropic or near-azeotropic composition comprising CF3CH2CF2H (245fa) and CF3CCICH2(1233xf).
In an embodiment, the azeotropic composition of the invention consists essentially of 245fa and 1233xf. In a further embodiment, the composition consists of 245fa and 1233xf.
By azeotrope or azeotropic composition, we mean a preferably binary composition which at vapour-liquid equilibrium has the same composition in both the liquid and vapour phase, and whose boiling point is lower than that of either of the pure components. By near-azeotrope or near-azeotropic composition (e.g. a near-azeotropic composition of 245fa and 1233xf), we mean a composition that behaves similarly to an azeotrope composition (i.e. the composition has constant boiling characteristics or a tendency not to fractionate upon boiling), but may not have all of the properties of an azeotrope, for example binary liquid compositions whose vapour pressure is above that of the pure component with the lower boiling point (e.g. 1233xf compared to 245fa) when measured at equivalent temperature, but whose equilibrium vapour composition may differ from the liquid composition.
In essence, at a given pressure, a boiling azeotrope or near azeotrope composition has substantially the same constituent proportions in the vapour phase as in the boiling liquid phase. This means that no (or substantially no) fractionation of the components in the liquid composition takes place.
Preferably, the azeotropic or near-azeotropic composition of the invention comprises, or preferably consists of, about 10 mol% to about 99 mol% 245fa and from about 90 mol% to about 1 mol% 1233xf. Alternatively, the azeotropic or near-azeotropic composition of the invention comprises, or preferably consists of, from about 20 mol% to about 99 mol% 245fa and from about 80 mol% to about 1 mol% 1233xf, such as about 30 mol% to about 99 mol% 245fa and from about 70 mol% to about 1 mol% 1233xf, for example about 30 mol% to about 98 mol% 245fa and from about 70 mol% to about 2 mol% 1233xf, preferably about 30 mol% to about 90 mol% 245fa and from about 70 mol% to about 10 mol% 1233xf, such as from about 30 mol% to about 80 mol% 245fa and from about 70 mol% to about 20 mol% 1233xf, for example from about 30 mol% to about 70 mol% 245fa and from about 70 mol% to about 30 mol% 1233xf, for instance from about 30 mol% to about 60 mol% 245fa and from about 70 mol% to about 40 mol% 1233xf, such as from about 35 mol% to about 60 mol% 245fa and from about 65 mol% to about 40 mol% 1233xf, for example from about 36 mol% to about 60 mol% 245fa and from about 64 mol% to about 40 mol% 1233xf, such as from about 40 mol% to about 60 mol% 245fa and from about 60 mol% to about 40 mol% 1233xf and conveniently from about 40 mol% to about 50 mol% 245fa and from about 50 mol% to about 60 mol% 1233xf.
In an embodiment, the azeotropic or near-azeotropic composition of the invention is present at temperatures of from about -20°C to about +80°C, such as from about from about 0°C to about +80°C, preferably from temperatures of from about +40°C to about +80°C.
In a further embodiment, the azeotropic or near-azeotropic composition of the invention is present at pressures of from about 0.5 bara to about 30 bara, for example from about 0.5 to about 20 bara.
In a preferred embodiment, the azeotropic or near-azeotropic composition of the invention comprises from about 30 mol% to about 60 mol% 245fa and from about 70 mol% to about 40 mol% 1233xf, wherein the azeotropic or near-azeotropic composition is present at temperatures of between about -20°C to about +80°C and pressures of between about 0.5 bara to about 20 bara.
In some embodiments, the azeotropic or near-azeotropic composition comprises from about 30 mol% to about 60 mol% 245fa and from about 70 mol% to about 40 mol% 1233xf at temperatures of about -20°C to about +80°C and pressures of about 0.26 bara to about 8.4 bara. In further embodiments, the azeotropic or near-azeotropic composition comprises from about 40 mol% to about 60 mol% 245fa and from about 60 mol% to about 40 mol% 1233xf at temperatures of about 0°C to about 80°C and pressures of about 0.66 bara to about 8.4 bara. In further embodiments, the azeotropic or near-azeotropic composition comprises from about 60 mol% to about 50 mol% 245fa and from about 50 mol% to about 40 mol% 1233xf at temperatures of from about 40°C to about 80°C and pressures of about 2.9 bara to about 8.4 bara.
In another aspect, the invention provides the use of an azeotropic or near-azeotropic composition comprising CF3CH2CF2H (245fa) and CF3CCICH2 (1233xf) (e.g. as an intermediate) in the manufacture of one or more hydrofluoroolefins. For example, the azeotropic or near-azeotropic composition of the invention has been found to be particularly useful in the manufacture of 1234yf and/or 1234ze and/or 2-chloro-3,3,3-trifluoropropene (1233xf).
In a further aspect, the invention provides a process for the separation of an azeotropic or near-azeotropic composition comprising CF3CH2CF2H (245fa) and CF3CCICH2 (1233xf) comprising separating the composition via the use of a pressure swing apparatus. Such pressure swing apparatus set-ups may comprise at least two columns, which may be operated sequentially at different pressures. Similarly, the columns may be operated sequentially at two different temperatures.
In an embodiment, a first column A may be operated at a pressure of from about 0.1 to about 15 bara, such as from about 0.1 to about 5 bara, preferably from about 0.1 to about 2 bara, for example about 0.5 bara.
In a further embodiment, a second column B may be operated at a pressure of from about 1 to about 20 bara, such as from about 5 to about 20 bara, preferably from about 10 to about 20 bara, for example about 10 bara.
In another embodiment, column A is operated at a temperature of from about -50°C to about 50°C, such as from about -25°C to about 25°C, preferably from about -10°C to about 0°C. In one embodiment, a temperature gradient exists in column A where the temperature varies from about -1 °C at one end of the column to about -6°C at the other end.
In another embodiment, column B is operated at a temperature of from about 50°C to about 150°C, such as from about 75°C to about 125°C, preferably from about 80°C to about 100°C. Advantageously, a temperature gradient exists in column B where the temperature varies from 87°C at one end of the column to 93°C at the other end.
In an embodiment, an azeotropic or near-azeotropic feed composition (Fi) of the invention comprising 245fa and 1233xf is fed into column A. Such compositions may comprise, or preferably consist of, about 35 mol% to about 99 mol% 245fa and from about 1 mol% to about 65 mol% 1233xf, advantageously from about 35 mol% to about 90 mol% 245fa and from about 65 mol% to about 10 mol% 1233xf, such as about 35 mol% to about 80 mol% 245fa and from about 65 mol% to about 20 mol% 1233xf, for example about 35 mol% to about 70 mol% 245fa and from about 65 mol% to about 30 mol% 1233xf, preferably about 35 mol% to about 60 mol% 245fa and from about 65 mol% to about 40 mol%1233xf. Advantageously, the Fi composition consists of greater than 35 mol% 245fa and less than 65 mol% 1233xf.
On entering column A, 245fa is separated from the Fi composition. As such, 245fa may be recovered from column A yielding a 245fa rich composition (Di) comprising greater than about 90 mol% 245fa, such as greater than about 95 mol% 245fa, preferably greater than 99 mol% 245fa, and an azeotropic or near-azeotropic composition (Ci) comprising 245fa and 1233xf in a molar ratio that is richer in 1233xf than Fi. Preferably, composition Di is recovered from column A at the higher temperature region of the column.
On recovering the composition Di from column, a preferably azeotropic or near-azeotropic composition Ci comprising 245fa and 1233xf is fed into column B, wherein the Ci composition is separated into two further fluid compositions, wherein 1233xf is separated from the azeotrope composition to yield a composition (D2) comprising greater than about 90 mol% 1233xf, such as greater than about 95 mol% 1233xf, preferably greater than 99 mol% 1233xf, and an azeotropic or near-azeotropic composition (C2) comprising 245fa and 1233xf in a molar ratio that is richer in 245fa than C1. Preferably, composition D2 is recovered from column B at the higher temperature region of the column.
The recovery of compositions D1 and C1 from column A may occur simultaneously or sequentially. Preferably, the recovery of compositions D1 and C1 occurs simultaneously.
On recovering the composition D2 from column B, a preferably azeotropic or near-azeotropic composition (C2) consisting of 245fa and 1233xf may be recovered at the opposite end of the column. As 1233xf has been recovered from composition C1, the C2 composition is richer in 245fa than C1. Preferably, such compositions comprise, or preferably consist of, about 50 mol% to about 70 mol% 245fa and from about 50 mol% to about 30 mol% 1233xf, such as from about 50 mol% to about 60 mol% 245fa and from 50 mol% to about 40 mol% 1233xf. Preferably, such compositions comprise, or preferably consist of, 59 mol% 245fa and 61 mol% 1233xf.
The recovery of compositions D2 and C2 from column B may occur simultaneously or sequentially. Preferably, the recovery of compositions D2 and C2 occurs simultaneously.
In an embodiment, upon recovery of the composition C2from column B, this composition may be recycled back into column A. Preferably, this process is, therefore, continuous.
Although it is preferred that the separation of composition F1 is via first entering column A then column B, it is envisaged that the process may be reversed and the azeotropic or near-azeotropic composition may be subjected to the separation process in column B first before being subjected to the separation process in column A.
Embodiments of the present invention will now be described with reference to the following drawings:
Figure 1 shows a pressure swing apparatus set-up, which is suitable for the separation of azeotropic or near-azeotropic compositions of the invention.
Figure 2 shows the results obtained when measuring the vapour mole fraction of 1233xf and liquid mole fraction of 1233xf using varying compositions of 1233xf and 245fa at pressures of 0.5 bar to 20 bar.
Figures 3 to 6 show the results obtained when measuring the vapour pressure of varying compositions of 1233xf and 245fa at temperatures of-20°C, 0°C, 40°C and 80°C.
The present invention provides an azeotropic or near-azeotropic composition comprising 245fa and 1233xf. Without wishing to be bound by theory, the existence of an azeotropic or near-azeotropic composition is generally dependent on temperature, pressure and the ratio of components in the composition. By varying the temperature, pressure and composition, an azeotrope or near-azeotropic composition of the invention may occur at any point between these values.
The components of azeotropic or near-azeotropic compositions may be separated via the use of a pressure swing distillation apparatus. Such set-ups typically comprise one or more distillation columns operated at temperatures and pressures specific to the azeotropic or near-azeotropic composition of interest. By fine tuning the temperature and pressure of the pressure swing distillation column(s), an azeotrope composition may be distilled from the column, wherein, depending on the pressure and temperature of the column, the resulting distillate may comprise the components of the azeotropic composition in different molar ratios than that of the original feed composition. This, therefore, can result in the liquid phase that is left in the column being richer in one component of the azeotropic composition than the other. In some cases, the liquid phase may be almost 100 mol% of the component left in the liquid phase.
An exemplary pressure swing apparatus set-up for the separation of azeotropic or near-azeotropic compositions of the invention is provided in Figure 1. This set-up comprises two columns (A and B), which are operated at different temperatures and pressures. Preferably, column A is operated at a lower pressure to the second column B. However, it is envisaged that column B may be operated at a lower pressure to column A. Similarly, column B is preferably operated at higher temperatures to column A. However, column A may just as easily be operated at higher temperatures to column B if the process requires.
In a specific embodiment, and with reference to Figure 1, a feed composition (Fi) comprising about 50 mol% to about 40 mol% 245fa and about 50 mol% to about 60 mol% 1233xf is fed into column A, which is operated at a pressure (Pa) of about 0.5 bara and temperatures of about -1 °C at the bottom (TAi) of the column and about -6 °C at the top (Ta2). Under these conditions, the Fi composition undergoes partial distillation, wherein a distillate composition (Ci) is distilled from the top of the column leaving a 245fa rich residue (Di). After this first separation process, the Ci composition comprises about 35 mol% 245fa and about 65 mol% 1233xf. Whereas, the Di residue composition comprises about 99 to about 100 mol% 245fa. The highly pure Di composition is removed from the column and collected, and the Ci composition is fed into column B, which is operated at a pressure (Pb) of about 10 bara and temperatures of about 93 °C at the bottom (Tbi) of the column and 87 °C at the top (Tb2). Under such conditions, the Ci composition undergoes distillation to provide a distillate composition (C2) comprising about 59 mol% 245fa and about 41 mol% 1233xf, which results in a 1233xf rich residue (D2) remaining in the column. This D2 residue typically comprises about 99 mol% to about 100 mol% 1233xf. After the separation process in column B, the highly pure D2 composition is removed from the column and collected, and the distillate composition C2 is recycled back into column A to repeat the process.
The graph in Figure 2 shows that the composition of the vapour phase and liquid phase of a 245fa and 1233xf binary mixture is the same, or essentially the same, in compositions wherein 1233xf is present in an amount of from about 40 mol% to about 65 mol% and 245fa is present in an amount of from about 60 mol% to about 35 mol% at pressures ranging from about 0.5 bar to about 20 bar, which is consistent with what would be expected of azeotropic compositions.
Examples Example 1 A binary azeotrope between 245fa and 1233xf was identified by a study of the vapour-liquid equilibrium of binary mixtures over a temperature range of -20°C to +80°C using a constant volume apparatus.
The experimental data were measured in a static constant volume apparatus consisting of a vessel of precisely known internal volume located in a temperature-controlled metal block. A magnetic stirring device was located inside the vessel. Refrigerated fluid was passed through the block to allow precise control of temperature inside the vessel. The cell was evacuated then known amounts of compositions of 245fa and 1233xf were charged to the cell. The temperature of the cell was then varied to temperatures between -20°C and +80°C. At each step the cell temperature and pressure were logged and recorded when stable conditions were reached.
The phase behaviour of these compositions at exemplary temperatures is illustrated in Figures 3 to 6, which show that a constant vapour pressure is reached at compositions wherein 1233xf is present in an amount of from about 60 mol% to about 35 mol% and 245fa is present in an amount of from about 40 mol% to about 65 mol% 1233xf, which is consistent with what would be expected of azeotropic compositions. This trend is evidenced across all temperature ranges tested. A pressure maxima demonstrates the presence of a minimum boiling azeotrope.
Figure 3 shows that a binary azeotrope/azeotrope like composition exists between 245fa and 1233xf at a temperature of -20°C and a pressure of 0.27 bara, wherein 245fa is present in an amount of about 41 mol% to about 30 mol% and 1233xf is present in an amount of about 59 mol% to about 70 mol%.
Figure 4 shows that a binary azeotrope/azeotrope like composition exists between 245fa and 1233xf at a temperature of 0°C and a pressure of 0.66 bara, wherein 245fa is present in an amount of about 44 mol% to about 30 mol% and 1233xf is present in an amount of about 56 mol% to about 70 mol%.
Figure 5 shows that a binary azeotrope/azeotrope like composition exists between 245fa and 1233xf at a temperature of 40°C and a pressure of 2.86 bara, wherein 245fa is present in an amount of about 53 mol% to about 39 mol% and 1233xf is present in an amount of about 47 mol% to about 61 mol%.
Figure 6 shows that a binary azeotrope/azeotrope like composition exists between 245fa and 1233xf at a temperature of 80°C and a pressure of 8.44 bara, wherein 245fa is present in an amount of about 63 mol% to about 57 mol% and 1233xf is present in an amount of about 37 mol% to about 43 mol%.
Preferences and options for a given aspect, feature or parameter of the invention should, unless the context indicates otherwise, be regarded as having been disclosed in combination with any and all preferences and options for all other aspects, features and parameters of the invention.
Claims (45)
1. An azeotropic or near-azeotropic composition comprising CF3CH2CF2H (245fa) and CF3CCICH2 (1233xf).
2. A composition according to Claim 1 consisting essentially of CF3CH2CF2H (245fa) and CF3CCICH2 (1233xf).
3. A composition according to Claim 1 or Claim 2 consisting of CF3CH2CF2H (245fa) and CF3CCICH2(1233xf).
4. A composition according to any one of Claims 1 to 3 containing from about 10 mol% to about 99 mol% 245fa and from about 90 mol% to about 1 mol% 1233xf.
5. A composition according to Claim 4 comprising from about 20 mol% to about 99 mol% 245fa and from about 80 mol% to about 1 mol% 1233xf, such as about 30 mol% to about 99 mol% 245fa and from about 70 mol% to about 1 mol% 1233xf, for example about 30 mol% to about 98 mol% 245fa and from about 70 mol% to about 2 mol% 1233xf, preferably about 30 mol% to about 90 mol% 245fa and from about 70 mol% to about 10 mol% 1233xf, such as from about 30 mol% to about 80 mol% 245fa and from about 70 mol% to about 20 mol% 1233xf, for example from about 30 mol% to about 70 mol% 245fa and from about 70 mol% to about 30 mol% 1233xf, for instance from about 30 mol% to about 60 mol% 245fa and from about 70 mol% to about 40 mol% 1233xf, such as from about 35 mol% to about 60 mol% 245fa and from about 65 mol% to about 40 mol% 1233xf, for example from about 36 mol% to about 60 mol% 245fa and from about 64 mol% to about 40 mol% 1233xf, such as from about 40 mol% to about 60 mol% 245fa and from about 60 mol% to about 40 mol% 1233xf and conveniently from about 40 mol% to about 50 mol% 245fa and from about 50 mol% to about 60 mol% 1233xf.
6. A composition according to any one of the preceding claims, wherein the azeotropic or near-azeotropic composition is present at temperatures of from about -20°C to about +80°C.
7. A composition according to Claim 6, wherein the azeotropic or near-azeotropic composition is present at temperatures of from about 0°C to about +80°C, preferably from temperatures of from about +40°C to about +80°C.
8. A composition according to any one of the preceding claims, wherein the azeotropic or near-azeotropic composition is present at pressures of from about 0.5 bara to about 30 bara, for example from about 0.5 to about 20 bara.
9. A composition comprising a lubricant and a composition according to any of the preceding claims.
10. A composition according to claim 9, wherein the lubricant is selected from mineral oil, silicone oil, polyalkyl benzenes (PABs), polyol esters (POEs), polyalkylene glycols (PAGs), polyalkylene glycol esters (PAG esters), polyvinyl ethers (PVEs), poly (alpha-olefins) and combinations thereof, preferably wherein the lubricant is selected from PAGs or POEs.
11. A composition comprising a stabiliser and a composition according to any of the preceding claims.
12. A composition according to Claim 11, wherein the stabiliser is selected from diene-based compounds, phosphates, phenol compounds and epoxides, and mixtures thereof.
13. A composition comprising a flame retardant and a composition according to any of the preceding claims.
14. A composition according to Claim 13, wherein the flame retardant is selected from the group consisting of tri-(2-chloroethyl)-phosphate, (chloropropyl) phosphate, tri-(2,3-dibromopropyl)-phosphate, tri-(1,3-dichloropropyl)-phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminium trihydrate, polyvinyl chloride, a fluorinated iodocarbon, a fluorinated bromocarbon, trifluoro iodomethane, perfluoroalkyl amines, bromo-fluoroalkyl amines and mixtures thereof.
15. The use of a composition (e.g. as an intermediate) according to any one of Claims 1 to 8 in the manufacture of one or more hydrofluoroolefins.
16. The use according to Claim 9, wherein the manufactured hydrofluoroolefin is one or both of CHFCHCFs (1234zeE) or CH2CFCF3 (1234yf).
17. The use of a composition according to any one of claims 1 to 14 as a heat transfer composition.
18. A heat transfer composition comprising a composition according to any one of Claims 1 to 14.
19. A method for cooling an article which comprises condensing a composition as defined in any one of Claims 1 to 14 and thereafter evaporating the composition in the vicinity of the article to be cooled.
20. A method for heating an article which comprises condensing a composition as defined in any one of Claims 1 to 14 in the vicinity of the article to be heated and thereafter evaporating the composition.
21. A mechanical power generation device containing a composition as defined in any one of Claims 1 to 14.
22. A mechanical power generating device according to Claim 21 which is adapted to use a Rankine Cycle or modification thereof to generate work from heat.
23. A method of retrofitting a heat transfer device comprising the step of removing an existing heat transfer composition, and introducing a composition as defined in any one of Claims 1 to 14.
24. A method according to Claim 23 wherein the heat transfer device is a refrigeration device.
25. A method according to Claim 23 wherein the heat transfer device is an air conditioning system, preferably an automobile air conditioning system.
26. A method for reducing the environmental impact arising from the operation of a product comprising an existing compound or composition, the method comprising replacing at least partially the existing compound or composition with a composition as defined in any one of claims 1 to 14.
27. A method for generating greenhouse gas emission credit comprising (i) replacing an existing compound or composition with a composition as defined in any one of claims 1 to 14, wherein the composition as defined in any one of claims 1 to 14 has a lower GWP than the existing compound or composition; and (ii) obtaining greenhouse gas emission credit for said replacing step.
28. A method according to Claim 27 wherein the use of the composition of the invention results in a lower Total Equivalent Warming Impact, and/or a lower Life-Cycle Carbon Production than is attained by use of the existing compound or composition.
29. A method according to Claims 27 or 28 carried out on a product from the fields of air-conditioning, refrigeration, heat transfer, blowing agents, aerosols or sprayable propellants, gaseous dielectrics, cryosurgery, veterinary procedures, dental procedures, fire extinguishing, flame suppression, solvents, cleaners, air horns, pellet guns, topical anesthetics, and expansion applications.
30. A process for the separation of an azeotropic or near-azeotropic composition according to any one of Claims 1 to 8.
31. A process according to Claim 30, wherein the azeotropic or near-azeotropic composition is separated via the use of a pressure swing distillation.
32. A process according to Claims 30 or 31, wherein the pressure swing apparatus comprises two columns operated sequentially at different pressures.
33. A process according to any one of Claim 32, wherein the first column (A) is operated at a lower pressure to the second column (B).
34. A process according to Claim 31 to 33, wherein column A is operated at a pressure of from about 0.1 to about 15 bara, such as from about 0.1 to about 5 bara, preferably from about 0.1 to about 2 bara, for example about 0.5 bara.
35. A process according to any one of Claims 31 to 34, wherein column B is operated at a pressure of from about 1 to about 20 bara, such as from about 5 to about 20 bara, preferably from about 10 to about 20 bara, for example about 10 bara.
36. A process according to any one of Claims 31 to 35, wherein the two columns are operated sequentially at different temperatures.
37. A process according to Claim 36, wherein column A is operated at a temperature of from about -50°C to about 50°C, such as from about -25°C to about 25°C, preferably from about -10°C to about 0°C.
38. A process according to Claims 36 or 37, wherein column B is operated at a temperature of from about 50°C to about 150°C, such as from about 75°C to about 125°C, preferably from about 80°C to about 100°C.
39. A process according to any one of Claims 31 to 38, wherein a composition (F-ι) is fed into the process, wherein Fi comprises 1 mol% to about 65 mol% 1233xf and from about 99 mol% to about 35 mol% 245fa, advantageously from about 10 mol% to about 65 mol% 1233xf and from about 90 mol% to about 35 mol% 245fa, such as about 20 mol% to about 65 mol% 1233xf and from about 80 mol% to about 35 mol% 245fa, for example about 30 mol% to about 65 mol% 1233xf and from about 70 mol% to about 35 mol% 245fa, preferably about 40 mol% to about 65 mol% 1233xf and from about 60 mol% to about 35 mol% 245fa.
40. A process according to any one of Claims 31 to 39, wherein the Fi composition is separated into two liquid compositions in column A, wherein 245fa is separated from the azeotrope composition to yield a composition (Di) comprising greater than about 90 mol% 245fa, such as greater than about 95 mol% 245fa, preferably greater than 99 mol% 245fa, and an azeotropic or near-azeotropic composition (Ci) comprising 245fa and 1233xf in a molar ratio that is richer in 1233xf than Fi.
41. A process according to any one of Claims 31 to 40, wherein Di is removed from the separating apparatus and Ci is fed into column B, wherein the Ci composition is separated into two further liquid compositions, wherein 1233xf is separated from the azeotrope composition to yield a composition (D2) comprising greater than about 90 mol% 1233xf, such as greater than about 95 mol% 1233xf, preferably greater than 99 mol% 1233xf, and an azeotropic or near-azeotropic composition (C2) comprising 245fa and 1233xf in a molar ratio that is richer in 245fa than Ci.
42. A process according to any one of Claims 31 to 41, wherein composition D2 is removed from the separating apparatus and composition C2 is recycled back into column A.
43. A process according to any one of Claims 31 to 42, wherein the process is continuous.
44. A process according to any one of Claims 31 to 43, wherein the azeotropic or near-azeotropic composition is subjected to the separation process in column B first before being subjected to the separation process in column A.
45. Any novel composition, method or process as described herein, optionally with reference to the examples.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1616785.0A GB2546129A (en) | 2016-10-03 | 2016-10-03 | Composition |
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| Application Number | Priority Date | Filing Date | Title |
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| GB1616785.0A GB2546129A (en) | 2016-10-03 | 2016-10-03 | Composition |
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|---|---|
| GB201616785D0 GB201616785D0 (en) | 2016-11-16 |
| GB2546129A true GB2546129A (en) | 2017-07-12 |
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| GB1616785.0A Withdrawn GB2546129A (en) | 2016-10-03 | 2016-10-03 | Composition |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160009555A1 (en) * | 2013-03-20 | 2016-01-14 | Arkema France | Composition comprising hf and 2,3,3,3-tetrafluoropropene |
| US20160023176A1 (en) * | 2013-03-20 | 2016-01-28 | Arkema France | Composition comprising hf and 3,3,3-trifluoro-2-chloropropene |
| US20160031773A1 (en) * | 2013-03-20 | 2016-02-04 | Arkema France | Composition comprising hf and 1,3,3,3-tetrafluoropropene |
-
2016
- 2016-10-03 GB GB1616785.0A patent/GB2546129A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160009555A1 (en) * | 2013-03-20 | 2016-01-14 | Arkema France | Composition comprising hf and 2,3,3,3-tetrafluoropropene |
| US20160023176A1 (en) * | 2013-03-20 | 2016-01-28 | Arkema France | Composition comprising hf and 3,3,3-trifluoro-2-chloropropene |
| US20160031773A1 (en) * | 2013-03-20 | 2016-02-04 | Arkema France | Composition comprising hf and 1,3,3,3-tetrafluoropropene |
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| GB201616785D0 (en) | 2016-11-16 |
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