CN102803427B - Heat transfer compositions and methods - Google Patents
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- CN102803427B CN102803427B CN201080030854.4A CN201080030854A CN102803427B CN 102803427 B CN102803427 B CN 102803427B CN 201080030854 A CN201080030854 A CN 201080030854A CN 102803427 B CN102803427 B CN 102803427B
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- 239000000203 mixture Substances 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title claims abstract description 23
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 claims abstract description 19
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims abstract description 8
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 claims description 33
- 239000012530 fluid Substances 0.000 claims description 15
- 238000010792 warming Methods 0.000 claims description 10
- 239000006200 vaporizer Substances 0.000 claims description 5
- VPAYJEUHKVESSD-UHFFFAOYSA-N trifluoroiodomethane Chemical compound FC(F)(F)I VPAYJEUHKVESSD-UHFFFAOYSA-N 0.000 abstract description 2
- NHGVZTMBVDFPHJ-UHFFFAOYSA-N formyl fluoride Chemical compound FC=O NHGVZTMBVDFPHJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000005057 refrigeration Methods 0.000 description 19
- 239000003507 refrigerant Substances 0.000 description 12
- 239000000314 lubricant Substances 0.000 description 11
- 238000001816 cooling Methods 0.000 description 9
- 230000008901 benefit Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000009418 renovation Methods 0.000 description 5
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 229920001515 polyalkylene glycol Polymers 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 238000004378 air conditioning Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- -1 polyol ester Chemical class 0.000 description 3
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 2
- CDOOAUSHHFGWSA-UHFFFAOYSA-N 1,3,3,3-tetrafluoropropene Chemical compound FC=CC(F)(F)F CDOOAUSHHFGWSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- LPSCRKGVODJZIB-UHFFFAOYSA-N [I].[C] Chemical compound [I].[C] LPSCRKGVODJZIB-UHFFFAOYSA-N 0.000 description 2
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920013639 polyalphaolefin Polymers 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AHSZBZTYLKTYJI-UHFFFAOYSA-N (2,2-dimethyl-3-nonanoyloxypropyl) nonanoate Chemical compound CCCCCCCCC(=O)OCC(C)(C)COC(=O)CCCCCCCC AHSZBZTYLKTYJI-UHFFFAOYSA-N 0.000 description 1
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 description 1
- PGJHURKAWUJHLJ-UHFFFAOYSA-N 1,1,2,3-tetrafluoroprop-1-ene Chemical compound FCC(F)=C(F)F PGJHURKAWUJHLJ-UHFFFAOYSA-N 0.000 description 1
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical group ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical group ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000006244 Medium Thermal Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 101100214695 Staphylococcus aureus aacA-aphD gene Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000009419 refurbishment Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Abstract
Disclosing compositions, method and system, it includes or utilizes multicomponent mixture, and this multicomponent mixture comprises: the HFC 32 of (a) about 10% to about 35% weight；The HFC 125 of (b) about 10% to about 35% weight；HFO 1234ze, the HFO 1234yf of (c) about 20% to about 50% weight and these combination；The HFC 134a of (d) about 15% to about 35% weight；With the CF3I and the HFCO 1233ze of at most about 5% weight of optional (e) at most about 10% weight, wherein said percetage by weight is based on the total amount of component (a) (e) in compositions.
Description
Related application
The application relates to claim the priority of following application: the U.S. Provisional Application Serial No. 61/176 that on May 8th, 2009 submits to, 773, the 61/240 of JIUYUE in 2009 submission on the 9th, 61/247,816 submitted on October 1st, 786,2009,61/329 submitted on April 30th, 2010, the U. S. application 12/511,954 that on July 29th, 955 and 2009 submits to, each application is incorporated herein by reference in full.
Technical field
The present invention relates to compositions, the method and system being particularly useful in cryogenic refrigeration application, and it is particularly directed to replace the refrigerant composition earl august eugene lund ian robert of the cold-producing medium HFC-404A used in heating and cooling application, and relate to the renovation of low-temperature refrigerant system, including the renovation in order to use HFC-404A and designed system.
Background technology
Use the mechanical refrigeration system of refrigerating fluid, and relevant heat-exchanger rig, such as heat pump and air-conditioner, be as known in the art for industry, business and domestic. applications.Liquid based on fluorocarbons (fluorocarbon) obtains extensively application in many houses, commercial and industrial application, including the working fluid in the system as the regulation of such as air, heat pump and refrigeration system.Because some suspicious environmental problem, including the global warming potential that the comparison relevant with the use of the some compositions being previously used for these application is high, increasingly it is desirable for having low or even zero ozone depletion and the fluid of global warming potential, such as hydrofluorocarbon (hydrofluorocarbons) (" HFCs ").Such as, a lot of governments have signed the Kyoto Protocol to protect the global environment, and announce to reduce CO2 discharge (global warming).Accordingly, it would be desirable to low-or substitute non-flammable, atoxic, to replace some high global warming HFCs.
The refrigeration system of a kind of important kind is referred to as " cryogenic refrigerating system ".This system is particular importance for food manufacturing, distribution and retail business, because they play important role during food is supplied to consumer with fresh and edible state guaranteeing.In this cryogenic refrigerating system, normally used refrigerating fluid is always in HFC-404A(this area, and the mixture of the HFC-125:HFC-143a:HFC134a that weight ratio is of about 44:52:4 is referred to as HFC-404A or R-404A).R-404A has the higher global warming potential (GWP) of estimation of 3922.
Therefore, there is, for new fluorocarbons and hydrofluorocarbon and compositions, the demand increased, they are the attractive substitutes being used in the compositions in these and other application in the past.Such as, have desired to by with will not the non-chloride refrigerant compound of ozone layer depletion, such as hydrofluorocarbon (HFC) substitutes chloride cold-producing medium and chloride refrigeration system is renovated.Generally industry and particularly heat exchange industry constantly looks for new mixture based on fluorocarbons, and it is the alternative of CFCs and HCFCs, and is considered as the substitute of Environmental security.But, for heat exchanging fluid, it is generally acknowledged it is of importance that any possible substitute must also have those character of many most widely used fluids, such as excellent heat exchange property, chemical stability, low-or not have-toxicity, non-combustible and/or lubricant compatibility and other character.
About service efficiency, it is important that the loss of cold-producing medium thermal performance or energy efficiency is probably due to increase electrical energy demands and cause increasing fossil fuel consumption and having secondary environment impacts.
Additionally, for CFC alternative refrigerants, it is often desirable that can effectively use, and without the common vapor compression technology of currently used CFC cold-producing medium is carried out bigger engineering change (EC).
Flammable is another important properties for many application.I.e. in including many application that heat exchange is applied especially, using non-flammable compositions is considered as important or necessity.Therefore, nonflammable compound is used to may often be such that in such a composition useful.As it is used herein, term " nonflammable " refers to compound or compositions, it is according to ASTM standard E-681(2002) measure be nonflammable, this standard is quoted whereby and is incorporated herein.Unfortunately, although many HFC in other side for being desired for refrigerant composition earl august eugene lund ian robert, but they are not nonflammable.Such as, fluoroalkane difluoroethane (HFC-152a) and fluoroolefin 1,1,1-trifluoro propene (HFO-1243zf) are all inflammable, therefore cannot be used in many application.
Therefore, applicants have recognized that and need compositions, particularly heat transfer compositions, it is highly advantageous in heating and cooling system and method, particularly in steam compressed heating and cooling system, and even more particularly in low-temperature refrigerant system, including using HFC-404A and/or being designed to use the system of HFC-404A.
Summary of the invention
Applicant have discovered that above-mentioned needs and other needs can be satisfied by comprising or utilize the compositions of multicomponent mixture, method and system, described multicomponent mixture comprises: the difluoromethane (HFC) of (a) about 10% to about 35% weight；The pentafluoroethane (HFC-125) of (b) about 10% to about 35% weight；HFO-1234ze, HFO-1234yf of (c) about 20% to about 50% weight and these combination；The 1,1,1,2-tetrafluoroethane (HFC-134a) of (d) about 15% to about 35% weight；CF with optional (e) at most about 10% weight3The HFCO-1233ze of I and at most about 5% weight, wherein said percetage by weight is based on the total amount of component (a) (e) in compositions.
In certain preferred aspects, described compositions comprises multicomponent mixture, and this multicomponent mixture comprises: the HFC-32 of (a) about 15% to about 25% weight；The HFC-125 of (b) about 10% to about 30% weight；HFO-1234ze, HFO-1234yf of (c) about 20% to about 50% weight and these combination；The HFC-134a of (d) about 15% to about 35% weight；With the CF3I and the HFCO-1233ze of at most about 5% weight of optional (e) at most about 5% weight, wherein said percetage by weight is based on the total amount of component (a) (e) in compositions.
Present invention also offers method and system, it utilizes the compositions of the present invention, including for heat exchange with for renovating the method and system of existing heat-exchange system.Some method for optimizing aspect of the present invention relates to the method providing relative low temperature cooling, the method such as providing relative low temperature cooling in cryogenic refrigerating system.Other method aspect of the present invention provides the method renovating existing cryogenic refrigerating system, described existing cryogenic refrigerating system is designed to comprise and/or comprise R-404A cold-producing medium, the method includes introducing the compositions of the present invention described system, and revises without described existing refrigeration system carries out the engineering of essence.
Term HFO-1234ze used herein usually refers to 1,1,1,3-tetrafluoropropene, either cis or trans.Term used herein " along HFO-1234ze " and " anti-HFO-1234ze " are respectively used to describe the cis-and trans-form of 1,1,1,3-tetrafluoropropene.Therefore term " HFO-1234ze " includes suitable HFO-1234ze, anti-HFO-1234ze and these all combinations and mixture in the range of it.
Term used herein " HFO-1233 " refers to all trifluoros, a chloropropene.Trifluoro, a chloropropene include 1,1,1, three fluoro-2, and chloro-propylene (HFCO-1233xf), including cis-and trans-1,1,1-tri-fluoro-3, chloropropene (HFCO-1233zd).Term HFCO-1233zd used herein usually refers to 1,1,1-tri-fluoro-3, and chloropropene, no matter it is cis or trans.Term " along HFCO-1233zd " and " anti-HFCO-1233zd " are respectively used to describe the 1,1,1-trifluoro of cis-and trans-form, chlorallylene herein.Therefore term " HFCO-1233zd " includes suitable HFCO-1233zd, anti-HFCO-1233zd and these all combinations and mixture in the range of it.
The detailed description of preferred embodiment
Cryogenic refrigerating system is important in numerous applications, such as, be important for food manufacturing, distribution and retail business.This system guarantee food with fresh and edible state supply consumer in play key player.In this cryogenic refrigerating system, a kind of refrigerating fluid the most always used is HFC-404A, and it has the higher global warming potential (GWP) of estimation of 3922.Applicant have discovered that, the compositions of the present invention by exception and unexpected in the way of meet for this kind of application in the alternative of cold-producing medium (especially and preferably HFC-404A) and/or the demand of sub, it has relatively low GWP value immediately, and providing substantial non-flammable, non-toxic fluid, this fluid mates with HFC-404A in this kind of system in refrigerating capacity and/or efficiency very much.
Heat transfer compositions
The compositions of the present invention is generally suitable for use in heat exchange application, i.e. as heating and/or cooling medium, but, just as described above, it is particularly suitable for using the cryogenic refrigerating system of HFC-404A in the past and/or using the system of R-22 in the past.
Applicant have discovered that, be described herein as wide and preferably in the range of, the component of the present invention is for obtaining described favourable it can be difficult to the bulk properties that the present composition that obtains is shown is important, particularly in preferred system and method, and outside scope determined by having been found that substantially, use these components same one or more important performances of the compositions of the present invention, system or method may be had adverse effect.The ratio obtaining highly preferred combining properties, the most about 1:1 for having the compositions of the HFC-32:HFC-125 weight ratio of about 0.9:1.2 to about 1.2:0.9 is preferred.It has been discovered by the applicants that the ratio that the compositions of the HFO-1234ze:HFO-1234yf weight ratio for having about 5:1 to about 3:1 obtains highly preferred combining properties, the most about 4:1 is preferred.
For convenience, HFO-1234ze and HFO-1234yf combination is referred to herein as " tetrafluoropropene component " or " TFC ", and in certain embodiments, it is preferred for including that the compositions of the HFC-134a:TFC weight ratio of about 5:7 to about 1:1 can obtain the ratio of highly preferred combining properties, the most about 4:6.
Although it is contemplated that any isomer of HFO-1234ze may be used to obtain advantage in certain aspects of the invention, applicant have discovered that, HFO-1234ze includes that anti-HFO-1234ze is preferred in certain embodiments, and preferably comprise anti-HFO-1234ze with larger proportion, and be the most substantially made up of anti-HFO-1234ze.
Just as described above, applicant have discovered that the compositions of the present invention is obtained in that the combining properties being difficult to obtain, including the lowest GWP.By means of limiting examples, lower Table A illustrates compared with the HFC-404A of the GWP with 3922, and the essence of the GWP that some compositions of the present invention shows is improved.
Table A
| The compositions (weight fraction based on indicating component) of the present invention | Title | GWP | GWP as the GWP percent of R404A |
| R125/R134a/R143a(0.44/0.04/0.52) | R404A | 3922 | |
| R32/R125/R134a/1234yf(0.25/0.25/0.2/0.3) | A1 | 1331 | 34% |
| R32/R125/R134a/1234ze(0.325/0.325/0.147/0.203) | A2 | 1568 | 40% |
| R32/R125/R134a/1234ze/1234yf(0.3/0.3/0.168/0.16/0.072) | A3 | 1494 | 38% |
| R32/R125/R134a/1234yf(0.13/0.13/0.3/0.44) | A4 | 974 | 25% |
| R32/R125/R134a/1234ze(0.125/0.125/0.315/0.435) | A5 | 975 | 25% |
| R32/R125/R134a/1234ze/1234yf(0.125/0.125/0.315/0.3/0.135) | A6 | 975 | 25% |
The compositions of the present invention can comprise other component, in order to improves some function of compositions or provides some function for compositions, or reducing the cost of compositions in some cases.Such as, the refrigerant composition earl august eugene lund ian robert of the present invention, especially for those of vapor compression system, comprises the lubricant generally accounting for compositions about 30 to about 50 percetage by weight, and its amount can be more than about 50% in some cases, and its amount can be low to about 5% in other cases.Additionally, the present composition can also comprise compatilizer, such as propane, in order to contribute to the compatibility and/or the solubility of lubricant.This kind of compatilizer, including propane, butane and pentane, preferably exists with about 0.5 to about 5 percetages by weight of compositions.Surfactant and solubilizing agent can also be added in combination the present composition, to help oil-soluble, such as United States Patent (USP) No.6, disclosed in 516,837, the disclosure of which is incorporated by reference the application.Normally used refrigeration lubricant, such as with hydrofluorocarbon (HFC) cold-producing medium for the polyol ester (POEs) of refrigeration machine and poly alkylene glycol (PAGs), PAG oil, silicone oil, mineral oil, alkylbenzene (ABs) and poly-(alpha-olefin) (PAO), can be used together with the refrigerant composition earl august eugene lund ian robert of the present invention.Commercially available mineral oil includes the Witco LP 250(registered trade mark from Witco), from Shrieve
The Zerol 300(registered trade mark of Chemical), the Sunisco 3GS from Witco and the Calumet R015 from Calumet.Commercially available alkyl benzene lubricants includes Zerol
150(registered trade mark).Commercially available ester includes neopentyl glycol dipelargonate, and it can be with Emery 2917(registered trade mark) and Hatcol 2370(registered trade mark) obtain.Other useful ester includes phosphate ester, dibasic acid ester and fluorinated ester.In some cases, oil based on hydrocarbon has the solubility of cold-producing medium that is sufficient and that be made up of iodine carbon compound (iodocarbon), and the combination of iodine carbon compound and hydrocarbon ils may be more more stable than other type of lubricant.Therefore this kind of combination is probably favourable.Preferably lubricant includes poly alkylene glycol and ester.Poly alkylene glycol is highly preferred in certain embodiments, because they are used at present in specifically applying such as air conditioning for automobiles.Of course, it is possible to use the different mixtures of dissimilar lubricant.
Those skilled in the art in view of the teachings contained herein, without departing substantially under the novelty of the present invention and basic feature premise, it is also possible to be incorporated herein other additive do not mentioned.
Heat-exchange method and system
Therefore, the inventive method, system and compositions are suitable for being used in combination with various common heat-exchange system, particularly refrigeration systems, such as air-conditioning (including static and automotive air-conditioning system), cold and heat pump systems processed etc..In certain preferred aspects, the present composition is used for being initially the refrigeration system using HFC refrigerant, such as R-404 and design.The preferred composition of the present invention tends to the feature with the R-404A desired by many, but there is the GWP lower than R-404A, there is similar or the most suitable and the highest compared with R-404A or higher capacity and/or efficiency simultaneously.Especially, Applicants have realized that the certain preferred embodiments of the present composition are tended to have relatively low global warming potential (" GWPs "), preferably less than about 2500, more preferably less than about 2400, and even more preferably no more than about 2300.In certain embodiments, the present composition has the GWP of about 1500 or lower, and even more preferably less than about 1000.
In some other preferred embodiment, the present composition is used for comprising and/or be originally designed as to use the refrigeration system of R-404A.The preferred refrigerant compositions of the present invention may be used for comprising the refrigeration system of the lubricant being generally used together with R-404A, described lubricant is such as mineral oil, polyoxyethylene alkylphenyl, poly alkylene glycol oil etc., or can be used together with other lubricant being used together with HFC traditionally.As it is used herein, term " refrigeration system " is often referred to any system or the device using cold-producing medium to provide cooling, or this kind of system or any part of device or local.This kind of refrigeration system includes such as air-conditioner, electric refrigerator, chiller (including using the chiller of centrifugal compressor) etc..
Just as described above, present invention obtains the additional advantage relevant with the system being referred to as cryogenic refrigerating system.As it is used herein, term " cryogenic refrigerating system " refers to vapor compression refrigeration system, it utilizes one or more compressor and the condenser temperature of about 35 DEG C to about 45 DEG C.In the preferred embodiment of this kind of system, described system has the evaporator temperature of about-25 DEG C to about-35 DEG C, and evaporator temperature is preferably about-32 DEG C.Additionally, in the preferred embodiment of this kind of system, described system has the evaporator outlet degree of superheat of about 0 DEG C to about 10 DEG C, evaporator outlet degree of superheat preferably about 4 DEG C to about 6 DEG C.Additionally, in the preferred embodiment of this kind of system, described system has the degree of superheat in the suction line of about 15 DEG C to about 25 DEG C, the degree of superheat in suction line preferably about 20 DEG C to about 25 DEG C.
Detailed description of the invention
Embodiment
Following example purpose in order to demonstrate the invention and provide, but do not limit its scope.
Embodiment 1: performance parameter
The coefficient of performance (COP) is that the refrigerant performance accepted extensively is measured, and to describing, cold-producing medium associated hot mechanical efficiency in including cold-producing medium evaporation or the specific heating of condensation or cooling circulation is particularly useful.In Refrigeration Engineering, the ratio of the energy that compressor the applies when refrigeration that this nomenclature is shown with and compressed vapour.The capacity of cold-producing medium represents the cooling or the amount of heating that cold-producing medium provides, and provides certain of for the cold-producing medium of the given volume flow ability of compressor pump heat and measure.In other words, in the case of given particular compressor, the cold-producing medium with higher capacity will transmit the cooling or heating power that more reach.A kind of method of the COP assessing cold-producing medium under certain operating conditions is based on the thermodynamic property (see for example R. C. Downing, fluorocarbons cold-producing medium handbook, the 3rd chapter, Prentice-Hall, 1988) using standard refrigeration cycle analytical technology.
Provide cryogenic refrigerating system.In the case of this system illustrated in this embodiment, condenser temperature is set to 40.55 DEG C, and it generally corresponds to the outdoor temperature of about 35 DEG C.Degree of supercooling at expansion device inlet is set to 5.55 DEG C.Evaporating temperature is set to-31.6 DEG C, and it corresponds approximately to the case temperature (box temperature) of-26 DEG C.Degree of superheat at evaporator outlet is set to 5.55 DEG C.Degree of superheat in suction line is set to 13.88 DEG C, and compressor efficiency is set to 65%.Connect the pressure drop in pipeline (sucking and liquid line) and heat exchange is considered as negligible, and be left in the basket by the heat leakage of compression case.According to having present invention determine that several operating parameters of the compositions A1 A6 indicated in above-mentioned Table A, and these operating parameters are reported in table 1 below, based on having 100%COP value, 100% capability value and the HFC-404A of 97.6 DEG C of discharge temperatures.
Table 1
| Title | GWP | Vaporizer sliding (DEG C) | Capacity (%) | COP(%) |
| R404A | 3922 | 0.5 | 100% | 100% |
| A1 | 1331 | 3.3 | 105% | 108% |
| A2 | 1568 | 4.7 | 107% | 108% |
| A3 | 1494 | 4.2 | 106% | 108% |
| A4 | 974 | 2.8 | 82% | 109% |
| A5 | 975 | 4.2 | 68% | 110% |
| A6 | 975 | 3.6 | 73% | 109% |
As seeing from above-mentioned table 1, applicant have discovered that the compositions of the present invention can obtain close to the important performance of refrigerant systems parameter of the many of R-404A parameter immediately, and it is the most close, thus allow that this compositions uses in cryogenic refrigerating system as (drop-in) substitute that can introduce at any time of R-404A, and/or for this existing system, only carry out less system amendment.Such as, compositions A1 A3 has the capacity in about the 8% and even more preferably about 6% of R404A and efficiency (COPs) in this cryogenic refrigerating system, and preferably in this limit, but it is above the capacity of R404A.Particularly, in view of the GWP of the improvement of compositions A1 A3, these compositionss of the present invention are excellent selection objects as (drop-in) sub that can introduce at any time of the cryogenic refrigerating system initially comprised and/or be designed to comprise R-404A.On the other hand, compositions A4 A6 has relatively low capacity (68% to 82%) and superior efficiency (high 9% to 10%), has tangible GWP simultaneously and improves, has the GWP less than about 1000 the most as shown, this minimizes total environment impact.The compositions A3 A6 of the present invention is for being excellent selection object for renovating the cryogenic refrigerating system initially comprising and/or being designed to comprise R-404A, need only to system is carried out again selecting of little adjustment, the such as size of some system element such as compressor and expansion valve.
Because many existing cryogenic refrigerating systems are designed to use R-404A, or other has the cold-producing medium being similar to R-404A performance, it would be recognized by those skilled in the art that and can serve as R-404A or the substitute of similar cold-producing medium, only system need to be carried out relatively minimal amendment, there is the substantial advantage of the cold-producing medium of low GWP and superior efficiency.Additionally, it would be recognized by those skilled in the art that the present composition is for using, in new or newly-designed refrigeration system (including preferably cryogenic refrigerating system), the advantage that can provide essence.
Embodiment 2: renovation parameter
Consider in certain embodiments, the present invention provides renovation method, it includes removing at least some of existing cold-producing medium from system and replacing the cold-producing medium removed at least partially with the present composition, the most system is not carried out substantial modification, and in major system elements (such as compressor, condenser, vaporizer and expansion valve), does not carries out any change.Some feature due to cryogenic refrigerating system, this cryogenic refrigerating system is particularly including the cryogenic refrigerating system comprising or be designed to comprise R404A cold-producing medium, in certain embodiments, it is important that this system can have reliable system operating parameters when using (drop-in) cold-producing medium that can introduce at any time.This kind of operating parameter includes:
● in use the high side pressure of system of R404A about 105% and the even more preferably still high side pressure in about 103%.In this kind of embodiment, this parameter is important, because it allows to use existing pressure elements.
● when using the R404A expansion valve of just size, being more than the evaporator superheat of about 0 DEG C, it allows the compositions using the present invention, and without replacing existing valve, therefore minimizes renovation cost and impact.
● it is preferably lower than about 130 DEG C, and the discharge temperature of even more preferably less than about 125 DEG C.The advantage of such feature is that it allows use existing equipment, it is not necessary to being activated by the thermal protection facility (aspects) of system, described facility is preferably designed so that can protect compressor element.This parameter is favourable, because it avoids uses the controller needing payment cost, such as, reduces the liquid jet of discharge temperature.
According to the present invention, the compositions A1 A6 indicated in above-mentioned Table A determined above-mentioned and other operating parameter, and these operating parameters reported in table 2 below:
Table 2
| Title | Discharge pressure (%) | Discharge temperature (DEG C) | Suction pressure (%) | Mass flow (%) | TXV import department fluid density (%) | Overheated (DEG C) |
| R404A | 100% | 91.9 | 100% | 100% | 100.0% | 5.55 |
| HDR-21 | 100% | 113.1 | 89% | 79% | 108.6% | 1.19 |
| HDR-31 | 100% | 123.5 | 89% | 73% | 100.1% | 0.25 |
| HDR-34 | 100% | 120.2 | 88% | 74% | 102.4% | 0.41 |
| HDR-23 | 81% | 101.8 | 69% | 67% | 110.3% | -3.51 |
| HDR-33 | 69% | 106.5 | 54% | 52% | 105.1% | -9.01 |
| HDR-36 | 74% | 104.5 | 59% | 57% | 106.4% | -6.92 |
In certain preferred aspects, described replacement step is that (drop-in) that can introduce at any time replaces, this refers to redesign or the amendment not requiring that system carries out essence, and in order to be suitable for the cold-producing medium of the present invention, it is not necessary to the major part of equipment is replaced.This uses the situation of compositions A1 A3 just, and they may be generally used to most refurbishment process, it is not necessary to critical piece is carried out any change.In all compositions A1 A3, discharge pressure and temperature are less than described limit, and expansion valve is enough overheated by producing in the exit of vaporizer.
Although compositions A4 A6 provides relatively good replacement performance, such compositions is used to would be required to the newest expansion gear as the substitute of R-404A in many cryogenic systems.Thus, in the case of the change of expansion valve and/or other equipment wherein is possible, these compositionss will provide advantage.Certainly, all compositions A1 A6 are for using the advantage providing excellent in new equipment.
Although by reference to preferred embodiment, invention has been described, it will be appreciated by those skilled in the art that on the premise of without departing substantially from the scope of the invention, its key element can carry out various change and can substitute its key element with equivalent.It addition, many amendments can be carried out on the premise of without departing substantially from essential scope of the present invention, in order to make concrete condition or material be suitable for the teachings of the present invention.Therefore, it is intended that the invention is not restricted to disclosed specific embodiments, present invention include all fall claims or any after increase right in embodiment.
Claims (19)
1. a heat transfer compositions, it comprises: the HFC-32 of (a) 10% to 35% weight；The HFC-125 of (b) 10% to 35% weight；The HFC-134a of (c) 15% to 35% weight；(d) combination of the HFO-1234ze of 20% to 50% weight, or HFO-1234ze and HFO-1234yf；Wherein said percetage by weight is based on the total amount of component (a) (d) in compositions；Wherein said heat transfer compositions has the global warming potential of no more than 1500.
2. the heat transfer compositions of claim 1, it comprises the HFC-32 of (a) 10% to 30% weight；(b) HFC-125 of 10% to 30% weight.
3. the heat transfer compositions of claim 1, wherein said HFO-1234ze includes trans-HFO-1234ze.
4. the heat transfer compositions of claim 1, it has the HFC-32:HFC-125 weight ratio of 0.9:1.2 to 1.2:0.9.
5. the heat transfer compositions of claim 1,2 or 4, it has the weight ratio of HFC-32:HFC-125 of 1:1.
6. the heat transfer compositions of claim 5, wherein the weight ratio of HFO-1234ze:HFO-1234yf is 5:1 to 3:1.
7. the heat transfer compositions of claim 5, wherein said HFO-1234ze is substantially made up of trans-HFO-1234ze.
8. the heat transfer compositions of claim 7, wherein the weight ratio of HFO-1234ze:HFO-1234yf is 5:1 to 3:1.
9. the heat transfer compositions of claim 1,2 or 4, wherein said HFO-1234ze is made up of trans-HFO-1234ze.
10. the heat transfer compositions of claim 9, wherein the weight ratio of HFO-1234ze:HFO-1234yf is 5:1 to 3:1.
The heat transfer compositions of 11. any one of claim 1-4, wherein the weight ratio of HFO-1234ze:HFO-1234yf is 5:1 to 3:1.
The heat transfer compositions of 12. claim 1,2 or 4, wherein the weight ratio of HFO-1234ze:HFO-1234yf is 4:1.
The heat transfer compositions of 13. claim 12, wherein said HFO-1234ze is substantially made up of trans-HFO-1234ze.
The heat transfer compositions of 14. claim 1,2 or 4, wherein said composition comprises HFO-1234ze and HFO-1234yf, and the weight ratio of the wherein HFC-134a:TFC of said composition is 5:7 to 1:1, the combination of HFO-1234ze and HFO-1234yf during wherein TFC refers to compositions.
The heat transfer compositions of 15. claim 14, wherein said HFO-1234ze is substantially made up of trans-HFO-1234ze.
The method of the existing heat exchanging fluid that 16. 1 kinds of replacements are included in heat-exchange system, comprising: remove at least some of described existing heat exchanging fluid from described system, described existing heat exchanging fluid is HFC-404A, and replacing at least some of described existing heat exchanging fluid by introducing described system one heat transfer compositions, described heat transfer compositions comprises: the HFC-32 of (a) 10% to 35% weight；The HFC-125 of (b) 10% to 35% weight；The HFC-134a of (c) 15% to 35% weight；(d) combination of the HFO-1234ze of 20% to 50% weight, or HFO-1234ze and HFO-1234yf；Wherein said percetage by weight is based on the total amount of component (a) (d) in compositions；Wherein said heat transfer compositions has the global warming potential of no more than 1500.
The method of 17. claim 16, wherein said heat transfer compositions comprises the HFC-32 of (a) 10% to 30% weight；(b) HFC-125 of 10% to 30% weight.
18. 1 kinds of heat-exchange systems, it comprises the compressor of fluid communication, condenser and vaporizer, and heat transfer compositions in the system, and described heat transfer compositions comprises: the HFC-32 of (a) 10% to 35% weight；The HFC-125 of (b) 10% to 35% weight；The HFC-134a of (c) 15% to 35% weight；(d) combination of the HFO-1234ze of 20% to 50% weight, or HFO-1234ze and HFO-1234yf；Wherein said percetage by weight is based on the total amount of component (a) (d) in compositions, and described condenser has the operation temperature of 35 DEG C to 45 DEG C；Wherein said heat transfer compositions has the global warming potential of no more than 1500.
The heat-exchange system of 19. claim 18, wherein said vaporizer has the operation temperature of-25 DEG C to-35 DEG C.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610918122.8A CN106905926B (en) | 2009-05-08 | 2010-05-07 | Heat exchange compositions and methods |
| CN201610918076.1A CN106905925A (en) | 2009-05-08 | 2010-05-07 | Heat transfer compositions and methods |
Applications Claiming Priority (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US17677309P | 2009-05-08 | 2009-05-08 | |
| US61/176773 | 2009-05-08 | ||
| US12/511,954 US20120097885A9 (en) | 2003-10-27 | 2009-07-29 | Compositions Containing Difluoromethane and Fluorine Substituted Olefins |
| US12/511954 | 2009-07-29 | ||
| US24078609P | 2009-09-09 | 2009-09-09 | |
| US61/240786 | 2009-09-09 | ||
| US24781609P | 2009-10-01 | 2009-10-01 | |
| US61/247816 | 2009-10-01 | ||
| US32995510P | 2010-04-30 | 2010-04-30 | |
| US61/329955 | 2010-04-30 | ||
| PCT/US2010/034120 WO2010129920A1 (en) | 2009-05-08 | 2010-05-07 | Heat transfer compositions and methods |
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| CN201610918076.1A Division CN106905925A (en) | 2009-05-08 | 2010-05-07 | Heat transfer compositions and methods |
| CN201610918122.8A Division CN106905926B (en) | 2009-05-08 | 2010-05-07 | Heat exchange compositions and methods |
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| US20080314073A1 (en) * | 2007-06-21 | 2008-12-25 | E. L. Du Pont De Nemours And Company | Method for leak detection in heat transfer systems |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5983657A (en) * | 1997-01-30 | 1999-11-16 | Denso Corporation | Air conditioning system |
| EP1022552A2 (en) * | 1999-01-19 | 2000-07-26 | Carrier Corporation | Test for the automated detection of leaks between high and low pressure sides of a refrigeration system |
| US20080314073A1 (en) * | 2007-06-21 | 2008-12-25 | E. L. Du Pont De Nemours And Company | Method for leak detection in heat transfer systems |
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