CN103635558A

CN103635558A - Heat transfer compositions and methods

Info

Publication number: CN103635558A
Application number: CN201280021647.1A
Authority: CN
Inventors: S·F·Y·莫塔; M·W·斯帕茨; R·P·富格尔; E·D·C·V·贝塞拉
Original assignee: Honeywell International Inc
Current assignee: Honeywell International Inc
Priority date: 2011-05-02
Filing date: 2012-05-02
Publication date: 2014-03-12
Also published as: EP2705107A4; WO2012151238A3; JP2014514423A; EP2705107A2; RU2013152876A; CA2834894A1; MX2013012673A; WO2012151238A2; KR20140027362A; AU2012250863A1; BR112013028071A2

Abstract

Compositions, methods and systems which comprise or utilize a multi-component mixture comprising: (a) from about 10% to about 35% by weight of HFC-32; (b) from about 10% to about 35% by weight of HFC-125; (c) from about 20% to about 50% by weight of HFO-1234ze, HFO-1234yf and combinations of these; (d) from about 15% to about 35% by weight of HFC-134a; and optionally (e) up to about 10% by weight of CF3I and up to about 5% by weight of HFCO-1233ze, with the weight percent being based on the total of the components (a)-(e) in the composition.

Description

Heat transfer compositions and heat-transferring method

Related application

The application relates to and requires No. 13/099,218, the U. S. application of on May 2nd, 2011 application and both right of priority of No. 61/598,056, the U. S. application applied on February 13rd, 2012.The full content of above-mentioned application is all incorporated to herein by reference in full.

Invention field

The present invention relates in refrigeration application, composition, method and system used in middle gentle cryogenic refrigeration application particularly, and be particularly related to the refrigerant composition for heating and cooling application of alternative refrigerant HFC-404A and relate to the gentle low-temperature refrigerant system of improvement, comprising the system that is designed to use HFC-404A.

Background technology

Use the mechanical refrigeration system of refrigerant liquid, and relevant heat transfer unit (HTU) is known in the art for industry, business and domestic use as heat pump and air-conditioning.Fluid based on hydrofluoric ether (fluorocarbon) is widely used in a lot of houses, commercial and industrial application, comprises as working fluid for for example system of air-conditioning, heat pump and refrigeration system.Due to some suspicious environmental problem, comprise the relatively high global warming up trend relevant to the use of some compositions that use before this in these application, more and more the fluid with low even zero ozone depletion and global warming up trend, for example hydrogen fluorohydrocarbon (" HFCs ") are used in expectation.For example, some governments have signed the Kyoto Protocol to protect the global environment and to have stipulated reduction CO2 quantity discharged (Global warming).Therefore, need to be low flammable or non-flammable, nontoxic substitute materials is to replace the HFCs of some high Global warming.

A kind of important refrigeration system type is called " cryogenic refrigerating system ".Because it plays fresh and suitable edible vital role while guaranteeing that food is in arriving human consumer's hand, so this type systematic is even more important for foodstuff production, circulation and retail trade.In this class cryogenic refrigerating system, HFC-404A (HFC-125:HFC-143a:HFC134a combines with the weight ratio of approximately 44: 52: 4, is called in the art HFC-404A or R-404A) is conventional refrigerant liquid.The estimation global warming up trend (GWP) of R-404A is up to 3922.

Therefore, more and more need novel hydrofluoric ether and hydrogen fluorocarbon compound and composition to substitute the composition using before this in these and other application.For example, expectation by use depletion not without chlorine refrigeration agent compound, for example hydrogen fluorohydrocarbon (HFC ' s), substitutes chloride refrigeration agent and improves chloride refrigeration system.General industry and the industry of particularly conducting heat are constantly find can CFC alternative s and HCFCs and be the novel mixture based on hydrofluoric ether of environmental safety surrogate.Yet, at least for heat-transfer fluid, importantly, any potential surrogate also must have those performances that many fluids of being widely used at present have, such as good thermal conduction, chemical stability, low or nontoxicity, non-combustible and/or lubricant compatibility etc.

For service efficiency, need emphasis to be pointed out that, the increase that the loss in refrigeration agent thermomechanical property or efficiency may be used by the fossil oil causing due to electrical energy demands increase causes secondary environmental influence.

In addition, conventionally expect that CFC alternative refrigerants does not need the steam compressed technology of routine of current use CFC refrigeration agent to do great engineered can coming into force.

For many application, combustibility is another important character.That is to say, in many application, comprise particularly in heat transfer applications, use non-flammable composition to be considered to important or requisite.Therefore, conventionally, it is favourable in this class combination, using non-flammable compound.Term as used herein " non-combustible " refers to that compound or composition measure according to the ASTM standard E-681 of 2002 that to be confirmed as be non-flammable, and described standard incorporated herein by reference.Regrettably, many HFC ' s that are expected to be useful in refrigerant composition are not the non-combustible like that of as used herein term definition.For example, fluoric ether C2H4F2 C2H4F2 (HFC-152a) and fluoroolefins 1,1,1-trifluoro propene (HFO-1234zf) is all flammable and is not therefore suitable in many application.

Therefore, applicant recognizes in heating and cooling system and method, particularly in steam compressed heating and cooling system, more particularly in low-temperature refrigerant system, comprise and using and/or design is used for using in the system of HFC-404A, the composition very with advantage is the demand of heat transfer compositions particularly.

Summary of the invention

Applicant has been found that composition, the method and system by comprising or use multicomponent mixture can meet the demand and other demand, and described mixture comprises: (a) approximately 10 % by weight are to the methylene fluoride (HFC-32) of approximately 35 % by weight; (b) approximately 10 % by weight are to the pentafluoride ethane (HFC-125) of approximately 35 % by weight; (c) approximately 20 % by weight are to HFO-1234ze, the HFO-1234yf of approximately 50 % by weight and their combination; (d) approximately 15 % by weight are to the HFA 134a (HFC-134a) of approximately 35 % by weight; (e) CF of approximately 10 % by weight at the most optionally ₃i and the at the most HFCO-1233ze of approximately 5 % by weight, described weight percent is in the total amount of component in composition (a)-(e).

Some preferred embodiment in, described composition comprises multicomponent mixture, this mixture comprises: (a) approximately 15 % by weight are to the HFC-32 of approximately 30 % by weight; (b) approximately 10 % by weight are to the HFC-125 of approximately 30 % by weight; (c) approximately 20 % by weight are to HFO-1234ze, the HFO-1234yf of approximately 50 % by weight and their combination; (d) approximately 15 % by weight are to the HFC-134a of approximately 35 % by weight; (e) CF3I and HFCO-1233ze of approximately 5 % by weight at the most of approximately 5 % by weight at the most optionally, described weight percent is in the total amount of component in composition (a)-(e).

In other embodiments, described composition comprises multicomponent mixture, and this mixture comprises: (a) approximately 20 % by weight are to the HFC-32 of approximately 30 % by weight; (b) approximately 20 % by weight are to the HFC-125 of approximately 30 % by weight; (c) HFO-1234ze of approximately 0 % by weight (and/or being greater than 0%) to the HFO-1234yf of approximately 15 % by weight and approximately 10 % by weight to approximately 30 % by weight; (d) approximately 15 % by weight are to the HFC-134a of approximately 30 % by weight, (e) CF3I and HFCO-1233ze of approximately 5 % by weight at the most of approximately 5 % by weight at the most optionally, the total amount meter of described weight percent based on component in composition (a)-(e).

The present invention also provides the method and system that uses the present composition, comprises for conducting heat and for improvement of the method and system of existing heat-transfer system.Some preferred method aspect of the present invention relates to is for example providing relative low temperature cooling method in cryogenic refrigerating system.Other preferred method aspect of the present invention provides improves the existing refrigeration system that design contains and/or comprise R-404A refrigeration agent, the method of preferred cryogenic refrigerating system, comprise in system and introduce composition of the present invention, and described existing refrigeration system is not carried out to the engineered of essence.

Term as used herein HFO-1234ze refers to 1,1,1,3-tetrafluoeopropene, and no matter it is cis or trans.Term as used herein " cis HFO-1234ze " and " trans HFO-1234ze " describe respectively cis and the trans forms of 1,1,1,3-tetrafluoeopropene.Therefore, the scope of term " HFO-1234ze " comprises cis HFO-1234ze, trans HFO-1234ze, and their all combinations and mixture.

Term as used herein " HFCO-1233 " refers to all trifluoro monochloro propylene.At trifluoro monochloro propylene, comprise 1,1,1, three is fluoro-2, chloro-propylene (HFCO-1233xf), and cis and trans 1,1,1-tri-is fluoro-3, propenyl chloride (HFCO-1233zd).It is fluoro-3 that term as used herein HFCO-1233zd typically refers to 1,1,1-tri-, chloro-propylene, and no matter it is cis or trans forms.Term as used herein " cis HFCO-1233zd " and " trans HFCO-1233zd " describe respectively cis and the trans forms of 1,1,1-trifluoro chlorallylene.Therefore, the scope of term " HFCO-1233zd " comprises cis HFCO-1233zd, trans HFCO-1233zd, and their all combinations and mixture.

Embodiment

In many application, for example, in foodstuff production, circulation and retail trade, cryogenic refrigerating system is very important.Fresh and suitable edible vital role when this type systematic plays and guarantees that food is in arriving human consumer's hand.In this class cryogenic refrigerating system, a kind of conventional refrigerant liquid is HFC-404A, and its estimation global warming up trend (GWP) is up to 3922.Applicant has been found that, composition of the present invention can meeting in the application of this class refrigeration agent with unforeseeable mode with excellence, special and preferred for the surrogate of HFC-404A and/or the demand of substitute, these surrogates have immediately lower GWP value and non-flammable nontoxic fluid are substantially provided, and it has the tight cooling capacity mating and/or efficiency with HFC-404A in this type systematic.

The present invention also comprises middle temperature refrigerant compositions, system and method.According to some preferred embodiment, method and system of the present invention adopts the evaporator temperature that is greater than approximately-15 ℃ to approximately 5 ℃.In this class, the example of warm system and method is included in the fresh food compartment of home freezer refrigeration is provided.

Heat transfer compositions

Conventionally, composition of the present invention is applicable in heat transfer applications, as heating and/or heat-eliminating medium, but as mentioned above, be specially adapted in gentle cryogenic refrigerating system, and the system that is preferably applicable to use before this cryogenic system of HFC-404A and/or uses before this R-22.

Applicant finds in wide and close limit as herein described, to use component of the present invention for realize that the present composition shows useful but be vital for the performance combination that is difficult to realize, particularly in preferred system and method, and beyond given scope, use identical component can produce adverse influence for one or more key propertys of the present composition, system or method.For HFC-32:HFC-125 weight ratio approximately 0.9: 1.2 to the about composition of 1.2: 0.9, realized performance combination very preferably, in some embodiments, approximately the ratio of 1: 1 is preferred.Applicant finds, for HFO-1234ze:HFC-1234yf weight ratio, at the composition of approximately 5: 1 to approximately 0.7: 1, has also realized performance combination very preferably, more preferably approximately 1: 1 to approximately 3: 1.In some preferred implementation, approximately the ratio of 4: 1 is preferred.

For easy object, the combination of HFO-1234ze and HFC-1234yf is referred to herein as " tetrafluoropropene component " or " TFC ", and in some embodiments, HFC-134a:TFC weight ratio can realize performance combination very preferably at the composition of approximately 5: 7 to approximately 1: 1, in some is implemented, approximately the ratio of 4: 6 is preferred.

Although, arbitrary isomer of expection HFO-1234ze all can be used, applicant finds in some embodiments, preferably HFO-1234ze comprises trans HFO-1234ze, and preferably with main ratio, comprise trans HFO-1234ze, and substantially by trans HFO-1234ze, formed in some embodiments.

As mentioned above, applicant finds that composition of the present invention can overcome difficulties and realize the combination of performance, comprises low especially GWP.As nonrestrictive example, the HFC-404A that is 3922 with GWP compares, and lower Table A has illustrated the obvious improvement of the GWP that some compositions table of the present invention reveals.

Table A

In order to strengthen or for composition provides certain function, or reduce in some cases the object of the cost of composition, composition of the present invention can comprise other component.For example, according to refrigerant compositions of the present invention, particularly those are for the composition of vapor compression system, conventionally the content with approximately 30 % by weight-50 % by weight of composition comprises lubricant, and content can higher than approximately 50% and content can be lower than approximately 5% in other cases in some cases.In addition, composition of the present invention can also comprise expanding material, and propane for example, in order to contribute to consistency and/or the deliquescent object of lubricant.This class expanding material, comprises propane, butane and pentane, and preferably the content with approximately 0.5 % by weight-5 % by weight of composition exists.As United States Patent (USP) 6,516, No. 837 disclosed, can also add the combination of tensio-active agent and solubilizing agent to increase oil soluble in composition of the present invention, and the content disclosed in this patent incorporated herein by reference.Be used from the conventional refrigeration lubricant of refrigerating machine with hydrogen fluorohydrocarbon (HFC) refrigeration agent one, for example polyol ester (POEs) and polyalkylene glycol (PAGs), PAG oil, silicone oil, mineral oil, alkylbenzene (ABs) and poly-(alpha-olefin) (PAO) can be used together with refrigerant compositions of the present invention.Commercially available mineral oil comprises the Witco LP250 (registered trademark) from Witco, from the Zerol300 (registered trademark) of Shrieve Chemical, and from the Sunisco3GS of Witco, and from the Calumet R015 of Calumet.Commercially available alkyl benzene lubricants comprises Zerol150 (registered trademark).Commercially available ester comprises the neopentyl glycol dipelargonate that can be used as Emery2917 (registered trademark) and Hatcol2370 (registered trademark) acquisition.Other available esters comprise phosphoric acid ester, diester class and fluoroester class.In some cases, alkyl is oily and comprise that the refrigeration agent of idohydrocarbon (iodocarbon) has enough solvabilities, and the combination of idohydrocarbon and hydrocarbon ils may be more stable than the lubricant of other type.Therefore, this combination may be preferred.Preferred lubricant comprises polyalkylene glycols and ester class.In some embodiments, because they are at present for application-specific, for example, in movable air conditioner, polyalkylene glycols is very preferred.Certainly, also can use the different mixtures of dissimilar lubricant.

To those skilled in the art, according to the instruction comprising, in the situation that not deviating from novel feature of the present invention and essential characteristic, can also comprise NM other additive herein herein.

Heat-transferring method and system

Therefore, method of the present invention, system and composition are specially adapted in conjunction with the heat-transfer system of various routines and particularly refrigeration system, such as air-conditioning (comprising fixed air-conditioning and movable air conditioner system), refrigeration, heat pump etc.Some preferred embodiment in, composition of the present invention is used to the refrigeration system that initial design is used HFC refrigeration agent (for example R404).The present invention preferred composition has substantially similar to R-404A or match, preferably the same with R-404A high or higher than performance and/or the usefulness of R-404A, meanwhile trend towards demonstrating the performance of multiple desired R-404A but there is the remarkable lower GWP than R-404A.Especially, applicant recognizes that some preferred implementation of the present composition trends towards showing relatively low global warming up trend (" GWPs "), preferably lower than approximately 2500, and more preferably less than approximately 2400, and further more preferably no higher than approximately 2300.In some embodiments, composition of the present invention has approximately 1500 or lower GWP, and further more preferably less than approximately 1000.

At some other preferred embodiment in, composition of the present invention is for containing and/or initial design is used the refrigeration system of R-404A.The preferred refrigerant compositions of the present invention can be for comprising the lubricant conventionally using together with R-404A, for example, in the refrigeration system of mineral oil, polyalkylbenzene, polyalkylene glycol wet goods, or can use together with other lubricant conventionally using together with HFC refrigeration agent.Term used herein " refrigeration system " is often referred to any use refrigeration agent so that cooling any system or equipment to be provided, or any parts or the part of this type systematic or equipment.This class refrigeration system comprises, for example, and air-conditioning, refrigerator, water cooler (comprising the water cooler that uses centrifugal compressor) etc.

As mentioned above, the present invention has realized remarkable advantage in conjunction with the known system as cryogenic refrigerating system.Term used herein " cryogenic refrigerating system " refers to use the vapor compression refrigeration system that one or more compressors and condenser temperature are approximately 35 ℃ to 45 ℃.In the preferred implementation of this type systematic, the evaporator temperature of this type systematic is for approximately-40 ℃ extremely lower than approximately-15 ℃, and more preferably approximately-35 ℃ to approximately-25 ℃, evaporator temperature is preferably approximately-32 ℃.In addition, this type systematic preferred embodiment in, this type systematic has the superheating temperature of approximately 0 ℃ to approximately 10 ℃ at evaporator outlet, preferably at evaporator outlet, have the superheating temperature of approximately 4 ℃ to approximately 6 ℃.In addition, in the preferred implementation of this type systematic, this type systematic has the superheating temperature of approximately 15 ℃ to approximately 25 ℃ in suction line, preferably in suction line, has the superheating temperature of approximately 20 ℃ to approximately 25 ℃.

In a nonrestrictive embodiment, can improve existing refrigeration system with heat transfer compositions of the present invention, wherein change or do not change in fact system and discharge or not exclusively discharge existing refrigeration agent completely.On the one hand, part refrigerant charge is discharged from system, and it can comprise higher than 5%, 10%, 25%, 50%, 75% etc.Afterwards, the refrigerant charge shifting out is replaced by a kind of or combination in the refrigeration agent of non-combustible, low GWP as herein described.

In optional embodiment, can after part refrigrant leakage, with refrigeration agent of the present invention, carry out " having mended (top off) " existing system, rather than partly drain existing system.A lot of commercial systems, for example, have the commercial system of higher refrigrant leakage rate, need to add termly refrigeration agent in the length of life of system.In a method of the present invention, coolant system provides full refrigerant charge or the refrigeration agent design charging that is less than this system, this is the result that refrigeration agent leaks from system in a preferred embodiment, and use refrigerant composition of the present invention to recharge this system, preferably during routine recharges maintenance.If system leak R404A, for example, with a kind of or combination in determined blend herein, recharge.Method of the present invention allows the generation that this kind of thing, substantially performance simultaneously that kept system, keep or improved efficiency (lower electric consumption, for user, be equivalent to running cost still less), and reduced the GWP of contained refrigeration agent in system (having reduced the impact on environment).In a preferred embodiment, no matter how many refrigeration agents leak, the method can both be implemented, preferably there is no hybrid (blend calculation), and the method provides a kind of conventional maintenance project that does not deviate from described system, reduce easy (and low cost) approach that recharges relevant environmental influence with existing system.

According to aforementioned content, applicant recognizes, when being combined with blend of the present invention, even relatively a large amount of R404A, no matter be the form that is not intended to impurity, or as component or the residual refrigerant as System Replacement or after recharging of having a mind to add, can not produce to the performance of refrigeration agent of the present invention and/or refrigeration system the disadvantageous effect of essence.On the contrary, applicant also recognizes blends of the present invention relatively a large amount of in R404A, no matter is to be not intended to the form of impurity or as the component of having a mind to add, can not produce to the performance of this refrigeration agent the disadvantageous effect of essence.Correspondingly, although in other cases, it is defective that the existence of this class impurity may make to have the use of refrigeration agent of this impurity, and applicant recognizes that the use of this class refrigerant mixture is normally acceptable for expection object.Correspondingly, angle from workability (workability), an advantage of method and composition of the present invention is, conventionally do not exist very large motivation to guarantee to get rid of R404A completely from low GWP refrigeration agent, and vice versa, in this case, do not use method provided by the present invention, along with the operation generation question of substance of a lot of existing automatic scavenge systems and the possibility of serious problems increase.Yet method of the present invention has overcome these problems and has strengthened reliability, security and the efficiency of system.

Embodiment

For illustrating object of the present invention, provide following examples, but scope of the present invention is not construed as limiting.

Embodiment 1: performance perameter

The coefficient of performance (COP) is that generally accepted refrigerant performance is measured, especially for representing that refrigeration agent is comprising refrigeration agent evaporation or the specific heating of condensation or the relative thermodynamic(al) efficiency in refrigeration cycle.In refrigeration engineering, this nomenclature is shown with the ratio of effect refrigeration and the energy that compressor applies in the process of compressed vapour.It is cooling or add heat and provide for certain of the ability of given cooling agent volumetric flow rate compressor pump heat and measure that the capacity of refrigeration agent represents that it provides.In other words, given specific compressor, the capacity of cooling agent is higher, carry cooling or heating power is larger.Under estimation specific operation condition, a kind of means of cooling agent COP are the thermomechanical properties based on this cooling agent, with standard refrigerant cycles analytical technology carry out (referring to, R.C.Downing for example, FLUOROCARBON REFRIGERANTS HANDBOOK, Chapter3, Prentice-Hall, 1988).

Cryogenic refrigerating system is provided.In the situation of the system given an example in the present embodiment, condenser temperature is set as 40.55 ℃, and it is conventionally corresponding to the external temperature of approximately 35 ℃.The condensate depression of bloating plant entrance is set as 5.55 ℃.Vaporization temperature is set as-31.6 ℃, corresponding to the case temperature of approximately-26 ℃ (box temperature).The superheating temperature of evaporator outlet is set as 5.55 ℃.Superheating temperature in suction line is set as 13.88 ℃, and compressor efficiency is set as 65%.Pressure drop and heat transmission in connection line (sucking and liquid line) are negligible, and ignore the heat leak by compression case.In mensuration, in Table A, give according to the certain operations parameter of composition A1-A4 of the present invention, and in following table 1, recorded these operating parameterss, based on HFC-404A, there is 100% COP value, 100% capability value and the outflow temperature (discharge temperature) of 97.6 ℃.

Table 1

Title	GWP	Vaporizer slippage (℃)	Capacity (%)	COP(％)
					R404A	3922	0.5	100％	100％
A1	1344	4.9	96％	110％
					A2	1330	3.5	103％	108％
A3	1386	4.7	99％	109％
					A4	1386	5.4	95％	110％

From upper table 1, can find out, applicant finds that composition of the present invention can realize a plurality of important performance of refrigerant systems parameters close to R-404A parameter simultaneously, and particularly fully approaches and make said composition can in cryogenic refrigerating system, be used as the direct surrogate (drop-in replacement) of R404A and/or for this class existing system, only do the less system reform.For example, the capacity that composition A1-A4 shows in this cryogenic refrigerating system is in approximately 8% scope of R404A capacity, even more preferably in 5% scope.These blends all have the usefulness (COPs) higher than R404A, differ 10% more than, and this expects very much.The angle of the GWP particularly improving from composition A1-A4, for initially containing and/or designing the cryogenic refrigerating system that contains R-404A, these compositions of the present invention are the good candidate as direct surrogate.

Because a lot of existing cryogenic refrigerating systems are designed to use R-404A, or there is other refrigeration agent of similar performance to R-404A, those skilled in the art will recognize that can be as the surrogate of R-404A or similar refrigeration agent, simultaneously for the remarkable advantage of the relatively little refrigeration agent with low GWP and higher performance of the transformation of system.In addition, those skilled in the art will recognize that composition of the present invention, for novel or newly-designed refrigeration system, preferably includes cryogenic refrigerating system, when middle, can provide significant advantage.

Embodiment 2: modified parameters

Expection in some embodiments, the invention provides and improve one's methods, it comprises the refrigeration agent that shifts out the existing refrigeration agent of at least a portion and use composition of the present invention to replace at least a portion to shift out from system, preferably for system not substantially transformation and more preferably for Major Systems assembly, for example compressor, condenser, vaporizer and expansion valve without any change.Some characteristic due to cryogenic refrigerating system, comprise and particularly contain or design the cryogenic refrigerating system that contains R404A refrigeration agent, in some embodiments, importantly this system is used directly replacement (drop-in) refrigeration agent can show reliable system operating parameters.This generic operation parameter comprises:

In approximately 105% scope of high side pressure of system of high side pressure (high-side pressure) in using R404A, and more preferably from about in 103% scope.In this class embodiment, this parameter is important, because it allows to use existing pressure assembly.

Preferably lower than approximately 130 ℃, and more preferably less than the outflow temperature of approximately 125 ℃.The advantage of this characteristic is, it allows to use existing equipment, and does not need to start the heat protection of system, and the heat protection preferred design of described system is used for protecting compressor assembly.This parameter is favourable, and it avoids using in order to reduce outflow temperature expensive control, and for example liquid injects.

Lower suction pressure is acceptable, as long as it does not cause that system becomes negative pressure under low vaporization temperature.Need this positive pressure guarantee that system always has positive pressure, avoid any pollution of wet air under leakage situation.In order to assess this demand, be by means of the character (NBT: the boiling temperature under normal atmosphere) that is called " standard boiling temperature (normal boiling tempeature) " of paid close attention to fluid.This NBT should approach the NBT of the fluid (R404A) replacing as far as possible, and at least will for example, lower than the minimum vaporization temperature (:-40 ℃) of typical commercial system.

Measurement is according to the aforesaid operations parameter of determined composition A1-A4 in upper Table A of the present invention and other operating parameters, and these operating parameterss are recorded in following table 2:

Table 2

Some preferred embodiment in, alternative steps is directly to substitute, the meaning is that system not to need substantial redesign or transformation and not have the major parts of equipment need to be replaced in order adapting with refrigeration agent of the present invention.Composition A1-A4 just belongs to this situation, and they conventionally can be in most improvement operations, and without the change of any primary clustering.In composition therefor A1-A4, outlet pressure is all similar to R404A lower than limits value and standard boiling temperature with temperature, so they can be in the existing refrigeration system of the overwhelming majority.

Although, with reference to preferred embodiment describing the present invention, it will be understood by those skilled in the art that and can make various changes and can be equal to and substitute and do not deviate from scope of the present invention for its key element.In addition, according to instruction of the present invention, can make multiple modification to adapt to concrete situation or material, and not deviate from essential scope of the present invention.Therefore, the present invention is not limited to disclosed embodiment, the present invention includes the whole embodiments in the scope of any claim that falls into claims or follow-up increase.

Claims

1. heat transfer compositions, comprises: (a) approximately 20 % by weight are to the HFC-32 of approximately 30 % by weight; (b) approximately 20 % by weight are to the HFC-125 of approximately 30 % by weight; (c) approximately 0 % by weight is to the HFO-1234yf of approximately 15 % by weight, and approximately 10 % by weight are to the HFO-1234ze of approximately 30 % by weight; (d) approximately 15 % by weight are to the HFC-134a of approximately 30 % by weight, and described weight percent is in the total amount of component in composition (a)-(d).

2. the heat transfer compositions of claim 1, wherein said HFO-1234ze comprises trans-HFO-1234ze.

3. the heat transfer compositions of claim 1, the weight ratio of HFC-32 and HFC-125 is approximately 0.9: 1.2 to approximately 1.2: 0.9.

4. the heat transfer compositions of claim 1, comprises and be greater than 0 % by weight to the HFO-1234yf of approximately 15 % by weight, and approximately 10 % by weight is to the HFO-1234ze of approximately 30 % by weight.

5. the heat transfer compositions of claim 1, the weight ratio of the combination of the relative HFO-1234ze of 134a and HFO-1234yf is approximately 5: 7 to approximately 1: 1.

6. the heat transfer compositions of claim 1, wherein the content of HFO-1234ze is approximately 20%, and the content of HFO-1234yf is approximately 9%.

7. the heat transfer compositions of claim 1, wherein the content of HFO-1234ze is approximately 26%.

8. the heat transfer compositions of claim 1, wherein the content of HFO-1234ze is approximately 17%, and the content of HFO-1234yf is approximately 9%.

9. substitute the method for existing heat-transfer fluid contained in heat-transfer system, comprise at least a portion that removes described existing heat-transfer fluid from described system, described existing heat-transfer fluid is HFC-404A, and by introduce at least a portion that following heat transfer compositions substitutes described existing heat-transfer fluid in described system, described heat transfer compositions comprises: (a) approximately 20 % by weight are to the HFC-32 of approximately 30 % by weight; (b) approximately 20 % by weight are to the HFC-125 of approximately 30 % by weight; (c) approximately 0 % by weight is to the HFO-1234yf of approximately 15 % by weight, and approximately 15 % by weight are to the HFO-1234ze of approximately 30 % by weight; (d) approximately 15 % by weight are to the HFC-134a of approximately 30 % by weight, and described weight percent is in the total amount of component in composition (a)-(d).

10. heat-transfer system, it comprises compressor, condenser and vaporizer that fluid is communicated with, and the heat transfer compositions that is arranged in described system, described heat transfer compositions comprises: (a) approximately 20 % by weight are to the HFC-32 of approximately 30 % by weight; (b) approximately 20 % by weight are to the HFC-125 of approximately 30 % by weight; (c) approximately 0 % by weight is to the HFO-1234yf of approximately 15 % by weight, and approximately 15 % by weight are to the HFO-1234ze of approximately 30 % by weight; (d) approximately 15 % by weight are to the HFC-134a of approximately 30 % by weight, and described weight percent is in the total amount of component in composition (a)-(d), and the service temperature of described condenser is approximately 35 ℃ to approximately 45 ℃.