RU2574656C2 - Heat transfer compositions - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention refers to a heat exchange composition, which is applicable to substitute existing coolants, which are expected to have a reduced global warming potential (GWP). A heat transfer composition contains trans-1,3,3,3-tetrafluorpropene (R-1234ze(E)), carbon dioxide (R-744) and a third component specified in 2,3,3,3-tetrafluorpropene (R-1234yf), 3,3,3-trifluorpropene (R-1243zf) and mixtures thereof.

EFFECT: inventions provide coolants with a combination of the improved properties - reduced global warming potential, inflammability and toxicity alongside with good cooling performance and miscibility with lubricants.

47 cl, 2 dwg, 34 tbl

Description

FIELD OF THE INVENTION

The present invention relates to compositions for heat transfer, and in particular, to compositions for heat transfer, which may be suitable as a replacement for existing refrigerants, such as R-134a, R-152a, R-1234yf, R-22, R-410A , R-407A, R-407B, R-407C, R507 and R-404a.

State of the art

The listing or discussion of previously published documents or any literary data in the description does not have to be taken as an admission that the document or literary data is part of the state of the art or is a common common knowledge.

Mechanical refrigeration systems and associated heat transfer devices, such as heat pumps and air conditioning systems, are well known. In such systems, the liquid refrigerant evaporates at low pressure, drawing heat from the surrounding area. Then the resulting pairs are compressed and passed to the condenser, where they condense and give off heat in the second zone, the condensate is returned through the expansion valve to the evaporator, thus completing the cycle. The mechanical energy necessary for vapor compression and fluid pumping is provided, for example, by an electric motor or an internal combustion engine.

In addition to having a suitable boiling point and high latent heat of vaporization, properties preferred for the refrigerant include low toxicity, non-flammability, non-corrosiveness, high stability and no unpleasant odors. Other desirable properties are high compressibility at pressures below 25 bar, low compression release temperature, high cooling ability, high efficiency (high efficiency) and evaporator pressure in excess of 1 bar at the desired evaporation temperature.

Dichlorodifluoromethane (R-12 refrigerant) has an appropriate combination of properties, and for many years it has been the most widely used refrigerant. Due to international problems related to the fact that fully and partially halogenated chlorofluorocarbons damage the protective ozone layer of the Earth, there is a general agreement that their production and use should be strictly limited and, ultimately, it should be completely stopped. The use of dichlorodifluoromethane was discontinued in the 1990s.

Chlorodifluoromethane (R-22) was introduced as a replacement for R-12 due to its lower ozone depletion potential. After problems with the fact that R-22 is a gas causing a strong greenhouse effect, its use was also discontinued.

Although heat transfer devices of the type to which the present invention relates are generally closed systems, refrigerant losses to the atmosphere can occur due to leakage during equipment operation or during maintenance procedures. It is important, for this reason, to replace fully and partially halogenated chlorofluorocarbon refrigerants with materials that have zero ozone depletion potentials.

In addition to the potential for destruction of the ozone layer, it is believed that significant concentrations of halocarbon refrigerants in the atmosphere could contribute to global warming (the so-called greenhouse effect). For this reason, it is desirable to use refrigerants that have relatively short lifetimes in the atmosphere as a result of their ability to interact with other atmospheric components, such as hydroxyl radicals, or as a result of light degradation through photolytic processes.

R-410A and R-407 refrigerants (including R-407A, R-407B and R-407C) were introduced as refrigerant to replace R-22. However, all R-22, R-410A and R-407 refrigerants have a high global warming potential (GWP, also known as the greenhouse effect potential).

1,1,1,2-tetrafluoroethane (R-134a refrigerant) was introduced as a refrigerant to replace R-12. R-134a is the energy-efficient refrigerant currently used for air conditioning in cars. However, it is a greenhouse gas with GWP 1430 with respect to CO ₂ (GWP CO ₂ is 1 by definition). The share of the total environmental impact from automotive air conditioning systems using this gas, which can be attributed to direct refrigerant emissions, is usually in the range of 10-20%. European Union lawmakers are banning the use of refrigerants with more than 150 GWPs for new car models starting in 2011. The automotive industry works with global technology platforms, and in any case, greenhouse gas emissions have global impacts, so there is a need to find fluids that have reduced environmental impact (e.g., reduced GWP) compared to HFC-134a.

R-152a (1,1-difluoroethane) is identified as an alternative to R-134a. It is slightly more effective than R-134a and has a greenhouse effect potential of 120. However, the flammability of R-152a is considered too high, for example, to allow its safe use in mobile air conditioning systems. In particular, it is believed that its lower flammability limit in air is too low, its flame spreads too quickly and its ignition energy is too low.

Thus, there is a need to create alternative refrigerants having improved properties, such as low flammability. The chemistry of fluorocarbon combustion is complex and unpredictable. It is not always the rule that mixing non-flammable fluorocarbon with flammable fluorocarbon reduces the flammability of a fluid or reduces the range of compositions that are flammable in air. For example, the authors found that if non-flammable R-134a is mixed with flammable R-152a, the lower flammability of the mixture changes in a way that is not predictable. The situation becomes even more complex and less predictable if three- or four-component compositions are considered.

There is also a need for alternative refrigerants that can be used in existing devices, such as refrigeration units, with little or no modification.

R-1234yf (2,3,3,3-tetrafluoropropene) has been identified as a candidate for alternative refrigerants to replace R-134a in certain applications, namely in applications for mobile air conditioning or in applications for heat pumps. Its GWP is approximately 4. The R-1234yf is flammable, but its flammability characteristics are generally considered acceptable for some applications, including mobile air conditioning systems or heat pumps. In particular, when compared with R-152a, its lower ignition limit is higher, its minimum ignition energy is higher, and the speed of flame propagation in air is much lower than for R-152a.

The environmental impact of the operation of an air conditioning system or a refrigeration system, in terms of greenhouse gas emissions, should be considered not only with the so-called “direct” GWP refrigerant, but also with the so-called “indirect” emissions that mean those emissions carbon dioxide, which result from the consumption of electricity or fuel to operate the system. Several quantitative indicators of this total GWP impact have been developed, including those known as the Total Equivalent Warming Index (TEWI) analysis or the Climate Impact Ratio Analysis for the entire life cycle of the low temperature system (LCCP). Both of these parameters include an assessment of the effect of the GWP refrigerant and its energy efficiency on the greenhouse effect as a whole. Carbon dioxide emissions associated with the production of refrigerant and system equipment should also be considered.

The energy efficiency and cooling capacity of R-1234yf was found to be significantly lower than that of R-134a, and in addition, the fluid was found to exhibit an increased pressure drop in the system piping and in the heat exchangers. The consequence of this is that in order to use R-1234yf and to achieve energy efficiency and cooling performance equivalent to R-134a, it is necessary to increase the complexity of the equipment and increase the size of pipelines, which leads to an increase in indirect emissions associated with the equipment. In addition, the production of R-1234yf is considered more complex and less efficient in its use of the starting materials (fluorinated and chlorinated) than R-134a. Current predictions of long-term price changes for R-1234yf are in the range of 10-20-fold compared to R-134a. Price differences and the need for additional hardware costs will limit the speed at which refrigerants are replaced, and therefore limit the speed at which the overall environmental impact of cooling or air conditioning can decrease. As a result, the adoption of R-1234yf to replace R-134a will lead to the consumption of more raw materials, and lead to an increase in indirect greenhouse gas emissions compared to R-134a.

Some existing technologies developed for R-134a may not be able to absorb even the limited flammability of some heat transfer compositions (any composition having a GWP of less than 150 is considered flammable to some extent).

For this reason, the main objective of the present invention is to provide a composition for heat transfer, which can be used on its own or is suitable for use as a replacement for existing cooling applications, which should have reduced GWP, and in addition, have cooling ability and energy efficiency (which can be conveniently expressed as a "coefficient of performance") ideally within 10% of those, for example, values obtained using existing refrigerants (e.g. Imer, R-134a, R-152a, R-1234yf, R-22, R-410A, R-407A, R-407B, R-407C, R507 and R-404a), and preferably within less than 10% ( for example, approximately 5%) of these values. In this area it is known that differences of this order between fluids can usually be taken into account by changing the design of the equipment and the characteristics of the system. The composition should also ideally have reduced toxicity and acceptable flammability.

Disclosure of invention

The subject invention compensates for these drawbacks by providing a heat transfer composition comprising (i) a first component selected from trans-1,3,3,3-tetrafluoropropene (R-1234ze (E)), cis-1,3,3,3 -tetrafluoropropene (R-1234ze (Z)) and mixtures thereof; (ii) carbon dioxide (CO ₂ or R-744); and (iii) a third component selected from 2,3,3,3-tetrafluoropropene (R-1234yf), 3,3,3-trifluoropropene (R-1243zf), and their mixtures.

All chemicals described herein are commercially available. For example, fluorochemicals can be obtained from Apollo Scientific (UK).

Typically, the compositions of the present invention contain trans-1,3,3,3-tetrafluoropropene (R-1234ze (E)). Most of the specific compositions described herein contain R-1234ze (E). It should be understood, of course, that some or all of R-1234ze (E) in such compositions may be replaced by R-1234ze (Z). However, the trans isomer is currently preferred.

Typically, the compositions of the present invention contain at least about 5 wt.% R-1234ze (E), preferably at least about 15 wt.%. In one embodiment, the compositions of the present invention comprise at least about 45% by weight of R-1234ze (E), for example about 50 to about 98% by weight.

Preferred amounts and selection of components for the present invention are determined by a combination of properties:

(a) Flammability: non-flammable or slightly flammable compositions are preferred.

(b) Effective refrigerant operating temperature in the air conditioning evaporator.

(c) The temperature "glide" of the mixture and its effect on the performance of the heat exchanger.

(d) Critical temperature of the composition. It should be higher than the maximum expected temperature of the condenser.

The effective operating temperature in the air conditioning cycle, in particular when air conditioning in the car, is limited by the need to avoid the formation of ice on the surface of the refrigerant in the evaporator from the air side. As a rule, air conditioning systems should cool moist air and drain it; in this case, liquid water will form on the surface from the air side. Most evaporators (without exception for automotive applications) have plate surfaces with narrow gaps between the plates. If the evaporator is too cooled, then ice may form between the plates, restricting the air flow above the surface and degrading overall performance by reducing the working area of the heat exchanger.

For automotive air conditioning applications, it is known (Modern Refrigeration and Air Conditioning by AD Althouse et al., 1988 edition, Chapter 27, which is incorporated herein by reference) that refrigerant vaporization temperatures of -2 ° C or higher are preferred, to thereby eliminate the problem of ice formation.

It is also known that non-azeotropic mixtures of refrigerants exhibit a temperature glide during evaporation or condensation. In other words, when the refrigerant gradually evaporates or condenses at constant pressure, the temperature rises (during evaporation) or drops (during condensation), while the total temperature difference (between inlet and outlet) is referred to as the temperature glide. The effect of glide on the temperature of evaporation and condensation should also be taken into account.

The critical temperature of the heat transfer composition should be higher than the maximum expected temperature of the condenser. This is due to the fact that the efficiency of the cycle decreases when approaching the critical temperature. When this happens, the latent heat of the refrigerant decreases and there is a greater heat dissipation from the condenser due to cooling of the gaseous refrigerant; this requires a larger area per unit of heat transferred.

The R-410A is widely used in heat pump systems for large buildings and small private houses, and, as an illustration, its critical temperature, approximately 71 ° C, is higher than the highest normal condensation temperature required to produce usable warm air at about 50 ° C. Use in automobiles requires air at about 50 ° C, so that the critical temperature of the fluids of the present invention should be higher than this value if a conventional vapor compression cycle is to be used. The critical temperature is preferably at least 15 K higher than the maximum air temperature.

In one aspect, the compositions of the present invention have a critical temperature higher than about 65 ° C, preferably higher than about 70 ° C.

The carbon dioxide content of the compositions of the present invention is mainly limited by considerations (b) and / or (c) and / or (d) above. Conveniently, the compositions of the present invention typically contain up to about 35 wt.% R-744, preferably up to about 30 wt.%.

In a preferred aspect, the compositions of the present invention comprise from about 4 to about 30 wt.% R-744, preferably from about 4 to about 28 wt.%, Or from about 8 to about 30 wt.%, Or from about 10 to about 30 wt.%.

The content of the third component, which may include flammable refrigerants, such as R-1234yf, is chosen so that even in the absence of a carbon dioxide element in the composition, the remaining fluorocarbon mixture has a lower flammability limit in air at ambient temperature (e.g. 23 ° C) (as determined in a test apparatus with a 12 liter flask ASHRAE-34) which is greater than 5% v / v, preferably greater than 6% v / v, most preferably such that the mixture is non-flammable. Flammability problems are discussed further in the present description, below.

Typically, the compositions of the present invention contain up to about 60 wt.% Of the third component. Preferably, the compositions of the present invention contain up to about 50 wt.% Of the third component. Conveniently, the compositions of the present invention contain up to about 45% by weight of the third component. In one aspect, the compositions of the present invention comprise from about 1 to about 40 wt.% Of the third component.

In one embodiment, the compositions of the present invention comprise from about 10 to about 95 wt.% R-1234ze (E), from about 2 to about 30 wt.% R-744, and from about 3 to about 60 wt.% Third component.

As used herein, all% of the amount referred to in the compositions herein, including the claims, represent mass% with respect to the total weight of the compositions, unless otherwise stated.

For the avoidance of doubt, it is necessary to understand that the stated upper and lower values for the ranges of the amounts of components in the compositions of the present invention described herein can be interchanged in any way, provided that the resulting ranges fall within the broadest scope of the present invention.

In one embodiment, the compositions of the present invention consist essentially of (or consist of) a first component (e.g., R-1234ze (E)), R-744, and a third component.

By using the term "consist essentially of", the authors indicate that the compositions of the present invention essentially do not contain other components, in particular, no (hydro) (fluorine) compounds (e.g., (hydro) (fluorine) alkanes or (hydro ) (fluorine) alkenes), which are known to be used in compositions for heat transfer. The authors include the term "consists of" in the meaning of "consists mainly of".

For the avoidance of doubt, any compositions of the present invention described herein include compositions with specifically defined compounds and amounts of compounds or components, may consist essentially of (or consist of) the compounds or components defined in these compositions.

The third component is selected from R-1234yf, R-1243zf and mixtures thereof.

In one aspect, the third component contains only one of the listed components. For example, the third component may contain only one component from R-1234yf or R-1243zf. Thus, the compositions of the present invention can be ternary mixtures of R-1234ze (E), R-744 and one of these third components (for example, R-1234yf or R-1243zf).

However, mixtures of R-1234yf and R-1243zf can be used as the third component.

The present invention provides compositions in which additional compounds are included in the third component. Examples of such compounds include difluoromethane (R-32), 1,1-difluoroethane (R-152a), fluoroethane (R-161), 1,1,1,2-tetrafluoroethane (R-134a), 1,1,1- trifluoropropane (R-263fb), 1,1,1,2,3-pentafluoropropane (R-245eb), propylene (R-1270), propane (R-290), n-butane (R-600), isobutane (R -600a), ammonia (R-717) and mixtures thereof.

For example, the compositions of the present invention may include R-134a. If present, R-134a is typically present in an amount of from about 2 to about 50 wt.%, For example, from about 5 to about 40 wt.% (For example, from about 5 to about 20 wt.%).

Preferably, compositions of the present invention that contain R-134a are non-flammable at a study temperature of 60 ° C. using the ASHRAE-34 methodology. Advantageously, vapor mixtures that exist in equilibrium with the compositions of the present invention at any temperature in the range of between about -20 ° C and about 60 ° C are also non-flammable.

In one preferred embodiment, the third component comprises R-1234yf. The third component may consist mainly of (or consists of) R-1234yf.

Compositions of the present invention that contain R-1234yf typically contain it in an amount of from about 2 to about 60 wt.%, For example from about 4 to about 50 wt.%. Conveniently, R-1243yf is present in an amount of from about 6 to about 40%.

Preferred compositions of the present invention contain from about 10 to about 92 wt.% R-1234ze (E), from about 4 to about 30 wt.% R-744, and from about 4 to about 60 wt.% R-1234yf. For example, such compositions may contain from about 22 to about 84 wt.% R-1234ze (E), from about 10 to about 28 wt.% R-744, and from about 6 to about 50 wt.% R-1234yf.

In addition, preferred compositions of the present invention contain from about 14 to about 86 wt.% R-1234ze (E), from about 4 to about 26 wt.% R-744, and from about 10 to about 60 wt.% R-1234yf .

Another group of compositions of the present invention, containing R-1234yf, contains from about 32 to about 88 wt.% R-1234ze (E), from about 8 to about 28 wt.% R-744 and from about 4 to about 40 wt. % R-1234yf.

In one embodiment, the third component comprises R-1243zf. The third component may consist mainly of (or consist of) R-1243zf.

Compositions of the present invention that contain R-1243zf typically contain it in an amount of from about 2 to about 60 wt.%, For example, about 4 to about 50 wt.%. Conveniently, R-1243zf is present in an amount of about 6 to about 40%.

Preferred compositions of the present invention contain from about 20 to about 92 wt.% R-1234ze (E), from about 4 to about 30 wt.% R-744, and from about 4 to about 50 wt.% R-1243zf. For example, such compositions may contain from about 32 to about 88 wt.% R-1234ze (E), from about 6 to about 28 wt.% R-744, and from about 6 to about 40 wt.% R-1243zf.

Additional advantageous compositions of the present invention contain from about 25 to about 91 wt.% R-1234ze (E), from about 4 to about 30 wt.% R-744, and from about 5 to about 45 wt.% R-1243zf. For example, such compositions may contain from about 27 to about 85 wt.% R-1234ze (E), from about 10 to about 28 wt.% R-744, and from about 5 to about 45 wt.% R-1243zf.

The compositions of the present invention may further comprise pentafluoroethane (R-125). If present, R-125 is typically present in amounts up to about 40% by weight, preferably about 2 to about 20% by weight.

It is convenient that the compositions in accordance with the present invention essentially did not contain R-1225 (pentafluoropropene), essentially did not contain R-1225ye (1,2,3,3,3-pentafluoropropene) or R-1225zc (1, 1,3,3,3-pentafluoropropene), these compounds may have toxicity problems.

Using "substantially free", the authors include the meaning that the compositions of the present invention contain 0.5 wt.% Or less of the considered component, preferably 0.1% or less, relative to the total weight of the composition.

Certain compositions of the present invention cannot essentially contain:

(i) 2,3,3,3-tetrafluoropropene (R-1234yf),

(ii) cis-1,3,3,3-tetrafluoropropene (R-1234ze (Z)) and / or

(iii) 3,3,3-trifluoropropene (R-1243zf).

The compositions of the present invention have zero ozone depletion potential.

Typically, the compositions of the present invention have a GWP that is less than 1300, preferably less than 1000, more preferably less than 800, 500, 400, 300 or 200, in particular less than 150 or 100, even less than 50, in some cases . Unless stated otherwise, IPCC (Intergovernmental Panel on Climate Change) GWP FROM TAR (Third Report) is used in this document.

Advantageously, the compositions have a reduced flammability risk compared to the third component (s) per se, for example R-1234yf or R-1243zf. Preferably, the compositions have a reduced flammability risk compared to R-1234yf.

In one aspect, the compositions have one or more advantages of (a) a higher lower flammability limit; (b) a higher ignition energy or (c) a lower flame propagation rate compared to a third component (s), such as R-1234yf or R-1243zf. In a preferred embodiment, the compositions of the present invention are non-flammable. Advantageously, vapor mixtures that exist in equilibrium with the compositions of the present invention at any temperature in the range of between about -20 ° C and about 60 ° C are also non-flammable.

Flammability can be determined in accordance with ASHRAE Standard 34, including ASTM Standard E-681 (American Society for Testing Materials, Standard E-681), using a research methodology in accordance with Appendix 34p of 2004, the entire contents of which are incorporated herein by reference links.

In some applications, it may not be necessary to classify the drug as non-flammable according to ASHRAE-34; fluids can be developed in which the flammability limits are sufficiently reduced in air to make them safe for use in use, for example, if it is physically impossible to obtain a flammable mixture by leakage of charging refrigeration equipment into the environment.

R-1234ze (E) is non-flammable in air at 23 ° C, although it exhibits flammability at higher temperatures in humid air. The authors determined experimentally that mixtures of R-1234ze (E) with flammable fluorocarbons such as R-32, R-152a or R-161 will remain non-flammable in air at 23 ° C if the “fluorine ratio” R _{f of the} mixture greater than about 0.57, where R _f is determined by gram moles of the mixture of refrigerants as a whole as

R _f = (gram-mol of fluorine) / (gram-mol of fluorine + gram-mol of hydrogen).

Thus, for R-161, R _f = 1 / (1 + 5) = 1/6 (0.167), and it is flammable, in contrast to R-1234ze (E), it has R _f = 4/6 (0.667) and it is non-flammable. The authors found through experiments that a mixture of 20% volume / volume R-161 in R-1234ze (E) is similarly non-flammable. The fluorine ratio for this non-flammable mixture is 0.2 · (1/6) + 0.8 · (4/6) = 0.567.

The correctness of this relationship between flammability and a fluorine ratio of 0.57 or higher has so far been experimentally proven for HFC-32, HFC-152a, and mixtures of HFC-32 with HFC-152a.

Preferred compositions of the present invention have a fluorine ratio (F / (F + H)) from about 0.42 to about 0.7, preferably from about 0.44 to about 0.67.

Takizawa et al., Reaction Stoichiometry for Combustion of Fluoroethane Blends, ASHRAE Transactions 112 (2) 2006 (which is incorporated herein by reference), shows that there is a non-linear relationship between this ratio and flame propagation velocity in mixtures containing R- 152a, wherein an increase in the fluorine ratio leads to a decrease in the flame propagation velocity. The data in this link say that the fluorine ratio should be greater than about 0.65 so that the flame propagation rate drops to zero, in other words, so that the mixture is non-flammable.

Similarly, Minor et al. (Du Pont Patent Application WO 2007/053697) offer the concept of flammability of a variety of hydrofluoroolefins, showing that such compounds can be expected to be non-flammable if the fluorine ratio is greater than about 0.7.

Given this concept, known from the literature, it is unexpected that mixtures of R-1234ze (E) with flammable fluorocarbons such as R-1234yf or R-1243zf will remain non-flammable in air at 23 ° C if the fluorine ratio R _{f of the} mixture is greater than about than 0.57.

In addition, the authors determined that if the fluorine ratio is greater than about 0.46, then the composition can, as expected, have a lower flammability limit in air of more than 6% v / v at room temperature.

By producing low flammable or non-flammable mixtures of R-744 / third component / R-1234ze (E) containing unexpectedly low amounts of R-1234ze (E), the amounts of the third component, in particular in such compositions, are increased. This is believed to result in heat transfer compositions exhibiting improved cooling ability and / or reduced pressure drop compared to equivalent compositions containing higher amounts (e.g., almost 100%) of R-1234ze (E).

Thus, the compositions of the present invention exhibit a completely unexpected combination of low flammability / non-flammability properties, low GWP and improved cooling capacity. Some of these cooling capacities are explained in more detail below.

The temperature glide, which can be considered as the difference between the boiling point and the condensation temperature of a zeotropic (non-azeotropic) mixture at constant pressure, is a characteristic of the refrigerant; if it is desired to replace the fluid with a mixture, then it is often preferable to have the same or reduced glide in an alternative fluid. In one embodiment, the compositions of the present invention are zeotropic.

Advantageously, the volumetric cooling capacity of the compositions of the present invention is at least 85% of that of the existing liquid refrigerant to be replaced, preferably at least 90% or even at least 95%.

The compositions of the present invention typically have a volumetric cooling capacity which is at least 90% of R-1234yf. Preferably, the compositions of the present invention have a volumetric cooling capacity that is at least 95% of R-1234yf, for example from about 95% to about 120% of volumetric cooling capacity of R-1234yf.

In one embodiment, the cycle efficiency (coefficient of performance, COP) of the compositions of the present invention is in the range of about 5%, or even better, from the corresponding rate of the existing liquid refrigerant to be replaced.

Conveniently, the temperature at the outlet of the compressor for the compositions of the present invention is within about 15 K from the corresponding indicator of the existing liquid refrigerant to be replaced, preferably within about 10 K or even about 5 K.

The compositions of the present invention preferably have an energy efficiency of at least 95% (preferably at least 98%) of the corresponding value for R-134a under equivalent conditions, while having reduced or equivalent differential pressure characteristics and a cooling capacity of 95% or higher than values for R-134a. Advantageously, the compositions have higher energy efficiency and lower differential pressure characteristics than R-134a under equivalent conditions. The compositions also advantageously have better energy efficiency and differential pressure characteristics than the R-1234yf alone.

The heat transfer compositions of the present invention are suitable for use in existing equipment designs and are compatible with all classes of lubricants currently used in conjunction with HFC refrigerants. They may optionally stabilize or compatibilize with mineral oils through the use of appropriate additives.

Preferably, when used in heat transfer equipment, the composition of the present invention is combined with a lubricant.

Conveniently, the lubricant is selected from the group consisting of mineral oil, silicone oil, polyalkylbenzenes (PAB), polyol esters (POE), polyalkylene glycols (PAG), polyalkylene glycol esters (PAG esters), polyvinyl ethers (PVE), poly (alpha olefins) and combinations thereof.

Advantageously, the lubricant further comprises a stabilizer.

Preferably, the stabilizer is selected from the group consisting of compounds based on dienes, phosphates, phenolic compounds and epoxides and mixtures thereof.

Conveniently, the composition of the present invention can be combined with a flame retardant.

Preferably, the combustion retardant is selected from the group consisting of three (2-chloroethyl) phosphate, (chloropropyl) phosphate, three (2,3-dibromopropyl) phosphate, three (1,3-dichloropropyl) phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, fluorinated iodine carbon, fluorinated bromocarbon, trifluoroiodomethane, perfluoroalkylamines, bromo-fluoroalkylamines and mixtures thereof.

Preferably, the heat transfer composition is a refrigerant composition.

In one embodiment, the present invention provides a heat transfer device comprising a composition of the present invention.

Preferably, the heat transfer device is a refrigeration device.

Conveniently, the heat transfer device is selected from the group consisting of automotive air conditioning systems, residential air conditioning systems, commercial air conditioning systems, housing refrigeration systems, housing freezing systems, industrial refrigeration systems, industrial freezing systems, chiller air conditioning systems, chiller refrigeration systems and commercial or residential heat pump systems. Preferably, the heat transfer device is a refrigeration device or an air conditioning system.

The compositions of the present invention are particularly suitable for use in mobile air conditioning applications such as automotive air conditioning systems (e.g., a heat pump cycle for automotive air conditioning).

Advantageously, the heat transfer device comprises a centrifugal type compressor.

The present invention also provides the use of a composition of the present invention in a heat transfer apparatus as described herein.

In accordance with another aspect of the present invention, there is provided a purge agent comprising a composition of the present invention.

In accordance with another aspect of the present invention, there is provided a foaming composition comprising one or more components capable of forming a foam and a composition of the present invention.

Preferably, one or more components capable of forming a foam is selected from polyurethanes, thermoplastic polymers and resins, such as polystyrene and epoxy resins, and mixtures thereof.

In accordance with a further aspect of the present invention, there is provided a foam obtainable from the foaming composition of the present invention.

Preferably, the foam contains the composition of the present invention.

In accordance with another aspect of the present invention, there is provided a sprayable composition comprising the material to be sprayed and a propellant containing the composition of the present invention.

In accordance with another aspect of the present invention, there is provided a method of cooling an article, which comprises condensing a composition of the present invention, and then evaporating said composition in the vicinity of the article to be cooled.

In accordance with another aspect of the present invention, there is provided a method of heating an article, which comprises condensing a composition of the present invention near an article to be heated, and then evaporating said composition.

In accordance with another aspect of the present invention, there is provided a method for extracting a substance from a biological mass, comprising contacting the biological mass with a solvent containing the composition of the present invention and separating the substance from the solvent.

In accordance with another aspect of the present invention, there is provided a method for cleaning an article comprising contacting the article with a solvent containing the composition of the present invention.

In accordance with a further aspect of the present invention, there is provided a method for extracting a material from an aqueous solution, comprising contacting the aqueous solution with a solvent containing the composition of the present invention and separating the material from the solvent.

In accordance with another aspect of the present invention, there is provided a method for extracting material from a ground solid matrix, comprising contacting the ground solid matrix with a solvent containing the composition of the present invention and separating the material from the solvent.

In accordance with another aspect of the present invention, there is provided an apparatus for generating mechanical energy comprising a composition of the present invention.

Preferably, the mechanical energy generating device is adapted to use a Rankin cycle or a modification thereof to generate work from heat.

In accordance with another aspect of the present invention, there is provided a method for upgrading a heat transfer apparatus, comprising the step of removing existing heat transfer fluid and introducing a composition of the present invention. Preferably, the heat transfer device is a refrigeration device or a (static) air conditioning system. Advantageously, the method further includes the step of obtaining distributed benefits for reducing greenhouse gas emissions (eg, carbon dioxide).

According to the upgrade method described above, existing heat transfer fluid can be completely removed from the heat transfer device before introducing the composition of the present invention. Existing heat transfer fluid can also be partially removed from the heat transfer device, followed by the introduction of the composition of the present invention.

In another embodiment, wherein the existing heat transfer fluid is R-134a and the composition of the present invention comprises R134a, R-1234ze (E), R-744, a third component, and any R-125 present (and optional components, such as a lubricant, stabilizer or additional flame retardant), R-1234ze (E) and R-744 and the like can be added to R-134a in a heat transfer device, thereby forming the compositions of the present invention and a heat transfer device of the present invention, in situ. Some of the existing R-134a can be removed from the heat transfer device before adding R-1234ze (E), R-744 and the like to facilitate the preparation of the components of the compositions of the present invention in the desired proportions.

Thus, the present invention provides a method for producing a composition and / or heat transfer device of the present invention, comprising administering R-1234ze (E), R-744, a third component, any desired R-125, and optional components, such as a lubricant, a stabilizer or additional combustion retardant to a heat transfer device containing an existing heat transfer fluid, which is R-134a. Optionally, at least a portion of R-134a is removed from the heat transfer device before introducing R-1234ze (E), R-744 and the like.

Of course, the compositions of the present invention can also be obtained simply by mixing R-1234ze (E), R-744, the third component, any desired R-125 (and optional components, such as a lubricant, stabilizer or additional flame retardant) in the desired proportions. The compositions may then be added to a heat transfer device (or used in any other way as defined herein) that does not contain R-134a or any other existing heat transfer fluid, such as a device from which R-134a is removed or any other existing heat transfer fluid.

In another aspect of the present invention, there is provided a method of reducing environmental impact resulting from the operation of a product containing an existing compound or composition, the method comprising replacing, at least in part, an existing compound or composition with the composition of the present invention. Preferably, this method includes the step of obtaining distributed benefits for reducing greenhouse gas emissions.

As an environmental impact, the authors include the generation and release of warming greenhouse gases during product operation.

As discussed above, this environmental impact can be considered as including not only those emissions of compounds or compositions that have significant environmental impacts due to leaks or other losses, but also including carbon dioxide emissions resulting from the energy consumption of the device throughout his time. This environmental impact can be quantified using an indicator known as the Total Equivalent Warming Factor (TEWI). This indicator is used to quantify the environmental impact of certain stationary refrigeration and air conditioning equipment, including, for example, supermarket refrigeration systems (see, for example, http://en.wikipedia.org/wiki/Total_equivalent warming impact).

The environmental impact can, in addition, be considered as including emissions of greenhouse gases arising from the synthesis and production of compounds or compositions. In this case, production emissions are added to the effects of energy consumption and direct losses to produce an indicator known as the climate coefficient for the entire life cycle of the low temperature system (LCCP, see, for example, http://www.sae.org/events/aars/presentations /2007papasavva.pdf). The use of LCCP is common in assessing the environmental impact of automotive air conditioning systems.

The benefit (s) for reducing emissions is given for reducing emissions of pollutants that contribute to global warming, and they can be, for example, used in banking operations, exchanged or sold. They are usually expressed in equivalent amounts of carbon dioxide. Thus, if 1 kg of R-134a is prevented, then an exemption can be obtained for reducing emissions of 1 × 1300 = 1300 kg of CO ₂ equivalent.

In another embodiment, the present invention provides a method of generating benefits for reducing greenhouse gas emissions, comprising (i) replacing an existing compound or composition with a composition of the present invention, wherein the composition of the present invention has lower GWP than the existing compound or composition; and (ii) obtaining benefits for reducing greenhouse gas emissions for the indicated replacement stage.

In a preferred embodiment, the use of the compositions of the present invention results in equipment having a lower overall equivalent warming coefficient and / or lower climate impact coefficient for the entire life cycle of the low temperature system than would be obtained using an existing compound or composition.

These methods can be carried out on any suitable product, for example, in the areas of air conditioning, cooling (for example, cooling at low and medium temperatures), heat transfer, blowing agents, aerosols or sprayed propellants, gaseous dielectrics, cryosurgery, veterinary procedures, dental procedures, fire fighting , cessation of combustion, solvents (e.g., carriers for fragrances and fragrances), cleaning products, air guides, non-firing weapons, local anesthetics and extended product. Preferably, the area is air conditioning or cooling.

Examples of suitable products include heat transfer devices, blowing agents, foaming compositions, sprayable compositions, solvents, and mechanical energy generating devices. In a preferred embodiment, the product is a heat transfer device, such as a refrigeration device or an air conditioning unit.

An existing compound or composition has environmental effects, as measured by GWP and / or TEWI and / or LCCP, which are higher than for the composition of the present invention, which replaces it. An existing compound or composition may contain a fluorocarbon compound, such as a perfluorocarbon, fluorocarbon, chlorofluorocarbon or chlorofluorocarbon compound, or it may contain a fluorinated olefin.

Preferably, the existing compound or composition is a heat transfer compound or composition, such as a refrigerant. Examples of refrigerants that can be replaced include R-134a, R-152a, R-1234yf, R-410A, R-407A, R-407B, R-407C, R507, R-22 and R-404A. The compositions of the present invention are particularly suitable as a substitute for R-134a, R-152a or R-1234yf, in particular for R-134a or R-1234yf.

Any amount of an existing compound or composition may be replaced in such a way as to reduce environmental impacts. This may depend on the environmental impact of the existing compound or composition that is being replaced, and on the environmental impact of the replacement composition of the present invention. Preferably, the existing compound or composition in the product is completely replaced by the composition of the present invention.

The present invention is illustrated by the following non-limiting examples.

The implementation of the invention

Examples

Flammability

It was found, through experiments using the research method according to ASHRAE Standard 34, that the flammability of mixtures of R1243zf and R-1234ze (E) is significantly reduced compared to the flammability of pure R-1243zf or R-1234yf.

In particular, it was found that mixtures of R-1243zf and R-1234ze (E) are non-flammable at 23 ° C in air with a relative humidity of 50% if the molar ratio R-1243zf: R-1234ze (E) is less than about 14:86 , which corresponds to a mass ratio of 12:88.

In addition, the lower flammability limit of mixtures containing higher amounts of R-1243zf was found to be greater than 6% v / v if the molar ratio R1243zf: R1234ze (E) was less than about 1. The lower flammability limit of R-1234yf, as determined is ~ 6% in the same research device, and thus the binary mixtures R-1243zf: R1234ze (E) having a molar ratio zf: ze of less than about 1: 1 exhibit an improved lower flammability value compared to clean R-1234yf.

Simulated performance data

Generating an accurate model of physical properties

The physical properties of R-1234yf and R-1234ze (E) needed to simulate the performance of the refrigeration cycle, namely the critical temperature, vapor pressure, enthalpy of the liquid and vapor, the density of the liquid and vapor, and the specific heat of the vapor and liquid, are precisely determined using experimental methods in the pressure range 0-200 bar and in the temperature range from -40 to 200 ° C and the obtained data are used to generate Helmholtz free energy of models with Span-Wagner type equations of state for a fluid using software echeniya NIST REFPROP Version 8.0, which is described more fully in the user manual www.nist.gov/srd/PDFfiles/REFPROP8.PDF. and it is incorporated herein by reference. The change in the ideal gas enthalpy for both fluids with temperature is evaluated using the Hyperchem v7.5 molecular modeling software (which is incorporated herein by reference), and the obtained ideal gas enthalpy function is used in the regression fitting of the equation of state for these fluids. The predictions of this model for R1234yf and R1234ze (E) are compared with the predictions obtained using standard files for R1234yf and R1234ze (E) included in REFPROP Version 9.0 (incorporated by reference herein). It was found that a close match is obtained for each of the properties of the fluid.

The behavior of R-1234ze (E) in vapor-liquid equilibrium is studied for a number of binary mixtures with carbon dioxide, R-32, R-125, R-134a, R-152a, R-161, propane and propylene in the temperature range from -40 up to + 60 ° C, which covers the practical operating range of most refrigeration and air conditioning systems. The composition is changed in the entire space of compositions for each binary mixture in the experimental program. The mixture parameters for each binary mixture are adjusted regressively to the experimentally obtained data and the parameters are also included in the model for the REFPROP software. Then, a search is carried out in the scientific literature regarding the behavior in equilibrium of pairs — liquid for carbon dioxide with fluorocarbons R-32, R-125, R-152a, R-161 and R-152a. VLE data obtained from sources mentioned in Application of the simple multi-fluid model to correlations of the vapor-liquid equilibrium refrigerant mixture containing carbon dioxide, by R. Akasaka, Journal of Thermal Science and Technology, 159-168, 4, 1, 2009 (which is incorporated herein by reference) is then used to generate blending parameters for the respective binary mixtures and they are then also included in the REFPROP model. REFPROP standard mixing parameters for carbon dioxide with propane and propylene are also included in this model.

The resulting software model is used to compare the performance of the selected fluids of the present invention with R-134a for use in a heat pump cycle.

Comparison for heat pump cycle

In the first comparison, the behavior of the fluids is evaluated for a simple vapor compression cycle under conditions typical of an automobile heat pump at low winter ambient temperatures. In this comparison, the differential pressure effects are incorporated into the model by assigning a representative expected differential pressure for the reference fluid (R-134a), followed by an assessment of the equivalent differential pressure for the mixed refrigerant of the present invention with the same equipment and heating capacity. The comparison is based on the same heat exchanger area for the reference fluid (R-134a) and for the mixed fluids of the present invention. The methodology used for this model is obtained using assumptions about the effective coefficient for heat transfer as a whole for the processes of condensation of the refrigerant, evaporation of the refrigerant, supercooling of the liquid refrigerant and superheating of the refrigerant vapor to obtain the so-called UA model for the process. The preparation of such a model for non-azeotropic refrigerant mixtures in heat pump cycles is explained in more detail in the cited text of Vapor Compression Heat Pumps with refrigerant mixture by R. Radermacher & Y. Hwang (pub. Taylor & Francis, 2005) Chapter 3, which is incorporated herein by as a link.

In short, the simulation begins with an initial assessment of the condensation and evaporation pressures for the refrigerant mixture and estimates of the corresponding temperatures at the beginning and end of the condensation process in the condenser and the evaporation process in the evaporator. These temperatures are then used in combination with predetermined changes in air temperatures above the condenser and evaporator to estimate the required total heat exchanger area for each device from the condenser and evaporator. This is an iterative calculation: the condensing and vapor pressures are adjusted to ensure that the total areas of the heat exchanger are the same for the reference fluid and for the mixed refrigerant.

To compare the worst case for a heat pump in automotive applications, the following assumptions are made for air temperature and for R-134a cycle conditions.

Cycle conditions

Ambient temperature on condenser and evaporator -15 ° C Evaporator outlet air temperature -25 ° C Condenser outlet air temperature (air for passengers) + 45 ° C Evaporation Temperature R134a -30 ° C Condensing Temperature R134a + 50 ° C Refrigerant Subcooling in a Condenser 1 K Evaporator refrigerant overheating 5 K Condenser suction temperature 0 ° C Isoentropic compressor efficiency 66% Thermal load of air for passengers 2 kW Evaporator Differential Pressure for R-134a 0.03 bar Condenser differential pressure for R-134a 0.03 bar Suction line pressure drop for R-134a 0.03 bar

The model assumes a countercurrent flow for each heat exchanger when calculating the effective temperature differences for each of the heat transfer processes.

The condensation and evaporation temperatures for the compositions are selected to obtain equivalent use of the heat transfer area, as in a reference fluid. Use the following input parameters.

Parameter Reference Refrigerant R134a Average condenser temperature ° C fifty The average temperature of the evaporator ° C -thirty Condenser Subcooling K one Evaporator Overheat K 5 Suction diameter mm 16,2 Heating ability kw 2 Evaporator Pressure Difference bar 0,03 Differential line pressure suction bar 0,03 Condenser differential pressure bar 0,03 Suction temperature capacitor ° C 0 Ientropic Efficiency 66% Evaporator Inlet Air ° C -15.00 Evaporator Outlet Air ° C -25.00 Condenser inlet air ° C -15.00 Air outlet condenser ° C 45.00 Capacitor area 100.0% 100.0% Evaporator Area 100.0% 100.0%

The performance data for the reference R-134a obtained using the above model are shown below.

COP (heating) 2.11 COP (heating) in relation to the standard 100.0% Volumetric suction heating capacity kJ / m ³ 879 Heating ability in relation to the standard 100.0% Critical temperature ° C 101.06 Critical pressure bar 40.59 Capacitor enthalpy variation kJ / kg 237.1 Pressure ratio 16.36 Mass flow of refrigerant kg / hour 30,4 Compressor Release Temperature ° C 125.5 Evaporator Inlet Pressure bar 0.86 Condenser Inlet Pressure bar 13,2

Evaporator Inlet Temperature ° C -29.7 Evaporator Condensing Temperature ° C -30.3 Evaporator outlet gas temperature ° C -25.3 The average temperature of the evaporator ° C -30.0 Evaporator Glide (In-Out) K -0.6 Compressor suction pressure bar 0.81 Compressor release pressure bar 13,2 Suction pressure drop Pa / m 292 Differential pressure in relation to the standard 100.0% Condenser condensation temperature ° C 50,0 Capacitor boiling point ° C 50,0 Liquid temperature at condenser outlet ° C 49.0 Average condenser temperature ° C 50,0 Capacitor Glide (input-output) K 0.1

The performance data further generated for the selected compositions of the present invention are shown in the following tables. The tables show the key parameters of the heat pump cycle, including operating pressures, volumetric heating ability, energy efficiency (expressed as the coefficient of efficiency for heating the COP), temperature of release from the compressor, and pressure drops in the pipelines. The volumetric heating ability of a refrigerant is an indication of the amount of heating that can be obtained for a given size of compressor operating at a fixed speed. Coefficient of performance (COP) is the ratio of the amount of thermal energy supplied to the capacitor of a heat pump cycle to the amount of work consumed by the compressor.

The performance of R-134a is taken as a reference point for comparing heating capacity, energy efficiency and pressure drop. This fluid is used as a reference to compare the feasibility of using the fluids of the present invention in the heat pump mode of a combined air conditioning system and a vehicle heat pump.

It should be noted here that the usefulness of the fluids of the present invention is not limited to automobile systems. In fact, these fluids can be used in so-called stationary (home or industrial) equipment. Currently, the main fluids used in such stationary equipment are R-410A (having GWP 2100) or R22 (having GWP 1800 and the ozone depletion potential of 0.05). The use of the fluids of the present invention in such stationary equipment makes it possible to realize similar beneficial properties, but using fluids that do not have the potential to destroy the ozone layer and have significantly lower GWP compared to R410A.

It is obvious that the fluids of the present invention can provide improved energy efficiency compared to R-134a or R-410A. It has been unexpectedly discovered that the addition of carbon dioxide to the refrigerants of the present invention can increase the COP of the resulting cycle higher than that of R-134a, even when mixing the other components of the mixture would give a fluid having poorer energy efficiency than R-134a.

In addition, it was found, for all fluids of the present invention, that compositions containing up to about 30% w / w can be used. CO _2, which give the liquid refrigerant whose critical temperature is about 70 ° C or higher. This is especially important for stationary applications for heat pumps where the R-410A is currently used. The fundamental thermodynamic efficiency of the vapor compression process depends on the proximity of the critical temperature to the condensation temperature. R-410A has a higher acceptability and may be considered an acceptable fluid for such use; its critical temperature is 71 ° C. It has surprisingly been found that significant amounts of CO ₂ (critical temperature 31 ° C) can be introduced into the fluids of the present invention to produce mixtures having critical temperatures close to R-410A or higher. Preferred compositions of the present invention, therefore, have critical temperatures of about 70 ° C or higher.

The heating capacity of the preferred fluids of the present invention is generally higher than that of R134a. It is believed that the R-134a alone, operating in an automotive air conditioning system and heat pump, cannot provide all the potential needs of passengers to heat the air in heat pump mode. For this reason, higher heating capacities than R-134a are preferred for potential use in automotive air conditioning and heat pump applications. The fluids of the present invention make it possible to optimize the heating ability and energy efficiency of the fluid for both the air conditioning mode and the cooling mode in order to provide an improvement in overall energy efficiency for both operations.

In comparison, the heating ability of R-410A for the same cycle conditions is estimated to be approximately 290% of the values for R-134a, and the corresponding energy efficiency was found to be approximately 106% of the reference value for R-134a.

When examining the tables, it is clear that the fluids of the present invention have been discovered that have heating capabilities and energy efficiencies comparable to R-410A that allow adaptation of existing technology to R-410A using the fluids of the present invention, if desired.

Some other advantages of the fluids of the present invention are described in more detail below.

With equivalent cooling capacity, the compositions of the present invention give a reduced pressure drop compared to R-134a. This characteristic of reducing the differential pressure, as expected, leads to an additional improvement in energy efficiency (by reducing pressure loss) in a real system. Differential pressure effects are especially important for automotive air conditioning and heat pump applications, so these fluids provide a significant advantage for this application.

The fluid performance of the present invention is compared with binary mixtures of CO ₂ / R1234ze (E). For all three-component compositions of the present invention, except for CO ₂ / R1234yf7R1234ze (E), the energy efficiency increases relative to a binary mixture having an equivalent CO ₂ content. Therefore, these mixtures represent an improved solution for a binary mixture of refrigerants CO ₂ / R1234ze (E), at least for the content of CO ₂ less than 30% wt./wt.

Mixtures of CO ₂ / R1234yf7R1234ze (E) can be generated having an energy efficiency comparable to or slightly higher than that of R-134a. Thus, unexpectedly, this three-component fluid system of the present invention provides means for improving the poor intrinsic energy efficiency of R-1234yf.

The performance characteristics of the selected ternary compositions of the present invention R-744 / R-1243zf7R-1234ze (E) are also modeled using the heat pump cycle discussed previously. The results are tabulated in the attached tables. The addition of R1243zf to R1234ze (E) was found to improve the specific pressure drop and volumetric cooling ability of the mixture for any given amount of mixed R-744. It was also found that the critical temperature of the ternary mixture would increase in comparison with the binary mixture R-744 / R-1234ze (E) having an equivalent volumetric cooling capacity. Increasing the critical temperature is important for improving performance, for example, in a dual-mode system (air conditioning / heat pump) operating as an air conditioner in a hot environment.

The energy efficiency (COP) of the mixtures shows maxima corresponding to the optimal R-744 content for a given level of R-1243zf in the mixture. It is also observed that the maximum COP value obtained in this way rises when the level of R-1243zf rises.

Table 1 Theoretical data on the performance characteristics of selected R-744 / R-1234yf7R-1234ze (E) mixtures containing 0-14% R-744 and 5% R-1234yf Composition CO ₂ / R-1234yf / R-1234ze (E), wt.% 0/5/95 2/5/93 4/5/91 6/5/89 8/5/87 10/5/85 12/5/83 14/5/81 COP (heating) 1.99 2.05 2.10 2.13 2.16 2.18 2.19 2.20 COP (heating) in relation to the standard 94.2% 97.2% 99.4% 101.0% 102.3% 103.2% 103.9% 104.5% Volumetric suction heating capacity kJ / m ³ 638 721 807 896 987 1082 1180 1280 Heating ability in relation to the standard 72.6% 82.1% 91.8% 101.9% 112.4% 123.2% 134.3% 145.7% Critical temperature ° C 109.13 105.19 101.49 98.00 94.71 91.59 88.65 85.86 Critical pressure bar 36.92 37.75 38.58 39.40 40.22 41.03 41.84 42.64 Capacitor enthalpy variation kJ / kg 208.0 221.4 232.7 242.2 250,4 257.6 264.1 269.9 Pressure ratio 18.41 18.67 18.74 18.64 18.40 18.08 17.70 17.28 Mass flow of refrigerant kg / hour 34.6 32,5 30.9 29.7 28.8 27.9 27.3 26.7 Compressor Release Temperature ° C 112.1 116.4 120,4 124.0 127.2 130.2 133.0 135.6 Evaporator Inlet Pressure bar 0.68 0.72 0.78 0.84 0.91 0.99 1,07 1.16 Condenser Inlet Pressure bar 11.0 12,2 13.5 14.7 15.9 17.1 18.3 19.5 Evaporator Inlet Temperature ° C -29.0 -29.7 -30.4 -31.2 -32.0 -32.8 -33.7 -34.7 Evaporator Condensing Temperature ° C -30.0 -29.5 -28.8 -28.0 -pa -26.4 -25.7 -24.9 Evaporator outlet gas temperature ° C -25.0 -24.5 -23.8 -23.0 -22.2 -21.4 -20.7 -19.9 The average temperature of the evaporator ° C -29.5 -29.6 -29.6 -29.6 -29.6 -29.6 -29.7 -29.8 Glide evaporator (output-input) K -1.0 0.2 1,6 3,1 4.7 6.4 8.1 9.7 Suction compressor pressure bar 0.60 0.66 0.72 0.79 0.87 0.95 1,03 1.13 Compressor Release Pressure bar 11.0 12,2 13.5 14.7 15.9 17.1 18.3 19.5 Suction pressure drop Pa / m 449 379 327 285 252 226 203 184 Differential pressure in relation to the standard 153.8% 129.8% 111.8% 97.7% 86.5% 77.2% 69.5% 63.0% Condenser condensation temperature ° C 53.3 55.3 56.9 58.2 59.2 60.0 60.5 60.8 Capacitor boiling point ° C 52.8 46.9 42,4 38.8 36.0 33.7 31.9 30,4 Liquid temperature at the outlet of the condenser ° C 51.8 45.9 41,4 37.8 35.0 32,7 30.9 29.4 Average condenser temperature ° C 53.1 51.1 49.6 48.5 47.6 46.9 46.2 45.6 Capacitor Glide (input-output) K 0.6 8.3 14.5 19,4 23.3 26.3 28.6 30,4

table 2 Theoretical data on the performance characteristics of the selected R-744 / R-1234yf / R-1234ze (E) mixtures containing 16-30% R-744 and 5% R-1234yf Composition CO ₂ / R-1234yf / R-1234ze (E), wt.% 16/5/79 18/5/77 20/5/75 22/5/73 24/5/71 26/5/69 28/5/67 30/5/65 COP (heating) 2.21 2.22 2.23 2.23 2.23 2.23 2.23 2.23 COP (heating) in relation to the standard 105.0% 105.3% 105.6% 105.7% 105.8% 105.8% 105.8% 105.7% Volumetric suction heating capacity kJ / m ³ 1383 1488 1594 1702 1810 1920 2030 2141 Heating ability in relation to the standard 157.4% 169.3% 181.4% 193.7% 206.0% 218.5% 231.0% 243.6% Critical temperature ° C 83.21 80.69 78.29 76.01 73.83 71.75 69.76 67.85 Critical pressure bar 43,44 44.24 45.04 45.83 46.62 47.41 48.19 48.97 Capacitor enthalpy variation kJ / kg 275.3 280.3 285.1 289.6 294.0 298.2 3023 306.4 Pressure ratio 16.85 16,42 16.00 15,59 15,20 14.82 14.47 14.14 Mass flow of refrigerant kg / hour 26.2 25.7 25.3 24.9 24.5 24.1 23.8 23.5 Compressor Release Temperature ° C 138.1 140.5 142.8 145.0 147.3 149.5 151.6 153.8 Evaporator Inlet Pressure bar 1.25 1.35 1.45 1,56 1,67 1.78 1.89 2.01 Condenser Inlet Pressure bar 20.6 21.7 22.8 23.9 25.0 26.1 27.1 28,2 Evaporator Inlet Temperature ° C -35.6 -36.7 -37.7 -38.8 -39.8 -40.9 -41.9 -42.9 Evaporator Condensing Temperature ° C -24.2 -23.5 -22.9 -22.4 -21.9 -21.5 -21.2 -20.9 Evaporator outlet gas temperature ° C -19.2 -18.5 -17.9 -17.4 -16.9 -16.5 -16.2 -15.9 The average temperature of the evaporator ° C -29.9 -30.1 -30.3 -30.6 -30.9 -31.2 -31.5 -31.9 Glide evaporator (output-input) K 11,4 13.1 14.8 16,4 17.9 19,4 20.8 22.0 Suction compressor pressure bar 1.22 1.32 1.43 1,53 1.65 1.76 1.87 1.99 Compressor Release Pressure bar 20.6 21.7 22.8 23.9 25.0 26.1 27.1 28,2 Suction pressure drop Pa / m 168 154 142 131 122 114 107 one hundred Differential pressure in relation to the standard 57.5% 52.7% 48.6% 45.0% 41.8% 39.0% 36.5% 34.3% Condenser condensation temperature ° C 61.0 61.0 60.9 60.7 60,4 60.0 59.5 58.9 Capacitor boiling point ° C 29.2 28.1 27.3 26.5 25.9 25.3 24.9 24.4 Liquid temperature at the outlet of the condenser ° C 28,2 27.1 26.3 25.5 24.9 24.3 23.9 23,4 Average condenser temperature ° C 45.1 44.6 44.1 43.6 43.1 42.6 42,2 41.7 Capacitor Glide (input-output) K 31.8 32.9 33.7 34.2 34.5 34.6 34.6 34.5

Table 3 Theoretical data on the performance characteristics of selected R-744 / R-1234yf / R-1234ze (E) mixtures containing 0-14% R-744 and 10% R-1234yf Composition CO ₂ / R-1234yf / R-1234ze (E), wt.% 0/10/90 2/10/88 4/10/86 6/10/84 8/10/82 10/10/80 12/10/78 10/14/76 COP (heating) 1.98 2.05 2.09 2.12 2.15 2.17 2.18 2.20 COP (heating) in relation to the standard 94.0% 97.0% 99.2% 100.8% 102.0% 102.9% 103.6% 104.1% Volumetric suction heating capacity kJ / m ³ 661 747 835 927 1022 1119 1219 1322 Heating ability in relation to the standard 75.2% 85.0% 95.1% 105.5% 116.3% 127.3% 138.7% 150.5% Critical temperature ° C 108.37 104.45 100.77 97.30 94.03 90.94 88.01 85.24 Critical pressure bar 37.22 38.12 39.00 39.88 40.75 41.62 42.47 43.32 Capacitor enthalpy variation kJ / kg 205.7 219.1 230,2 239.7 247.7 254.8 261.0 266.7 Pressure ratio 18.07 18.35 18,42 18.33 18.09 17.78 17.40 16,99 Mass flow of refrigerant kg / hour 35.0 32.9 31.3 30,0 29.1 28.3 27.6 27.0 Compressor Release Temperature ° C 111.4 115.7 119.7 123.3 126.5 129.4 132.2 134.8 Evaporator Inlet Pressure bar 0.70 0.75 0.81 0.87 0.95 1,03 1,11 1.21 Condenser Inlet Pressure bar 11.3 12.6 13.9 15.1 16,4 17.6 18.8 20,0 Evaporator Inlet Temperature ° C -29.1 -29.8 -30.5 -31.3 -32.1 -32.9 -33.8 -34.8 Evaporator Condensing Temperature ° C -29.8 -29.3 -28.6 -27.9 -27.1 -26.3 -25.5 -24.8 Evaporator outlet gas temperature ° C -24.8 -24.3 -23.6 -22.9 -22.1 -21.3 -20.5 -19.8 The average temperature of the evaporator ° C -29.4 -29.5 -29.6 -29.6 -29.6 -29.6 -29.7 -29.8 Glide evaporator (output-input) K -0.7 0.5 1.9 3.4 5,0 6.6 8.3 10.0 Suction compressor pressure bar 0.63 0.69 0.75 0.83 0.90 0.99 1,08 1.18 Compressor Release Pressure bar 11.3 12.6 13.9 15.1 16,4 17.6 18.8 20,0 Suction pressure drop Pa / m 437 369 318 278 246 220 198 180 Differential pressure in relation to the standard 149.7% 126.3% 108.8% 95.2% 84.2% 75.3% 67.9% 61.6% Condenser condensation temperature ° C 53.5 55,4 57.0 58.3 59.3 60.0 60.5 60.7 Capacitor boiling point ° C 52.6 46.8 42,2 38.7 35.9 33.7 31.9 30,4 Liquid temperature at the outlet of the condenser ° C 51.6 45.8 41.2 37.7 34.9 32,7 30.9 29.4 Average condenser temperature ° C 53.1 51.1 49.6 48.5 47.6 46.8 46.2 45.6 Capacitor Glide (input-output) K 0.9 8.6 14.8 19.6 23,4 26.3 28.6 30.3

Table 4 Theoretical data on the performance characteristics of selected R-744 / R-1234yf / R-1234ze (E) mixtures containing 16-30% R-744 and 10% R-1234yf Composition CO ₂ / R-1234yf / R-1234ze (E), wt.% 10/16/74 18/10/72 10/10/70 10/22/68 10/24/66 10/26/64 10/28/62 10/30/60 COP (heating) 2.20 2.21 2.22 2.22 2.22 2.22 2.22 2.22 COP (heating) in relation to the standard 104.6% 104.9% 105.1% 105.3% 105.3% 105.3% 105.3% 105.2% Volumetric suction heating capacity kJ / m ³ 1427 1535 1644 1754 1866 1979 2093 2207 Heating ability in relation to the standard 162.4% 174.7% 187.1% 199.7% 212.4% 225.2% 238.2% 251.2% Critical temperature ° C 82.60 80,10 77.71 75.44 73.28 71.21 69.23 67.34 Critical pressure bar 44.17 45.00 45.84 46.66 47.49 48.30 49.12 49.93 Capacitor enthalpy variation kJ / kg 271.9 276.8 281.4 285.7 289.9 293.9 297.9 301.7 Pressure ratio 16.56 16.13 15.71 15.30 14.91 14.53 14.18 13.84 Mass flow of refrigerant kg / hour 26.5 26.0 25.6 25,2 24.8 24.5 24.2 23.9 Compressor Release Temperature ° C 137.2 139.5 141.8 144.0 146.2 148.3 150,4 152.5 Evaporator Inlet Pressure bar 1.30 1.41 1.51 1,62 1.74 1.86 1.98 2.10 Condenser Inlet Pressure bar 21.1 22.3 23,4 24.5 25.6 26.7 27.8 28.8 Evaporator Inlet Temperature ° C -35.7 -36.7 -37.8 -38.8 -39.9 -40.9 -41.9 -42.9 Evaporator Condensing Temperature ° C -24.1 -23.4 -22.9 -22.3 -21.9 -21.5 -21.1 -20.9 Evaporator outlet gas temperature ° C -19.1 -18.4 -17.9 -17.3 -16.9 -16.5 -16.1 -15.9 The average temperature of the evaporator ° C -29.9 -30.1 -30.3 -30.6 -30.9 -31.2 -31.5 -31.9 Gland Evaporator (output-input) K 11.7 13.3 14.9 16.5 18.0 19,4 20.8 22.0 Suction compressor pressure bar 1.28 1.38 1.49 1,60 1.72 1.84 1.96 2.08 Compressor Release Pressure bar 21.1 22.3 23,4 24.5 25.6 26.7 27.8 28.8 Suction pressure drop Pa / m 164 151 139 129 120 112 105 98 Differential pressure in relation to the standard 56.2% 51.6% 47.6% 44.1% 41.0% 38.2% 35.8% 33.6% Condenser condensation temperature ° C 60.8 60.8 60.6 60.3 60.0 59.5 59.0 58.4 Capacitor boiling point ° C 29.2 28,2 27.4 26.7 26.1 25.6 25.1 24.8 Liquid temperature at the outlet of the condenser ° C 28,2 27,2 26,4 25.7 25.1 24.6 24.1 23.8 Average condenser temperature ° C 45.0 44.5 44.0 43.5 43.0 42.6 42.1 41.6 Capacitor Glide (input-output) K 31.6 32.6 33,2 33.7 33.9 33.9 33.8 33.6

Table 5 Theoretical data on the performance characteristics of selected R-744 / R-1234yf / R-1234ze (E) mixtures containing 0-14% R-744 and 20% R-1234yf Composition CO ₂ / R-1234yf / R-1234ze (E), wt.% 0/20/80 2/20/78 4/20/76 6/20/74 8/20/72 10/20/70 12/20/68 14/20/66 COP (heating) 1.97 2.03 2.08 2.11 2.14 2.16 2.17 2.18 COP (heating) in relation to the standard 93.4% 96.5% 98.7% 100.2% 101.4% 102.2% 102.9% 103.4% Volumetric suction heating capacity kJ / m ³ 706 798 892 989 1089 1192 1297 1405 Heating ability in relation to the standard 80.3% 90.8% 101.5% 112.5% 123.9% 135.6% 147.6% 159.9% Critical temperature ° C 106.85 102.98 99.34 95.92 92.68 89.63 86.74 83,99 Critical pressure bar 37.65 38.69 39.70 40.70 41.68 42.65 43.61 44.55 Capacitor enthalpy variation kJ / kg 201.1 214.5 225.5 234.7 242.5 249.2 255.2 260.5 Pressure ratio 17.42 17.73 17.83 17.75 17.53 17.22 16.85 16,44 Mass flow of refrigerant kg / hour 35.8 33.6 31.9 30.7 29.7 28.9 28,2 27.6 Compressor Release Temperature ° C 110.0 114.4 118.4 121.9 125.1 128.0 130.7 133.2 Evaporator Inlet Pressure bar 0.76 0.81 0.87 0.94 1,02 1,11 1.21 1.31 Condenser Inlet Pressure bar 11.9 13,2 14.6 15.9 17,2 18.5 19.8 21.0 Evaporator Inlet Temperature ° C -29.2 -29.9 -30.6 -31.4 -32.2 -33.0 -33.9 -34.8 Evaporator Condensing Temperature ° C -29.5 -29.0 -28.3 -27.6 -26.8 -26.1 -25.3 -24.6 Evaporator outlet gas temperature ° C -24.5 -24.0 -23.3 -22.6 -21.8 -21.1 -20.3 -19.6 The average temperature of the evaporator ° C -29.3 -29.4 -29.5 -29.5 -29.5 -29.5 -29.6 -29.7 Glide evaporator (output-input) K -0.3 0.9 2,3 3.8 5,4 7.0 8.6 10,2 Suction compressor pressure bar 0.68 0.75 0.82 0.90 0.98 1,08 1.17 1.28 Compressor Release Pressure bar 11.9 13,2 14.6 15.9 17,2 18.5 19.8 21.0 Suction pressure drop Pa / m 416 351 302 265 235 210 190 172 Differential pressure in relation to the standard 142.6% 120.2% 103.5% 90.6% 80.3% 71.9% 64.9% 59.0% Condenser condensation temperature ° C 53.7 55.6 57.2 58.4 59.3 59.9 60.3 60.5 Capacitor boiling point ° C 52.6 46.6 42.0 38.5 35.8 33.6 31.9 30.5 Liquid temperature at the outlet of the condenser ° C 51.6 45.6 41.0 37.5 34.8 32.6 30.9 29.5 Average condenser temperature ° C 53,2 51.1 49.6 48.5 47.5 46.8 46.1 45.5 Capacitor Glide (input-output) K 1,1 9.0 15,2 19.9 23.6 26.3 28,4 29.9

Table 6 Theoretical data on the performance of selected R-744 / R-1234yf / R-1234ze (E) mixtures containing 16-30% R-744 and 20% R-1234yf Composition CO ₂ / R-1234yf / R-1234ze (E), wt.% 16/20/64 18/20/62 20/20/60 22/20/58 24/20/56 26/20/54 28/20/52 30/20/50 COP (heating) 2.19 2.19 2.20 2.20 2.20 2.20 2.20 2.20 COP (heating) in relation to the standard 103.7% 104.0% 104.2% 104.3% 104.4% 104.4% 104.3% 104.2% Volumetric suction heating capacity kJ / m ³ 1516 1629 1745 1862 1981 2101 2223 2347 Heating ability in relation to the standard 172.6% 185.4% 198.6% 211.9% 225.5% 239.2% 253.0% 267.1% Critical temperature ° C 81.39 78.92 76.56 74.32 72.18 70.13 68.18 6631 Critical pressure bar 45.48 46.40 47.31 48.21 49.10 49.99 50.87 51.74 Capacitor enthalpy variation kJ / kg 265.4 269.9 274.1 278.1 281.8 285.5 288.9 2923 Pressure ratio 16.01 15,58 15.15 14.74 14.34 13.96 13.60 13.25 Mass flow of refrigerant kg / hour 27.1 26.7 26.3 25.9 25.5 25,2 24.9 24.6 Compressor Release Temperature ° C 135.5 137.7 139.9 142.0 144.0 146.0 147.9 149.8 Evaporator Inlet Pressure bar 1.41 1,53 1,64 1.77 1.89 2.02 2.16 2,30 Condenser Inlet Pressure bar 22.2 23,4 24.6 25.7 26.9 28.0 29.1 30,2 Evaporator Inlet Temperature ° C -35.8 -36.8 -37.8 -38.8 -39.8 -40.8 -41.8 -42.7 Evaporator Condensing Temperature ° C -23.9 -23.3 -22.8 -22.3 -21.8 -21.5 -21.1 -20.9 Evaporator outlet gas temperature ° C -18.9 -18.3 -17.8 -17.3 -16.8 -16.5 -16.1 -15.9 The average temperature of the evaporator ° C -29.9 -30.0 -30.3 -30.5 -30.8 -31.1 -31.4 -31.8 Glide evaporator (output-input) K 11.8 13,4 15.0 16.5 18.0 19.3 20.6 21.8 Suction compressor pressure bar 1.39 1,50 1,62 1.74 1.87 2.00 2.14 2.28 Compressor Release Pressure bar 22.2 23,4 24.6 25.7 26.9 28.0 29.1 30,2 Suction pressure drop Pa / m 157 145 134 124 115 108 101 95 Differential pressure in relation to the standard 53.9% 49.5% 45.7% 42.4% 39.4% 36.8% 34.5% 32.4% Condenser condensation temperature ° C 60.5 60.3 60.0 59.6 59.2 58.6 58.0 57.3 Capacitor boiling point ° C 29.4 28.5 27.7 27.1 26.5 26.1 25.7 25,4 Liquid temperature at the outlet of the condenser ° C 28,4 27.5 26.7 26.1 25.5 25.1 24.7 24.4 Average condenser temperature ° C 44.9 44,4 43.9 43,4 42.9 42,4 41.8 41.3 Capacitor Glide (input-output) K 31.1 31.8 32,3 32.6 32.6 32,5 32,2 31.8

Table 7 Theoretical data on the performance of selected R-744 / R-1234yf / R-1234ze (E) mixtures containing 0-14% R-744 and 30% R-1234yf Composition CO ₂ / R-1234yf / R-1234ze (E), wt.% 0/30/70 2/30/68 4/30/66 6/30/64 8/30/62 10/30/60 12/30/58 14/30/56 COP (heating) 1.96 2.02 2.07 2.10 2.12 2.14 2.15 2.16 COP (heating) in relation to the standard 92.8% 95.9% 98.1% 99.7% 100.8% 101.6% 102.1% 102.6% Volumetric suction heating capacity kJ / m ³ 749 847 947 1049 1155 1263 1374 1488 Heating ability in relation to the standard 85.2% 96.4% 107.8% 119.4% 131.4% 143.7% 156.4% 169.4% Critical temperature ° C 105.33 101.51 97.92 94.53 91.34 88.32 85.46 82.75 Critical pressure bar 37.87 39.05 40,20 41.32 42,42 43.50 44.56 45.60 Capacitor enthalpy variation kJ / kg 196.5 210.0 221.1 230.1 237.7 244.1 249.8 254.8 Pressure ratio 16.80 17.16 17.30 17.24 17.03 16.72 16.35 15.94 Mass flow of refrigerant kg / hour 36.6 34.3 32.6 31.3 30.3 29.5 28.8 28.3 Compressor Release Temperature ° C 108.6 113.1 117.1 120.7 123.8 126.7 129.3 131.7 Evaporator Inlet Pressure bar 0.81 0.87 0.93 1.01 1.10 1.20 1.30 1.41 Condenser Inlet Pressure bar 12.5 13.9 15.3 16.7 18.1 19,4 20.7 22.0 Evaporator Inlet Temperature ° C -29.2 -29.9 -30.6 -31.4 -32.2 -33.0 -33.8 -34.7 Evaporator Condensing Temperature ° C -29.3 -28.8 -28.2 -27.4 -26.7 -26.0 -25.2 -24.6 Evaporator outlet gas temperature ° C -24.3 -23.8 -23.2 -22.4 -21.7 -21.0 -20.2 -19.6 The average temperature of the evaporator ° C -29.2 -29.3 -29.4 -29.4 -29.4 -29.5 -29.5 -29.6 Glide evaporator (output-input) K -0.1 1,1 2.5 3.9 5.5 7.0 8.6 10,2 Suction compressor pressure bar 0.74 0.81 0.89 0.97 1.06 1.16 1.27 1.38 Compressor Release Pressure bar 12.5 13.9 15.3 16.7 18.1 19,4 20.7 22.0 Suction pressure drop Pa / m 399 336 289 253 225 201 182 165 Differential pressure in relation to the standard 136.8% 115.0% 99.0% 86.7% 76.9% 68.9% 62.2% 56.6% Condenser condensation temperature ° C 53.8 55.8 57.3 58.5 59.3 59.9 60.1 60,2 Capacitor boiling point ° C 52.7 46.6 41.9 38.3 35.6 33.5 31.9 30.6 Liquid temperature at the outlet of the condenser ° C 51.7 45.6 40.9 37.3 34.6 32,5 30.9 29.6 Average condenser temperature ° C 53.3 51,2 49.6 48,4 47.5 46.7 46.0 45.4 Capacitor Glide (input-output) K 1,1 9.2 15.4 20,2 23.7 26.3 28.3 29.7

Table 8 Theoretical data on the performance of selected R-744 / R-1234yf / R-1234ze (E) mixtures containing 16-30% R-744 and 30% R-1234yf Composition CO ₂ / R-1234yf / R-1234ze (E), wt.% 16/30/54 18/30/52 20/30/50 22/30/48 24/30/46 26/30/44 28/30/42 30/30/40 COP (heating) 2.17 2.17 2.18 2.18 2.18 2.18 2.18 2.18 COP (heating) in relation to the standard 102.9% 103.1% 103.3% 103.4% 103.4% 103.4% 103.3% 103.2% Volumetric suction heating capacity kJ / m ³ 1605 1724 1847 1971 2098 2227 2358 2492 Heating ability in relation to the standard 182.7% 196.3% 210.2% 224.3% 238.8% 253.5% 268.4% 283.6% Critical temperature ° C 80.18 77.74 75.41 73.19 71.08 69.06 67.13 65.28 Critical pressure bar 46.62 47.63 48.62 49.60 50.57 51.52 52,47 53.40 Capacitor enthalpy variation kJ / kg 259.3 263.4 267.2 270.7 274.1 277.2 280.3 283.1 Pressure ratio 15,51 15.07 14.64 14.22 13.81 13,42 13.04 12.68 Mass flow of refrigerant kg / hour 27.8 27.3 26.9 26.6 26.3 26.0 25.7 25,4 Compressor Release Temperature ° C 133.9 136.0 138.0 140.0 141.8 143.7 145.4 147.2 Evaporator Inlet Pressure bar 1,53 1.65 1.78 1.91 2.05 2.20 2.35 2,51 Condenser Inlet Pressure bar 23.3 24.5 25.7 26.9 28.1 29.3 30,4 31.6 Evaporator Inlet Temperature ° C -35.7 -36.6 -37.6 -38.6 -39.6 -40.5 -41.4 -42.3 Evaporator Condensing Temperature ° C -23.9 -23.3 -22.8 -22.3 -21.9 -21.5 -21.2 -20.9 Evaporator outlet gas temperature ° C -18.9 -18.3 -17.8 -17.3 -16.9 -16.5 -16.2 -15.9 The average temperature of the evaporator ° C -29.8 -30.0 -30.2 -30.4 -30.7 -31.0 -31.3 -31.6 Glide evaporator (output-input) TO 11.8 13.3 14.8 16.3 17.7 19.0 20.3 21,4 Suction compressor pressure bar 1,50 1,63 1.76 1.89 2.03 2.18 2,33 2.49 Compressor Release Pressure bar 23.3 24.5 25.7 26.9 28.1 29.3 30,4 31.6 Suction pressure drop Pa / m 151 139 129 119 111 104 97 91 Differential pressure in relation to the standard 51.8% 47.7% 44.0% 40.8% 38.0% 35.5% 33.3% 31.2% Condenser condensation temperature ° C 60.1 59.8 59.5 59.0 58.4 57.7 57.0 56.2 Capacitor boiling point ° C 29.5 28.7 28.0 27.4 26.9 26.6 26.3 26.0 Liquid temperature at the outlet of the condenser ° C 28.5 27.7 27.0 26,4 25.9 25.6 25.3 25.0 Average condenser temperature ° C 44.8 44,2 43.7 43,2 42.7 42.1 41.6 41.1 Capacitor Glide (input-output) K 30.6 31,2 31.5 31.6 31,4 31.1 30.7 30.1

Table 9 Theoretical performance data for selected R-744 / R-1234yf / R-1234ze (E) mixtures containing 0-14% R-744 and 40% R-1234yf Composition CO ₂ / R-1234yf / R-1234ze (E), wt.% 0/40/60 2/40/58 4/40/56 6/40/54 8/40/52 10/40/50 12/40/48 14/40/46 COP (heating) 1.94 2.01 2.06 2.09 2.11 2.13 2.14 2.15 COP (heating) in relation to the standard 92.0% 95.4% 97.6% 99.1% 100.2% 100.9% 101.4% 101.8% Volumetric suction heating capacity kJ / m ³ 789 893 999 1107 1218 1332 1449 1568 Heating ability in relation to the standard 89.8% 101.6% 113.7% 126.0% 138.7% 151.6% 164.9% 178.5% Critical temperature ° C 103.81 100.04 96.49 93.14 89,99 87.01 84.18 81.51 Critical pressure bar 37.88 39.21 40.50 41.75 42.98 44.17 45.34 46.48 Capacitor enthalpy variation kJ / kg 192.1 206.0 217.1 226.1 233.4 239.6 244.9 249.6 Pressure ratio 16.25 16.66 16.83 16.80 16.60 16.30 15.93 15,51 Mass flow of refrigerant kg / hour 37.5 34.9 33,2 31.8 30.8 30,0 29.4 28.8 Compressor Release Temperature ° C 107.4 112.0 116.0 119.6 122.7 125.5 128.1 130,4 Evaporator Inlet Pressure bar 0.86 0.92 1.00 1,08 1.18 1.28 1.39 1.51 Condenser Inlet Pressure bar 13.0 14.5 16,0 17.5 18.9 20.3 21.7 23.0 Evaporator Inlet Temperature ° C -29.1 -29.8 -30.6 -31.3 -32.1 -32.9 -33.7 -34.6 Evaporator Condensing Temperature ° C -29.2 -28.7 -28.1 -27.4 -26.7 -26.0 -25.3 -24.6 Evaporator outlet gas temperature ° C -24.2 -23.7 -23.1 -22.4 -21.7 -21.0 -20.3 -19.6 The average temperature of the evaporator ° C -29.1 -29.3 -29.3 -29.4 -29.4 -29.4 -29.5 -29.6 Glide evaporator (output-input) K -0.1 1,1 2,4 3.9 5,4 6.9 8.4 10.0 Suction compressor pressure bar 0.80 0.87 0.95 1,04 1.14 1.25 1.36 1.48 Compressor Release Pressure bar 13.0 14.5 16,0 17.5 18.9 20.3 21.7 23.0 Suction pressure drop Pa / m 386 323 278 243 216 193 175 159 Differential pressure in relation to the standard 132.1% 110.7% 95.1% 83.2% 73.9% 66.2% 59.9% 54.6% Condenser condensation temperature ° C 53.9 55.9 57.5 58.6 59,4 59.9 60.1 60.0 Capacitor boiling point ° C 53.0 46.6 41.7 38.1 35,4 33.3 31.7 30.5 Liquid temperature at the outlet of the condenser ° C 52.0 45.6 40.7 37.1 34,4 32,3 30.7 29.5 Average condenser temperature ° C 53.5 51,2 49.6 48,4 47.4 46.6 45.9 45.3 Capacitor Glide (input-output) K 0.9 9.3 15.7 20.5 24.0 26.5 28.3 29.5

Table 10 Theoretical data on the performance of selected R-744 / R-1234yf / R-1234ze (E) mixtures containing 16-30% R-744 and 40% R-1234yf Composition CO ₂ / R-1234yf / R-1234ze (E), wt.% 16/40/44 18/40/42 20/40/40 22/40/38 24/40/36 26/40/34 28/40/32 30/40/30 COP (heating) 2.15 2.16 2.16 2.16 2.16 2.16 2.16 2.15 COP (heating) in relation to the standard 102.1% 102.3% 102.4% 102.5% 102.4% 102.4% 102.3% 102.2% Volumetric suction heating capacity kJ / m ³ 1691 1817 1946 2078 2213 2350 2491 2634 Heating ability in relation to the standard 192.5% 206.8% 221.5% 236.5% 251.8% 267.5% 283.5% 299.7% Critical temperature ° C 78.97 76.56 74.26 72.07 69.98 67,99 66.08 64.25 Critical pressure bar 47.60 48.70 49.78 50.84 51.88 52.91 53.92 54.92 Capacitor enthalpy variation kJ / kg 253.7 257.5 260.9 264.0 266.9 269.6 272.1 274.5 Pressure ratio 15.08 14.63 14.19 13.76 13.34 12.93 12.54 12.17 Mass flow of refrigerant kg / hour 28,4 28.0 27.6 27.3 27.0 26.7 26.5 26.2 Compressor Release Temperature ° C 132.5 134.5 136.4 138.2 139.9 141.5 143.1 144.7 Evaporator Inlet Pressure bar 1,64 1.77 1.91 2.06 2.22 2,38 2,55 2.73 Condenser Inlet Pressure bar 24.3 25.6 26.9 28.1 29.3 30.6 31.8 33.0 Evaporator Inlet Temperature ° C -35.5 -36.4 -37.3 -38.3 -39.2 -40.2 -41.1 -41.9 Evaporator Condensing Temperature ° C -23.9 -23.4 -22.8 -22.3 -21.9 -21.5 -21.2 -21.0 Evaporator outlet gas temperature ° C -18.9 -18.4 -17.8 -17.3 -16.9 -16.5 -16.2 -16.0 The average temperature of the evaporator ° C -29.7 -29.9 -30.1 -30.3 -30.6 -30.9 -31.2 -31.5 Glide evaporator (output-input) K 11.5 13.0 14.5 15.9 17.3 18.6 19.9 21.0 Suction compressor pressure bar 1,61 1.75 1.89 2.04 2.20 2,36 2,53 2.71 Compressor Release Pressure bar 24.3 25.6 26.9 28.1 29.3 30.6 31.8 33.0 Suction pressure drop Pa / m 146 134 124 115 107 one hundred 94 88 Differential pressure in relation to the standard 50.0% 46.0% 42.5% 39.5% 36.8% 34.4% 32.2% 30.3% Condenser condensation temperature ° C 59.8 59.5 59.0 58.4 57.7 56.9 56.1 55.1 Capacitor boiling point ° C 29.5 28.7 28.1 27.6 27,2 26.9 26.7 26.5 Liquid temperature at the outlet of the condenser ° C 28.5 27.7 27.1 26.6 26.2 25.9 25.7 25.5 Average condenser temperature ° C 44.7 44.1 43.5 43.0 42.5 41.9 41,4 40.8 Capacitor Glide (input-output) K 30.3 30.7 30.9 30.8 30.5 30,0 29.4 28.6

Table 11 Theoretical performance data for selected R-744 / R-1234yf / R-1234ze (E) mixtures containing 0-14% R-744 and 50% R-1234yf Composition CO ₂ / R-1234yf / R-1234ze (E), wt.% 0/50/50 2/50/48 4/50/46 6/50/44 8/50/42 10/50/40 12/50/38 14/50/36 COP (heating) 1.93 2.00 2.05 2.08 2.10 2.12 2.13 2.13 COP (heating) in relation to the standard 91.4% 94.9% 97.2% 98.7% 99.7% 100.3% 100.8% 101.1% Volumetric suction heating capacity kJ / m ³ 825 935 1048 1162 1278 1397 1519 1644 Heating ability in relation to the standard 93.9% 106.5% 119.2% 132.2% 145.4% 159.0% 172.8% 187.0% Critical temperature ° C 102.30 98.57 95.06 91.76 88.64 85.70 82.91 80.27 Critical pressure bar 37.69 39.17 40.61 42.00 43.35 44.66 45.94 47.19 Capacitor enthalpy variation kJ / kg 188.2 202.5 213.8 222.8 230,0 235.9 240.9 245.2 Pressure ratio 15.75 16.23 16.46 16.45 16.27 15.97 15.60 15.18 Mass flow of refrigerant kg / hour 38.3 35.5 33.7 32,3 31.3 30.5 29.9 29.4 Compressor Release Temperature ° C 106,2 110.9 115.1 118.7 121.8 124.6 127.1 1293 Evaporator Inlet Pressure bar 0.91 0.98 1.06 1.15 1.25 1.36 1.48 1,61 Condenser Inlet Pressure bar 13,4 15.0 16.6 18.2 19.7 21,2 22.6 24.0 Evaporator Inlet Temperature ° C -29.0 -29.7 -30.4 -31.2 -31.9 -32.7 -33.5 -34.5 Evaporator Condensing Temperature ° C -29.2 -28.8 -28.2 -27.5 -26.8 -26.0 -25.3 -24.7 Evaporator outlet gas temperature ° C -24.2 -23.8 -23.2 -22.5 -21.8 -21.0 -20.3 -19.7 The average temperature of the evaporator ° C -29.1 -29.2 -29.3 -29.3 -29.3 -29.4 -29.4 -29.5 Glide evaporator (output-input) K -0.2 1,0 2,3 3,7 5.1 6.6 8.2 9.7 Suction compressor pressure bar 0.85 0.92 1.01 1,11 1.21 1.33 1.45 1,58 Compressor Release Pressure bar 13,4 15.0 16.6 18.2 19.7 21,2 22.6 24.0 Suction pressure drop Pa / m 375 313 268 234 208 187 169 154 Differential pressure in relation to the standard 128.3% 107.0% 91.7% 80.2% 71.2% 63.9% 57.9% 52.8% Condenser condensation temperature ° C 53.9 56.0 57.6 58.8 59.6 60.0 60.1 60.0 Capacitor boiling point ° C 53.3 46.5 41.5 37.8 35.0 33.0 31,4 30,2 Liquid temperature at the outlet of the condenser ° C 52.3 45.5 40.5 36.8 34.0 32,0 30,4 29.2 Average condenser temperature ° C 53.6 51,2 49.5 48.3 47.3 46.5 45.8 45.1 Capacitor Glide (input-output) K 0.6 9.5 16,2 21.0 24.5 27.0 28.7 29.7

Table 12 Theoretical data on the performance of the selected R-744 / R-1234yf / R-1234ze (E) mixtures containing 16-30% R-744 and 50% R-1234yf Composition CO ₂ / R-1234yf / R-1234ze (E), wt.% 16/50/34 18/50/32 20/50/30 22/50/28 24/50/26 26/50/24 28/50/22 30/50/20 COP (heating) 2.14 2.14 2.14 2.14 2.14 2.14 2.14 2.13 COP (heating) in relation to the standard 101.4% 101.5% 101.5% 101.6% 101.5% 101.4% 101.3% 101.1% Volumetric suction heating capacity kJ / m ³ 1772 1903 2038 2175 2316 2460 2607 2757 Heating ability in relation to the standard 201.6% 216.6% 231.9% 247.6% 263.6% 280.0% 296.7% 313.7% Critical temperature ° C 77.76 75.37 73.11 70.94 68.88 66.91 65.03 63.23 Critical pressure bar 48.41 49.60 50.77 51.91 53.04 54.14 55.23 56.30 Capacitor enthalpy variation kJ / kg 249.0 252.4 255.4 258.1 260.7 263.0 265.1 267.1 Pressure ratio 14.73 14.28 13.83 13.39 12.96 12.55 12.16 11.79 Mass flow of refrigerant kg / hour 28.9 28.5 28,2 27.9 27.6 27.4 27,2 27.0 Compressor Release Temperature ° C 131.3 133.2 135.0 136.7 138.3 139.8 141.3 142.7 Evaporator Inlet Pressure bar 1.74 1.89 2.04 2.20 2,37 2,55 2.73 2.92 Condenser Inlet Pressure bar 25.3 26.6 27.9 29.2 30.5 31.8 33.0 34.3 Evaporator Inlet Temperature ° C -35.2 -36.1 -37.1 -38.0 -39.0 -39.9 -40.9 -41.8 Evaporator Condensing Temperature ° C -24.0 -23.4 -22.9 -22.4 -21.9 -21.6 -21.2 -21.0 Evaporator outlet gas temperature ° C -19.0 -18.4 -17.9 -17.4 -16.9 -16.6 -16.2 -16.0 The average temperature of the evaporator ° C -29.6 -29.8 -30.0 -30.2 -30.5 -30.7 -31.0 -31.4 Glide evaporator (output-input) K 11,2 12.7 14.2 15.6 17.0 18,4 19.6 20.8 Suction compressor pressure bar 1.72 1.87 2.02 2.18 2,35 2,53 2.72 2.91 Compressor Release Pressure bar 25.3 26.6 27.9 29.2 30.5 31.8 33.0 34.3 Suction pressure drop Pa / m 141 130 121 112 104 98 92 86 Differential pressure in relation to the standard 48.4% 44.6% 41.3% 38.4% 35.8% 33.4% 31.4% 29.5% Condenser condensation temperature ° C 59.7 59.2 58.7 58.0 57.2 56.3 55.3 54.3 Capacitor boiling point ° C 29.3 28.6 28.1 27.6 27.3 27.1 26.9 26.8 Liquid temperature at the outlet of the condenser ° C 28.3 27.6 27.1 26.6 26.3 26.1 25.9 25.8 Average condenser temperature ° C 44.5 43.9 43,4 42.8 42,2 41.7 41.1 40.5 Capacitor Glide (input-output) K 30,4 30.6 30.6 30.3 29.8 29.2 28,4 27.5

Table 13 Theoretical performance data for selected R-744 / R-1234yf / R-1234ze (E) mixtures containing 0-14% R-744 and 60% R-1234yf Composition CO ₂ / R-1234yf / R-1234ze (E), wt.% 0/60/40 2/60/38 4/60/36 6/60/34 8/60/32 10/60/30 12/60/28 14/60/26 COP (heating) 1.91 1.99 2.04 2.07 2.09 2.11 2.11 2.12 COP (heating) in relation to the standard 90.7% 94.4% 96.8% 98.3% 99.3% 99.9% 100.3% 100.5% Volumetric suction heating capacity kJ / m ³ 855 973 1091 1211 1332 1455 1581 1710 Heating ability in relation to the standard 97.4% 110.7% 124.2% 137.8% 151.6% 165.6% 179.9% 194.6% Critical temperature ° C 100.78 97.09 93.63 90.37 87.29 84.39 81.63 79.02 Critical pressure bar 37.30 38.94 40.52 42.05 43.53 44.97 46.37 47.72 Capacitor enthalpy variation kJ / kg 184.7 199.8 211.4 220.3 227.4 233.1 237.8 241.9 Pressure ratio 15.33 15.90 16.19 16.21 16.05 15.76 15.38 14.96 Mass flow of refrigerant kg / hour 39.0 36.0 34.1 32,7 31.7 30.9 30.3 29.8 Compressor Release Temperature ° C 105.1 110.1 114.4 118.1 121,2 124.0 126.4 128.6 Evaporator Inlet Pressure bar 0.96 1,03 1,11 1.20 1.31 1.43 1.55 1,69 Condenser Inlet Pressure bar 13.8 15,5 17,2 18.9 20.5 22.0 23.5 24.9 Evaporator Inlet Temperature ° C -28.9 -29.6 -30.3 -31.0 -31.8 -32.5 -33.4 -34.2 Evaporator Condensing Temperature ° C -29.2 -28.8 -28.3 -27.6 -26.9 -26.1 -25.4 -24.7 Evaporator outlet gas temperature ° C -24.2 -23.8 -23.3 -22.6 -21.9 -21.1 -20.4 -19.7 The average temperature of the evaporator ° C -29.0 -29.2 -29.3 -29.3 -29.3 -29.3 -29.4 -29.4 Glide evaporator (output-input) K -0.3 0.8 2.0 3.4 4.9 6.4 8.0 9.5 Suction compressor pressure bar 0.90 0.97 1.06 1.16 1.28 1.40 1,53 1.66 Compressor Release Pressure bar 13.8 15,5 17,2 18.9 20.5 22.0 23.5 24.9 Suction pressure drop Pa / m 366 304 259 227 201 181 164 150 Differential pressure in relation to the standard 125.4% 104.0% 88.8% 77.6% 68.9% 61.9% 56.1% 51.3% Condenser condensation temperature ° C 53.9 56.2 57.9 59.1 59.9 60,2 60.3 60.1 Capacitor boiling point ° C 53.5 46.3 41.0 37,2 34.5 32,4 30.9 29.8 Liquid temperature at the outlet of the condenser ° C 52,5 45.3 40,0 36,2 33.5 31,4 29.9 28.8 Average condenser temperature ° C 53.7 51,2 49.5 48,2 47.2 46.3 45.6 45.0 Capacitor Glide (input-output) K 0.4 9.9 16.9 21.9 25,4 27.8 29.4 30,4

Table 14 Theoretical data on the operating characteristics of the selected mixtures R-744 / R-1234yf7R-1234ze (E) containing 16-30% R-744 and 60% R-1234yf Composition CO ₂ / R-1234yf / R-1234ze (E), wt.% 16/60/24 18/60/22 20/60/20 22/60/18 24/60/16 26/60/14 28/60/12 30/60/10 COP (heating) 2.12 2.12 2.12 2.12 2.12 2.12 2.11 2.11 COP (heating) in relation to the standard 100.7% 100.7% 100.7% 100.7% 100.6% 100.4% 100.2% 100.0% Volumetric suction heating capacity kJ / m ³ 1841 1976 2114 2254 2398 2544 2692 2842 Heating ability in relation to the standard 209.5% 224.9% 240.5% 256.6% 272.9% 289.5% 306.4% 323.5% Critical temperature ° C 76.55 74.19 71.95 69.82 67.78 65.84 63.98 62,20 Critical pressure bar 49.05 50.34 51.60 52.84 54.05 55.23 56.39 57.53 Capacitor enthalpy variation kJ / kg 245.4 248.4 251.2 253.6 255.9 257.9 259.8 261.5 Pressure ratio 14.52 14.06 13.61 13.17 12.74 12.33 11.95 11.58 Mass flow of refrigerant kg / hour 29.3 29.0 28.7 28,4 28.1 27.9 27.7 27.5 Compressor Release Temperature ° C 130.6 132.4 134.1 135.7 137.2 138.7 140.1 141.5 Evaporator Inlet Pressure bar 1.83 1.99 2.15 2,32 2,50 2.68 2.87 3.07 Condenser Inlet Pressure bar 26.3 27.6 29.0 30.3 31.6 32.9 34.1 35,4 Evaporator Inlet Temperature ° C -35.1 -36.0 -36.9 -37.9 -38.9 -39.9 -40.9 -42.0 Evaporator Condensing Temperature ° C -24.0 -23.4 -22.9 -22.4 -21.9 -21.5 -21.1 -20.9 Evaporator outlet gas temperature ° C -19.0 -18.4 -17.9 -17.4 -16.9 -16.5 -16.1 -15.9 The average temperature of the evaporator ° C -29.5 -29.7 -29.9 -30.1 -30.4 -30.7 -31.0 -31.4 Glide evaporator (output-input) K 11.0 12.5 14.0 15,5 17.0 18,4 19.8 21.1 Suction compressor pressure bar 1.81 1.97 2.13 2,30 2.48 2.66 2.86 3.06 Compressor Release Pressure bar 26.3 27.6 29.0 30.3 31.6 32.9 34.1 35,4 Suction pressure drop Pa / m 138 127 118 110 102 96 90 85 Differential pressure in relation to the standard 47.1% 43.5% 40.3% 37.5% 35.0% 32.8% 30.8% 29.1% Condenser condensation temperature ° C 59.8 59.2 58.5 57.7 56.8 55.8 54.8 53.6 Capacitor boiling point ° C 28.9 28,2 27.7 27.4 27.1 26.9 26.8 26.7 Liquid temperature at the outlet of the condenser ° C 27.9 27,2 26.7 26,4 26.1 25.9 25.8 25.7 Average condenser temperature ° C 44.3 43.7 43.1 42.6 42.0 41,4 40.8 40.1 Capacitor Glide (input-output) K 30.9 31,0 30.8 30,4 29.7 28.9 28.0 26.9

Table 15 Theoretical data on the performance characteristics of the selected mixtures R-744 / R-1243zf / R-1234ze (E) containing 0-14% R-744 and 5% R-1243zf Composition CO ₂ / R-1234zf / R-1234ze (E), wt.% 0/5/95 2/5/93 4/5/91 6/5/89 8/5/97 10/5/85 12/5/83 14/5/81 COP (heating) 1.99 2.05 2.10 2.13 2.16 2.18 2.20 2.21 COP in relation to the standard 94.5% 97.4% 99.6% 101.2% 102.5% 103.4% 104.2% 104.8% Volumetric suction heating capacity kJ / m ³ 628 708 791 877 966 1058 1153 1251 Heating ability in relation to the standard 71.5% 80.6% 90.0% 99.8% 110.0% 120.4% 131.2% 142.4% Critical temperature ° C 109.58 105.66 101.97 98.50 95.22 92.12 89.19 86.40 Critical pressure bar 36.65 37.39 38.14 38.88 39.62 40.37 41.11 41.85 Capacitor enthalpy variation kJ / kg 211.1 224.3 235.5 245.1 253.4 260.8 267.4 273.5 Pressure ratio 18.46 18.68 18.72 18.62 18.38 18.07 17.70 17.30 Mass flow of refrigerant kg / hour 34.1 32.1 30.6 29.4 28,4 27.6 26.9 26.3 Compressor Release Temperature ° C 112.8 117.1 120.9 124.5 127.7 130.7 133.5 136.1 Evaporator Inlet Pressure bar 0.66 0.71 0.76 0.82 0.89 0.96 1,04 1.13 Condenser Inlet Pressure bar 10.8 12.0 13,2 14.3 15,5 16.7 17.8 18.9 Evaporator Inlet Temperature ° C -29.0 -29.7 -30.3 -31.1 -31.8 -32.7 -33.5 -34.5 Evaporator Condensing Temperature ° C -30.2 -29.6 -29.0 -28.2 -27.5 -26.7 -25.9 -25.1 Evaporator outlet gas temperature ° C -25.2 -24.6 -24.0 -23.2 -22.5 -21.7 -20.9 -20.1 The average temperature of the evaporator ° C -29.6 -29.6 -29.7 -29.7 -29.6 -29.7 -29.7 -29.8 Glide evaporator (output-input) K -1.2 0,0 1.4 2,8 4.4 6.0 7.6 9.3 Suction compressor pressure bar 0.59 0.64 0.70 0.77 0.84 0.92 1.01 1.09 Compressor Release Pressure bar 10.8 12.0 13,2 14.3 15,5 16.7 17.8 18.9 Suction pressure drop Pa / m 451 382 330 289 256 229 206 187 Differential pressure in relation to the standard 154.5% 131.0% 113.0% 99.0% 87.6% 78.3% 70.5% 63.9% Condenser condensation temperature ° C 53.1 55.0 56.6 57.9 58.9 59.7 60,2 60.6 Capacitor boiling point ° C 52.9 47.3 42.8 39.3 36,4 34.2 32,3 30.8 Liquid temperature at the outlet of the condenser ° C 51.9 46.3 41.8 38.3 35,4 33,2 31.3 29.8 Average condenser temperature ° C 53.0 51.1 49.7 48.6 47.7 46.9 46.3 45.7 Capacitor Glide (input-output) K 0.2 7.7 13.8 18.6 22.4 25.5 27.9 29.9

Table 16 Theoretical data on the operating characteristics of the selected mixtures R-744 / R-1243zf / R-1234ze (E) containing 16-30% R-744 and 5% R-1243zf Composition CO ₂ / R-1234zf / R-1234ze (E), wt.% 16/5/79 18/5/77 20/5/75 22/5/73 24/5/71 26/5/69 28/5/67 30/5/65 COP (heating) 2.22 2.23 2.23 2.24 2.24 2.24 2.24 2.24 COP in relation to the standard 105.3% 105.7% 106.0% 106.2% 106.3% 106.4% 106.4% 106.3% Volumetric suction heating capacity kJ / m ³ 1351 1453 1557 1663 1769 1876 1984 2092 Heating ability in relation to the standard 153.8% 165.4% 177.2% 189.2% 201.3% 213.5% 225.8% 238.1% Critical temperature ° C 83.76 81.24 78.85 76.57 74.39 72.31 70.32 68,42 Critical pressure bar 42.59 43.34 44.08 44.82 45.56 46.31 47.05 47.79 Capacitor enthalpy variation kJ / kg 279.1 284.3 289.2 294.0 298.5 302.9 307.2 311.4 Pressure ratio 16.88 16.46 16.05 15.65 15.26 14.90 14.55 14.23 Mass flow of refrigerant kg / hour 25.8 25.3 24.9 24.5 24.1 23.8 23,4 23.1 Compressor Release Temperature ° C 138.7 141.1 143.4 145.7 147.9 150.2 152.4 154.6 Evaporator Inlet Pressure bar 1.22 1.31 1.41 1.51 1,62 1.72 1.83 1.95 Condenser Inlet Pressure bar 20,0 21.1 22.2 23.3 24.3 25,4 26,4 27.4 Evaporator Inlet Temperature ° C -35.4 -36.4 -37.4 -38.5 -39.5 -40.5 -41.5 -42.5 Evaporator Condensing Temperature ° C -24.4 -23.8 -23.2 -22.6 -22.1 -21.7 -21.3 -21.0 Evaporator outlet gas temperature ° C -19.4 -18.8 -18.2 -17.6 -17.1 -16.7 -16.3 -16.0 The average temperature of the evaporator ° C -29.9 -30.1 -30.3 -30.5 -30.8 -31.1 -31.4 -31.8 Glide evaporator (output-input) K 11.0 12.6 14.3 15.8 17.4 18.8 20,2 21.5 Suction compressor pressure bar 1.19 1.28 1.39 1.49 1,59 1.70 1.81 1.93 Compressor Release Pressure bar 20,0 21.1 22.2 23.3 24.3 25,4 26,4 27.4 Suction pressure drop Pa / m 170 156 144 133 124 115 108 101 Differential pressure in relation to the standard 58.3% 53.4% 49.2% 45.5% 42.3% 39.4% 36.9% 34.6% Condenser condensation temperature ° C 60.8 60.9 60.9 60.7 60.5 60.1 59.7 59.3 Capacitor boiling point ° C 29.5 28,4 27.5 26.7 26.0 25,4 24.9 24.5 Liquid temperature at the outlet of the condenser ° C 28.5 27.4 26.5 25.7 25.0 24.4 23.9 23.5 Average condenser temperature ° C 45,2 44.7 44,2 43.7 43,2 42.8 42.3 41.9 Capacitor Glide (input-output) K 31,4 32,5 33,4 34.0 34.5 34.7 34.8 34.8

Table 17 Theoretical data on the performance characteristics of selected R-744 / R-1243zf / R-1234ze (E) mixtures containing 0-14% R-744 and 10% R-1243zf Composition CO ₂ / R-1234zf / R-1234ze (E), wt.% 0/10/90 2/10/88 4/10/86 6/10/84 8/10/82 10/10/80 12/10/78 10/14/76 COP (heating) 2.00 2.05 2.10 2.13 2.16 2.18 2.20 2.21 COP in relation to the standard 94.8% 97.4% 99.5% 101.2% 102.4% 103.4% 104.2% 104.8% Volumetric suction heating capacity kJ / m ³ 641 721 803 889 978 1070 1165 1263 Heating ability in relation to the standard 73.0% 82.0% 91.4% 101.1% 111.3% 121.8% 132.6% 143.7% Critical temperature ° C 109.27 105.40 101.75 98.32 95.07 92.00 89.09 86.33 Critical pressure bar 36.72 37.44 38.15 38.88 39.60 40.32 41.05 41.77 Capacitor enthalpy variation kJ / kg 212.1 224.9 236.0 245.5 253.8 261.2 267.8 273.9 Pressure ratio 18.10 18.38 18.41 18.31 18.07 17.77 17.42 17.03 Mass flow of refrigerant kg / hour 33.9 32,0 30.5 29.3 28,4 27.6 26.9 263 Compressor Release Temperature ° C 112.7 117.0 120.8 124.3 127.5 130.5 133.3 135.9 Evaporator Inlet Pressure bar 0.68 0.72 0.77 0.83 0.90 0.98 1.06 1.14 Condenser Inlet Pressure bar 10.9 12.1 13,2 14,4 15,5 16.7 17.8 18.9 Evaporator Inlet Temperature ° C -29.0 -29.7 -30.4 -31.1 -31.8 -32.6 -33.5 -34.4 Evaporator Condensing Temperature ° C -30.1 -29.6 -29.0 -28.2 -27.5 -26.7 -25.9 -25.2 Evaporator outlet gas temperature ° C -25.1 -24.6 -24.0 -23.2 -22.5 -21.7 -20.9 -20.2 The average temperature of the evaporator ° C -29.6 -29.6 -29.7 -29.7 -29.6 -29.7 -29.7 -29.8 Glide evaporator (output-input) K -1.1 0.1 1.4 2,8 4.4 5.9 7.5 9.2 Suction compressor pressure bar 0.60 0.66 0.72 0.79 0.86 0.94 1,02 1,11 Compressor Release Pressure bar 10.9 12.1 13,2 14,4 15,5 16.7 17.8 18.9 Suction pressure drop Pa / m 441 375 325 285 252 226 204 185 Differential pressure in relation to the standard 150.8% 128.4% 111.1% 97.5% 86.4% 77.3% 69.7% 63.2% Condenser condensation temperature ° C 52.9 54.9 56.4 57.6 58.6 59,4 59.9 60.3 Capacitor boiling point ° C 52.6 47.4 43.0 39.6 36.8 34.5 32,7 31.1 Liquid temperature at the outlet of the condenser ° C 51.6 46.4 42.0 38.6 35.8 33.5 31.7 30.1 Average condenser temperature ° C 52.8 51.1 49.7 48.6 47.7 46.9 46.3 45.7 Capacitor Glide (input-output) K 0.2 7.5 13,4 18.1 21.8 24.9 27.3 29.2

Table 18 Theoretical data on the operating characteristics of the selected mixtures R-744 / R-1243zf / R-1234ze (E) containing 16-30% R-744 and 10% R-1243zf Composition CO ₂ / R-1234zf / R-1234ze (E), wt.% 10/16/74 18/10/72 10/10/70 10/22/68 10/24/66 10/26/64 10/28/62 10/30/60 COP (heating) 2.22 2.23 2.24 2.24 2.24 2.24 2.25 2.24 COP in relation to the standard 105.3% 105.7% 106.0% 106.2% 106.4% 106.5% 106.5% 106.4% Volumetric suction heating capacity kJ / m ³ 1363 1465 1569 1675 1782 1889 1998 2107 Heating ability in relation to the standard 155.1% 166.7% 178.6% 190.6% 202.8% 215.0% 227.4% 239.8% Critical temperature ° C 83.70 81.21 78.83 76.57 74.40 72.34 70.36 68.47 Critical pressure bar 42.50 43.22 43.95 44.68 45.41 46.13 46.86 47.59 Capacitor enthalpy variation kJ / kg 279.5 284.7 289.7 294.4 299.0 303.4 307.7 311.8 Pressure ratio 16.62 16.22 15.82 15.43 15.05 14.70 14.36 14.03 Mass flow of refrigerant kg / hour 25.8 25.3 24.9 24.5 24.1 23.7 23,4 23.1 Compressor Release Temperature ° C 138.4 140.7 143.1 145.3 147.5 149.7 151.9 154.1 Evaporator Inlet Pressure bar 1.23 1.33 1.43 1,53 1,63 1.74 1.85 1.97 Condenser Inlet Pressure bar 20,0 21.1 22.2 23,2 24.3 25.3 26,4 27.4 Evaporator Inlet Temperature ° C -35.3 -36.3 -37.2 -38.2 -39.2 -40.2 -41.2 -42.1 Evaporator Condensing Temperature ° C -24.5 -23.9 -23.3 -22.7 -22.2 -21.8 -21.4 -21.1 Evaporator outlet gas temperature ° C -19.5 -18.9 -18.3 -17.7 -17.2 -16.8 -16.4 -16.1 The average temperature of the evaporator ° C -29.9 -30.1 -30.3 -30.5 -30.7 -31.0 -31.3 -31.6 Gland Evaporator (output-input) K 10.8 12,4 14.0 15,5 17.0 18,4 19.8 21.0 Suction compressor pressure bar 1.20 1.30 1.40 1.51 1,61 1.72 1.84 1.95 Compressor Release Pressure bar 20,0 21.1 22.2 23,2 24.3 25.3 26,4 27.4 Suction pressure drop Pa / m 169 155 142 132 123 114 107 one hundred Differential pressure in relation to the standard 57.7% 52.9% 48.8% 45.1% 42.0% 39.1% 36.6% 34.4% Condenser condensation temperature ° C 60.5 60.6 60.6 60,4 60,2 59.9 59.5 59.1 Capacitor boiling point ° C 29.8 28.7 27.8 27.0 26.3 25.7 25,2 24.8 Liquid temperature at the outlet of the condenser ° C 28.8 27.7 26.8 26.0 25.3 24.7 24.2 23.8 Average condenser temperature ° C 45,2 44.7 44,2 43.7 43.3 42.8 42,4 41.9 Capacitor Glide (input-output) K 30.7 31.9 32.8 33,4 33.9 34.2 34.3 34.3

Table 19 Theoretical data on the performance characteristics of selected mixtures R-744 / R-1243zf / R-1234ze (E) containing 0-14% R-744 and 15% R-1243zf Composition CO ₂ / R-1234zf / R-1234ze (E), wt.% 0/15/85 2/15/83 4/15/81 6/15/79 8/15/77 10/15/75 12/15/73 14/15/71 COP (heating) 2.00 2.05 2.10 2.13 2.16 2.18 2.20 2.21 COP in relation to the standard 94.6% 97.4% 99.5% 101.1% 102.4% 103.4% 104.1% 104.8% Volumetric suction heating capacity kJ / m ³ 653 733 815 900 989 1081 1176 1274 Heating ability in relation to the standard 74.4% 83.4% 92.8% 102.4% 112.6% 123.0% 133.8% 144.9% Critical temperature ° C 108.97 105.14 101.54 98.13 94.92 91.87 88,99 86.25 Critical pressure bar 36.76 37.46 38.16 38.86 39.56 40.27 40.97 41.68 Capacitor enthalpy variation kJ / kg 212.8 225.5 236.5 246.0 254.2 261.6 268.3 274.3 Pressure ratio 17.92 18.10 18.12 18.02 17.79 17.50 17.15 16.77 Mass flow of refrigerant kg / hour 33.8 31.9 30,4 29.3 28.3 27.5 26.8 26.2 Compressor Release Temperature ° C 112.9 117.0 120.7 124.2 127.3 130.3 133.0 135.6 Evaporator Inlet Pressure bar 0.69 0.73 0.79 0.85 0.92 0.99 1,07 1.16 Condenser Inlet Pressure bar 11.0 12,2 13.3 14,4 15.6 16.7 17.8 18.9 Evaporator Inlet Temperature ° C -29.1 -29.7 -30.4 -31.1 -31.8 -32.6 -33.4 -34.3 Evaporator Condensing Temperature ° C -30.1 -29.6 -28.9 -28.2 -27.5 -26.7 -26.0 -25.3 Evaporator outlet gas temperature ° C -25.1 -24.6 -23.9 -23.2 -22.5 -21.7 -21.0 -20.3 The average temperature of the evaporator ° C -29.6 -29.6 -29.6 -29.7 -29.6 -29.7 -29.7 -29.8 Glide evaporator (output-input) TO -1.0 0.1 1.4 2,8 4.3 5.9 7.4 9.0 Suction compressor pressure bar 0.62 0.67 0.73 0.80 0.88 0.95 1,04 1.13 Compressor Release Pressure bar 11.0 12,2 13.3 14,4 15.6 16.7 17.8 18.9 Suction pressure drop Pa / m 431 368 319 281 249 223 201 183 Differential pressure in relation to the standard 147.6% 126.0% 109.3% 96.1% 85.3% 76.4% 68.9% 62.6% Condenser condensation temperature ° C 53.1 54.8 56.2 57.4 58.4 59.1 59.7 60.0 Capacitor boiling point ° C 52.8 47.5 43.3 39.8 37.1 34.8 33.0 31.5 Liquid temperature at the outlet of the condenser ° C 51.8 46.5 42.3 38.8 36.1 33.8 32,0 30.5 Average condenser temperature ° C 52.9 51.1 49.7 48.6 47.7 47.0 46.3 45.7 Capacitor Glide (input-output) K 0.3 7.3 13.0 17.6 21.3 24.3 26.7 28.6

Table 20 Theoretical data on the performance characteristics of selected R-744 / R-1243zf / R-1234ze (E) mixtures containing 16-30% R-744 and 15% R-1243zf Composition CO ₂ / R-1234zf / R-1234ze (E), wt.% 16/15/69 18/15/67 20/15/65 22/15/63 24/15/61 26/15/59 28/15/57 30/15/55 COP (heating) 2.22 2.23 2.24 2.24 2.24 2.25 2.25 2.25 COP in relation to the standard 105.3% 105.7% 106.0% 106.3% 106.4% 106.5% 106.6% 106.5% Volumetric suction heating capacity kJ / m ³ 1374 1476 1580 1686 1793 1902 2011 2121 Heating ability in relation to the standard 156.3% 168.0% 179.9% 191.9% 204.1% 216.4% 228.9% 241.4% Critical temperature ° C 83.65 81.17 78.81 76.56 74.42 72.36 70.40 68.52 Critical pressure bar 42.39 43.10 43.81 44.53 45.24 45.95 46.67 47.38 Capacitor enthalpy variation kJ / kg 280,0 285.2 290.2 295.0 299.5 303.9 308.2 312.4 Pressure ratio 1638 15,99 15.60 15.22 14.85 14.50 14.17 13.85 Mass flow of refrigerant kg / hour 25.7 25,2 24.8 24.4 24.0 23.7 23,4 23.0 Compressor Release Temperature ° C 138.1 140.5 142.7 145.0 147.2 149.4 151.5 153.6 Evaporator Inlet Pressure bar 1.25 1.34 1.44 1.55 1.65 1.76 1.87 1.99 Condenser Inlet Pressure bar 20,0 21.1 22.1 23,2 24.2 25.3 26.3 27.3 Evaporator Inlet Temperature ° C -35.2 -36.1 -37.1 -38.0 -39.0 -40.0 -40.9 -41.8 Evaporator Condensing Temperature ° C -24.6 -24.0 -23.4 -22.8 -22.4 -21.9 -21.6 -21.3 Evaporator outlet gas temperature ° C -19.6 -19.0 -18.4 -17.8 -17.4 -16.9 -16.6 -16.3 The average temperature of the evaporator ° C -29.9 -30.0 -30.2 -30.4 -30.7 -30.9 -31.2 -31.5 Glide evaporator (output-input) K 10.6 12,2 13.7 15,2 16.6 18.0 19.3 20.5 Suction compressor pressure bar 1.22 1.32 1.42 1,52 1,63 1.74 1.86 1.97 Compressor Release Pressure bar 20,0 21.1 22.1 23,2 24.2 25.3 26.3 27.3 Suction pressure drop Pa / m 167 153 141 131 122 113 106 one hundred Differential pressure in relation to the standard 57.2% 52.5% 48.4% 44.8% 41.6% 38.8% 36.3% 34.1% Condenser condensation temperature ° C 60.3 60.3 60.3 60,2 60.0 59.7 59.3 58.9 Capacitor boiling point ° C 30,2 29.1 28.1 27.3 26.6 26.0 25.5 25.1 Liquid temperature at the outlet of the condenser ° C 29.2 28.1 27.1 26.3 25.6 25.0 24.5 24.1 Average condenser temperature ° C 45,2 44.7 44,2 43.8 43.3 42.9 42,4 42.0 Capacitor Glide (input-output) K 30.1 31.3 32,2 32.9 33.3 33.6 33.8 33.8

Table 21 Theoretical data on the performance characteristics of selected R-744 / R-1243zf / R-1234ze (E) mixtures containing 0-14% R-744 and 20% R-1243zf Composition CO ₂ / R-1234zf / R-1234ze (E), wt.% 0/20/80 2/20/78 4/20/76 6/20/74 8/20/72 10/20/70 12/20/68 14/20/66 COP (heating) 2.00 2.05 2.10 2.13 2.16 2.18 2.20 2.21 COP in relation to the standard 94.7% 97.4% 99.5% 101.1% 102.3% 103.3% 104.1% 104.8% Volumetric suction heating capacity kJ / m ³ 665 744 826 912 1000 1092 1187 1284 Heating ability in relation to the standard 75.7% 84.7% 94.0% 103.7% 113.8% 124.3% 135.0% 146.1% Critical temperature ° C 108.68 104.89 101.32 97.95 94.77 91.75 88.89 86.18 Critical pressure bar 36.79 37.47 38.15 38.83 39.51 40,20 40.89 41.58 Capacitor enthalpy variation kJ / kg 213.7 226.3 237.1 246.5 254.8 262.1 268.8 274.9 Pressure ratio 17.67 17.83 17.85 17.74 17.52 17.24 16.90 16.54 Mass flow of refrigerant kg / hour 33.7 31.8 30,4 29.2 28.3 27.5 26.8 26.2 Compressor Release Temperature ° C 113.0 117.0 120.7 124.1 127.2 130.1 132.8 135.4 Evaporator Inlet Pressure bar 0.70 0.75 0.80 0.86 0.93 1.01 1.09 1.17 Condenser Inlet Pressure bar 11.1 12,2 13,4 14.5 15.6 16.7 17.8 18.9 Evaporator Inlet Temperature ° C -29.1 -29.7 -30.4 -31.1 -31.8 -32.5 -33.4 -34.2 Evaporator Condensing Temperature ° C -30.0 -29.5 -28.9 -28.2 -27.5 -26.8 -26.1 -25.3 Evaporator outlet gas temperature ° C -25.0 -24.5 -23.9 -23.2 -22.5 -21.8 -21.1 -20.3 The average temperature of the evaporator ° C -29.6 -29.6 -29.6 -29.6 -29.6 -29.7 -29.7 -29.8 Glide evaporator (output-input) K -0.9 0.2 1,5 2,8 4.3 5.8 7.3 8.9 Suction compressor pressure bar 0.63 0.69 0.75 0.82 0.89 0.97 1.05 1.14 Compressor Release Pressure bar 11.1 12,2 13,4 14.5 15.6 16.7 17.8 18.9 Suction pressure drop Pa / m 422 361 314 277 246 221 199 181 Differential pressure in relation to the standard 144.5% 123.7% 107.6% 94.8% 84.3% 75.6% 68.2% 62.0% Condenser condensation temperature ° C 53.0 54.7 56.1 57.2 58.1 58.9 59,4 59.8 Capacitor boiling point ° C 52.8 47.6 43.5 40.1 37,4 35,2 33.3 31.8 Liquid temperature at the outlet of the condenser ° C 51.8 46.6 42.5 39.1 36,4 34.2 32,3 30.8 Average condenser temperature ° C 52.9 51.1 49.8 48.7 47.8 47.0 46.4 45.8 Capacitor Glide (input-output) K 0.3 7.1 12.6 17.1 20.8 23.7 26.1 28.0

Table 22 Theoretical data on the performance characteristics of the selected R-744 / R-1243zf / R-1234ze (E) mixtures containing 16-30% R-744 and 20% R-1243zf Composition CO ₂ / R-1234zf / R-1234ze (E), wt.% 16/20/64 18/20/62 20/20/60 22/20/58 24/20/56 26/20/54 28/20/52 30/20/50 COP (heating) 2.22 2.23 2.24 2.24 2.24 2.25 2.25 2.25 COP in relation to the standard 105.3% 105.7% 106.0% 106.3% 106.5% 106.6% 106.6% 106.7% Volumetric suction heating capacity kJ / m ³ 1384 I486 1591 1697 1804 1913 2023 2134 Heating ability in relation to the standard 157.5% 169.2% 181.0% 193.1% 205.3% 217.7% 230.2% 242.8% Critical temperature ° C 83.60 81.14 78.80 76.56 74.43 72.39 70,44 68.57 Critical pressure bar 42.28 42.97 43.67 44.37 45.07 45.77 46.47 47.17 Capacitor enthalpy variation kJ / kg 280.5 285.8 290.8 295.6 300,2 304.6 308.9 313.0 Pressure ratio 16.16 15.78 15.40 15.03 14.67 14.33 14.00 13.68 Mass flow of refrigerant kg / hour 25.7 25,2 24.8 24.4 24.0 23.6 23.3 23.0 Compressor Release Temperature ° C 137.8 140.2 142.5 144.7 146.9 149.0 151.1 153.2 Evaporator Inlet Pressure bar 1.26 1.36 1.46 1,56 1,67 1.78 1.89 2.01 Condenser Inlet Pressure bar 20,0 21.0 22.1 23.1 24.2 25,2 26.2 • pa Evaporator Inlet Temperature ° C -35.1 -36.0 -36.9 -37.8 -38.8 -39.7 -40.6 -41.5 Evaporator Condensing Temperature ° C -24.7 -24.1 -23.5 -22.9 -22.5 -22.1 -21.7 -21.4 Evaporator outlet gas temperature ° C -19.7 -19.1 -18.5 -17.9 -17.5 -17.1 -16.7 -16.4 The average temperature of the evaporator ° C -29.9 -30.0 -30.2 -30.4 -30.6 -30.9 -31.1 -31.4 Glide evaporator (output-input) K 10,4 11.9 13,4 14.9 16.3 17.6 18.9 20.1 Suction compressor pressure bar 1.24 1.33 1.44 1,54 1.65 1.76 1.87 1.99 Compressor Release Pressure bar 20,0 21.0 22.1 23.1 24.2 25,2 26.2 27,2 Suction pressure drop Pa / m 165 152 140 130 121 113 105 99 Differential pressure in relation to the standard 56.6% 52.0% 48.0% 44.4% 41.3% 38.5% 36.1% 33.8% Condenser condensation temperature ° C 60.0 60.1 60.1 60.0 59.8 59.5 59.1 58.7 Capacitor boiling point ° C 30.5 29.4 28,4 27.6 26.9 26.3 25.8 25.3 Liquid temperature at the outlet of the condenser ° C 29.5 28,4 27.4 26.6 25.9 25.3 24.8 24.3 Average condenser temperature ° C 45,2 44.7 44.3 43.8 43.3 42.9 42.5 42.0 Capacitor Glide (input-output) K 29.5 30.7 31.6 32,3 32.8 33,2 33.3 33,4

Table 23 Theoretical data on the operating characteristics of the selected mixtures R-744 / R-1243zf / R-1234ze (E) containing 0-14% R-744 and 25% R-1243zf Composition CO ₂ / R-1234zf / R-1234ze (E), wt.% 0/25/75 2/25/73 4/25/71 6/25/69 8/25/67 10/25/65 12/25/63 14/25/61 COP (heating) 2.00 2.05 2.10 2.13 2.16 2.18 2.19 2.21 COP in relation to the standard 94.8% 97.4% 99.5% 101.0% 102.3% 103.3% 104.1% 104.7% Volumetric suction heating capacity kJ / m ³ 677 756 837 922 1011 1102 1197 1294 Heating ability in relation to the standard 77.0% 86.0% 95.3% 105.0% 115.0% 125.4% 136.2% 147.3% Critical temperature ° C 108.39 104.64 101.11 97.77 94.62 91.63 88.80 86.10 Critical pressure bar 36.81 37.46 38.12 38.78 39.45 40.12 40.80 41.47 Capacitor enthalpy variation kJ / kg 214.6 227.0 237.7 247.1 255.3 262.7 269.4 275.5 Pressure ratio 17.44 17.58 17.59 17.48 17.27 16,99 16.67 16.32 Mass flow of refrigerant kg / hour 33.5 31.7 30.3 29.1 28,2 27.4 26.7 26.1 Compressor Release Temperature ° C 113.0 117.0 120.6 124.0 127.1 129.9 132.6 135.2 Evaporator Inlet Pressure bar 0.71 0.76 0.81 0.88 0.95 1,02 1.10 1.19 Condenser Inlet Pressure bar 11,2 12.3 13,4 14.5 15.6 16.7 17.8 18.9 Evaporator Inlet Temperature ° C -29.1 -29.7 -30.4 -31.0 -31.7 -32.5 -33.3 -34.1 Evaporator Condensing Temperature ° C -30.0 -29.5 -28.9 -28.2 -27.5 -26.8 -26.1 -25.4 Evaporator outlet gas temperature ° C -25.0 -24.5 -23.9 -23.2 -22.5 -21.8 -21.1 -20.4 The average temperature of the evaporator ° C -29.6 -29.6 -29.6 -29.6 -29.6 -29.7 -29.7 -29.8 Glide evaporator (output-input) K -0.9 0.2 1,5 2,8 4.2 5.7 7.2 8.7 Suction compressor pressure bar 0.64 0.70 0.76 0.83 0.90 0.98 1,07 1.16 Compressor Release Pressure bar 11,2 12.3 13,4 14.5 15.6 16.7 17.8 18.9 Suction pressure drop Pa / m 413 355 310 273 243 218 197 179 Differential pressure in relation to the standard 141.5% 121.6% 106.0% 93.5% 83.3% 74.7% 67.5% 61.4% Condenser condensation temperature ° C 53.0 54.6 55.9 57.0 57.9 58.6 59.2 59.5 Capacitor boiling point ° C 52.7 47.7 43.6 40,4 37.7 35.5 33.6 32.1 Liquid temperature at the outlet of the condenser ° C 51.7 46.7 42.6 39,4 36.7 34.5 32.6 31.1 Average condenser temperature ° C 52.9 51.1 49.8 48.7 47.8 47.0 46.4 45.8 Capacitor Glide (input-output) K 0.3 6.9 12.3 16.7 20.3 23,2 25.5 27.4

Table 24 Theoretical data on the operating characteristics of the selected mixtures R-744 / R-1243zf / R-1234ze (E) containing 16-30% R-744 and 25% R-1243zf Composition CO ₂ / R-1234zf / R-1234ze (E), wt.% 16/25/59 18/25/57 20/25/55 22/25/53 24/25/51 26/25/49 28/25/47 30/25/45 COP (heating) 2.22 2.23 2.24 2.24 2.25 2.25 2.25 2.25 COP in relation to the standard 105.3% 105.7% 106.1% 106.3% 106.5% 106.6% 106.7% 106.8% Volumetric suction heating capacity kJ / m ³ 1394 1496 1601 1707 1814 1923 2033 2145 Heating ability in relation to the standard 158.6% 170.3% 182.2% 194.2% 206.5% 218.9% 231.4% 244.1% Critical temperature ° C 83.54 81.11 78.78 76.56 74.44 72.41 70.47 68.61 Critical pressure bar 42.15 42.83 43.52 44,20 44.89 45.58 46.27 46.96 Capacitor enthalpy variation kJ / kg 281.2 286.5 291.5 296.3 300.9 305.3 309.6 313.7 Pressure ratio 15.95 15,58 15.21 14.84 14.50 14.16 13.84 13.53 Mass flow of refrigerant kg / hour 25.6 25.1 24.7 24.3 23.9 23.6 23.3 22.9 Compressor Release Temperature ° C 137.6 140.0 142.2 144.4 146.6 148.7 150.8 152.8 Evaporator Inlet Pressure bar 1.28 1.37 1.47 1,58 1.68 1.80 1.91 2.02 Condenser Inlet Pressure bar 19.9 21.0 22.1 23.1 24.1 25.1 26.2 27,2 Evaporator Inlet Temperature ° C -35.0 -35.9 -36.7 -37.7 -38.6 -39.4 -40.3 -41.1 Evaporator Condensing Temperature ° C -24.8 -24.2 -23.6 -23.1 -22.6 -22.2 -21.8 -21.5 Evaporator outlet gas temperature ° C -19.8 -19.2 -18.6 -18.1 -17.6 -17.2 -16.8 -16.5 The average temperature of the evaporator ° C -29.9 -30.0 -30.2 -30.4 -30.6 -30.8 -31.1 -31.3 Glide evaporator (output-input) K 10,2 11.7 13,2 14.6 16,0 17.3 18.5 19.7 Suction compressor pressure bar 1.25 1.35 1.45 1,56 1.66 1.78 1.89 2.01 Compressor Release Pressure bar 19.9 21.0 22.1 23.1 24.1 25.1 26.2 27,2 Suction pressure drop Pa / m 164 151 139 129 120 112 105 98 Differential pressure in relation to the standard 56.1% 51.6% 47.6% 44.1% 41.0% 38.3% 35.8% 33.6% Condenser condensation temperature ° C 59.8 59.9 59.9 59.8 59.6 59.3 59.0 58.6 Capacitor boiling point ° C 30.8 29.7 28.7 27.9 27,2 26.6 26.0 25.6 Liquid temperature at the outlet of the condenser ° C 29.8 28.7 27.7 26.9 26.2 25.6 25.0 24.6 Average condenser temperature ° C 45.3 44.8 44.3 43.8 43,4 42.9 42.5 42.1 Capacitor Glide (input-output) K 29.0 30,2 31.1 31.9 32,4 32,7 32.9 33.0

Table 25 Theoretical data on the operating characteristics of the selected mixtures R-744 / R-1243zf / R-1234ze (E) containing 0-14% R-744 and 30% R-1243zf Composition CO ₂ / R-1234zf / R-1234ze (E), wt.% 0/30/70 2/30/68 4/30/66 6/30/64 8/30/62 10/30/60 12/30/58 14/30/56 COP (heating) 2.00 2.06 2.10 2.13 2.16 2.18 2.19 2.21 COP in relation to the standard 94.9% 97.5% 99.5% 101.0% 102.3% 103.3% 104.1% 104.7% Volumetric suction heating capacity kJ / m ³ 688 766 848 932 1020 1112 1206 1303 Heating ability in relation to the standard 78.3% 87.2% 96.5% 106.1% 116.1% 126.6% 137.3% 148.3% Critical temperature ° C 108.11 104.40 100.90 97.60 94.48 91.51 88.70 86.03 Critical pressure bar 36.81 37.44 38.08 38.73 39.38 40.03 40.69 41.35 Capacitor enthalpy variation kJ / kg 215.6 227.8 238.5 247.8 256,0 263.3 270,0 276.2 Pressure ratio 17.21 17.35 17.35 17.24 17.03 16.76 16.45 16.11 Mass flow of refrigerant kg / hour 33,4 31.6 30,2 29.1 28.1 27.3 26.7 26.1 Compressor Release Temperature ° C 113.1 117.0 120.6 123.9 127.0 129.8 132.5 135.0 Evaporator Inlet Pressure bar 0.73 0.77 0.83 0.89 0.96 1,03 1.12 1.20 Condenser Inlet Pressure bar 11.3 12,4 13.5 14.5 15.6 16.7 17.8 18.9 Evaporator Inlet Temperature ° C -29.1 -29.7 -30.4 -31.0 -31.7 -32.4 -33.2 -34.0 Evaporator Condensing Temperature ° C -30.0 -29.5 -28.9 -28.3 -27.6 -26.9 -26.2 -25.5 Evaporator outlet gas temperature ° C -25.0 -24.5 -23.9 -23.3 -22.6 -21.9 -21.2 -20.5 The average temperature of the evaporator ° C -29.6 -29.6 -29.6 -29.6 -29.6 -29.7 -29.7 -29.8 Glide evaporator (output-input) K -0.8 0.2 1,5 2,8 4.1 5,6 7.0 8.5 Suction compressor pressure bar 0.66 0.71 0.78 0.84 0.92 1.00 1,08 1.17 Compressor Release Pressure bar 11.3 12,4 13.5 14.5 15.6 16.7 17.8 18.9 Suction pressure drop Pa / m 405 349 305 270 240 216 195 178 Differential pressure in relation to the standard 138.8% 119.6% 104.5% 92.3% 82.3% 73.9% 66.9% 60.9% Condenser condensation temperature ° C 53.0 54.5 55.8 56.8 57.7 58.4 58.9 59.3 Capacitor boiling point ° C 52.7 47.8 43.8 40.6 37.9 35.7 33.9 32,4 Liquid temperature at the outlet of the condenser ° C 51.7 46.8 42.8 39.6 36.9 34.7 32.9 31,4 Average condenser temperature ° C 52.8 51.1 49.8 48.7 47.8 47.1 46.4 45.8 Capacitor Glide (input-output) K 0.3 6.7 11.9 16.3 19.8 22.7 25.0 26.9

Table 26 Theoretical data on the performance characteristics of selected mixtures R-744 / R-1243zf / R-1234ze (E) containing 16-30% R-744 and 30% R-1243zf Composition CO ₂ / R-1234zf / R-1234ze (E), wt.% 16/30/54 18/30/52 20/30/50 22/30/48 24/30/46 26/30/44 28/30/42 30/30/40 COP (heating) 2.22 2.23 2.24 2.24 2.25 2.25 2.25 2.25 COP in relation to the standard 105.3% 105.7% 106.1% 106.4% 106.6% 106.7% 106.8% 106.8% Volumetric suction heating capacity kJ / m ³ 1403 1505 1610 1716 1823 1932 2043 2155 Heating ability in relation to the standard 159.7% 171.3% 183.2% 195.3% 207.5% 219.9% 232.5% 245.2% Critical temperature ° C 83.49 81.07 78.76 76.56 74.45 72.44 70.51 68.66 Critical pressure bar 42.02 42.69 43.36 44.03 44.71 45.38 46.06 46.74 Capacitor enthalpy variation kJ / kg 281.9 287.2 292.2 297.0 301.6 306.1 310,4 314.5 Pressure ratio 15.75 15.39 15.03 14.68 14.33 14.00 13.69 13.38 Mass flow of refrigerant kg / hour 25.5 25.1 24.6 24.2 23.9 23.5 23,2 22.9 Compressor Release Temperature ° C 137.4 139.7 142.0 144.2 146.3 148.4 150.5 152.5 Evaporator Inlet Pressure bar 1.29 1.39 1.49 1,59 1.70 1.81 1.92 2.04 Condenser Inlet Pressure bar 19.9 21.0 22.0 23.0 24.1 25.1 26.1 27.1 Evaporator Inlet Temperature ° C -34.9 -35.7 -36.6 -37.5 -38.3 -39.2 -40.0 -40.9 Evaporator Condensing Temperature ° C -24.9 -24.3 -23.7 -23.2 -22.7 -22.3 -21.9 -21.6 Evaporator outlet gas temperature ° C -19.9 -19.3 -18.7 -18.2 -17.7 -17.3 -16.9 -16.6 The average temperature of the evaporator ° C -29.9 -30.0 -30.1 -30.3 -30.5 -30.7 -31.0 -31.2 Glide evaporator (output-input) K 10.0 11.5 12.9 14.3 15.6 16.9 18.1 19.3 Suction compressor pressure bar 1.26 1.36 1.46 1,57 1.68 1.79 1.91 2.02 Compressor Release Pressure bar 19.9 21.0 22.0 23.0 24.1 25.1 26.1 27.1 Suction pressure drop Pa / m 163 149 138 128 119 111 104 98 Differential pressure in relation to the standard 55.7% 51.2% 47.2% 43.8% 40.7% 38.0% 35.6% 33.4% Condenser condensation temperature ° C 59.5 59.6 59.6 59.6 59,4 59.1 58.8 58.4 Capacitor boiling point ° C 31.1 29.9 29.0 28,2 27.4 26.8 26.3 25.8 Liquid temperature at the outlet of the condenser ° C 30.1 28.9 28.0 27,2 26,4 25.8 25.3 24.8 Average condenser temperature ° C 45.3 44.8 44.3 43.9 43,4 43.0 42.5 42.1 Capacitor Glide (input-output) K 28.5 29.7 30.7 31,4 31.9 32,3 32.6 32,7

Table 27 Theoretical data on the performance of selected R-744 / R-1243zf / R-1234ze (E) mixtures containing 0-14% R-744 and 35% R-1243zf Composition CO ₂ / R-1234zf / R-1234ze (E), wt.% 0/35/65 2/35/63 4/35/61 6/35/59 8/35/57 10/35/55 12/35/53 14/35/51 COP (heating) 2.00 2.06 2.10 2.13 2.16 2.18 2.19 2.21 COP in relation to the standard 94.9% 97.5% 99.5% 101.0% 102.2% 103.2% 104.1% 104.7% Volumetric suction heating capacity kJ / m ³ 699 777 858 942 1030 1121 1215 1312 Heating ability in relation to the standard 79.5% 88.4% 97.6% 107.2% 117.2% 127.6% 138.3% 149.3% Critical temperature ° C 107.83 104.16 100.70 97.43 94.33 91.40 88.61 85.96 Critical pressure bar 36.79 37.41 38.03 38.66 39.30 39.94 40.58 41.23 Capacitor enthalpy variation kJ / kg 216.6 228.7 239.2 248.5 256.7 264.1 270.8 276.9 Pressure ratio 17.00 17.12 17.12 17.01 16.81 16.55 16.24 15.91 Mass flow of refrigerant kg / hour 33,2 31.5 30.1 29.0 28.0 27.3 26.6 26.0 Compressor Release Temperature ° C 113.2 117.0 120.5 123.8 126.9 129.7 132.3 134.9 Evaporator Inlet Pressure bar 0.74 0.78 0.84 0.90 0.97 1.05 1.13 1.21 Condenser Inlet Pressure bar 11,4 12,4 13.5 14.6 15.6 16.7 17.8 18.8 Evaporator Inlet Temperature ° C -29.2 -29.7 -30.4 -31.0 -31.7 -32.4 -33.2 -33.9 Evaporator Condensing Temperature ° C -30.0 -29.5 -28.9 -28.3 -27.6 -26.9 -26.2 -25.6 Evaporator outlet gas temperature ° C -25.0 -24.5 -23.9 -23.3 -22.6 -21.9 -21.2 -20.6 The average temperature of the evaporator ° C -29.6 -29.6 -29.6 -29.6 -29.7 -29.7 -29.7 -29.8 Glide evaporator (output-input) K -0.8 0.3 1.4 2.7 4.1 5.5 6.9 8.4 Suction compressor pressure bar 0.67 0.73 0.79 0.86 0.93 1.01 1.09 1.18 Compressor Release Pressure bar 11,4 12,4 13.5 14.6 15.6 16.7 17.8 18.8 Suction pressure drop Pa / m 398 344 301 266 238 214 194 176 Differential pressure in relation to the standard 136.2% 117.6% 103.0% 91.1% 81.4% 73.2% 66.3% 60.3% Condenser condensation temperature ° C 52.9 54,4 55.6 56.7 57.5 58.2 58.7 59.1 Capacitor boiling point ° C 52.7 47.9 44.0 40.8 38,2 36.0 34.2 32.6 Liquid temperature at the outlet of the condenser ° C 51.7 46.9 43.0 39.8 37,2 35.0 33,2 31.6 Average condenser temperature ° C 52.8 51.1 49.8 48.7 47.8 47.1 46.4 45.9 Capacitor Glide (input-output) K 0.3 6.5 11.6 15.9 19,4 22.2 24.6 26.5

Table 28 Theoretical data on the performance characteristics of selected R-744 / R-1243zf / R-1234ze (E) mixtures containing 16-30% R-744 and 35% R-1243zf Composition CO ₂ / R-1234zf / R-1234ze (E), wt.% 16/35/49 18/35/47 20/35/45 22/35/43 24/35/41 26/35/39 28/35/37 30/35/35 COP (heating) 2.22 2.23 2.24 2.24 2.25 2.25 2.25 2.25 COP in relation to the standard 105.3% 105.7% 106.1% 106.4% 106.6% 106.8% 106.9% 106.9% Volumetric suction heating capacity kJ / m ³ 1412 1514 1618 1724 1832 1941 2051 2163 Heating ability in relation to the standard 160.7% 172.3% 184.1% 196.2% 208.4% 220.9% 233.5% 246.2% Critical temperature ° C 83,44 81.04 78.75 76.56 74.47 72.46 70.55 68.71 Critical pressure bar 41.88 42.53 43.19 43.85 44.51 45.18 45.85 46.52 Capacitor enthalpy variation kJ / kg 282.6 288.0 293.0 297.9 302.5 306.9 311.2 315.4 Pressure ratio 15,56 15.21 14.86 14.52 14.18 13.86 13.55 13.25 Mass flow of refrigerant kg / hour 25.5 25.0 24.6 24.2 23.8 23.5 23.1 22.8 Compressor Release Temperature ° C 137.3 139.6 141.8 143.9 146.1 148.1 150.2 152.2 Evaporator Inlet Pressure bar 1.31 1.40 1,50 1,60 1.71 1.82 1.94 2.05 Condenser Inlet Pressure bar 19.9 20.9 22.0 23.0 24.0 25.0 26.0 27.0 Evaporator Inlet Temperature ° C -34.8 -35.6 -36.4 -37.3 -38.1 -39.0 -39.8 -40.6 Evaporator Condensing Temperature ° C -24.9 -24.3 -23.8 -23.3 -22.8 -22.4 -22.0 -21.7 Evaporator outlet gas temperature ° C -19.9 -19.3 -18.8 -18.3 -17.8 -17.4 -17.0 -16.7 The average temperature of the evaporator ° C -29.9 -30.0 -30.1 -30.3 -30.5 -30.7 -30.9 -31.2 Glide evaporator (output-input) K 9.8 11,2 12.6 14.0 15.3 16.6 17.8 18.9 Suction compressor pressure bar 1.28 1.38 1.48 1,58 1,69 1.80 1.92 2.04 Compressor Release Pressure bar 19.9 20.9 22.0 23.0 24.0 25.0 26.0 27.0 Suction pressure drop Pa / m 161 148 137 127 118 110 103 97 Differential pressure in relation to the standard 55.2% 50.8% 46.9% 43.5% 40.5% 37.8% 35.4% 33.2% Condenser condensation temperature ° C 59.3 59,4 59.5 59,4 59.2 59.0 58.7 58.3 Capacitor boiling point ° C 31.3 30,2 29.2 28,4 27.7 27.0 26.5 26.0 Liquid temperature at the outlet of the condenser ° C 30.3 29.2 28,2 27.4 26.7 26.0 25.5 25.0 Average condenser temperature ° C 45.3 44.8 44.3 43.9 43,4 43.0 42.6 42,2 Capacitor Glide (input-output) K 28.0 29.3 30,2 31,0 31.6 32,0 32,2 32,3

Table 29 Theoretical data on the operating characteristics of the selected mixtures R-744 / R-1243zf / R-1234ze (E) containing 0-14% R-744 and 40% R-1243zf Composition CO ₂ / R-1234zf / R-1234ze (E), wt.% 0/40/60 2/40/58 4/40/56 6/40/54 8/40/52 10/40/50 12/40/48 14/40/46 COP (heating) 2.00 2.06 2.10 2.13 2.16 2.18 2.19 2.21 COP in relation to the standard 95.0% 97.5% 99.5% 101.0% 102.2% 103.2% 104.0% 104.7% Volumetric suction heating capacity kJ / m ³ 709 787 867 951 1039 1130 1223 1320 Heating ability in relation to the standard 80.7% 89.5% 98.7% 108.3% 118.2% 128.6% 139.2% 150.2% Critical temperature ° C 107.55 103.92 100.50 97.26 94.19 91.28 88.52 85.89 Critical pressure bar 36.76 37.36 37.97 38.58 39.20 39.83 40.46 41.09 Capacitor enthalpy variation kJ / kg 217.7 229.6 240.1 249.3 257.5 264.8 271.6 277.7 Pressure ratio 16.80 16.91 16.91 16.80 16.61 16.35 16.05 15.73 Mass flow of refrigerant kg / hour 33.1 31,4 30,0 28.9 28.0 27,2 26.5 25.9 Compressor Release Temperature ° C 113.3 117.0 120.5 123.8 126.8 129.6 132.2 134.7 Evaporator Inlet Pressure bar 0.75 0.80 0.85 0.91 0.98 1.06 1.14 1.23 Condenser Inlet Pressure bar 11.5 12.5 13.5 14.6 15.7 16.7 17.8 18.8 Evaporator Inlet Temperature ° C -29.2 -29.8 -30.4 -31.0 -31.7 -32.3 -33.1 -33.9 Evaporator Condensing Temperature ° C -29.9 -29.5 -28.9 -28.3 -27.7 -27.0 -26.3 -25.7 Evaporator outlet gas temperature ° C -24.9 -24.5 -23.9 -23.3 -22.7 -22.0 -21.3 -20.7 The average temperature of the evaporator ° C -29.6 -29.6 -29.6 -29.6 -29.7 -29.7 -29.7 -29.8 Glide evaporator (output-input) K -0.8 0.3 1.4 2.7 4.0 5,4 6.8 8.2 Suction compressor pressure bar 0.68 0.74 0.80 0.87 0.94 1,02 1,11 1.20 Compressor Release Pressure bar 11.5 12.5 13.5 14.6 15.7 16.7 17.8 18.8 Suction pressure drop Pa / m 391 338 297 263 235 212 192 175 Differential pressure in relation to the standard 133.8% 115.8% 101.6% 90.0% 80.5% 72.5% 65.7% 59.8% Condenser condensation temperature ° C 52.9 54.3 55.5 56.5 57.4 58.0 58.5 58.9 Capacitor boiling point ° C 52.6 48.0 44.1 41.0 38,4 36,2 34,4 32.9 Liquid temperature at the outlet of the condenser ° C 51.6 47.0 43.1 40,0 37,4 35,2 33,4 31.9 Average condenser temperature ° C 52.8 51.1 49.8 48.8 47.9 47.1 46.5 45.9 Capacitor Glide (input-output) K 0.3 6.3 11,4 15,5 19.0 21.8 24.1 26.0

Table 30 Theoretical data on the operating characteristics of the selected mixtures R-744 / R-1243zf / R-1234ze (E) containing 16-30% R-744 and 40% R-1243zf Composition CO ₂ / R-1234zf / R-1234ze (E), wt.% 16/40/44 18/40/42 20/40/40 22/40/38 24/40/36 26/40/34 28/40/32 30/40/30 COP (heating) 2.22 2.23 2.24 2.24 2.25 2.25 2.26 2.26 COP in relation to the standard 105.3% 105.8% 106.1% 106.4% 106.7% 106.8% 107.0% 107.0% Volumetric suction heating capacity kJ / m ³ 1420 1521 1625 1731 1839 1948 2059 2171 Heating ability in relation to the standard 161.6% 173.1% 185.0% 197.0% 209.3% 221.7% 234.3% 247.0% Critical temperature ° C 83.39 81.01 78.73 76.56 74.48 72.49 70.58 68.75 Critical pressure bar 41.73 42.37 43.02 43.67 44.32 44.97 45.63 46.29 Capacitor enthalpy variation kJ / kg 283.5 288.8 293.9 298.8 303.4 307.9 312.2 316.4 Pressure ratio 15.39 15.05 14.71 14.37 14.04 13.73 13,42 13.13 Mass flow of refrigerant kg / hour 25,4 24.9 24.5 24.1 23.7 23,4 23.1 22.8 Compressor Release Temperature ° C 137.1 139.4 141.6 143.8 145.9 147.9 149.9 151.9 Evaporator Inlet Pressure bar 1.32 1.41 1.51 1,62 1.72 1.84 1.95 2.07 Condenser Inlet Pressure bar 19.9 20.9 21.9 22.9 23.9 24.9 25.9 26.9 Evaporator Inlet Temperature ° C -34.7 -35.5 -36.3 -37.1 -38.0 -38.8 -39.6 -40.4 Evaporator Condensing Temperature ° C -25.0 -24.4 -23.9 -23.4 -22.9 -22.5 -22.1 -21.8 Evaporator outlet gas temperature ° C -20.0 -19.4 -18.9 -18.4 -17.9 -17.5 -17.1 -16.8 The average temperature of the evaporator ° C -29.8 -30.0 -30.1 -30.3 -30.4 -30.6 -30.9 -31.1 Glide evaporator (output-input) K 9.6 11.0 12,4 13.7 15.0 16.3 17.4 18.5 Suction compressor pressure bar 1.29 1.39 1.49 1,60 1.70 1.82 1.93 2.05 Compressor Release Pressure bar 19.9 20.9 21.9 22.9 23.9 24.9 25.9 26.9 Suction pressure drop Pa / m 160 147 136 126 117 110 103 96 Differential pressure in relation to the standard 54.8% 50.4% 46.6% 43.2% 40.2% 37.5% 35.1% 33.0% Condenser condensation temperature ° C 59.1 59.3 59.3 59.2 59.1 58.9 58.6 58.2 Capacitor boiling point ° C 31.5 30,4 29.5 28.6 27.9 27,2 26.7 26.2 Liquid temperature at the outlet of the condenser ° C 30.5 29.4 28.5 27.6 26.9 26.2 25.7 25,2 Average condenser temperature ° C 45.3 44.8 44,4 43.9 43.5 43.0 42.6 42,2 Gland capacitor (input-output) K 27.6 28.8 29.8 30.6 31,2 31.6 31.9 32,0

Table 31 Theoretical data on the performance characteristics of the selected R-744 / R-1243zf / R-1234ze (E) mixtures containing 0-14% R-744 and 45% R-1243zf Composition CO ₂ / R-1234zf / R-1234ze (E), wt.% 0/45/55 2/45/53 4/45/51 6/45/49 8/45/47 10/45/45 12/45/43 14/45/41 COP (heating) 2.01 2.06 2.10 2.13 2.15 2.18 2.19 2.21 COP in relation to the standard 95.1% 97.5% 99.5% 101.0% 102.2% 103.2% 104.0% 104.7% Volumetric suction heating capacity kJ / m ³ 719 796 876 960 1047 1138 1231 1328 Heating ability in relation to the standard 81.8% 90.6% 99.7% 109.3% 119.2% 129.5% 140.1% 151.1% Critical temperature ° C 107.28 103.69 100.30 97.09 94.06 91.17 88.43 85.83 Critical pressure bar 36.72 37.31 37.90 38.49 39.10 39.71 40.33 40.95 Capacitor enthalpy variation kJ / kg 218.8 230.6 241.0 250.1 258.3 265.7 272.4 278.6 Pressure ratio 16.61 16.71 16.71 16.60 16.41 16.16 15.87 15,56 Mass flow of refrigerant kg / hour 32.9 31,2 29.9 28.8 27.9 27.1 26,4 25.8 Release temperature from compressor ° C 113,4 117.1 120.6 123.8 126.8 129.5 132.1 134.6 Evaporator Inlet Pressure bar 0.76 0.81 0.86 0.93 0.99 1,07 1.15 1.24 Condenser Inlet Pressure bar 11.5 12.5 13.6 14.6 15.7 16.7 17.7 18.8 Evaporator Inlet Temperature ° C -29.2 -29.8 -30.3 -31.0 -31.6 -32.3 -33.0 -33.8 Evaporator Condensing Temperature ° C -29.9 -29.5 -29.0 -28.3 -27.7 -27.0 -26.4 -25.7 Evaporator outlet gas temperature ° C -24.9 -24.5 -24.0 -23.3 -22.7 -22.0 -21.4 -20.7 The average temperature of the evaporator ° C -29.6 -29.6 -29.6 -29.7 -29.7 -29.7 -29.7 -29.8 Glide evaporator (output-input) TO -0.8 0.3 1.4 2.6 3.9 5.3 6.6 8.0 Suction compressor pressure bar 0.69 0.75 0.81 0.88 0.95 1,03 1.12 1.21 Compressor Release Pressure bar 11.5 12.5 13.6 14.6 15.7 16.7 17.7 18.8 Suction pressure drop Pa / m 384 333 293 260 233 210 190 173 Differential pressure in relation to the standard 131.4% 114.1% 100.3% 89.0% 79.6% 71.8% 65.1% 59.4% Condenser condensation temperature ° C 52.8 54,2 55,4 56.4 57.2 57.8 58.3 58.7 Capacitor boiling point ° C 52.6 48.0 44.3 41.2 38.6 36,4 34.6 33.1 Liquid temperature at the outlet of the condenser ° C 51.6 47.0 43.3 40,2 37.6 35,4 33.6 32.1 Average condenser temperature ° 52.7 51.1 49.8 48.8 47.9 47.1 46.5 45.9 Capacitor Glide (input-output) K 0.2 6.1 11.1 15,2 18.6 21,4 23.7 25.6

Table 32 Theoretical data on the performance characteristics of selected R-744 / R-1243zf / R-1234ze (E) mixtures containing 16-30% R-744 and 45% R-1243zf Composition CO ₂ / R-1234zf / R-1234ze (E), wt.% 16/45/39 18/45/37 20/45/35 22/45/33 24/45/31 26/45/29 28/45/27 30/45/25 COP (heating) 2.22 2.23 2.24 2.25 2.25 2.25 2.26 2.26 COP in relation to the standard 105.3% 105.8% 106.2% 106.5% 106.7% 106.9% 107.0% 107.1% Volumetric suction heating capacity kJ / m ³ 1427 1528 1632 1738 1845 1954 2065 2177 Heating ability in relation to the standard 162.4% 173.9% 185.7% 197.8% 210.0% 222.4% 235.0% 247.7% Critical temperature ° C 83.34 80.98 78.72 76.56 74.49 72.51 70.62 68.80 Critical pressure bar 41.58 42.21 42.84 43,48 44.12 44.76 45.41 46.05 Capacitor enthalpy variation kJ / kg 284.4 289.8 294.9 299.8 304.4 308.9 313.3 317.5 Pressure ratio 15.23 14.90 14.56 14.23 13.91 13.60 13.30 13.01 Mass flow of refrigerant kg / hour 25.3 24.8 24.4 24.0 23.7 23.3 23.0 22.7 Compressor Release Temperature ° C 137.0 139.3 141.5 143.6 145.7 147.7 149.7 151.7 Evaporator Inlet Pressure bar 1.33 1.42 1,52 1,63 1.73 1.85 1.96 2.08 Condenser Inlet Pressure bar 19.8 20.8 21.9 22.9 23.9 24.9 25.8 26.8 Evaporator Inlet Temperature ° C -34.6 -35.4 -36.2 -37.0 -37.8 -38.6 -39.4 -40.1 Evaporator Condensing Temperature ° C -25.1 -24.5 -24.0 -23.5 -23.0 -22.6 -22.2 -21.9 Evaporator outlet gas temperature ° C -20.1 -19.5 -19.0 -18.5 -18.0 -17.6 -17.2 -16.9 The average temperature of the evaporator ° C -29.8 -29.9 -30.1 -30.2 -30.4 -30.6 -30.8 -31.0 Glide evaporator (output-input) K 9,4 10.8 12,2 13.5 14.8 16,0 17.1 18.2 Suction compressor pressure bar 1.30 1.40 1,50 1,61 1.71 1.83 1.94 2.06 Compressor Release Pressure bar 19.8 20.8 21.9 22.9 23.9 24.9 25.8 26.8 Suction pressure drop Pa / m 159 146 135 125 117 109 102 96 Differential pressure in relation to the standard 54.4% 50.1% 46.3% 42.9% 40.0% 37.3% 35.0% 32.8% Condenser condensation temperature ° C 59.0 59.1 59.1 59.1 58.9 58.7 58.5 58.2 Capacitor boiling point ° C 31.8 30.6 29.7 28.8 28.1 27.4 26.9 26,4 Liquid temperature at the outlet of the condenser ° C 30.8 29.6 28.7 27.8 27.1 26,4 25.9 25,4 Average condenser temperature ° C 45.4 44.9 44,4 43.9 43.5 43.1 42.7 42.3 Capacitor Glide (input-output) K 27,2 28.5 29.5 30.3 30.9 31.3 31.6 31.8

Table 33 Theoretical data on the performance characteristics of selected mixtures R-744 / R-1234ze (E) containing 0-14% R-744 Composition CO ₂ / R-1234ze (E), wt.% 0/100 2/98 4/96 6/94 8/92 10/90 12/88 14/86 COP (heating) 1.99 2.05 2.10 2.14 2.16 2.18 2.20 2.21 COP (heating) in relation to the standard 94.4% 97.4% 99.6% 101.3% 102.5% 103.5% 104.3% 104.9% Volumetric suction heating capacity kJ / m ³ 615 695 778 864 953 1046 1141 1239 Heating ability in relation to the standard 70.0% 79.1% 88.6% 98.3% 108.5% 119.0% 129.8% 141.0% Critical temperature ° C 109.89 105.93 102,20 98.69 95.38 92.25 89.29 86.48 Critical pressure bar 36.57 37.34 38.10 38.87 39.63 40.40 41.16 41.92 Capacitor enthalpy variation kJ / kg 210.2 223.7 235.1 244.8 253.2 260.5 267.2 273.2 Pressure ratio 18.75 18,99 19.05 18.95 18.71 18.39 18.00 17.58 Mass flow of refrigerant kg / hour 34.2 32,2 30.6 29.4 28,4 27.6 27.0 26,4 Compressor Release Temperature ° C 112.8 117.1 121.1 124.7 127.9 131.0 133.8 136.5 Evaporator Inlet Pressure bar 0.65 0.69 0.74 0.80 0.87 0.95 1,03 1,11 Condenser Inlet Pressure bar 10.7 11.9 13.1 14.3 15,5 16.7 17.8 19.0 Evaporator Inlet Temperature ° C -28.9 -29.6 -30.3 -31.1 -31.9 -32.7 -33.6 -34.5 Evaporator Condensing Temperature ° C -30.3 -29.7 -29.0 -28.3 -27.5 -26.6 -25.8 -25.1 Evaporator outlet gas temperature ° C -25.3 -24.7 -24.0 -23.3 -22.5 -21.6 -20.8 -20.1 The average temperature of the evaporator ° C -29.6 -29.7 -29.7 -29.7 -29.7 -29.7 -29.7 -29.8 Glide evaporator (output-input) K -1.3 -0.1 1.3 2,8 4.4 6.0 7.7 9,4 Suction compressor pressure bar 0.57 0.63 0.69 0.75 0.83 0.91 0.99 1,08 Compressor Release Pressure bar 10.7 11.9 13.1 14.3 15,5 16.7 17.8 19.0 Suction pressure drop Pa / m 462 390 336 294 259 231 208 189 Differential pressure in relation to the standard 158.3% 133.6% 115.0% 100.5% 88.8% 79.2% 71.3% 64.6% Condenser condensation temperature ° C 53.1 55.1 56.7 58.1 59.2 60.0 60.5 60.9 Capacitor boiling point ° C 53.0 47.1 42.6 38.9 36.1 33.8 31.9 30,4 Liquid temperature at the outlet of the condenser ° C 52.0 46.1 41.6 37.9 35.1 32.8 30.9 29.4 Average condenser temperature ° C 53.1 51.1 49.7 48.5 47.6 46.9 46.2 45.7 Capacitor Glide (input-output) K 0.1 7.9 14.2 19.1 23.1 26.2 28.6 30.6

Table 34 Theoretical data on the performance characteristics of selected mixtures R-744 / R-1234ze (E) containing 16-30% R-744 Composition CO ₂ / R-1234ze (E), wt.% 16/84 18/82 20/80 22/78 24/76 26/74 28/72 30/70 COP (heating) 2.22 2.23 2.23 2.24 2.24 2.24 2.24 2.24 COP (heating) in relation to the standard 105.4% 105.7% 106.0% 106.2% 106.3% 106.3% 106.3% 106.2% Volumetric suction heating capacity kJ / m ³ 1339 1441 1545 1650 1756 1862 1969 2076 Heating ability in relation to the standard 152.4% 164.0% 175.8% 187.7% 199.8% 211.9% 224.1% 236.3% Critical temperature ° C 83.81 81.28 78.87 76.57 74.38 72.28 70.28 68.37 Critical pressure bar 42.68 43,44 44,20 44.96 45.72 46.47 47.23 47.98 Capacitor enthalpy variation kJ / kg 278.7 283.9 288.9 293.6 298.1 302.5 306.8 311.0 Pressure ratio 17.15 16.72 16.29 15.88 15.49 15.12 14.77 14.44 Mass flow of refrigerant kg / hour 25.8 25,4 24.9 24.5 24.2 23.8 23.5 23.1 Compressor Release Temperature ° C 139.0 141.4 143.8 146.1 148.4 150.6 152.9 155.1 Evaporator Inlet Pressure bar 1.20 1.29 1.39 1.49 1,60 1.70 1.81 1.92 Condenser Inlet Pressure bar 20.1 21,2 22.3 23.3 24.4 25,4 26.5 27.5 Evaporator Inlet Temperature ° C -35.5 -36.5 -37.6 -38.7 -39.7 -40.8 -41.9 -42.9 Evaporator Condensing Temperature ° C -24.4 -23.7 -23.1 -22.5 -22.0 -21.6 -21.2 -20.9 Evaporator outlet gas temperature ° C -19.4 -18.7 -18.1 -17.5 -17.0 -16.6 -16.2 -15.9 The average temperature of the evaporator ° C -29.9 -30.1 -30.3 -30.6 -30.9 -31.2 -31.5 -31.9 Glide evaporator (output-input) K 11,2 12.9 14.5 16,2 17.7 19,2 20.7 22.0 Suction compressor pressure bar 1.17 1.27 1.37 1.47 1,57 1.68 1.79 1.90 Compressor Release Pressure bar 20.1 21,2 22.3 23.3 24.4 25,4 26.5 27.5 Suction pressure drop Pa / m 172 157 145 134 125 116 109 102 Differential pressure in relation to the standard 58.8% 53.9% 49.7% 45.9% 42.7% 39.8% 37.2% 35.0% Condenser condensation temperature ° C 61.2 61.2 61.2 61.0 60.8 60,4 60.0 59.5 Capacitor boiling point ° C 29.1 28.0 27.1 26.3 25.7 25.1 24.6 24.1 Liquid temperature at the outlet of the condenser ° C 28.1 27.0 26.1 25.3 24.7 24.1 23.6 23.1 Average condenser temperature ° C 45.1 44.6 44.1 43.7 43,2 42.7 42.3 41.8 Capacitor Glide (input-output) K 32.1 33,2 34.1 34.7 35.1 35.3 35,4 35.3

As a result, the present invention provides new compositions that exhibit an unexpected combination of advantageous properties, including good cooling capacity, low flammability, low GWP and / or miscibility with lubricants, compared to existing refrigerants such as R-134a and the proposed refrigerant R-1234yf .

The present invention is defined by the following claims.

Claims (47)

1. Composition for heat transfer, containing:
(i) from about 10 to about 95 wt.% trans-1,3,3,3-tetrafluoropropene (R-1234ze (E));
(ii) from about 2 to about 30 wt.% carbon dioxide (R-744) and
(iii) from about 3 to about 60 wt.% of a third component selected from 2,3,3,3-tetrafluoropropene (R-1234yf), 3,3,3-trifluoropropene (R-1243zf) and mixtures thereof, where, if R-1234yf is present, the composition contains from about 6 to about 40 wt.% R-1234yf. 2. The composition according to claim 1, containing from about 4 to about 30 wt.% R-744, preferably from about 4 to about 28 wt.% R-744, or from about 8 to about 30 wt.%, Or from 10 to about 30 wt.% R-744. 3. The composition according to p. 1, containing up to about 50 wt.% The third component. 4. The composition according to claim 1, which has a critical temperature greater than about 65 ° C, preferably greater than about 70 ° C. 5. The composition according to p. 1, where the third component contains R-1234yf, preferably from about 4 to about 60% wt. R-1234yf. 6. The composition according to claim 5, containing from about 10 to about 92 wt.% R-1234ze (E), from about 4 to about 30 wt.% R-744 and from about 4 to about 60 wt.% R-1234yf . 7. The composition according to claim 6, containing from about 22 to about 84 wt.% R-1234ze (E), from about 10 to about 28 wt.% R-744 and from about 6 to about 50 wt.% R-1234yf . 8. The composition according to claim 6, containing from about 14 to about 86 wt.% R-1234ze (E), from about 4 to about 26 wt.% R-744 and from about 10 to about 60 wt.% R-1234yf or containing from about 32 to about 88 wt.% R-1234ze (E), from about 8 to about 28 wt.% R-744 and from about 4 to about 40 wt.% R-1234yf. 9. The composition according to p. 1, where the third component contains R-1243zf, preferably from about 4 to about 60% wt. R-1243zf. 10. The composition according to p. 9, containing from about 20 to about 92% wt. R-1234ze (E), from about 4 to about 30 wt.% R-744 and from about 4 to about 50 wt.% R-1243zf. 11. The composition according to p. 10, containing from about 32 to about 88 wt.% R-1234ze (E), from about 6 to about 28 wt.% R-744 and from about 6 to about 40 wt.% R-1243zf . 12. The composition according to any one of the preceding paragraphs, mainly consisting of R-1234ze (E), R-744 and the third component. 13. The composition of claim 1, further comprising pentafluoroethane (R-125). 14. The composition according to any one of paragraphs. 1-11 or 13, which is less flammable than R-1234yf alone or R-1243zf alone. 15. The composition according to p. 14, which has:
(a) a higher flammability limit;
(b) higher ignition energy and / or
(c) lower flame propagation speed
compared to the R-1234yf alone or the R-1243zf alone. 16. The composition according to any one of paragraphs. 1-11 or 13, which has a fluorine ratio (F / (F + H)) from about 0.42 to about 0.7, preferably from about 0.44 to about 0.67. 17. The composition according to any one of paragraphs. 1-11 or 13, which is non-flammable. 18. The composition according to any one of paragraphs. 1-15 or 17, optionally containing a lubricant. 19. The composition of claim 18, wherein the lubricant is selected from mineral oil, silicone oil, polyalkylbenzenes (PAB), polyol esters (POE), polyalkylene glycols (PAG), polyalkylene glycol esters (PAG esters), polyvinyl ethers (PVE ), poly (alpha-olefins) and their combinations. 20. The composition of claim 18, further comprising a stabilizer. 21. The composition according to p. 20, where the stabilizer is selected from compounds based on diene, phosphates, phenolic compounds and epoxides and mixtures thereof. 22. The composition according to any one of paragraphs. 1-11 or 13, optionally containing a combustion retardant. 23. The composition according to p. 22, where the combustion retardant is selected from the group consisting of three (2-chloroethyl) phosphate, (chloropropyl) phosphate, three (2,3-dibromopropyl) phosphate, three (1,3-dichloropropyl) phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, fluorinated iodine carbon, fluorinated bromocarbon, trifluoroiodomethane, perfluoroalkylamines, bromo-fluoroalkylamines and mixtures thereof. 24. A device for transferring heat, comprising a composition according to any one of paragraphs. 1-23. 25. The use of a composition according to any one of paragraphs. 1-23 in the device for transferring heat. 26. A device for transferring heat according to claim 24, which is a refrigeration device. 27. The heat transfer device according to claim 26, which is selected from the group consisting of automotive air conditioning systems, residential air conditioning systems, commercial air conditioning systems, housing refrigeration systems, housing freezing systems, industrial refrigeration systems, industrial freezing systems, chiller air conditioning systems, chiller refrigeration systems and commercial or residential heat pump systems, preferably the heat transfer device is an automatic a mobile air conditioning system. 28. A device for transferring heat according to claim 26 or 27, which comprises a compressor. 29. A purge agent containing the composition according to any one of paragraphs. 1-23. 30. A foaming composition containing one or more components capable of forming foam, and a composition according to any one of paragraphs. 1-23, where one or more components capable of forming foam, selected from polyurethanes, thermoplastic polymers and resins, such as polystyrene and epoxy resins, and mixtures thereof. 31. A foam containing the composition according to any one of paragraphs. 1-23. 32. A sprayable composition containing the material to be sprayed and a propellant containing the composition according to any one of claims. 1-23. 33. A method of cooling an article, which comprises condensing a composition according to any one of claims. 1-23, and then evaporation of the composition near the product, which should be cooled. 34. A method of heating an article, which comprises condensing a composition according to any one of claims. 1-23 near the product, which should be heated, and then the evaporation of the composition. 35. A method of extracting a substance from a biological mass, comprising contacting the biological mass with a solvent containing the composition according to any one of paragraphs. 1-23, and the separation of the substance from the solvent. 36. The method of cleaning the product, comprising contacting the product with a solvent containing the composition according to any one of paragraphs. 1-23. 37. A method of extracting material from an aqueous solution or from a crushed solid matrix, comprising contacting the aqueous solution or matrix with a solvent containing the composition according to any one of claims. 1-23, and separation of the material from the solvent. 38. A device for generating mechanical energy containing a composition according to any one of paragraphs. 1-23. 39. The device for generating mechanical energy according to claim 38, which is adapted to use the Rankine cycle or its modifications to generate work from heat. 40. A method of upgrading a heat transfer device, comprising the step of removing R-134a, R-152a, R-1234yf, R-22, R-410A, R-407A, R-407B, R-407C, R-407D, R- 407E, R-407F, R-507 or R-404A and administering a composition according to any one of claims. 1-23. 41. The method of claim 40, wherein the heat transfer device is a refrigeration device. 42. The method of claim 41, wherein the heat transfer device is an air conditioning system. 43. A method of reducing environmental impacts arising from the operation of a product containing a compound or composition, which includes replacing at least partially R-134a, R-152a, R-1234yf, R-22, R-410A, R-407A, R-407B, R-407C, R-407D, R-407E, R-407F, R-507 or R-404A by the composition according to any one of claims. 1-23. 44. A method of obtaining a composition according to any one of paragraphs. 1-23 and / or device for heat transfer according to any one of paragraphs. 24 or 26-28, where the composition or device for heat transfer contains R-134a, which includes the introduction of R-1234ze (E), R-744, the third component and, optionally, R-125, a lubricant, stabilizer and / or moderator burning into a heat transfer device comprising an existing heat transfer fluid, which is R-134a. 45. The method of claim 44, comprising the step of removing at least some of the existing R-134a from the heat transfer device before introducing R-1234ze (E), R-744, the third component, and optionally R-125, lubricant, stabilizer and / or flame retardant. 46. The method according to p. 43, where the product is selected from a device for transferring heat, a blowing agent, a foaming composition, a sprayable composition, a solvent, or a device for generating mechanical energy. 47. The method of claim 46, wherein the product is a heat transfer device.

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