CN104797677A - Low GWP heat transfer compositions - Google Patents
Low GWP heat transfer compositions Download PDFInfo
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- CN104797677A CN104797677A CN201380054119.0A CN201380054119A CN104797677A CN 104797677 A CN104797677 A CN 104797677A CN 201380054119 A CN201380054119 A CN 201380054119A CN 104797677 A CN104797677 A CN 104797677A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
- C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
- C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/126—Unsaturated fluorinated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/22—All components of a mixture being fluoro compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/40—Replacement mixtures
- C09K2205/43—Type R22
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Abstract
The invention provides heat transfer compositions and methods including (a) HFC-32; (b) HFO-1234ze; and (c) either or both of HFC-152a and/or HFC-134a.
Description
The cross reference of related application
This application claims the right of priority that the series number submitted on August 20th, 2012 is the U.S. Provisional Application of 61/684,883, the mode that the content of this application is quoted in full is incorporated to herein.
The application is also the series number submitted on November 9th, 2011 is 13/292, the continuation-in-part application of the U. S. application of 374, and the 61/413rd of the application requirement submission on November 12nd, 2010 just mentioned the, the benefit of priority of No. 000 U.S. Provisional Application, the mode that the content of above-mentioned each application is quoted in full is incorporated to herein.
Technical field
The present invention relates to composition, the method and system particularly in refrigeration application with practicality, and relate in specific and be applicable to usually utilize refrigeration agent HCFC-22 to carry out heat transfer and the refrigerant composition of the system heating and/or cool application.
Background technology
The mechanical refrigeration system of refrigerant liquid and relevant heat transfer unit (HTU) (as heat pump and air conditioner) is used to be well-known in industry, commercialization and domestic environments.Chlorofluorocarbons (CFCs) (CFC) is developed as the refrigeration agent being used for this type systematic in the thirties in 20th century.But since the eighties in 20th century, CFC has become the focus of attracting attention on the impact of advection ozonosphere.In 1987, the government of some countries endorsed the Montreal Protocol of protecting the global environment, and set the timetable progressively eliminating CFC product.CFC is replaced with the material of the more environmental protection containing hydrogen or HCFC (HCFC).Subsequently progressively eliminating of these CFC accelerated to the amendment of Montreal Protocol and also contemplate progressively superseded HCFC.
Correspondingly, therefore and day by day increase for as the former new fluorine carbon of attractive substitute of composition that uses in these and other application and the demand of fluorocarbon and composition.Such as, desirably by with the non-chlorine-containing compound (as fluorocarbon, HFC) of depletion replacing chloride heat transfer compositions to transform chloride refrigeration and air conditioning system.General industry circle and industry circle of particularly conducting heat constantly are being found and can provided the replacement scheme of CFC and HCFC and the new mixture based on fluorocarbon being considered to the safer substitute of the environment of CFC and HCFC.But, at least with regard to heat-transfer fluid, it has been generally acknowledged that importantly, any potential substitute also must possess those character that the most widely used many fluid has, as the heat transfer character of excellence, chemical stability, low toxicity or nontoxicity, low combustible and/or lubricant compatibility, etc.R-22 provides an example of this refrigerant composition, and it is used in many refrigeration and air conditioning system, and is progressively eliminated due to aforesaid environmental problem.
Advise replacing HCFC-22 during many patents are open.That is, these patents openly suggested the refrigeration agent or artificial atmosphere composition that can HCFC-22 be replaced to use in the new system that will build or install.The 5th is included in the middle of this kind of patent is open, 185, No. 094 United States Patent (USP), 5th, 370, No. 811 United States Patent (USP)s, 5th, 438, No. 849 United States Patent (USP)s, 5th, 643, No. 492 United States Patent (USP)s, 5th, 709, No. 092 United States Patent (USP), 5th, 722, No. 256 United States Patent (USP)s, 6th, 018, No. 952 United States Patent (USP)s, 6th, 187, 219B1 United States Patent (USP), 6th, 606, 868B1 United States Patent (USP), 6th, 669, 862B1 United States Patent (USP), the US2004/00691091A1 U. S. application announced and the EP0430169A1 of announcement, EP0509673A1 and EP0811670A1 European application.Although the many tertiary mixtures disclosing methylene fluoride (HFC-32), pentafluoride ethane (HFC-125) and Tetrafluoroethane (HFC134a) in the application of these United States Patent (USP)s and announcement are used for refrigeration or air conditioning system, but they all could not solve such capability problems, namely HCFC-22 is replaced to obtain significantly reduced GWP and to obtain the similar performance of R-22 simultaneously, and do not need to change system, particularly do not need to change major parts (such as, compressor and expansion valve).In order to alternative is as the R-22 in current R-22 AC system, what be necessary is that the performance characteristics (as evaporator superheat, cooling capacity, refrigerant mass fluxes, efficiency and pressure) of replacing refrigeration agent is in close proximity to the situation of the HCFC-22 refrigeration agent be replaced for specifically conducting heat and other performance specification of existing system.This replacement refrigeration agent in nature close to the HCFC-22 in coupling original system for they being used in this kind of existing AC system or being designed for that to use in the system of R-22 refrigeration agent to prevent equipment replacement or change (such as change or change expansion valve) be vital.
About efficiency, then it is also important to note that it should be noted that, the loss of refrigerant thermodynamic performance or energy efficiency may by producing the fossil oil usage quantity of increase because increasing the demand of electric energy and cause secondary environmental influence.Therefore, desirably substitute has equal with R-22 or close to equal efficiency.
In addition, it has been generally acknowledged that preferably CFC and/or HFC refrigerant replacement is effectively and to using the conventional steam compress technique of CFC and/or HFC refrigeration agent not have great engineering variation at present.
Combustibility is another critical nature for many application.That is, in numerous applications, particularly including in heat transfer applications, use non-flammable or only there is slight flammable composition be considered to important or necessity.Therefore, use in this based composition slightly flammable or even flammable be usually useful than slight flammable also low compound.As used herein, term " slightly flammable " refers to and is classified as according to ASHRAE standard 34 (2010) (this standard is incorporated to herein by reference) compound or composition that belong to 2L.Regrettably, many HFC are flammable and classify as 2 and 3 by ASHRAE, otherwise they to be used in may be desirable in refrigerant composition.Such as, fluoric ether C2H4F2 C2H4F2 (HFC-152a) is flammable A2, and therefore in numerous applications in a pure form use be infeasible.
Therefore applicant has realized needs exploitation very favorable composition (and particularly heat transfer compositions) in the steam compressed heating and cooling system and method system of R-22 (be particularly designed to use).
Summary of the invention
Applicant has been found that can according to an aspect of the present invention by comprising or utilizing a kind of composition of multicomponent mixture, method, purposes and system to meet above-mentioned demand and other demand, and described multicomponent mixture comprises: (a) HFC-32; (b) HFO-1234ze more than 25%, and (c) is optionally but in certain embodiments preferably, HFC-152a and/or HFC-134a.Of the present invention preferred but nonrestrictive in, select each component (a), (b) and (c) amount to guarantee that the combustionvelocity of composition is less than about 10, the global warming potential of composition is less than about 500, and (although specially not referring to) is when testing under the heating determined herein and/or cooling test condition especially, capacity in AC, refrigeration agent or heat pump is up and down within about 10% of the capacity of R-22, or is up and down within about 8% of capacity of R-22 in further embodiment.About the latter, in certain embodiments, the capacity that has of composition more than R-22 95% and less than 115% of R-22; In certain embodiments, this capacity more than R-22 95% and less than 110% of R-22; And in further embodiment, this capacity more than R-22 95% and less than 108% of R-22.
Foregoing teachings some in or in any embodiment herein, component (b) can also comprise be selected from the propylene class that undersaturated end group is-CF3, undersaturated end group is the butylene class of-CF3 and at least one compound of these combination, wherein this compound is the compound being different from HFO-1234ze.
In further embodiment, composition of the present invention can comprise the HFC-32 of (a) about 33 % by weight to about 55 % by weight; (b) HFO-1234ze of about 25 % by weight to about 66 % by weight; (c) HFC-152a, HFC-134a or these the combination of about 0 % by weight to about 30 % by weight is exceeded.In further embodiment, composition comprises the HFC-32 of (a) about 35 % by weight to about 55 % by weight; B HFO-1234ze and (c) of () about 30 % by weight to about 55 % by weight exceed the HFC-152a of about 0 % by weight to about 22 % by weight or exceed the HFC-134a of about 0 % by weight to about 15 % by weight.Except separately pointing out herein, term " % by weight " refers to the weight percent amounted to based on component (a) – (c) in composition.
In a further preferred embodiment, composition of the present invention comprises the HFC-32 of (a) about 33 % by weight to about 55 % by weight; (b) HFO-1234ze more than 25%, (c) exceedes the HFC-152a of about 0 % by weight to about 25 % by weight; (d) exceed the HFC-134a of about 0 % by weight to about 20 % by weight, wherein in some aspects, the total amount of HFC-152a and HFC-134a does not exceed 30 % by weight.In further embodiment, composition comprises the HFC-32 of (a) about 35 % by weight to about 55 % by weight; The HFO-1234ze of (b) about 30 % by weight to about 55 % by weight; C () exceedes the HFC-152a of about 0 % by weight to about 22 % by weight; (d) exceed the HFC-134a of about 0 % by weight to about 15 % by weight, wherein in some aspects, the total amount of HFC-152a and HFC-134a does not exceed 30 % by weight.Except separately pointing out herein, term " % by weight " refers to the weight percent amounted to based on component (a) – (d) in composition.
Again, in in some is preferred, heat transfer compositions of the present invention, method, purposes and system provide a kind of GWP (as hereafter define) be no more than 500 and even more preferably no more than about 400 and even more preferably no more than about 350 composition.Heat transfer compositions of the present invention, method, purposes and system also preferably provide ignition hazard grade (ignition hazard level) (as hereafter define) be no more than about 7, even more preferably no more than composition as described in about 5.Usually further preferably, composition of the present invention have be no more than about 10 combustionvelocity (as hereafter define).Heat transfer compositions of the present invention, method, purposes and system also preferably provide such capacity, particularly in AC, refrigeration agent and heat pump, its be the capacity of R-22 be up and down within about 8% of the capacity of R-22 up and down within about 10% or in further embodiment.In further embodiment, the capacity that composition has more than R-22 95% and less than R-22 115%, more than R-22 95% and less than R-22 110% or more than R-22 95% and less than 108% of R-22.
In certain preferred aspects, component (b) of the present invention comprises HFO-1234ze, is substantially made up of HFO-1234ze or is made up of HFO-1234ze.Term HFO-1234ze is with typically referring to 1,1,1,3-tetrafluoeopropene in this article, and no matter it is cis or trans forms.Term " cis HFO-1234ze " and " trans HFO-1234ze " are used for the cis of description 1,1,1,3-tetrafluoeopropene and trans forms in this article respectively.Therefore term " HFO-1234ze " comprises cis HFO-1234ze, trans HFO-1234ze and these all combinations and mixture within the scope of it.
Accompanying drawing explanation
Fig. 1 illustrates the combustionvelocity (BV) of the mixture of HFC-152a and 1234ze (E).
Fig. 2 illustrates the combustionvelocity (BV) of the mixture of HFC-32 and 1234ze (E).
Fig. 3 illustrates the schematic diagram of the experimental installation for detecting inflammable gas.
Embodiment
R-22 is commonly used in cryogenic refrigerating system and some air conditioning system.Its global warming potential (GWP) estimated is 1810, and this is far above the value expected or require.Applicant has been found that, composition of the present invention meets the demand to the novel composition for this kind of application (particularly but specially do not refer to air conditioning system, heat pump and commercial refrigeration) in special and beyond thought mode, novel composition has the performance of improvement in environmental influence, and provide other important performance, as capacity, efficiency, combustibility and toxicity simultaneously.In preferred embodiments, the present composition provides substituting and/or replacing material at present with refrigeration agent (especially and preferably HCFC-22) in this type of application, it has lower GWP value simultaneously and provides such refrigerant composition, it has combustibility to a certain degree (slightly flammable or even flammable flammable also lower than slightly), and there is desirable low toxicity, and also preferred cooling capacity in this type systematic mates with HCFC-22 very much.
The application some in, when testing under heating and cooling test condition, the described composition exhibiting capacity gone out in AC, refrigeration agent or heat pump be the heating of R-22 or cooling capacity be up and down within about 8% of the heating of R-22 or cooling capacity up and down within about 10% or in further embodiment.Term " air conditioning system " or " AC system " to refer in given environment cooling or add any system of warm air.Provide an example of the test condition that can be used for the capacity evaluated in this type systematic in embodiment 3 below, it measures the capacity having starting air temperature, start condenser temperature, start the given composition of evaporator temperature etc.But the person skilled in the art will easily understand, the present invention is never limited to provided starting conditions and parameter, and test condition can be different according to standard industry practice, or otherwise is as known in the art.The non-limiting scope of condenser temperature can be such as 35 DEG C to 55 DEG C for heating and cooling, and can be 3 DEG C to 14 DEG C for the non-limiting scope of evaporator temperature for heating application and can be-20 DEG C to 14 DEG C for cooling application.It will be appreciated by those skilled in the art that this change in test procedure is intended to the simulation change of varying environment and the change in given space needed for envrionment temperature.
As mentioned above, present invention achieves and business-use refrigrating system and (in some is preferred) special benefits that fixed refrigeration system is relevant.The limiting examples of this kind of fixed refrigeration system is provided in the following examples 4 and 5.For this reason, this type systematic can comprise low temperature commercial applications (embodiment 6), comprises commercial refrigerator or can be used for storing and preserving the system of frozen goods.They also can comprise middle temperature commercial applications (embodiment 5), as commercial refrigerator, comprise the system for storing fresh goods.The following examples are provided for representative condition and the parameter of this kind of application.But these conditions are not considered to be limitation of the present invention because it will be appreciated by those skilled in the art that they can according to permitted in many factors one or more and change to some extent, include but not limited to envrionment conditions, expection application, annual time etc.This kind of embodiment also might not be limited to the definition of term " fixed refrigeration " or " commercial refrigeration ".Composition provided in this article can be used for the system of similar type or is suitable for maybe can being suitable for use as any alternative system of refrigeration agent for wherein R-22 in certain embodiments.
Can imagine in certain embodiments, the invention provides remodeling method, it is included in the heat-transfer fluid (comprising refrigeration agent and optional lubricant) replacing at least considerable part in existing system when substantially not changing system with composition of the present invention.In certain preferred aspects, in order to make composition of the present invention adapt to as heat-transfer fluid, not requiring to carry out substantial redesign to system, and not needing the main object of more exchange device, in this sense, replacement step is a kind of simple and easy replacement.In certain preferred aspects, described method comprises simple and easy replacement, wherein the capacity of system be before replacing it power system capacity at least about 70%, preferably at least about 85%, even more preferably at least about 90% and even more preferably at least about 95%, and preferably more than about 130%, even more preferably less than about 115%, even more preferably less than about 110% and even more preferably less than about 105%.In certain preferred aspects, described method comprises simple and easy replacement, wherein the suction pressure of system and/or blowdown presssure and even more preferably both be the suction pressure before replacing it and/or blowdown presssure at least about 70%, more preferably at least about 90% and even more preferably at least about 95%, and preferably more than about 130%, even more preferably less than about 115, even more preferably less than about 110% and even more preferably less than about 105%.In certain preferred aspects, described method comprises simple and easy replacement, wherein the mass rate of system is at least about 80%, even more preferably at least 90% and even more preferably at least 95% of mass rate before replacing it, and preferably more than about 130%, even more preferably less than about 115, even more preferably less than about 110% and even more preferably less than about 105%.
Heat transfer compositions
Composition of the present invention is suitable for being used in heat transfer applications usually, that is, as heating and/or heat-eliminating medium, but be suitable for well especially using at AC system, heat pump and commercial refrigeration or use so far in other system any of R-22 as mentioned above.
Applicant finds, use within the limits prescribed component of the present invention for realize important but be difficult to realize the various character demonstrated by the present composition combination be important, particularly in preferred system and method, and the component using these same but substantially then can produce adverse influence to one or more critical natures of composition of the present invention outside determined scope.
In certain preferred aspects, HFC-32 amount is in the present compositions about 33 % by weight to about 55 % by weight of composition.
In certain preferred aspects, second component comprises HFO-1234ze, is substantially made up of HFO-1234ze, is made up of HFO-1234ze, and the amount of comprising of HFO-1234ze can for about or more than 25 % by weight or about 25 % by weight to about 66 % by weight.In in some is preferred, HFO-1234ze comprises trans HFO-1234ze, is substantially formed by trans HF O-1234ze or be made up of trans HFO-1234ze.This second component also can comprise the other compound that one or more are different from HFO-1234ze, it can be selected from the propylene class that undersaturated end group is-CF3, undersaturated end group is-CF3 butylene class and these combination, but further in can comprise the other compound that one or more are different from HFO-1234ze.
Aforesaid composition can comprise the HFC-32 of (a) about 40 % by weight to about 50 % by weight; (b) HFO-1234ze of about 50 % by weight to about 60 % by weight.Again, component (b) comprises HFO-1234ze in certain embodiments, is substantially made up of HFO-1234ze or is made up of HFO-1234ze.
In a further preferred embodiment, the composition amount of comprising of the present invention exceed about 0 % by weight to about 25 % by weight or exceed in certain embodiments about 0 % by weight to about 22 % by weight HFC-152a.In further embodiment, the amount of providing of HFC-152a is about 1 % by weight to about 22 % by weight, about 3 % by weight to about 22 % by weight or about 5 % by weight to about 22 % by weight.This based composition can also or alternatively the amount of comprising exceed about 0 % by weight to about 20 % by weight or in certain embodiments more than 0 % by weight to the HFC-134a of about 18 % by weight.In certain aspects, composition comprises HFC-152a, HFC-134a or their combination, and it is measured more than 0 % by weight to about 30 % by weight.
Aforementioned further composition can comprise the HFC-32 of (a) about 33 % by weight to about 55 % by weight; The HFO-1234ze of (b) about 25 % by weight to about 66 % by weight; (c) HFC-152a or HFC-134a of about 0 % by weight to about 25 % by weight is exceeded.In further embodiment, this based composition comprises the HFC-32 of (a) about 35 % by weight to about 55 % by weight; The HFO-1234ze of (b) about 30 % by weight to about 55 % by weight; (c) exceed about 0 % by weight to about 22 % by weight HFC-152a or more than 0 % by weight to the HFC-134a of about 15 % by weight.As previously mentioned, in certain embodiments, (b) component in these compositions comprises HFO-1234ze, is substantially made up of HFO-1234ze or is made up of HFO-1234ze.
In further embodiment, aforesaid composition can comprise the HFC-32 of (a) about 33 % by weight to about 55 % by weight; The HFO-1234ze of (b) about 25 % by weight to about 66 % by weight; C () exceedes the HFC-152a of about 0 % by weight to about 25 % by weight; (d) HFC-134a of about 0 % by weight to about 20 % by weight is exceeded.In even further embodiment, this based composition comprises the HFC-32 of (a) about 35 % by weight to about 55 % by weight; The HFO-1234ze of (b) about 20 % by weight to about 60 % by weight; C () exceedes the HFC-152a of about 0 % by weight to about 22 % by weight; (d) HFC-134a of about 0 % by weight to about 15 % by weight is exceeded.In certain embodiments, (b) component in these compositions comprises HFO-1234ze, is substantially made up of HFO-1234ze or is made up of HFO-1234ze.
As mentioned above, applicant finds, and composition of the present invention can realize the difficult combinations of the various character comprising low GWP.By means of nonrestrictive example, lower Table A illustrates the essence GWP superiority of some composition of the present invention (weight fraction of often kind of component is described in bracket) compared to the GWP (its GWP is 1810) of HFC-22.
Applicant also finds surprisingly, in each foregoing embodiments of the present invention, (although specially not referring to ground) is in the embodiment that wherein component (b) is HFO-1234ze especially, then according to formula I, the combustionvelocity of the present composition substantially with the weight average combustionvelocity linear dependence of each component:
BVcomp=∑ (% by weight i BVi)
Wherein BVcomp is the combustionvelocity of composition, and
For often kind of above-listed component in composition, i is sued for peace; and preferably select the amount of often kind of above-listed component to guarantee that BVcomp based on the result of this unexpected formula is less than about 10; more preferably less than about 9 and even more preferably less than about 8, and simultaneously the GWP of composition less than about 500, less than about 400 or more preferably less than about 350.
Also as mentioned above, composition exhibiting of the present invention goes out to be no more than the dangerous values degree of about 7.As used herein, carry out the result of cubes test by observing the composition involved by using, and give a value according to provided in the following table guidance to this test below, measure risk degree thus.
Dangerous values guidance table
| test result | dangerous values scope |
| missing of ignition).The example of this danger classes is pure substance R-134a and trans HFO-1234ze. | 0 |
| imperfect combustion process and seldom or do not have transmission ofenergy to instruction ball and do not have significant pressure to raise in cubes (to look from cubic pore, the rise of all balls is only can observe or not observe at all reluctantly, and does not substantially observe cubical movement).The example of this danger classes is pure substance HFO-1234yf, and value is 2. | 1 – 2 |
| substantially combustion processes and a small amount of transmission ofenergy are given some balls and be there is no in cubes that pressure raises (some balls increase observable short range and turn back to zero position, and substantially do not observe cubical movement) completely.The example of this danger classes is pure substance R-32, and value is 4. | 3 – 5 |
| substantially combustion processes and the transmission ofenergy of significant quantity are given most of ball and are had high pressure to raise in cubes but be seldom with or without cubical movement (most of ball increases observable distance completely, and do not turn back to cubical top, but observe little or do not observe cubical movement). | 6 – 7 |
| high-risk Tiao Jian – rapid combustion and significantly pass to all balls and significant transmission ofenergy to cubes (substantially all balls raise and do not turn back to zero position from cubes, and observe cubical remarkable movement).The example of this danger classes is pure substance R-152a and R-600a, and value is respectively 8 and 10. | 8-10 |
Cubes test is carried out as indicated in the following examples.
Composition of the present invention can comprise other component and strengthen composition to reach or provide certain function or reduce the object of composition cost in some cases.Such as, lubricant is comprised according to refrigerant composition of the present invention (be particularly used in steam compression system those), common amount is about 30 to about 50 % by weight of composition, and amount possible in some cases exceedes about 50%, and amount is in other cases low to moderate about 5%.
The conventional refrigeration lubricant used together with fluorocarbon (HFC) refrigeration agent in refrigerating machine can use together with refrigerant composition of the present invention, and these conventional refrigeration lubricants are as polyol ester (POE) and polyalkylene glycol (PAG), PAG oil, silicone oil, mineral oil, alkylbenzene (AB) and poly-(alpha-olefin) (PAO).Commercially available mineral oil comprises the Witco LP 250 (registered trademark) deriving from Witco, the Zerol 300 (registered trademark) deriving from Shrieve Chemical, derives from the Sunisco 3GS of Witco and derive from the Calumet R015 of Calumet.Commercially available alkyl benzene lubricants comprises Zerol 150 (registered trademark).Commercially available ester comprises neopentyl glycol dipelargonate, and it is commercially available is Emery 2917 (registered trademark) and Hatcol 2370 (registered trademark).Other useful ester comprises phosphoric acid ester, diester and fluoroester.In some cases, the oil based on hydrocarbon has enough solubleness to the refrigeration agent be made up of iodine carbon compound (iodocarbon), and wherein the combination of iodine carbon compound and hydrocarbon ils is more stable than the lubricant of other type.Therefore this kind of combination is favourable.Preferred lubricant comprises polyalkylene glycol and ester.Polyalkylene glycol is very preferred in certain embodiments, because they use in the application-specific such as moving artificial atmosphere and so at present.Certainly, the different mixtures of dissimilar lubricant can also be used.
Heat-transferring method and system
Therefore the inventive method, system and composition are suitable for associating with general many kinds of heat-transfer systems using, and particularly refrigeration system, as artificial atmosphere (comprising fixed and mobile air conditioning system), refrigeration (comprising commercial refrigeration), heat pump etc.In certain preferred aspects, composition of the present invention is used in the refrigeration system being originally designed to use HCFC refrigeration agent (citing is as R-22).Preferred composition of the present invention often demonstrates many desirable characteristic of R-22, but has the significantly low GWP than R-22, and has simultaneously and be substantially similar to R-22 or substantially mate R-22 and preferably equally high with R-22 or higher than the capacity of R-22.Particularly, applicant has realized that some preferred embodiment of the present composition often demonstrates relatively low global warming potential (" GWP "), preferably less than about 500, and more preferably no more than about 400, and even more preferably no more than about 350.
At some in other preferred embodiment, the present composition is used in design originally and uses in the refrigeration system of R-22.Preferred refrigerant compositions of the present invention can be used in the refrigeration system containing the lubricant (as polyol ester wet goods) conventionally used together with R-22, or can use together with other lubricant used together with HFC refrigeration agent traditionally.As used herein, term " refrigeration system " typically refers to and adopts refrigeration agent to provide any system of cooling or any parts of device or this system or device or part.This kind of air-refrigeration system comprises such as air conditioner, refrigerator, refrigerator etc.
Embodiment
Following examples are provided, its objective is that the present invention will be described, but do not limit its scope.
Embodiment 1: the combustibility of mixture
The combustionvelocity of conventional pure component refrigerants is provided in following table 1.
Table 1: the combustionvelocity of pure component
。
Combustionvelocity (BV) measuring result of some mixture HFC-152a/1234ze (E) and HFC-32/1234ze (E) blend is shown in Fig. 1-2.Iso standard 817 is adopted to carry out combustionvelocity measurement with the vertical tube method described in ASHRAE standard 34.Fig. 1-2 also show the GWP of mixture.The accident that result in Fig. 1-2 shows applicant finds, namely can be close to maximum combustion speed by the linear relationship of % by weight with component.Therefore according to some preferred embodiment, select the amount of each component of the present invention above according to the formula I provided, that is, carried out the combustionvelocity of approximate blend by operating weight % pure component combustionvelocity, select the amount of each component of the present invention thus.In preferred embodiments, composition comprise at most about 30 % by weight HFC-152a, more preferably maximum 20% HFC-152a, the combustionvelocity of the blend simultaneously demonstrated is still lower than about 10 cm/s, and what therefore form is 2L refrigeration agent.
For some HFC-32/HFO-1234ze/HFC-152a blend, adopt iso standard 817 and the vertical tube method described in ASHRAE standard 34 to carry out combustionvelocity (BV) and measure.Result shows unexpected discovery, namely can be close to maximum combustion speed by the linear relationship of % by weight with component.Therefore according to some preferred embodiment, select the amount of each component of the present invention above according to the formula I provided, that is, carried out the combustionvelocity of approximate blend by operating weight % pure component combustionvelocity, select the amount of each component of the present invention thus.In preferred embodiments, composition comprises the HFC-152a of at most about 20 % by weight, and the combustionvelocity of the blend simultaneously demonstrated is still lower than about 10 cm/s, and what therefore form is 2L refrigeration agent.
As shown in data above, find to be multiplied by pure component combustionvelocity to calculate combustionvelocity according to mixture of the present invention, as described in formula 1 above by % by weight.
In reckoner A all mixtures combustionvelocity and be shown in following table 2.Therefore the combustionvelocity of all mixtures less than 10 cm/s, and can expect and be classified as A2L refrigeration agent.
Table 2: the combustionvelocity of mixture
。
Embodiment 2: Risk Assessments
Cubes test is carried out according to program described herein.Particularly, often kind of tested material being rendered to separately internal volume is 1 ft
3transparent cubes room in.Low power fan is used to mix each component.Energy is used to be enough to the electrical spark lighting test fluid flow.Use the result of all tests of video camera record.Cubes is filled to guarantee that often kind of tested refrigeration agent is stoichiometric concentration with tested composition.Fan is used to mix each component.Make great efforts to use spark generator to light fluid 1 minute.Use the test of HD camera record.
Schematic diagram for the experimental installation testing inflammable gas is shown in Fig. 3.
In reckoner A, the danger of all mixtures is graded and is shown in following table 3.The danger grading of all mixtures, less than 7, therefore expects that it is safe for using in air conditioning system.
Table 3: the dangerous values of mixture
。
About HFC-152a, when being used in one or more compositions herein, in numerous applications importantly, the amount of this component less than about 20 % by weight of composition, and preferably less than 15 % by weight.In table 3, the dangerous values that wherein 152a (B3) of 20% obtains is 6, and this is in close proximity to safety margin 7 in this display.
Embodiment 3: performance perameter.
The coefficient of performance (COP) is measuring of generally accepted refrigerant performance, is specially adapted to the relative thermodynamic efficiency representing refrigeration agent in the specific heating or refrigeration cycle of the evaporation or condensation that relate to refrigeration agent.In refrigeration engineering, the ratio of refrigeration useful when this nomenclature is shown in compressed vapour and the energy applied by compressor.The capacity of refrigeration agent represents its cooling provided or adds heat, and to this provide compressor be that some of the ability of the pump refrigerant heat of given volume flow are measured.In other words, consider specific compressor, the refrigeration agent with higher capacity will send more cooling or heating power.A kind of method of COP for estimating refrigeration agent is under specified operating conditions that the analysis of refrigeration cycle technology of employing standard is started with (see such as from the thermodynamic property of refrigeration agent, R.C. Downing, FLUOROCARBON REFRIGERANTS HANDBOOK, 3rd chapter, Prentice-Hall, 1988).
There is provided an example air regulation system below, its condenser temperature is set as 40.55 DEG C, and this corresponds to the external temperature of about 35 DEG C usually.5.55 DEG C are set as in the condensate depression at expansion device inlet place.Vaporization temperature is set as 7 DEG C, and this corresponds to the indoor environment temperature of about 20 DEG C.5.55 DEG C are set as in the superheating temperature at evaporator outlet place.Superheating temperature in suction line is set as 10 DEG C, and compressor efficiency is set as 70%.Pressure Drop in connection line (sucking and liquid line) and heat transfer are considered to negligible, and ignore the heat leak by compression case.Some operating parameterss are determined to the composition confirmed in upper Table A according to the present invention, and record these operating parameterss in following tables 4, based on be the COP value of R-22 be 1.00, capability value is 1.00 and exhaust temperature is 83.06 DEG C.
In certain preferred aspects, replacement should not need to carry out substantial redesign to system, and does not need the important objects of more exchange device to adapt to refrigeration agent of the present invention.For this purpose, replace and preferably meet one or more and preferably whole following requirements:
● high wall pressure (High-Side Pressure) is within about 115% of the high wall pressure of the identical systems using R-22 and even more preferably from about within 110%.This parameter may be important in this kind of embodiment, because it can improve the ability using existing press member in this type systematic.
● exhaust temperature be R22 ± 5 DEG C.An advantage of this characteristic is, it can allow to use existing establishing to be ready just in case the Thermal protection aspect that startup is preferably designed to the system of protection compressor part.Also advantageously, it can help avoid and use expensive control device (as fluid injector) to reduce exhaust temperature this parameter.
● cooling capacity is within+115% (preferably 110%) and 95% of the cooling capacity of the identical systems using R-22.This parameter may be important in certain embodiments, because it can contribute to guaranteeing fully to cool the product that will be frozen.It should also be noted that too much capacity may make electromotor overload, therefore they also should be avoided.
● efficiency (COP) is similar to R-22 (± 5%) and can not causes excessive capacity as noted above.
● keep superheating temperature to be at least+1 DEG C, be preferably+3 DEG C.If adopt the superheating temperature less than 1 DEG C, then liquid flooding is had to return the danger of compressor.
● blend be 2L class refrigeration agent and BV less than 10 cm/s.
● GWP less than 500, preferably less than 400, and for the blend of some of the recommendations even less than 350.
Can be seen by upper table 4, applicant finds, composition of the present invention once can realize the parameter making many important performance of refrigerant systems parameters close to R-22, and particularly enough only does small system change close to allow this based composition to be used in cryogenic refrigerating system to replace R-22 and/or be used in this kind of existing system.
As implied above, the capacity that composition demonstrates in this cryogenic refrigerating system is up and down within about 8% of capacity in this system of R-22.Also as shown, all blends of test demonstrate as preferred acceptable performance, because all requirements are met.
Because many existing air conditioning systems are for R-22 design, therefore it will be recognized by those skilled in the art the remarkable advantage with the refrigeration agent of low GWP and excellent efficiency that can be used to replace R-22 or similar refrigeration agent when carrying out minimum change relatively to system.In addition, it will be recognized by those skilled in the art, the present composition can provide and be used in new or in newly-designed refrigeration system (preferably including air conditioning system) remarkable advantage.
Embodiment 4: sensitivity analysis.
Adopt the operational condition identical with embodiment 3, we create for the lower data with the R32 of higher amount, as shown in table 5.For each group, we have employed representational mixture (A2, B2, C2 and D2) and increase/decrease the content of R32, until one of environmental performance parameter is in (see embodiment 3) outside preferable range.
When relating to BV and danger classes, the amount of R32 or 1234ze can not force any special restriction (table 6 and 7).
R32/1234ze binary blend has the preferred GWP less than 350, and therefore we select A2 to carry out this analysis.At R32 lower limit, we notice that capacity is in the limit value (95%) of preferred value.When using identical expansion gear, we also never get temperature.For the high scope of R32, we obtain the excessive capacity (116%) that can make electromotor overload.In addition, the GWP of this blend is 374, that is out preferred limit value 350 (table 5).
R32/1234ze/R152a ternary blends has the preferred GWP less than 350, and therefore we select B2 to carry out this analysis.At R32 lower limit, we notice that capacity is in the limit value (95%) of preferred value.When using identical expansion gear, we also never get temperature.For the high scope of R32, we obtain the excessive capacity (114%) that can make electromotor overload.In addition, the GWP of this blend is 392, that is out preferred limit value 350 (table 5).
R32/1234ze/R134a ternary blends has the preferred GWP less than 400, and therefore we select C2 to carry out this analysis.At R32 lower limit, we notice that capacity is in the limit value (95%) of preferred value.When using identical expansion gear, we also never get temperature.For the high scope of R32, we obtain the excessive capacity (117%) that can make electromotor overload.In addition, the GWP of this blend is 459, that is out preferred limit value 400 (table 5).
R32/1234ze/R152a/R134a quaternary blend has the preferred GWP less than 500, and therefore we select D2 to carry out this analysis.At R32 lower limit, we notice that capacity is in the limit value (95%) of preferred value.When using identical expansion gear, we also never get temperature.For the high scope of R32, we obtain the excessive capacity (116%) that can make electromotor overload.In addition, the GWP of this blend is 557, that is out preferred limit value 500 (table 5).
Embodiment 5: the performance in fixed refrigeration (commercial refrigeration)-middle temperature application
Other refrigerant composition is contrasted to evaluate the performance of some preferred compositions under the representative condition of middle temperature refrigeration.This application covers the refrigeration of fresh provisions.The condition evaluated residing for composition is shown in table 9:
Table 9
| Vaporization temperature | 20℉(-6.7℃) |
| Condensing temperature | 110℉(43.3℃) |
| Evaporator superheat | 10℉(5.5℃) |
| Condenser is excessively cold | 9℉(5℃) |
| Compressor discharge rate | 1.0 ft 3/min(0.028m 3/min) |
| Compressor isentropic efficiency | 65％ |
| Compressor return temperature | 45℉(7.2℃) |
Paid close attention to composition and base line system cryogen R-22 compare by table 10 in typical middle temperature application.
Can see, composition efficiency at base line system cryogen R-22 up and down within 5%, and capacity is within upper and lower 5%.
Performance-lower temperature application in the fixed refrigeration of embodiment 6 – (commercial refrigeration)
Other refrigerant composition is contrasted to evaluate the performance of some preferred compositions under the representative condition of cryogenic refrigeration.This application covers the refrigeration of frozen product.The condition evaluating composition is shown in table 11:
Table 11
| Vaporization temperature | -15℉(-26.1℃) |
| Condensing temperature | 110℉(43.3℃) |
| Evaporator superheat | 10℉(5.5℃) |
| Condenser is excessively cold | 9℉(5℃) |
| Compressor discharge rate | 1.0 ft 3/min(0.028m 3/min) |
| Compressor isentropic efficiency | 65％ |
| Compressor return temperature | 30℉(-1.1℃) |
Paid close attention to composition and base line system cryogen R-22 compare by table 12 in typical lower temperature application.
Can see, composition efficiency at base line system cryogen R-22 up and down within 5%, and capacity is within upper and lower 10%.
Claims (10)
1. heat transfer compositions, it has the combustionvelocity less than about 10 cm/s, and less than the global warming potential of about 500, and capacity in cryogenic refrigerating system is at up and down within about 10% of cooling capacity of R-22, and described composition comprises:
The HFC-32 of (a) about 33 % by weight to about 55 % by weight;
(b) at least about 25 % by weight HFO-1234ze; With
C () exceedes HFC-152a, HFC-134a and these the combination of about 0 % by weight to about 30 % by weight, condition is chosen to guarantee that the combustionvelocity of described composition is less than about 10 the amount of each in component (a), (b) and (c), the global warming potential of described composition is less than about 500, and its capacity is at up and down within about 10% of cooling capacity of R-22.
2. heat transfer compositions according to claim 1, wherein component (b) also comprises the compound that at least one is different from HFO-1234ze, it is selected from the propylene class that undersaturated end group is-CF3, undersaturated end group is-CF3 butylene class and these combination.
3. heat transfer compositions according to claim 1, it comprises the HFC-32 of about 33 % by weight to about 55 % by weight; The HFO-1234ze of about 25 to about 66 % by weight; With the HFC-152a exceeding about 0 % by weight to about 25 % by weight.
4. heat transfer compositions according to claim 3, it comprises the HFC-32 of about 35 % by weight to about 55 % by weight; The HFO-1234ze of about 30 to about 55 % by weight; With the HFC-152a exceeding about 0 % by weight to about 22 % by weight.
5. heat transfer compositions according to claim 4, it comprises the HFC-32 of about 35 % by weight to about 55 % by weight; Component; The HFO-1234ze of about 30 to about 55 % by weight; The HFC-152a of about 5 % by weight to about 22 % by weight.
6. heat transfer compositions according to claim 1, it comprises the HFC-32 of about 33 % by weight to about 55 % by weight; The HFO-1234ze of about 45 to about 66 % by weight; With the HFC-134a exceeding about 0 % by weight to about 20 % by weight.
7. heat transfer compositions according to claim 1, it comprises the HFC-32 of about 33 % by weight to about 55 % by weight; Component; The HFO-1234ze of about 25 to about 66 % by weight; With exceed the HFC-134a of about 0 % by weight to about 20 % by weight and exceed the HFC-152a of about 0 % by weight to about 25 % by weight, wherein the total amount of HFC-134a and HFC-152a does not exceed 30 % by weight.
8. replace the method for existing heat-transfer fluid contained in heat-transfer system, it comprises and shifts out described existing heat-transfer fluid at least partially and by the heat transfer compositions according to any one of claim 1-7 being incorporated in described system the described existing heat-transfer fluid replaced at least partially, described existing heat-transfer fluid is HFC-22 from described system.
9. heat-transfer system, it comprises compressor, condenser and the vaporizer in fluid connection and the heat transfer compositions in described system, and described heat transfer compositions comprises the composition according to any one of claim 1-7.
10. heat transfer is to fluid or object or the method from fluid or object heat transfer, and it comprises the phase transformation in the composition caused according to any one of claim 1-7, and carries out heat exchange with described fluid or object during described phase transformation.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
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| US201261684883P | 2012-08-20 | 2012-08-20 | |
| US61/684883 | 2012-08-20 | ||
| US13/796,270 US20130186115A1 (en) | 2010-11-12 | 2013-03-12 | Low gwp heat transfer compositions |
| US13/796270 | 2013-03-12 | ||
| PCT/US2013/053887 WO2014031336A1 (en) | 2012-08-20 | 2013-08-07 | Low gwp heat transfer compositions |
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| EP (1) | EP2885366A4 (en) |
| CN (1) | CN104797677A (en) |
| BR (1) | BR112015003635A2 (en) |
| IN (1) | IN2015DN01145A (en) |
| MX (1) | MX2015002083A (en) |
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| CN106350017A (en) * | 2016-08-26 | 2017-01-25 | 北方工业大学 | Ternary mixed refrigerant and preparation method thereof |
| CN106543963A (en) * | 2015-09-21 | 2017-03-29 | 浙江省化工研究院有限公司 | A kind of environmental protection type refrigeration composition |
| CN115493308A (en) * | 2017-06-21 | 2022-12-20 | 霍尼韦尔国际公司 | Refrigeration system and method |
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Also Published As
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| MX2015002083A (en) | 2015-05-11 |
| RU2015108379A (en) | 2016-10-10 |
| WO2014031336A1 (en) | 2014-02-27 |
| BR112015003635A2 (en) | 2017-07-04 |
| IN2015DN01145A (en) | 2015-06-26 |
| EP2885366A1 (en) | 2015-06-24 |
| EP2885366A4 (en) | 2016-04-13 |
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