DE202007008290U1 - Heat transfer compositions - Google Patents

Abstract

A heat transfer composition comprising:
(i) R-1225ye;
(ii) at least one further refrigerant selected from carbon dioxide (R-744); Fluoromethane (R-41); Difluoromethane (R-32); Fluoroethane (R-161); 1,1,1-trifluoroethane (R-143a); 1,1,1,2-tetrafluoroethane (R-134a); 1,1,2,2-tetrafluoroethane (R-134); dimethyl ether; Heptafluoropropane (R-227ea); Propane (R-290); Propene (R-1270); Isobutane (R-600a); n-butane (R-600); 2,3,3,3-tetrafluoropropene (R-1234yf); 1,1-difluorocyclopropane; 1,1,2-Trifluorcyclopropan; 1,1,2,2-tetrafluoro cyclopropane; Pentafluorocyclopropane, or ammonia, or mixtures thereof.

Description

These Invention relates to heat transfer compositions, and in particular heat transfer compositions, as a substitute for existing refrigerants such as R-134a, R-410A, R-407C, R-404a and R-507, however especially for R-134a and R-407C.

mechanical refrigeration systems (and related heat transfer devices like heat pumps and Air conditioners) are well known. In such systems evaporates a refrigerant liquid at low pressure, giving off heat from the surrounding area. The resulting vapor then becomes compressed and fed to a condenser where it condenses and Heat on emits a second zone, the condensate through an expansion valve fed to an evaporator and in this way the cycle is completed. The mechanical Energy that to compressing the vapor and pumping the liquid need is, for example, by an electric motor or an internal combustion engine delivered.

In addition to the properties of having a suitable boiling point as well a high latent heat of evaporation, are the for a refrigerant preferred properties low toxicity, non-flammability, non-corrosivity, high stability and freedom from unacceptable smell. Other desired properties are a simple compressibility at pressures below 25 bar, one low conveying temperature when compacting, a high cooling capacity, a high Efficiency (a high coefficient of performance) and an evaporator pressure above 1 bar at the desired Evaporation temperature.

Dichlorodifluoromethane (Refrigerant R-12) has a suitable combination of properties and was for many Years the most widely used refrigerant. Due to international Concern that completely and partially halogenated chlorofluorocarbons such as dichlorodifluoromethane and chlorodifluoromethane the protective Damage the earth's ozone layer, there was a general agreement, that their production and use are severely restricted and after all completely should be adjusted. The use of dichlorofluoromethane was discontinued in the 1990s.

1,1,1,2 tetrafluoroethane (Refrigerant R-134a) was used as a replacement refrigerant for R-12 introduced. Although it has a low ozone damage potential R-134a has a global warming potential (GWP) of 1300 on.

Even though Heat transfer devices of the type to which the present invention relates essentially Closed systems can cause a loss of refrigerant to the atmosphere due to Leaks during plant operation or during maintenance. It is therefore important to complete and partially halogenated chlorofluorocarbon refrigerants to replace with materials, the ozone damaging potential of zero exhibit.

In addition to possibility the ozone damage it was considered that considerable concentrations of Halocarbon refrigerants in the atmosphere to global warming can contribute (the so-called greenhouse effect). It is therefore desirable to use refrigerant to use, which have relatively short atmospheric lifetimes because of their ability with other atmospheric Ingredients such as hydroxyl radicals to react or im result a rapid degradation due to photolytic process.

It there is a need after providing alternative refrigerants with improved Properties such as low flammability. There is also a need after providing alternative refrigerants that exist in existing Devices, such as refrigeration devices, in only one little or no adaptation can be used.

US 2004/0127383 (US-B2-6858571) (Honeywell International, Inc.) the use of pentafluoropropene (R-1225), in particular R-1225ye, in combination with R-1243zf, R-152a and R-1234ze.

US 2004/0119047 and US 2004/0256594 (Honeywell International, Inc.) discloses heat transfer compositions comprising a fluoroalkene of the formula XCF _z R _3-z , where x is an unsaturated, substituted or unsubstituted C ₂ or C ₃ alkyl radical, R = Cl, F, Br, I or H and z is 1 to 3, the compositions having a reduced global warming potential (GWP).

US-A-7098176 B and US 2006/0022166 (Honeywell International Inc.) describe azeotrope-like additions compositions containing effective amounts of R-1234yf and R-1225yeZ.

WHERE 2006/094303 (DuPont) describes compositions containing heat transfer compositions could be, the R-1225ye and another refrigerant include. Specifically disclosed compositions include another is a combination of R-1225ye and R-32; R-1225ye and R-134a; R-1225ye, R-134a and R-32; R-1225ye, R-1234yf, R-32 and R-134a; and azeotropic and azeotrope-like compositions containing 1% to 99 R-1225ye and 99% to 1% R-134a.

R-1225ye (also known as HCF-1225ye) is 1,2,3,3,3-pentafluoropropene (CF ₃ -CF = CHF). It may exist in the form of two stereoisomers, Z and E, which are known to have very similar boiling points. Our reference to R-1225ye includes both isomers as well as mixtures thereof.

at some embodiments the isomers are preferably in such a mass ratio of Z to E predicts that at least 50% of the R-1225ye is present as the Z isomer, even stronger preferably at least 80%.

R-1225ye is non-flammable and has a low greenhouse warming potential (compared to CO ₂ ). Its boiling point is about -18 ° C (for the isomer mixture), and its critical temperature is estimated to be 113 ° C. These properties are well comparable to those of R-134a (1,1,1,2-tetrafluoroethane), which has a boiling point of -26.4 ° C, a critical temperature of 101 ° C and a GWP of 1300. R-1225ye is therefore a potential alternative to R-134a.

The However, properties of this fluid alone do not make it more direct Replacement for R-134a suitable. In particular, its capacity is too low, which means is that a chiller or air conditioning with a fixed compressor displacement and designed for R-134a a lower cooling supplies when fed with R-1225ye and at the same Operating temperatures is set. The capacity for air conditioning applications (Evaporation temperature in the range 0 to 10 ° C) is typically 75% of that from R-134a.

A fundamental It is therefore an object of the present invention to provide a heat transfer composition which is usable or suitable as such as replacement for existing refrigeration uses, which has a reduced greenhouse warming potential, and nevertheless a capacity and energy efficiency (which are conveniently expressed can be called "COP", which ideally within 20% of the values of, for example, R-134a, preferably within 10% of these values, and even more preferably within 5 % of these values. It is known to those skilled in the art that differences in of this magnitude between different fluids usually are manageable by using the equipment and operating features of a system without significant cost differences leads.

at certain preferred embodiments can the capacity and the energy efficiency of mixtures according to the invention those from R-134a.

• (i) R-1225ye; und
• (ii) wenigstens eine weitere Verbindung (ein weiteres Kältemittel), die ausgewählt ist aus Kohlendioxid (R-744); Fluormethan (R-41); Difluormethan (R-32); Fluorethan (R-161); 1,1,1-Trifluorethan (R-143a); 1,1,1,2-Tetrafluorethan (R-134a); 1,1,2,2-Tetrafluorethan (R-134); Dimethylether; Heptafluorpropan (R-227ea); Propan (R-290); Propen (R-1270); Isobutan (R-600a); n-Butan (R-600); 2,3,3,3-Tetrafluorpropen (R-1234yf); 1,1-Difluorcyclopropan; 1,1,2-Trifluorcyclopropan; 1,1,2,2-Tetrafluorcyclopropan; Pentafluorcyclopropan, oder Ammoniak, oder Mischungen davon.

According to one aspect of the invention, there is provided a composition which may be a heat transfer composition comprising:

• (i) R-1225ye; and
• (ii) at least one further compound (another refrigerant) selected from carbon dioxide (R-744); Fluoromethane (R-41); Difluoromethane (R-32); Fluoroethane (R-161); 1,1,1-trifluoroethane (R-143a); 1,1,1,2-tetrafluoroethane (R-134a); 1,1,2,2-tetrafluoroethane (R-134); dimethyl ether; Heptafluoropropane (R-227ea); Propane (R-290); Propene (R-1270); Isobutane (R-600a); n-butane (R-600); 2,3,3,3-tetrafluoropropene (R-1234yf); 1,1-difluorocyclopropane; 1,1,2-Trifluorcyclopropan; 1,1,2,2-tetrafluoro cyclopropane; Pentafluorocyclopropane, or ammonia, or mixtures thereof.

at a preferred embodiment is the other refrigerant selected from R-134a, dimethyl ether, R-161, R-32, R-744, R-41, R-290, R-1270, ammonia, R-600 or R-1243zf.

• (i) R-1225yeZ;
• (ii) R-32, R-161 oder R-152a; und
• (iii) wenigstens eine weitere Verbindung (ein weiteres Kältemittel), die ausgewählt ist aus Kohlendioxid (R-744); Fluormethan (R-41); Fluorethan (R-161); 1,1,1-Trifluorethan (R-143a); 1,1,1,2-Tetrafluorethan (R-134a); 1,1,2,2-Tetrafluorethan (R-134); Dimethylether; Heptafluorpropan (R-227ea); Propan (R-290); Propen (R-1270); Isobutan (R-600a); n-Butan (R-600); 2,3,3,3-Tetrafluorpropen (R-1234yf); 1,1-Difluorcyclopropan; 1,1,2-Trifluorcyclopropan; 1,1,2,2-Tetrafluorcyclopropan; Pentafluorcyclopropan, Pentafluorethan (R-125) oder Ammoniak, oder Mischungen davon.

According to another preferred aspect of the invention, there is provided a composition which may be a heat transfer composition comprising:

• (i) R-1225yeZ;
• (ii) R-32, R-161 or R-152a; and
• (iii) at least one further compound (another refrigerant) selected from carbon dioxide (R-744); Fluoromethane (R-41); Fluoroethane (R-161); 1,1,1-trifluoroethane (R-143a); 1,1,1,2-tetrafluoroethane (R-134a); 1,1,2,2-tetrafluoroethane (R-134); dimethyl ether; Heptafluoropropane (R-227ea); Propane (R-290); Propene (R-1270); Isobutane (R-600a); n-butane (R-600); 2,3,3,3-tetrafluoropropene (R-1234yf); 1,1-difluorocyclopropane; 1,1,2-Trifluorcyclopropan; 1,1,2,2-tetrafluoro cyclopropane; Pentafluorocyclopropane, pentafluoroethane (R-125) or ammonia, or mixtures thereof.

According to one preferred aspect of this embodiment is the other refrigerant R-134a or R-125.

According to one highly preferred aspect, the R-32, R-161 or R-152a is only R-32, and the other refrigerant is R-134a.

According to one another preferred aspect is R-32, R-161 or R-152a only R-152a, and the other refrigerant is R-125.

According to others preferred aspects can ternary Heat transfer compositions provided which include R-1225yeZ, R-161 and R-134a; R-1225yeZ, R-161 and R-125; and R-1225yeZ, R-125 and R-32.

• (i) R-1225yeZ;
• (ii) R-32;
• (iii) R-1234yf; und
• (iv) wenigstens eine weitere Verbindung (ein weiteres Kältemittel), die ausgewählt ist aus Kohlendioxid (R-744); Fluormethan (R-41); Fluorethan (R-161); 1,1,1-Trifluorethan (R-143a); 1,1,1,2-Tetrafluorethan (R-134a); 1,1,2,2-Tetrafluorethan (R-134); Dimethylether; Heptafluorpropan (R-227ea); Propan (R-290); Propen (R-1270); Isobutan (R-600a); n-Butan (R-600); 1,1-Difluorcyclopropan; 1,1,2-Trifluorcyclopropan; 1,1,2,2-Tetrafluorcyclopropan; Pentafluorcyclopropan, Pentafluorethan (R-125) oder Ammoniak, oder Mischungen davon.

According to another preferred aspect of the invention, there is provided a composition which may be a heat transfer composition comprising:

• (i) R-1225yeZ;
• (ii) R-32;
• (iii) R-1234yf; and
• (iv) at least one further compound (another refrigerant) selected from carbon dioxide (R-744); Fluoromethane (R-41); Fluoroethane (R-161); 1,1,1-trifluoroethane (R-143a); 1,1,1,2-tetrafluoroethane (R-134a); 1,1,2,2-tetrafluoroethane (R-134); dimethyl ether; Heptafluoropropane (R-227ea); Propane (R-290); Propene (R-1270); Isobutane (R-600a); n-butane (R-600); 1,1-difluorocyclopropane; 1,1,2-Trifluorcyclopropan; 1,1,2,2-tetrafluoro cyclopropane; Pentafluorocyclopropane, pentafluoroethane (R-125) or ammonia, or mixtures thereof.

In A preferred facet of this aspect of the invention is the further one refrigerant R-134a.

• (i) R-1225yeZ;
• (ii) R-32;
• (iii) R-125; und
• (iv) R-161 oder R-152a.

According to another preferred aspect of the invention, there is provided a composition which may be a heat transfer composition comprising:

• (i) R-1225yeZ;
• (ii) R-32;
• (iii) R-125; and
• (iv) R-161 or R-152a.

Preferably indicates any heat transfer composition obtained a GWP lower than that of the refrigerant they replace should, for example, R-134a or R-407C.

in the Context of the invention, unless otherwise stated When we refer to an R-1225yeZ ingredient, it becomes a compound containing R-1225yeZ in the R-1225ye component, the at least 95 Z-isomer is stronger preferably at least 98% Z-isomer, even more preferably at least 99 % Z isomer and in some cases may be pure Z isomer. The remaining minor component any such R-1225yeZ or any such R-1225ye composition is the E isomer.

• – R-125 (1 bis 3 Teile): R-152 a (1 bis 12 Teile): R-1225yeZ (85 bis 98 Teile;
• – R-125 (1 bis 4 Teile): R-161 (1 bis 4 Teile): R-1225yeZ (92 bis 98 Teile),
• – R-161 (1 bis 4 Teile): R-134a (1 bis 10 Teile): R-1225yeZ (86 bis 98 Teile);
• – R-32 (1 bis 3 Teile): R-125 (1 bis 3 Teile): R-152a (1 bis 13 Teile), R-1225yeZ (81 bis 97 Teile);
• – R-32 (1 bis 3 Teile): R-125 (1 bis 3 Teile): R-161 (1 bis 5 Teile): R-1225yeZ (89 bis 97 Teile).

Some particularly preferred specific heat transfer compositions according to the present invention are listed below (all parts given for a given composition add up to 100 and are given on a weight basis):

• R-125 (1 to 3 parts): R-152 a (1 to 12 parts): R-1225yeZ (85 to 98 parts;
• R-125 (1 to 4 parts): R-161 (1 to 4 parts): R-1225yeZ (92 to 98 parts),
• R-161 (1 to 4 parts): R-134a (1 to 10 parts): R-1225yeZ (86 to 98 parts);
• R-32 (1 to 3 parts): R-125 (1 to 3 parts): R-152a (1 to 13 parts), R-1225yeZ (81 to 97 parts);
• R-32 (1 to 3 parts): R-125 (1 to 3 parts): R-161 (1 to 5 parts): R-1225yeZ (89 to 97 parts).

• – R-32 (1 bis 9 Teile): R-134a (4 bis 8 Teile): R-1234yf (4 bis 44 Teile): R-1225yeZ (48 bis 89 Teile);
• – R-32 (3 bis 9 Teile): R-134a (4 bis 8 Teile): R-1234yf (4 bis 28 Teile): R-1225yeZ (55 bis 88 Teile);
• – R-32 (4 bis 9 Teile): R-134a (4 bis 6 Teile): R-1234yf (4 bis 24 Teile): R-1225yeZ (73 bis 88 Teile) – diese Zusammensetzung ist bevorzugt, da sie eine überlegene Kapazität und eine passende COP mit einem Verdampfer-Glide von weniger als 5°C bietet;
• – R-32 (1 bis 4 Teile): R-134a (4 bis 8 Teile): R-1234yf (4 bis 44 Teile): R-1225yeZ (48 bis 89 Teile) – diese Zusammensetzung ist bevorzugt, da sie ein Glide von weniger als oder gleich 2,5°C aufweist bei einer Kapazität, die größer oder gleich ist 80 % derjenigen von R-134a, bei einer gut passenden COP.

In addition to those mentioned, the following are specific heat transfer compositions Compositions preferred:

• R-32 (1 to 9 parts): R-134a (4 to 8 parts): R-1234yf (4 to 44 parts): R-1225yeZ (48 to 89 parts);
• R-32 (3 to 9 parts): R-134a (4 to 8 parts): R-1234yf (4 to 28 parts): R-1225yeZ (55 to 88 parts);
• R-32 (4 to 9 parts): R-134a (4 to 6 parts): R-1234yf (4 to 24 parts): R-1225yeZ (73 to 88 parts) - this composition is preferable because it is a superior one Capacity and a matching COP with an evaporator glide of less than 5 ° C provides;
• R-32 (1 to 4 parts): R-134a (4 to 8 parts): R-1234yf (4 to 44 parts): R-1225yeZ (48 to 89 parts) - this composition is preferred because it is a glide of less than or equal to 2.5 ° C, with a capacity greater than or equal to 80% of that of R-134a, with a well-fitting COP.

Preferably the nature and quantities of the other refrigerant are such that the resulting binary (or higher) Mixture is non-flammable. When this term is used herein "non-flammable" refers to compounds or compositions, for which has been found to be non-flammable, and indeed in a determination according to ASHRAE standard 34 with the included ASTM standard E-681 methodology according to Addendum p34 of 2004, the entire contents of which are hereby incorporated by reference becomes. The test used for the determination is described in section X.2.4.1 "Leaks under storage / shipping conditions "and represents the worst case of fractionation.

compositions according to the invention typically have an improved compared to R-1225ye alone capacity on, as well as an improved capacity compared to R-1225yeZ. According to one Facet can be the incorporation of a relatively small proportion of one or more refrigerants Component (ii) of the composition according to the broadest aspect of the invention Invention), whereby this) further refrigerant (s) are flammable, a higher one GWP value or both, to a resulting heat transfer composition to lead, which are both low GWP and essentially none Flammability properties and only a relatively low temperature "Glide" has, and still an improved capacity and optionally has an improved coefficient of performance.

The Temperature glide, which is conceivable as the difference between the bubbling temperature and the dew point temperature of a non-azeotropic Mixture at constant pressure, is a characteristic of a refrigerant; if so desired It is often preferable to replace a fluid with a mixture, a similar one or reduced temperature glide in the alternative fluid to have.

compositions according to the invention can Conveniently, they are considered to be non-azeotropic, "azeotrope-close" or "azeotrope-like" and may in fact be considered "non-azeotropic". This means they show a temperature glide during evaporation or condensation.

In In this context, in the temperature "Glide" with regard to refrigerant blends the one Temperature change, which occurs during the evaporation or condensation of the refrigerant mixture in the heat exchangers a chiller.

We refer in this context to a standardized (simplified) Vapor compression refrigeration cycle, comprising: an evaporator, a compressor, a condenser and an expansion valve with appropriate piping and controls etc. The evaporator is operated at low pressure and the condenser at high pressure. The refrigerant is considered a liquid supplied from the condenser through the expansion valve. Of the Pressure loss leads to that part of the liquid evaporates, so that the fluid that enters the evaporator, a Mixture of liquid and steam is.

The Condenser Glide is the difference between the dew point and the bubble boiling point temperature of the fluid mixture at the condensation pressure. The dew point temperature is for a predetermined pressure the temperature at which the first liquid drops can be condensed. The bubbling temperature at the same Pressure is the temperature at which the first vapor bubble evaporates can be.

Of the Dew point is higher as the bubble boiling point in a mixture that has a temperature glide shows. When the pressure increases the difference between the dew point and the bubble boiling point will increase from. For refrigeration systems the lowest pressure (evaporator pressure) will normally be set to 1 the atmosphere designed (an inward directed air leakage), and the highest pressure is usually chosen at 25 bar or less (the cost of the pressure vessels, etc. increase when the pressure rises).

The evaporator glide is the difference between the dew point temperature and the inlet temp in the evaporator. The inlet temperature is determined by the proportion of evaporation that occurred during the initial expansion of the associated liquid such that the evaporator inlet temperature is between the dew point and the bubble boiling point at the evaporator pressure.

Usually For example, the composition comprises the at least one additional refrigerant in an amount of about 1 to 30% by weight of the composition.

advantageously, For example, the composition comprises the at least one additional refrigerant in an amount of about 1 to about 10% by weight of the composition.

Preferably For example, the composition comprises the at least one refrigerant in an amount of about 1 to about 6% by weight of the composition.

advantageously, For example, the composition comprises the at least one refrigerant in an amount of about 1 to 5% by weight of the composition.

Preferably the composition is azeotrope like the composition in certain highly preferred embodiments also as non-azeotrope can be viewed.

suitably the composition has a GWP of about 750 or less.

advantageously, the composition has a GWP of about 500 or less.

Preferably the composition has a GWP of about 250 or less.

suitably the composition has a GWP of about 150 or less.

advantageously, For example, the composition has a GWP of about 100 or less.

The Heat transfer compositions according to the invention generally have substantially similar thermodynamic characteristics like those that can replace them, but typically a lower greenhouse warming potential on.

The Heat transfer compositions are suitable for use in existing equipment construction types, and are compatible with all lubricant classes currently available with conventional HFC refrigerants be used. You can optionally stabilized by use of suitable additives or made compatible with mineral oils be.

Preferably includes the composition as well a lubricant.

suitably For example, the lubricant is selected from the group consisting of mineral oil, silicone oil, polyalkylbenzenes (PABs), polyol esters (POEs), polyalkylene glycols (PAGs), polyalkylene glycol esters (PAG esters), Polyvinyl ethers (PVEs), poly (alpha-olefins) and combinations thereof.

advantageously, includes the composition as well a stabilizer.

Preferably the stabilizer is selected from the group consisting of compounds diene based, phosphates, phenolic compounds and epoxides and Mixtures thereof.

suitably includes the composition as well an additional Flame retardants.

advantageously, is the extra Flame retardant 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, aluminum trihydrate, polyvinyl chloride, a fluorinated Iodocarbon, a fluorinated bromocarbon, trifluorodimethane, Perfluoroalkylamines, Bromfluoralkylaminen and mixtures thereof.

Preferably the composition is a refrigerant composition.

According to a further aspect of the invention, a heat transfer device is provided, containing the composition of the invention.

Preferably is the heat transfer device a chiller.

suitably is the heat transfer device selected from the group, which consists of air conditioners for Automobiles, air conditioners for the living area, commercial air conditioners, residential cooling systems, Freezing systems for the living area, commercial refrigeration systems, commercial freezer systems, radiator air conditioners, Radiator cooling systems, heat pump systems.

advantageously, contains the heat transfer device a compressor. The compressor may be of the centrifugal type or any type with positive displacement, such as rotary valves, Scroll, swashplate, screw or piston types.

According to one Another aspect of the invention provides a blowing agent which a composition of the invention includes.

According to one Another aspect of the invention provides a foamable composition which includes one or more constituents that are capable of one To form foam, and a composition of the invention.

Preferably are the one or more ingredients that cause foaming are able to selected from polyurethanes, thermoplastic polymers and resins such as polystyrene and epoxy resins.

According to one Another aspect of the invention provides a foam which is made the foamable composition of the invention available is.

Preferably the foam comprises a composition according to the invention.

According to one Another aspect of the invention is a sprayable composition created, a material to be sprayed and a propellant comprising a composition of the invention.

According to one Another aspect of the invention is a method for cooling a Subject matter, which is the condensation of a composition according to the invention and then evaporating the composition in the vicinity of the cooling The subject matter.

According to one Another aspect of the invention is a method for heating a An object of the invention is the condensation of a composition the invention in the vicinity an object to be heated and thereafter evaporating the composition.

According to one Another aspect of the invention is a method for extracting a substance made of biomass, which brings the contacting the biomass with a solvent which comprises a composition according to the invention and separating the substance from the solvent.

According to one Another aspect of the invention is a method for purifying a Object, which is the contacting of the object with a solvent which comprises a composition according to the invention includes.

According to one Another aspect of the invention is a method for extracting a material from an aqueous solution created, which is the contacting of the aqueous solution with a solvent which comprises a composition according to the invention and separating the substance from the solvent.

According to one Another aspect of the invention is a method of extraction a material made of a particulate solid matrix, contacting the particulate solid matrix with a solvent which comprises a composition according to the invention as well as the separation of the substance from the solvent.

According to one Another aspect of the invention provides a mechanical power generation device. the one composition of the invention contains.

Preferably is the mechanical power generation device for use a Rankine cycle or a modification thereof Work of heat to create.

According to one Another aspect of the invention is a method for adjusting a existing refrigeration device created that the stages of removal of an existing heat transfer fluid and the introduction a composition of the invention includes.

Under certain circumstances it is preferred that the compositions have a GWP of about 150 or has less. However, it may be acceptable for other applications be that the composition has a higher GWP, for example a GWP of up to 250, 500 or 750.

The GWP values of the additional candidate fluids dictate the maximum allowable percentages for each application. Internationally accepted GWP values for selected refrigerant fluids according to the invention are as follows:

If the extra refrigerant has a GWP lower than the desired value, then the maximum amount in the composition of considerations of flammability or similarity of obtained mixture with the fluid to replace it dictates.

If the extra refrigerant has a GWP higher is as desired Value, then the GWP value can also be used to a preferred one Set the composition range.

For example, if a GWP of less than 150 is needed, and the fluid to replace is R-134a, and if, in addition, the mixture is not flammable, then the preferred compositions are selected additional refrigerants with a GWP higher than 150, as follows:
R-32 6% weight basis; R-134a 9% weight basis; R-227ea 4 weight basis; R-125 4% weight basis.

If the wished GWP is sufficiently high (with the proviso that it is lower than in the fluid replacing the invention), then it is possible to use the Flammability of a first substitute additive by that you have a second or further substitute additive to the mixture adding; this allows the use of slightly higher proportions of the flammable additive.

For example has a mixture of R-32 (10%); R-125 (10%) and R-1225ye (80 %) has a GWP of 403. Your refrigeration capacity is very similar to those of R-134a (estimated typically 100-104 % of that of R-134a), and has a similar COP characteristic.

For example is the existing refrigerant fluid R-407C a ternary Mixture of R-32, R-125 and R-134a in proportions of 23% / 25 % / 52% in weight and has a GWP of 1652. A suitable one Replacement fluid for this refrigerant may therefore be a mixture of R-32, R-125 and R-1225ye. The coolant additive is in this case a mixture of R-32 and R-125, so the mass ratio from R-125 to R-32 in the mixture is at least 1: 1, which is ensures non-flammability of the resulting mixture. When using a non-flammable blend of R-32 / R-125 / R-1225ye to replace the 52% R-134a in the R-407C composition, the resulting mixture behaves in a similar way R-407C, however, has a GWP compared to that of R-407C is much lower.

The The above example teaches that the optimal tuning of properties replacement requires the use of more than one additional fluid can, so that the substitute mixtures according to the invention ternary or higher Mixtures may include.

The Kältemittelzusammenstzungen can changed by a professional be that they comply with the usage requirements and the desired Flammability characteristics are adjusted.

In particular, he may opt for the addition of ingredients such as CF ₃ I to the refrigerant blends of the invention which are known to reduce or suppress flammability. In many preferred aspects of the invention, because of the potential toxicity and reactivity of CF3I, compositions of the invention may be substantially free thereof (eg, contain less than about 3%), and ideally be completely free of CF3I.

It was for the ternary ones and quaternaries Compositions according to the invention found that such compositions have surprising properties have, in particular with regard to properties that are responsible for the behavior the composition in air conditioners are important, especially in mobile (e.g., automotive) air conditioning systems, especially if it is necessary, that they approximate the behavior and characteristics of R-134a.

Flammability have been performed on mixtures of R-32 in air with R-1225yeZ and R-134a as a flammable diluent. It was found that the maximum concentration of R-32 in R-1225yeZ, to ensure that the mixture is at the Air under test conditions of a test temperature of 100 ° C non-flammable is 69 vol.% R-32. The maximum amount of R-32 in R-134a at the same test temperature, the air-non-flammable mixtures 72% is R-32 in volume. It therefore became a conservative one Evaluation criterion used; the maximum concentration of R-32 in the fluid vapor should be 68 vol.% to be non-flammable sure.

These Evaluation was carried out for mixtures, the R-134a contained between 0 and 10 wt% in the mixture. Higher shares of R-134a were not used in this review because the entire GWP should be lower than 150. The GWP values included in this Examination used are: R-32 = 550, R-134a = 1300 and R-1225ye = 10.

• • Eine volumetrische Kapazität innerhalb von 90 % von R-134a;
• • Energieeffizienz (ausgedrückt als Leistungszahl) innerhalb von 95 % von R-134a, oder Idealerweise vergleichbar mit oder besser als die von R-134a;
• • Betriebsdrücke ähnlich (vorzugsweise innerhalb etwa 10 %)
• • Kompressor-Austrittstemperatur ähnlich (innerhalb von 10°C);
• • nicht-entflammbar gemäß den Anforderungen des ASHRAE-Standards 34, Addendum p34 (Version 2004);
• • Temperatur-"Glide" von weniger als etwa 5°C; und
• • GWP niedriger als 150, um die europäische F-Gas-Direktive bei mobilen Klimaanlagen(MAC)-Anwendungen zu erfüllen.

A replacement fluid for R-134a in an air conditioner has a number of desirable characteristics. These include:

• • A volumetric capacity within 90% of R-134a;
• • Energy efficiency (expressed as COP) within 95% of R-134a, or ideally comparable to or better than that of R-134a;
• • Operating pressures similar (preferably within about 10%)
• • Compressor outlet temperature similar (within 10 ° C);
• • non-flammable according to the requirements of ASHRAE standard 34, Addendum p34 (version 2004);
• Temperature glide of less than about 5 ° C; and
• • GWP lower than 150 to meet the European F-Gas Directive for mobile air conditioning (MAC) applications.

at many embodiments preferred compositions of the invention are "non-azeotropic" as described above; these in particular include the ternary described herein and quaternaries Compositions. Such compositions may be described as Zeotropic, zeotropic mixtures and non-azeotropic refrigerant mixtures (NARMS). Such compositions show different Degree of temperature glide during of boiling or condensing, and also show differences in the vapor composition and liquid composition in Balance.

The tables 1 to 7 mentioned in the following examples are in the figure part as 1 to 7 to find.

Examples

example 1

The data in Table 1 provide an illustration of the behavior of exemplary, non-limiting, blends for the replacement of R-134a. The thermodynamic properties used to calculate the behavior were determined as follows:
The Peng-Robinson equation of state was used to calculate gas density, enthalpy and entropy values and was used to calculate the latent heat of vaporization and the vapor to predict equilibrium data for the mixtures of interest. The basic properties of the fluids required by this equation (critical temperature, critical pressure and acentric factor), with the exception of those for the fluorinated propenes R-1234yf and R-1225ye, were taken from reliable sources; mainly the NIST webbook site http://webbook.nist.gov. The critical properties of R-1234yf were determined by measurement using a static cell. The critical properties of R-1225ye were estimated using the boiling point for the isomer mixture of -18 ° C and the Joback group contribution method. The acentric factor for R-1234yf was calculated from measurements of vapor pressure. The acentric factor for R-1225ye was estimated using the Lee-Kesler relationship. The ideal gas enthalpy data for the propenes were also estimated using the Joback group contribution method. All of the above estimation techniques are described in the text "The Properties of Gases &Liquids" by RC Reid, JM PraGusnitz &% BE Poling, 4th Edition, published by McGraw-Hill.

The Peng-Robinson equation uses a binary interaction constant to describe the vapor-liquid equilibrium of binary pairs. This constant was set to zero if no data were available for mix pairs; otherwise, their value was chosen to provide a good representation of the known equilibrium data at temperatures near 0 ° C. Binary data for pairs in fluids R-32 / R-125 / R-134a were obtained from measurements published in M. Nagel, K. Bier, Int. J. Refrig. 18 (1995) 534-543. Binary data for R-1225ye with R-1234yf was taken from US patent application US 2005/02339321 A1. Binary data for R-32 with CO ₂ were removed from Rivollet et al., Fluid Phase Equilibria 218 (2004), pp 95-101. Binary data for R-32 with propane were taken from Fluid Phase Equilibria 199 (2002) 175-183. Binary data for R-1270 (propene) with R-134a and R-152a were taken from Kleiber Fluid Phase Equilibria 92 (1994) 149-194. Other data were measured using a static cell technique to measure the total pressure of a mixture of known composition. The data was then regressioned using Barker's technique, with the data points weighted using the maximum probabilistic principle to account for temperature and pressure measurement errors, so that the required binary interaction parameters are suitable for use with the equation of state ,

All References to literature and sources of publication hereby incorporated by reference in the relevant part.

Example 2

Of the ASHRAE standard 34 (which is the safety classification of refrigerants in its addendum p34 gives a series of flammability testing tests at. These require the measurement or prediction under application a verified computer model of the degree to which a fractionation of the Concentration of flammable species in the refrigerant vapor and / or liquid phases affected. This work focused on the test protocol according to Addendum p34 for the evaluation of the vapor concentration in an initially 90% filled Cylinder, if this at 10 ° C above its Bubble point at atmospheric pressure chilled was subjected to mass deprivation by steam extraction, until the cylinder is no liquid contains more. The reason is that the flammable ingredient in these blends, R-32, also the most volatile is, so he is during the fractionation the strongest enriched in the vapor phase. The other test protocols included in the addendum p34 results in a less strong one Fractionation of the R-32.

The Fractionation evaluation was carried out by means of a computer model according to the conditions specified in the p34 protocol. The "worst case formulation "(WCF) was estimated by giving the nominal mass ratios "as fed" of each constituent in the mixture took 0.5 to the mass of the flammable ingredient (R-32) and 1% of the mass of nonflammable ingredients (R-134a and R-1225ye). For example, the mixture will have a "like charged" formulation R-32 / R-134a / R-1225ye (6% / 7% / 87% by weight) a WCF rate of mass ratios of these components from 6.5 / 6/86.

The Fractionation of the mixture was modulated using the Peng-Robinson equation of state to the vapor-liquid equilibrium of the system. The equation parameters have been optimized using measured vapor-liquid equilibrium data for the binary Pairs R-32 / R-1225ye and R-32 / R-134a. The balance between R-134a and R-1225ye were modeled as ideal.

The Modeled compositions are shown in Table 2.

Based of the compositions shown in Table 2 becomes a Number of important characteristic determined. In particular exists an area for Compositions, for a COP higher than that of R-134a is found. When R-32 is added to the mixture, the COP rises above the for R-134a on, reaches a maximum and then decreases. It was found that this effect does not compare to one Adding R-134a to the system is sensitive. To a maximum To obtain COP, it is preferred that the mass ratio of R-32 to R-1225yeZ in a mixture that contains both of them (binary, ternary or quaternary) between 0.20 and 0.35.

Since it is an important task to reduce emissions greenhouse gases, increasing the energy efficiency of an R-134a replacement, particularly (but not limited to) in a mobile air conditioning system, is desirable, as well as a reduction in the direct greenhouse effect potential of the air conditioning system refrigerant. In the context of mobile air conditioners, the reason is that the work of an air conditioner is driven by the burning of car fuel, and thus with a release of CO ₂ into the atmosphere.

Further shows the fractionation analysis that mixtures with a mass ratio of R-32: R-1225yeZ greater than about 0.25: 1 flammable vapors at the -20 ° C fractionation analysis condition deliver. It is therefore advantageous, the mass ratio of this keep both components below this threshold.

Additionally takes the evaporator temperature glide when R-32 is added to the mixture becomes. Temperature glides of 5K or less are achieved when the mass ratio from R-32 to R-1225yeZ is less than 0.15. Temperature glides of 4K or less is achieved when the mass ratio is lower is 0.11.

It was also advantageously found that the volumetric capacity of mixtures, the R-32 and R-1225yeZ contain 90% or more of the capacity of R-134a amount if the mass ratio R-32: R-1225yeZ is 0.04: 1 or more.

in the With regard to preferred compositions containing both R-32 and R-1225yeZ included, the mass fraction R-32 should be up to 0.35 of the bulk fraction of R-1225yeZ in the composition amount to to maximize the COP. additionally should the mass fraction of R-32: R-1225yeZ be up to about 0.25, to ensure maximum COP for a non-flammable classification. Furthermore, the mass ratio should from R-32: R-1225yeZ up to about 0.15 to contribute to the glide of the composition 5 ° C or to hold under it.

Further should be the mass ratio from R-32: R-1225yeZ are between 0.04 and 0.15, to the capacity of the composition within 10% of those of R-134a, in a glide less than 5 ° C.

Further should be the mass ratio from R-32: R-1225yeZ are between about 0.04 and 0.11, to be an acceptable one capacity to obtain, and a glide of less than 4 ° C.

A Composition with a mass ratio of 5 to 7 parts R-32, 6 to 8 parts R-134a and 86 to 88 parts R-1225yeZ (where the sum all parts is 100), preferably from 6: 7: 87 R-32: R-134a: R-1225yeZ, combines these advantageous attributes.

Example 3

The Tables 3 to 7 provide a similar Information like the one shown in the context of Example 2 will, for different formulations.

In The following tables correspond to rows marked with a are compositions in which the "worst case" fractional formulation in the Low temperature 90% test (according to ASHRAE p34) has a flammable vapor according to the test protocol at 100 ° C, as specified in ASHRAE p34.

Claims (56)

Heat transfer composition which includes: (i) R-1225ye; (ii) at least one more Refrigerant that selected is made of carbon dioxide (R-744); Fluoromethane (R-41); difluoromethane (R-32); Fluoroethane (R-161); 1,1,1-trifluoroethane (R-143a); 1,1,1,2-tetrafluoroethane (R-134a); 1,1,2,2-tetrafluoroethane (R-134); dimethyl ether; heptafluoropropane (R-227ea); Propane (R-290); Propene (R-1270); Isobutane (R-600a); n-butane (R-600); 2,3,3,3-tetrafluoropropene (R-1234yf); 1,1-difluorocyclopropane; 1,1,2-Trifluorcyclopropan; 1,1,2,2-tetrafluoro cyclopropane; Pentafluorocyclopropane, or ammonia, or mixtures thereof. Heat transfer composition which includes: (i) R-1225yeZ; (ii) R-32, R-161 or R-152a; and (iii) at least one further refrigerant selected from carbon dioxide (R-744); Fluoromethane (R-41); Fluoroethane (R-161); 1,1,1-trifluoroethane (R-143a); 1,1,1,2-tetrafluoroethane (R-134a); 1,1,2,2-tetrafluoroethane (R-134); dimethyl ether; heptafluoropropane (R-227ea); Propane (R-290); Propene (R-1270); Isobutane (R-600a); n-butane (R-600), 2,3,3,3-tetrafluoropropene (R-1234yf); 1,1-difluoro-cyclopropane; 1,1,2-Trifluorcyclopropan; 1,1,2,2-tetrafluoro cyclopropane; Pentafluorocyclopropane, Pentafluoroethane (R-125) or ammonia, or mixtures thereof. Heat transfer composition which includes: (i) R-1225yeZ; (ii) R-32; and (Iii) R-1234yf; and (iv) at least one additional refrigerant, that selected is made of carbon dioxide (R-744); Fluoromethane (R-41); Fluoroethane (R-161); 1,1,1-trifluoroethane (R-143a); 1,1,1,2-tetrafluoroethane (R-134a); 1,1,2,2-tetrafluoroethane (R-134); dimethyl ether; heptafluoropropane (R-227ea); Propane (R-290); Propene (R-1270); Isobutane (R-600a); n-butane (R-600); 1,1-difluorocyclopropane; 1,1,2-Trifluorcyclopropan; 1,1,2,2-tetrafluoro cyclopropane; Pentafluorocyclopropane, Pentafluoroethane or ammonia, or mixtures thereof. Heat transfer composition which includes: (i) R-1225yeZ; (ii) R-32 and (iii) R-125; and (iv) R-161 or R152a. A composition according to claim 2 or claim 3, the additional refrigerant R-134a or R-125 is, preferably R-134a. A composition according to claim 2, wherein the R-32, R-161 or R-152a is only R-32. Composition according to any of the preceding Claims, wherein the R-1225ye comprises at least 80% Z isomer. Composition according to any of the preceding Claims, wherein the heat transfer composition R-1225yeZ, R-152a and R-125. Composition according to any of the preceding Claims, wherein the heat transfer composition R-1225yeZ, R-161 and R-134a. Composition according to any of the preceding Claims, wherein the heat transfer composition R-1225yeZ, R-161 and R-125. Composition according to any of the preceding Claims, wherein the heat transfer composition R-1225yeZ, R-125 and R-32. Composition according to any of the preceding Claims, wherein the heat transfer composition R-125 (1 to 3 parts), R-152a (1 to 12 parts) and R-1225yeZ (85 to 98 parts). Composition according to any of the preceding Claims, wherein the heat transfer composition R-125 (1 to 4 parts), R-161 (1 to 4 parts) and R-1225yeZ (92 to 98 parts). Composition according to any of the preceding Claims, wherein the heat transfer composition R-161 (1 to 4 parts), R-134a (1 to 10 parts), and R-1225yeZ (86 to 98 parts). Composition according to any of the preceding Claims, wherein the heat transfer composition R-32 (1 to 3 parts), R-125 (1 to 3 parts), R-152a (1 to 13 parts) and R-1225yeZ (81 to 97 parts). Composition according to any of the preceding Claims, wherein the heat transfer composition R-32 (1 to 3 parts), R-125 (1 to 3 parts), R-161 (1 to 5 parts) and R-1225yeZ (89 to 97 parts). Composition according to any of the preceding Claims, wherein the heat transfer composition R-32 (1 to 9 parts), R-134a (4 to 8 parts), R-1234yf (4 to 44 parts) Parts) and R-1225yeZ (48 to 89 parts). Composition according to any of the preceding Claims, wherein the heat transfer composition R-32 (3 to 9 parts), R-134a (4 to 8 parts), R-1234yf (4 to 28 parts) Parts) and R-1225yeZ (55 to 88 parts). Composition according to any of the preceding Claims, wherein the heat transfer composition R-32 (4 to 9 parts), R-134a (4 to 6 parts), R-1234yf (4 to 24 parts) Parts) and R-1225yeZ (73 to 88 parts). Composition according to any of the preceding Claims, wherein the heat transfer composition R-32 (1 to 4 parts), R-134a (4 to 8 parts), R-1234yf (4 to 44 parts) Parts) and R-1225yeZ (48 to 89 parts). Composition according to any of the preceding Claims, wherein the composition has a coefficient of performance (COP) within 10% of the fluid that it is to replace, for example R-134a. Composition according to any of the preceding Claims, wherein the composition has a capacity that is larger as the R-1225ye and / or R-1225yeZ. Composition according to any of the preceding Claims, wherein the composition is not azeotropic. Composition according to any of the preceding Claims, where the mass ratio of R-32 to R-1225yeZ in the composition between 0.20 and 0.35: 1 lies. Composition according to any of the preceding Claims, where the mass ratio of R-32 to R-1225yeZ in the composition is below 0.25: 1. Composition according to any of the preceding Claims, where the mass ratio of R-32 to R-1225yeZ is less than 0.15: 1. A composition according to claim 26, wherein the mass ratio of R-32 to R-1225yeZ is less than 0.11: 1. Composition according to any of the preceding Claims, where the mass ratio of R-32 to R-1225yeZ is 0.04: 1 or more. Composition according to any of the preceding Claims, where the mass ratio of R-32 to R-1225yeZ is between 0.06 and 0.08. A composition according to any one of the preceding claims, wherein the mass ratio from R-32 to R-1225yeZ is 0.07: 1. Composition according to any of the preceding Claims, the composition being 6% R-32, 7 R-134a and 87% R-1225yeZ includes. Composition according to any of the preceding Claims, wherein the R-1225yeZ ingredient comprises at least 95% Z isomer. The composition of claim 32, wherein the R-1225yeZ ingredient is at least 98% Z isomer. Composition according to any of the preceding Claims, which has a GWP of about 150 or less. Composition according to any of the preceding Claims, which has a GWP of about 100 or less. Composition according to any of the preceding Claims, the 5 to 7 parts R-32 or R-161, preferably R-32, 6 to 8 parts R-134a or R-125, preferably R-134a, and 86 to 88 parts R-1225yeZ wherein the sum of all parts is 100. Composition according to any of the preceding Claims, 2 to 5 parts R-32, 2 to 5 parts R-125, 2 to 6 parts R-161 and 84 to 94 parts R-1225yeZ, where the sum of all parts 100 is. Composition according to any of the preceding Claims, the 2 to 4 parts R-32, 2 to 4 parts R-125, 10 to 13 parts R-152a and 79 to 86 parts R-1225yeZ includes, where the sum of all parts 100 is. Composition according to any of the preceding Claims, the 2 to 4 parts R-161, 2 to 4 parts R-125 and 92 to 96 parts R-1225yeZ, where the sum of all parts is 100. Composition according to any of the preceding Claims, the moreover includes a lubricant. A composition according to claim 40, wherein the lubricant selected is from mineral oil, Silicone oil, Polyalkylbenzenes (PABs), polyol esters (POEs), polyalkylene glycols (PAGs), polyalkylene glycol esters (PAG esters), polyvinyl ethers (PVEs), Poly (alpha-olefins) and mixtures thereof. Composition according to any of the preceding Claims, the moreover includes a stabilizer. The composition of claim 42, wherein the stabilizer selected is composed of diene-based compounds, phosphates, phenolic compounds and epoxides and mixtures thereof. Composition according to any of the preceding Claims, the moreover an additional flame retardant agent. A composition according to claim 44, wherein the additional Flame retardant agent selected from tri (2-chloroethyl) phosphate, (chloropropyl) phosphate, tri- (2,3-dibromopropyl) phosphate, Tri- (1,3-dichloropropyl) phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, Polyvinyl chloride, a fluorinated iodocarbon, a fluorinated one Bromocarbon, trifluoroiodomethane, perfluoroalkylamines, bromofluoroalkylamines and mixtures thereof. Composition according to any of the preceding Claims, wherein the composition is non-flammable. Composition according to any of the preceding Claims, the one refrigerant composition is. Heat transfer device which contains a composition, as stated in any of the claims 1 to 47 is defined. Heat transfer device according to claim 48, which is a refrigeration device is. Heat transfer device according to claim 49 selected is from air conditioners for Automobiles, air conditioners for the living area, commercial air conditioners, residential cooling systems, freezer systems for the Residential area, commercial refrigeration systems, commercial freezer systems, radiator air conditioners, Radiator cooling systems and heat pump systems. Heat transfer device according to claim 49 or 50, which contains a compressor. Propellant comprising a composition, such as in any of the claims 1 to 46 is defined. 53 Foamable composition, the contains one or more constituents capable of foaming, and a composition as defined in any of claims 1 to 46 is defined. expandable The composition of claim 53, wherein the one or more Component (s) capable of forming a foam are selected from polyurethanes, thermoplastic polymers and resins such as Polystyrene and epoxy resins and mixtures thereof. Foam made from the foamable composition of Claim 53 or 54 available is. A foam according to claim 55 which is a composition comprises as defined in any one of claims 1 to 46. Composition that is sprayable and one to be sprayed Material and a propellant comprising a composition, as stated in any of the claims 1 to 46 is defined.