CN105164226A - Low GWP heat transfer compositions including CO2 - Google Patents

Low GWP heat transfer compositions including CO2 Download PDF

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Publication number
CN105164226A
CN105164226A CN201380076343.XA CN201380076343A CN105164226A CN 105164226 A CN105164226 A CN 105164226A CN 201380076343 A CN201380076343 A CN 201380076343A CN 105164226 A CN105164226 A CN 105164226A
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weight
component
amount
composition
heat transfer
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Inventor
陆骏
R.R.辛赫
卢智利
C.J.西顿
周永
R.汪
林云
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Honeywell International Inc
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Honeywell International Inc
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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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/104—Carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/13—Inert gases
    • 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

Abstract

Disclosed are heat transfer compositions and methods, wherein the compositions include CO2; one or more additional components selected from R-116, R-23, a C1-C5 substituted or unsubstituted, saturated or unsaturated hydrocarbon (other than R-116, R-23), a noble gas or combinations thereof. Such compositions, in certain aspects of the invention, may be used as a replacement refrigerant for R-508B, particularly, though not exclusively, in low or ultralow temperature refrigeration applications.

Description

Comprise the low GWP heat transfer compositions of CO2
Invention field
The present invention relates to the composition, the method and system that are particularly useful for refrigeration purposes, relate to the refrigerant composition that can be used on especially in the system usually using refrigeration agent R-508B before this in certain aspects, particularly as the refrigeration agent in low temperature or very low temperature purposes.
Background
Use the mechanical refrigeration system of refrigerant liquid and associated heat transfer device, as heat pump and air conditioning machinery in the field of business known for industry, business and domestic use.Fluid based on fluorocarbon has been widely used in many houses, commercial and industrial purposes, comprises as the working fluid in the system of such as air-conditioning, heat pump and refrigeration system and so on.Due to so far for some suspicious environmental problem that the use of the some compositions of these purposes is relevant, comprise relatively high global warming up trend, more and more wish to use to there is fluid that is low or even zero ozone depletion potential, as hydrogen fluorohydrocarbon (" HFC ").In addition, the many governments signeds Kyoto Protocol is to protect the global environment, and it proposes to reduce CO 2discharge (Global warming).Therefore, need low inflammable or nonflammable non-toxic alternative to substitute some high Global warming HFC.
A kind of refrigeration system of important kind is referred to as " cryogenic refrigerating system " or " super low temperature refrigeration system ".Such system needs to be equal to or less than-20 DEG C usually, is equal to or less than-40 DEG C in some cases, is equal to or less than the vaporization temperature of-80 DEG C in other situations.In such cryogenic refrigerating system, conventional refrigerant liquid is that R-508B(HFC-23:HFC-116 is with the combination of the approximate ratio of 46:54 weight ratio).But this refrigeration agent has high global warming up trend (GWP=13,396), this is considered to higher than the value expected and/or require.Along with Global warming is more and more troubling, refrigerating industry is just for the solution with GWP that is low or that reduce is sought by each department.
Therefore the novel cpd as the attractive substitute of the composition be used in before this in these and other purposes and composition is more and more needed.But, at least with regard to heat-transfer fluid, usually be considered to importantly, any possible surrogate also must have those character existed in the most widely used many fluid, such as excellent heat transfer character, chemical stability, hypotoxicity or nontoxicity, low inflammableness and/or lubricant compatibility etc.
With regard to service efficiency, be important to note that, the loss of refrigerant thermodynamic performance or energy efficiency has secondary environmental influence by the increase of fossil oil consumption that caused by the increase of electrical energy demands.
In addition, refrigeration agent surrogate be not considered to desirable usually to the current situation using the conventional steam compress technique of existing refrigeration agent to make Important Project change is effectively worked.
Combustibility is another critical nature in many purposes.That is, in many purposes, particularly including in heat transfer applications, use non-combustible or only have slight flammable composition to be considered to important or basic.Therefore, use slightly flammable or even flammable usually useful lower than slightly flammable compound in such composition.Term used herein " slightly flammable " refers to that according to ASHRAE standard 34(date of being incorporated herein by this reference be 2010) be classified as compound or the composition of 2L.
Show to meet all requirements to R-508B substitute without any single molecule so far, included, but is not limited to non-inflammability, good volume cooling power (volumetriccoolingcapacity), good cooling efficiency, low GWP and acceptable exhaust temperature.Therefore, applicant has recognized that to be needed in steam compressed heating and cooling system and method, particularly in low temperature and super low temperature refrigeration agent system, comprises very favorable composition, particularly heat transfer compositions in the system be designed so that with R-508B.
Summary of the invention
Applicant has been found that, according to an aspect of the present invention can by comprising or utilizing the composition of multicomponent mixture, method, purposes and system to meet above-mentioned needs and other needs, described multicomponent mixture comprises: (a) CO2 is as the first component; B () is selected from the second component of R-116, R-23 or its combination; (c) three components of substituted or unsubstituted, the saturated or unsaturated hydrocarbons (being different from the compound of component (b)) of C1-C5, rare gas or its combination optionally, is selected from.Composition of the present invention has the GWP lower than R-508A in some preferred embodiment.In certain aspects, this GWP lower than 10,000, lower than 7,500 or in some is preferred in lower than 5,000.
In in some is non-limiting, three components comprises saturated, unsubstituted C1-C5 straight or branched alkane (such as but not limited to ethane) and/or C1-C5 straight or branched alkene (such as but not limited to vinylidene fluoride).Some other non-limiting in, three components comprises rare gas (such as but not limited to xenon).
Component (a) can provide to about amount of 85 % by weight to about 90 % by weight or in certain embodiments about 35 % by weight with about 10 % by weight of the gross weight of component (a)-(c).Unless indicated separately in literary composition, term " % by weight " refers to the weight percent based on the total amount of component (a) – (c) in described composition.
Component (b) can with about 5 % by weight of the gross weight of component (a)-(c) to about amount of 50 % by weight, or with about 20 % by weight to about amount of 40 % by weight, or provide to about amount of 30 % by weight with about 10 % by weight.
Component (c) with about 5 % by weight of the gross weight of component (a)-(c) to about amount of 35 % by weight, or can provide to about amount of 30 % by weight with about 5 % by weight.
In other non-limiting embodiments, the present invention includes the composition, method, purposes and the system that comprise or utilize multicomponent mixture, described multicomponent mixture comprises: (a) CO2 is as the first component; B () is selected from the second component of R-116, R-23 or its combination; (c) three components of ethane, vinylidene fluoride, xenon and combination thereof optionally, is selected from.
Above-mentioned in some in, component (b) is basic to be made up of R-116 and described component (c) comprises ethane.In such embodiments, CO2 can provide to about amount of 90 % by weight with about 55 % by weight; R-116 can provide to about amount of 30 % by weight with about 5 % by weight; And ethane can provide to about amount of 15 % by weight with about 5 % by weight.
Above-mentioned in other in, component (b) is basic to be made up of R-116 and described component (c) comprises xenon.In such embodiments, CO2 can provide to about amount of 75 % by weight with about 10 % by weight; R-116 can provide to about amount of 45 % by weight with about 20 % by weight; And xenon can provide to about amount of 65 % by weight with about 5 % by weight.
Above-mentioned in other in, component (b) is basic to be made up of R-116 and described component (c) comprises vinylidene fluoride.In such embodiments, CO2 can provide to about amount of 70 % by weight with about 30 % by weight; R-116 can provide to about amount of 40 % by weight with about 20 % by weight; And vinylidene fluoride can provide to about amount of 30 % by weight with about 10 % by weight.
Above-mentioned in other in, component (b) is basic to be made up of R-23 and described component (c) comprises ethane.In such embodiments, CO2 can provide to about amount of 75 % by weight with about 30 % by weight; R-23 can provide to about amount of 40 % by weight with about 10 % by weight; And ethane can provide to about amount of 30 % by weight with about 5 % by weight.
Above-mentioned in other in, component (b) is basic to be made up of R-23 and described component (c) comprises vinylidene fluoride.In such embodiments, CO2 can provide to about amount of 90 % by weight with about 50 % by weight; R-23 can provide to about amount of 25 % by weight with about 5 % by weight; And vinylidene fluoride can provide to about amount of 25 % by weight with about 5 % by weight.
In other non-limiting embodiments, the present invention includes the composition, method, purposes and the system that comprise or utilize multicomponent mixture, described multicomponent mixture comprises: (a) CO2 is as the first component; (b) second component of R-116, R-23 or its combination is selected from.Above-mentioned in some in, CO2 to provide and R-116 provides to about amount of 50 % by weight with about 20 % by weight to about amount of 80 % by weight with about 50 % by weight.Above-mentioned in other in, CO2 to provide and R-23 provides to about amount of 30 % by weight with about 10 % by weight to about amount of 90 % by weight with about 70 % by weight.
In other non-limiting embodiments, the present invention includes the composition, method, purposes and the system that comprise or utilize multicomponent mixture, described multicomponent mixture comprises: (a) CO2 is as the first component; (b) second component of substituted or unsubstituted, the saturated or unsaturated hydrocarbons (being different from R-116, R-23) of R-116, R-23, C1-C5, rare gas or its combination is selected from.In certain aspects, component (b) comprises saturated, unsubstituted C1-C5 straight or branched alkane (such as but not limited to ethane) and/or optionally by C1-C5 straight or branched alkene (such as but not limited to VDF) that one or more substituting group replaces.Some other non-limiting in, second component comprises rare gas (such as but not limited to xenon).
In such embodiments, component (a) can be present in said composition to about amount of 85 % by weight to about amount of 90 % by weight or about 35 % by weight with about 10 % by weight of the gross weight of component (a)-(b).Component (b) can be present in said composition to about amount of 65 % by weight to about amount of 90 % by weight or about 15 % by weight with about 10 % by weight of the gross weight of component (a)-(b).
In other non-limiting embodiments, the present invention includes the composition, method, purposes and the system that comprise or utilize multicomponent mixture, described multicomponent mixture comprises: (a) CO2 is as the first component; (b) second component of R-116, R-23, ethane, vinylidene fluoride, xenon and combination thereof is selected from.
In such embodiments, described component (a) can be present in said composition to about amount of 85 % by weight to about amount of 90 % by weight or about 35 % by weight with about 10 % by weight of the gross weight of component (a)-(b).Component (b) can be present in said composition to about amount of 90 % by weight with about 10 % by weight of the gross weight of component (a)-(b).
Comprise in the embodiment of R-116 in component (b), it can be present in said composition to about amount of 65 % by weight with about 15 % by weight of the gross weight of component (a)-(b).
Comprise in component (b), substantially by or by the embodiment that xenon is formed, xenon can provide to about amount of 85 % by weight or about 25 % by weight to about amount of 70 % by weight to about amount of 90 % by weight, about 15 % by weight with about 10 % by weight of the gross weight of component (a)-(b).
Comprise in component (b), substantially by or by the embodiment that ethane is formed, ethane can provide to about amount of 90 % by weight with about 10 % by weight of the gross weight of component (a)-(b), can provide with about 15 % by weight to about amount of 65 % by weight or about 20 % by weight to about amount of 60 % by weight.
Comprise in component (b), substantially by or by the embodiment that vinylidene fluoride is formed, vinylidene fluoride can provide to about amount of 65 % by weight or about 20 % by weight to about amount of 60 % by weight to about amount of 90 % by weight, about 15 % by weight with about 10 % by weight of the gross weight of component (a)-(b).
The present invention also provides the method, purposes and the system that utilize composition of the present invention, comprises method, purposes and system for conducting heat and for transforming existing heat-transfer system.Some preferred method aspect of the present invention relates to the method providing relative low temperature or very low temperature cooling, as in low temperature or super low temperature refrigeration system.Additive method aspect of the present invention provides improvement and design to become the method for existing cryogenic refrigerating system containing R-508B refrigeration agent, comprises and from this system, to take out R-508B and/or composition of the present invention is introduced this system and does not make the essence engineering amendment of described existing refrigeration system.
Accompanying drawing is sketched
Fig. 1 diagram CO 2the phasor of/VDF blend.
DESCRIPTION OF THE PREFERRED
As mentioned above, low temperature and super low temperature refrigeration system important in many purposes, such as medicine industry or wherein lower than other purposes that the temperature of-20 DEG C ,-40 DEG C or-80 DEG C is important.In such cryogenic refrigerating system, one of conventional refrigerant liquid is R-508B.This composition has about 13, the estimation global warming up trend (GWP) of 000, and this is more much higher than the value expected or require.
All requirements can be met without any single molecule so far, comprise non-inflammability, good volume cooling power, good cooling efficiency, low GWP and acceptable exhaust temperature.The possible component with suitable boiling point comprises R-116(hexafluoroethane), R-23(trifluoromethane), vinylidene fluoride (VDF or R1132a), xenon or ethane.But all these compounds have one or more shortcoming separately.Such as, VDF and ethane height inflammable; R116 and R23 has high GWP; And xenon is expensive and have maximum discharge temperature.
Independent CO 2(carbonic acid gas) is not regarded as the working fluid for this low temperature range, because its triple point is-56.5 DEG C.Therefore, form solid when it works under condition of ultralow temperature and block evaporator coil.
Applicant has been found that, composition of the present invention meets for the performance in environmental influence with improvement of low temperature applications, the performance characteristic that provides other important simultaneously, as the needs of the novel compositions of ability (capacity), efficiency, combustibility and toxicity in outstanding and unexpected mode.More specifically, applicant of the present invention is surprising and have unexpectedly discovered that several blend, and they can comprise one or more said components, has GWP(and the R508B being less than 5000 and compares reduction by more than 60%).In some preferred embodiment, applicant is surprising and be surprised to find that, other molecule and CO 2some blend by CO 2zero pour be brought down below temperature needed for very low temperature purposes, namely lower than-20 DEG C, preferably lower than-40 DEG C, then more preferably less than approximately-80 DEG C.Such blend also show surprising in this article and low GWP be unexpectedly provided, flammable suppress, ability (capacity) and low cost, and in the preferred embodiment of this composition, provide the substitute to the current refrigeration agent for very low temperature purposes (special and preferably R-508B) and/or surrogate.
Heat transfer compositions
Composition of the present invention is applicable to heat transfer applications usually, namely as heating and/or heat-eliminating medium, but is particularly suitable for as mentioned above for using low temperature or the super low temperature refrigeration system of R-508B before this.
Applicant has been found that, use component of the present invention to achieve in stated limit this compositions table reveals the important but combination of properties of difficult realization, particularly in preferred system and method, but use one or more critical natures to composition of the present invention of obvious these same composition outside stated limit have deleterious effect.
In some preferred embodiment, composition of the present invention comprises, substantially by or by (a) CO2 as the first component; B () is selected from substituted or unsubstituted, the saturated or unsaturated hydrocarbons (being different from R-116, R-23) of R-116, R-23, C1-C5, the second component of rare gas or its combination is formed.In certain aspects, this hydrocarbon comprises C1-C5 straight or branched alkane.In in some is preferred, this hydrocarbon comprises, substantially by or be made up of ethane.In the embodiment substituting (or additional), this hydrocarbon comprises can optionally by C1-C5 straight or branched alkene that one or more substituting group (it comprises one or more halogen atom in certain embodiments) replaces.The example of such compound includes, but are not limited to vinylidene fluoride (VDF), ethene or propylene.In in some is preferred, this hydrocarbon comprises, substantially by or be made up of vinylidene fluoride.Rare gas can comprise helium (He), neon (Ne), argon gas (Ar), Krypton (Kr) and xenon (Xe).In in some is preferred, this rare gas comprises, substantially by or be made up of xenon.
In some preferred embodiment, such composition can comprise, substantially by or by (a) CO2 as the first component; B () is selected from R-116, R-23, ethane, vinylidene fluoride, ethene, propylene, xenon or its second component combined and forms.In other preferred embodiments, such composition can comprise, substantially by or by (a) CO2 as the first component; B () is selected from R-116, R-23, ethane, vinylidene fluoride, xenon or its second component combined and forms.
CO2 can with about 10 % by weight of said composition weight to about amount of 90 % by weight, in in some is preferred with about 35 % by weight of said composition weight to about amount of 85 % by weight, and in other are preferred in provide to about amount of 80 % by weight with about 40 % by weight of said composition weight.
Second component provided herein---be no matter a kind of component, separately or the combination of component---with about 10 % by weight of said composition weight to about amount of 90 % by weight, can provide to about amount of 60 % by weight to about 20 % by weight of about 65 % by weight or said composition weight with about 15 % by weight of said composition weight in some is preferred.
R-116 is independent, R-23 is independent or both combinations, with about 5 % by weight of said composition weight to about amount of 50 % by weight, can provide to about amount of 30 % by weight to about 10 % by weight of about 40 % by weight or said composition weight with about 20 % by weight of said composition weight in some is preferred.
In other embodiments, (b) composition comprises R-116 as a main Zu of – namely based on the total weight of any other (b) component, and R-116 provides with the amount being greater than 50 % by weight.In the embodiment that another is such, R-116 is sole component (b) and based on the total amount of compound meter in (a) and (b) with about 20 % by weight of said composition weight to about 50 % by weight, about 25 % by weight to about 45 % by weight of said composition weight, or about 30 % by weight of said composition weight provide to about amount of 40 % by weight.
In other embodiments, R-23 can be used as main ingredient provides (namely based on the total weight of other (b) component, R-23 provides with the amount being greater than 50 % by weight).In the embodiment that another is such, R-23 is sole component (b) and based on the total amount of compound meter in (a) and (b) with about 5 % by weight of said composition weight to about 50 % by weight, about 10 % by weight to about 35 % by weight of said composition weight, or about 15 % by weight of said composition weight provide to about amount of 25 % by weight.
In other embodiments, (b) composition comprises xenon as a main Zu of – namely based on the total weight of any other (b) component, and xenon provides with the amount being greater than 50 % by weight.In the embodiment that another is such, xenon is sole component (b) and based on the total amount of compound meter in (a) and (b) with about 10 % by weight of said composition weight to about 90 % by weight, about 15 % by weight to about 85 % by weight of said composition weight, or about 25 % by weight of said composition weight provide to about amount of 70 % by weight.
In other embodiments, (b) composition comprises ethane as a main Zu of – namely based on the total weight of any other (b) component, and ethane provides with the amount being greater than 50 % by weight.In the embodiment that another is such, ethane is sole component (b) and based on the total amount of compound meter in (a) and (b) with about 10 % by weight of said composition weight to about 90 % by weight, about 15 % by weight to about 65 % by weight of said composition weight, or about 20 % by weight of said composition weight provide to about amount of 60 % by weight.
In other embodiment, (b) composition comprises VDF as a main Zu of – namely based on the total weight of any other (b) component, and VDF provides with the amount being greater than 50 % by weight.In the embodiment that another is such, VDF is sole component (b) and based on the total amount of compound meter in (a) and (b) with about 10 % by weight of said composition weight to about 90 % by weight, about 15 % by weight to about 65 % by weight of said composition weight, or about 20 % by weight of said composition weight provide to about amount of 60 % by weight.
Or, but in some preferred situation, composition of the present invention can comprise, substantially by or by (a) CO2 as the first component; B () is selected from the second component of R-116, R-23 or its combination; (c) optionally, be selected from substituted or unsubstituted, the saturated or unsaturated hydrocarbons of C1-C5 (be different from component (b) those), the three components of rare gas or its combination forms.
About three components, this hydrocarbon can comprise saturated, unsubstituted C1-C5 straight or branched alkane in certain embodiments.In in some is preferred, this hydrocarbon comprises, substantially by or be made up of ethane.In the embodiment substituting (or additional), this hydrocarbon comprises can optionally by C1-C5 straight or branched alkene that one or more substituting group (it comprises one or more halogen atom in certain embodiments) replaces.The example of such compound includes, but are not limited to vinylidene fluoride (VDF), ethene or propylene.In in some is preferred, this hydrocarbon comprises, substantially by or be made up of vinylidene fluoride.
Rare gas can comprise helium (He), neon (Ne), argon gas (Ar), Krypton (Kr) and xenon (Xe).In in some is preferred, this rare gas comprises, substantially by or be made up of xenon.
Of the present invention in some in, said composition, particularly refrigerant composition, comprise, substantially by or be made up of component (a) and (b).In such composition, CO2 can with about 10 % by weight of said composition weight to about amount of 90 % by weight, in in some is preferred with about 35 % by weight of said composition weight to about amount of 85 % by weight, and in other are preferred in provide to about amount of 70 % by weight with about 40 % by weight of said composition weight.
No matter second component---is that R-116 is independent, R-23 independent or both combinations---can with about 5 % by weight of said composition weight to about amount of 50 % by weight, there is provided to about amount of 30 % by weight to about 10 % by weight of about 40 % by weight or said composition weight with about 20 % by weight of said composition weight in some is preferred, and depend on the composition of component (b) and (c) (if existence).In some preferred embodiment, the total amount of R-116 and R-23 with about 5 % by weight of said composition weight to about amount of 50 % by weight, there is provided to about amount of 30 % by weight with about 20 % by weight of said composition weight to about 40 % by weight or about 10 % by weight, depend on the composition of component (b) and (c) (if existence).
Comprise (a) and (b) in said composition but do not comprise in some embodiment of (c), b () composition comprises R-116 as a main Zu of – namely based on the total weight of R-116 and R-23, R-116 provides with the amount being greater than 50 % by weight.In the embodiment that another is such, R-116 is sole component (b) and based on the total amount of compound meter in (a) and (b) with about 20 % by weight of said composition weight to about 50 % by weight, about 25 % by weight to about 45 % by weight of said composition weight, or about 30 % by weight of said composition weight provide to about amount of 40 % by weight.
Comprise in some embodiment of (a), (b) and (c) in said composition, b () component can comprise R-116 as main ingredient (namely based on the total weight of R-116 and R-23, R-116 provides with the amount being greater than 50 % by weight).Or in such composition, R-23 can be used as main ingredient provides (namely based on the total weight of R-116 and R-23, R-23 provides with the amount being greater than 50 % by weight) or R-23 and R-116 roughly equivalent to provide.In the embodiment that another is such, R-116 or R-32 is sole component (b).
Comprise each component (a)-(c) and component (b) only comprises in embodiment of the present invention of R-116 in said composition, R-116 can provide to about amount of 50 % by weight with about 5 % by weight of said composition weight based on the total amount of compound meter in (a), (b) and (c).Comprise in the above-mentioned embodiment of ethane in component (c), R-116 can provide to about amount of 30 % by weight with about 5 % by weight of the total amount of compound in (a), (b) and (c).Be in the embodiment of xenon in component (c), R-116 can provide to about amount of 45 % by weight with about 20 % by weight of the total amount of compound in (a), (b) and (c).Be in the embodiment of vinylidene fluoride in component (c), R-116 can provide to about amount of 40 % by weight with about 20 % by weight of the total amount of compound in (a), (b) and (c).
Comprise each component (a)-(c) and component (b) only comprises in the embodiment of R-23 in said composition, R-23 can provide to about amount of 50 % by weight with about 5 % by weight of said composition weight based on the total amount of compound meter in (a), (b) and (c).Comprise in the above-mentioned embodiment of ethane in component (c), R-23 can provide to about amount of 40 % by weight with about 10 % by weight of the total amount of compound in (a), (b) and (c).Be in the embodiment of vinylidene fluoride in component (c), R-23 can provide to about amount of 25 % by weight with about 5 % by weight of the total amount of compound in (a), (b) and (c).
Comprise in composition of the present invention in the embodiment of component (c), in certain aspects, it based on the total amount of compound meter in (a), (b) and (c) with about 5 % by weight of said composition weight to about 65 % by weight, and can provide to about amount of 30 % by weight with about 5 % by weight of said composition weight in some preferred embodiment.
As limiting examples, comprise in embodiment of the present invention of ethane in component (c), this compounds based on the total amount of compound meter in (a), (b) and (c) with about 5 % by weight of said composition weight to about 30 % by weight, or about 5 % by weight can provide to about amount of 15 % by weight in certain embodiments.Such as, comprise in the embodiment of R-116 in component (b), ethane can provide to about amount of 15 % by weight with about 5 % by weight of the total amount of compound in (a), (b) and (c).Be in the embodiment of R-23 in component (b), ethane can provide to about amount of 30 % by weight with about 5 % by weight of the total amount of compound in (a), (b) and (c).
Comprise in embodiment of the present invention of xenon in component (c), this compounds can based on the total amount of compound meter in (a), (b) and (c) with about 5 % by weight of said composition weight to about 65 % by weight, or about 5 % by weight provide to about amount of 15 % by weight in certain embodiments, especially, although be not limited to, comprise in the embodiment of R-116 in component (b).
Comprise in embodiment of the present invention of vinylidene fluoride in component (c), this compounds can provide to about amount of 35 % by weight with about 5 % by weight of said composition weight based on the total amount of compound meter in (a), (b) and (c).Such as, comprise in the embodiment of R-116 in component (b), vinylidene fluoride can provide to about amount of 30 % by weight with about 10 % by weight of the total amount of compound in (a), (b) and (c).Be in the embodiment of R-23 in component (b), vinylidene fluoride can provide to about amount of 25 % by weight with about 5 % by weight of the total amount of compound in (a), (b) and (c).
As mentioned above, applicant has been found that composition of the present invention can realize inaccessible combination of properties, comprises GWP low especially.As limiting examples, the GWP(of lower Table A example and R-508B its have about 13, the GWP of 000) compare the remarkable GWP advantage of some composition of the present invention (describing the weight fraction of each component in bracket).
Composition of the present invention can comprise for strengthening or providing some function for said composition or reduce other component of cost of said composition in some cases.Such as, refrigerant composition of the present invention, especially for use in those in vapor compression system, comprise be generally said composition about 30 to about amount of 50 % by weight, the lubricant of the amount that may be greater than about 50% in some cases and the amount being low to moderate about 5% in other situations.
The conventional refrigeration lubricant used together with hydrogen fluorohydrocarbon (HFC) refrigeration agent in refrigerating machine, as polyol ester (POE) and polyalkylene glycol (PAG), PAG oil, silicone oil, mineral oil, alkylbenzene (AB) and poly-(alpha-olefin) (PAO) can use together with refrigerant composition of the present invention.Commercial mineral oil comprises WitcoLP250(registered trademark from Witco), from the Zerol300(registered trademark of ShrieveChemical), the Sunisco3GS from Witco and the CalumetR015 from Calumet.Commercially available alkyl benzene lubricants comprises Zerol150(registered trademark).Commercially available ester comprise can be used as Emery2917(registered trademark) and Hatcol2370(registered trademark) the neopentyl glycol dipelargonate supplied.Other available ester comprises phosphoric acid ester, diester and fluoroester.Preferred emollient comprises polyalkylene glycol and ester.Certainly, the different mixtures of dissimilar lubricant can be used.
Heat-transferring method and system
Therefore present method, system and composition are applicable to generally speaking diversified heat-transfer system, particularly refrigeration system, as the cargo refrigeration etc. in air-conditioning, cold and heat pump systems processed, food freeze-drying, transport.In some preferred embodiment, become to use HFC refrigeration agent in original design, such as, in the refrigeration system of R-508B, use composition of the present invention.Preferred composition of the present invention tends to the many desired features showing R-508B, but has the GWP being starkly lower than R-508B, has coupling substantially similar to or basic R-508B and preferably equally high or higher ability simultaneously.Especially, applicant has recognized that, some preferred embodiment of this composition is tended to show relatively low global warming up trend (" GWP "), preferably be less than about 10,000, and more preferably no more than about 7,500, then more preferably no more than about 5,000.
In other preferred embodiments, become in original design in the refrigeration system of use R-508B and use this composition.Preferred refrigerant compositions of the present invention can be used on the lubricant containing using together with R-508B as usual, in the refrigeration system as polyol ester wet goods, or can use together with other lubricant used together with HFC refrigeration agent traditionally.Term used herein " refrigeration system " roughly refers to and uses refrigeration agent to provide any system of cooling or any parts of device or this system or device or part.Such refrigeration system comprises such as air conditioning machinery, refrigerator, refrigerator, refrigerated item warehouse etc.
As mentioned above, the present invention realizes outstanding advantage in the system being referred to as low temperature or super low temperature refrigeration system.That is, composition of the present invention provides the surprising and unexpected advantage relevant to the system of the condenser temperature adopting one or more compressor and about-40 DEG C to about-20 DEG C.In the preferred embodiment of this type systematic, this system has the evaporator temperature of approximately-90 DEG C to about-70 DEG C, and evaporator temperature is preferably approximately-80 DEG C.In addition, in the preferred embodiment of this type systematic, this system has the evaporator outlet superheating temperature of about 5 DEG C to about 30 DEG C, and evaporator outlet superheating temperature is preferably about 8 DEG C to about 12 DEG C.
Embodiment
The following example is used for example the present invention but does not limit its scope.
The research of embodiment 1 – combustibility
At the temperature of 60 DEG C, the critical flammable ratio (CriticalFlammableRatio) of the composition of CO2/VDF and R-116/VDF is measured according to ASTME681 standard.Result shows that the critical flammable ratio/CFR of R116/VDF be 81,/19 % by weight, CO2/VDF is 76,/24 % by weight.
Embodiment 2 – CO2 freezes research
Fig. 1 shows CO 250/50 blend of/VDF solidifies at-75 DEG C.Under higher VDF measures, CO can be reduced further 2freezing temperature.More specifically, by with this cylinder of liquid nitrogen freezing, CO2 is transferred in high pressure sample cylinder.Then, while maintenance is freezing, VDF is transferred in same sample cylinder.This cylinder is risen to room temperature with the mixture of CO2 and VDF that thaw.Then while by cooled with liquid nitrogen, this mixture is transferred in Glass tubing.Thermopair is placed in this pipe with measuring tempeature.Then this Glass tubing is proposed from liquid nitrogen this solid mixture is thawed.Then put back in liquid nitrogen and freezed to be cooled to.In this process of cooling, by the temperature of this mixture of computer recording.Fusing point can be read when starting to occur solid.
Embodiment 3 – performance study
The coefficient of performance (COP) is that the generally acknowledged of refrigerant performance is measured, and especially can be used for representing the refrigeration agent relative thermodynamic efficiency in the specific heating or refrigeration cycle of the evaporation or condensation that relate to refrigeration agent.In refrigeration engineering, this nomenclature is shown with the ratio of the energy that effect refrigeration applies when compressed vapour with compressor.The ability (capacity) of refrigeration agent represents its cooling provided or adds heat and provide necessarily measuring of the ability of compressor pumping heat under the given volume flow velocity of refrigeration agent.In other words, given specific compressor, has the refrigeration agent higher cooling of conveying or the heated power of high ability.A kind of mode of assessment refrigeration agent COP under certain operating conditions uses standard refrigeration cycle analytical technology to assess (see such as by the thermodynamic property of this refrigeration agent, R.C.Downing, FLUOROCARBONREFRIGERANTSHANDBOOK, the 3rd chapter, Prentice-Hall, 1988).
The exemplary super low temperature refrigeration system with the condenser temperature being set as-30 DEG C is provided below.The condensate depression at expansion device inlet place is set as ~ 2 DEG C to ~ 10 DEG C.Vaporization temperature is set as-80 DEG C.The superheating temperature at evaporator outlet place is set as ~ 5 DEG C.Superheating temperature in suction line is set as ~ 10 DEG C to ~ 30 DEG C, and compressor efficiency is set as 60%.Pressure drop in connection line (suction line and liquid line) and heat transfer are considered to ignore, and ignore the heat leak via compressor housing.To measure in following table 1 several operating parameters of the composition of regulation according to the present invention, these operating parameters are reported in following table 2, by COP value be 1.00, ability value is 1.00 and exhaust temperature is based on the R-508B of 33.1 DEG C.
In some preferred embodiment, this replacement does not require the substantial re-design of this system and does not need to change major equipment part just can adapt to refrigeration agent of the present invention.For this reason, this replacement preferably meets one or more, preferably all following requirements:
High wall pressure use R-508B identical systems high wall pressure about 115% in, more more preferably in about 110%.This parameter is important in such embodiments, because it can improve the ability using existing press member in such a system.
Efficiency (COP) is similar to R-508(± 5%), and do not cause the surplus of ability as above
This blend is the 2L class refrigeration agent that BV is less than 10cm/s.
GWP, lower than 10,000, is preferably less than 7,500, for the blend that some is recommended, is less than 5,000.
This blend is non-combustible according to ASHRAE34.
Exhaust temperature is not higher than 110 DEG C.
Table 1 shows the thermodynamic cycle performance of the 14 kinds of blends compared with R-508B according to above-mentioned parameter.All blends have the GWP of <5000, this >60% lower than R508B.All blends have similar cooling efficiency but higher volume cooling power.
。

Claims (19)

1. a heat transfer compositions, it comprises:
(a)CO2；
At least one of (b) R-116 and R-23;
C () optionally, is different from R-116 and is different from substituted or unsubstituted, the saturated or unsaturated hydrocarbons of at least one C1-C5 of R-23; With
(d) optionally, rare gas.
2., wherein there is described component (c) and be selected from ethane, vinylidene fluoride and combination thereof in the heat transfer compositions of claim 1.
3. the heat transfer compositions of claim 1, wherein said component (d) comprises xenon.
4. the heat transfer compositions of claim 1, wherein said CO2 is present in described composition to about amount of 90 % by weight with about 10 % by weight of the gross weight of component (a)-(d).
5. the heat transfer compositions of claim 1, wherein said component (b) is present in described composition to about amount of 50 % by weight with about 5 % by weight of the gross weight of component (a)-(d).
6. the heat transfer compositions of claim 1, wherein said component (b) comprises the R-23 be present in about amount of 30 % by weight with about 10 % by weight of the gross weight of component (a)-(d) in described composition.
7. the heat transfer compositions of claim 1, the total amount of component (c) described in wherein said composition and (d) is about 5 % by weight of the gross weight of component (a)-(d) to about 35 % by weight.
8. the heat transfer compositions of claim 1, wherein said component (c) is present in described composition to about amount of 30 % by weight with about 5 % by weight of the gross weight of component (a)-(d).
9. the heat transfer compositions of claim 1, wherein said component (b) is substantially made up of R-116 and described component (c) comprises ethane, and wherein said composition comprises about 55 % by weight to about CO2 of 90 % by weight, about 5 % by weight to about R-116 of 30 % by weight; With about 5 % by weight to about ethane of 15 % by weight.
10. the heat transfer compositions of claim 1, wherein said component (b) is substantially made up of R-116 and described component (d) comprises xenon, and wherein CO2 provides to about amount of 75 % by weight with about 10 % by weight; R-116 exists to about amount of 45 % by weight with about 20 % by weight; And xenon exists to about amount of 65 % by weight with about 5 % by weight.
The heat transfer compositions of 11. claims 1, wherein said component (b) is substantially made up of R-116 and described component (c) comprises vinylidene fluoride, and wherein said CO2 exists to about amount of 70 % by weight with about 30 % by weight; R-116 exists to about amount of 40 % by weight with about 20 % by weight; And vinylidene fluoride exists to about amount of 30 % by weight with about 10 % by weight.
The heat transfer compositions of 12. claims 1, wherein said component (b) is substantially made up of R-23 and described component (c) comprises ethane, and wherein CO2 exists to about amount of 75 % by weight with about 30 % by weight; R-23 exists to about amount of 40 % by weight with about 10 % by weight; And ethane exists to about amount of 30 % by weight with about 5 % by weight.
The heat transfer compositions of 13. claims 1, wherein said component (b) is substantially made up of R-23 and described component (c) comprises vinylidene fluoride, and wherein CO2 exists to about amount of 90 % by weight with about 50 % by weight; R-23 provides to about amount of 25 % by weight with about 5 % by weight; And vinylidene fluoride exists to about amount of 25 % by weight with about 5 % by weight.
The heat transfer compositions of 14. claims 1, wherein said component (d) is made up of xenon substantially, and it exists to about amount of 90 % by weight with about 10 % by weight of the gross weight of component (a)-(d).
The heat transfer compositions of 15. claims 1, wherein said component (d) is made up of xenon substantially, and it exists to about amount of 70 % by weight with about 25 % by weight of the gross weight of component (a)-(d).
The heat transfer compositions of 16. claims 1, wherein said component (c) is made up of ethane substantially, and it exists to about amount of 90 % by weight with about 10 % by weight of the gross weight of component (a)-(d).
The heat transfer compositions of 17. claims 1, wherein said component (c) is made up of ethane substantially, and it exists to about amount of 60 % by weight with about 20 % by weight of the gross weight of component (a)-(d).
The heat transfer compositions of 18. claims 1, wherein said component (c) is made up of vinylidene fluoride substantially, and it exists to about amount of 90 % by weight with about 10 % by weight of the gross weight of component (a)-(d).
The heat transfer compositions of 19. claims 1, wherein said component (c) is made up of vinylidene fluoride substantially, and it exists to about amount of 60 % by weight with about 20 % by weight of the gross weight of component (a)-(d).
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