CN1177371A

CN1177371A - Refrigeration working fluid compositions for use in recompression type cooling system

Info

Publication number: CN1177371A
Application number: CN95191673A
Authority: CN
Inventors: M·A·克里瓦利斯; C·B·当肯; R·H·施劳斯伯格
Original assignee: Exxon Chemical Patents Inc
Current assignee: ExxonMobil Chemical Patents Inc
Priority date: 1994-11-17
Filing date: 1995-11-16
Publication date: 1998-03-25
Also published as: EP0804517A1; WO1997019144A1; NZ296904A; ZA959743B; IL116043A0; AR000158A1; CA2181387A1; BR9509790A; AU4164296A

Abstract

A refrigeration working fluid composition which is miscible or partially miscible at temperatures of less than 120 DEG C and which is immiscible at temperatures of at least about 120-180 DEG C, the refrigeration working fluid comprising: (i) about 65 to 95 weight % of a refrigerant, based on the total weight of the working fluid composition, the refrigerant comprising a blend of pentafluoroethane, 1,1,1-trifluoroethane, and 1,1,1,2-tetrafluorothane, wherein the tetrafluoroethane is present in an amount of between about 0.5 to 10 weight %, based on the total weight of the refrigerant, and (ii) about 5 to 35 weight % of a polyol ester lubricant, based on the total weight of the working fluid composition.

Description

The refrigeration working fluid compositions that is used for recompression type cooling system

The application is the part continuation application of U.S. Patent application (application number is 08/340,961).The present invention relates to specialize in the refrigeration working fluid compositions of valid function recompression type cooling system.Specifically, the present invention relates to refrigeration working fluid compositions, comprise fluorocarbon (HFC) refrigeration agent adulterant and some polyol ester lubricant, described lubricant suitable viscosity is arranged and when low temperature (for example being lower than 120 ℃) and refrigeration agent miscible and at high temperature (for example about 120 ℃～180 ℃ or higher) down and the refrigeration agent unmixing, show the reversible compatibility thus.

Background of invention

Mechanical vapour recompression type refrigeration system comprises refrigerator, refrigerator-freezer, and heat pump, air-conditioning systems etc. are well-known.In this kind equipment, suitably the refrigeration agent of boiling point under low pressure evaporates, and absorbs heat from the peripheral region.Gained steam compresses then and enters condenser, at this vapor condensation and emit heat and give second district.Phlegma turns back to vaporizer through expansion valve then, thereby finishes circulation.

Chloride refrigeration agent such as the Refrigerant 12 of recognizing present use now will be replaced by no chlorine refrigerant fluid, because chloride material is to the harmful effect of atmospheric ozonosphere.Tetrafluoroethane isomers, particularly " refrigeration agent 134a " (it is 1,1,1, the 2-Tetrafluoroethane) are considered to be used for the desirable fluid of refrigeration system now.

The refrigeration agent working fluid requires that a kind of lubricant is arranged, and its compatible with refrigeration agent and miscible so that moving-member of this system is by proper lubrication.At present, this series lubricant agent is made up of hydrocarbon mineral oil, and this mineral oil and chloride refrigerant fluid are miscible and effective lubricating is provided.

Use no chlorine HFC (fluorocarbon) refrigeration agent to need new lubricant, because mineral oil is incompatible with these materials.This need be in this area generally acknowledge and a large amount of nearest public publications and patent disclosure have been arranged various types of synthetic lubricants, it is said that these lubricants can be compatible with the Tetrafluoroethane refrigerant fluid.The ester of polyvalent alcohol is fit to and the Tetrafluoroethane refrigeration agent by lay special stress on, and particularly refrigerant R134a uses together.

The United States Patent (USP) 5,021,179 that licensed to people such as Zehler on June 4th, 1991 discloses the ester of polyvalent alcohol, and wherein acyl group has (a) branching acyl group of at least 22% or (b) contains the acyl group of no more than 6 carbon atoms.This patent shows that also this ester contains 8 or have certain ratio and this ratio to be not more than 1.56 greater than 8 carbon atoms and for the percentage ratio of nonbranched acyl group and branching and percentage ratio that contain greater than the acyl group of 6 carbon atoms.This patent requires have the percentage ratio of at least 9 carbon atoms, branching or nonbranched acyl group to be not more than 81 in addition.

Disclosed PCT application on people's such as Jalley November 1 nineteen ninety WO90/12849 discloses general liquid composition, contain the hydrocarbon that contains at least one fluorine atom and one or two carbon atom of main amount and contain a spot of at least a solubility organic lubricant, this lubricant comprises the ester of at least a carboxylic acid of polyol, and polyol contains at least 2 hydroxyls and general formula is R[OC (O) R '] _nWherein R is an alkyl, and each R ' is hydrogen independently, the straight chain lower alkyl, branched hydrocarbyl or contain 8 to the straight-chain alkyls of about 22 carbon atoms, supplementary condition are that at least one R ' group is a hydrogen, and lower straight alkyl or branched hydrocarbyl or the alkyl and the n that contain carbonyl acid or contain carboxylicesters are at least 2.

Licensed to Imperial Chemical Industries on October 23rd, 1991 and in disclosed English Patent 2 on October 11st, 1989,216,541 disclose that to use any molecular weight be 250 or bigger ester, and they are suitable as the compatible lubricant of relevant with some refrigerant fluid with refrigeration agent 134a (R-134a).This patent example has gone out adipic acid ester, and 1,2,4,5-pyromellitic acid ester and benzoic ether.

On August 7th, 1991, the European publication application 440069 of disclosed Kao Corporation disclosed by fluorinated ethanic and the refrigeration agent working fluid be made up of the ester that aliph polyols and straight or branched alcohol and fatty polynary acid-responss by 2 to 10 carbon atoms make.

On March 6th, 1991, the European publication application 415778 of disclosed Kao Corporation disclosed refrigeration working fluid compositions, the ester cpds that they contain the hydrogenation fluoroethane and are obtained by aliph polyols, saturated fatty diprotic acid and saturated fatty monoprotic acid.

On January 9th, 1991 disclosed Kyodo oil Technical ResearchCenter Co., the European application 406479 of Ltd. discloses lubricant, they it is said compatible with R134a.Suitable lubricant is: neopentyl glycol and the ester that the straight or branched unary fatty acid of 3-18 carbon atom is arranged; The C of tetramethylolmethane, Dipentaerythritol and tripentaerythritol and straight or branched ₂-C ₁₈The ester of unary fatty acid; Formula RC (CH ₂OH) ₃Wherein R is C ₁-C ₃The trihydroxy-polyvalent alcohol of alkyl with the straight or branched unary fatty acid of 2-18 carbon atom is arranged and is no more than the polybasic ester of at least a 4-36 of having the carbon atom of whole lipid acid 25mol%.

On July 3rd, 1991 disclosed Nippon Oil Co., the Europe of Ltd applies for that openly 435253 disclose a large amount of esters compatible with R134a that it is said, these esters are defined as special construction and are one, two or tripentaerythritol and other polyvalent alcohols such as trimethylolethane, TriMethylolPropane(TMP), tri hydroxy methyl butane or its dipolymer or trimer and the monoprotic acid of 2-15 carbon atom is arranged and the ester of the diprotic acid of 2-10 carbon atom is arranged.These esters it is said that molecular weight is about 200-3000.

On June 5th, 1991, the European disclosed application 430657 of disclosed Ashai Denka Kogyo Kabushiki disclosed the lubricant compatible with R134a, and this lubricant is the DOPCP that 2 to 6 carbon atom fatty acids are arranged.If in this application, it is said C ₂-C ₆The amount of acid be lower than 20mol% so that for each hydroxyl of new pentane diacid the lipid acid average carbon atom number be 6 or less than 6, then using has the acid of 7 or 7 above carbon atoms can cause incompatible.Suitable neopentyl glycol comprises one, two and tripentaerythritol, TriMethylolPropane(TMP) and trimethylolethane.Polyvalent alcohol must have at least 3 OH.

In the work of typical refrigeration system, the working fluid composition that comprises the mixture of refrigeration agent and lubricant is transported to condenser (descending in this temperature) from compressor (compressor temperature the highest and need lubricant), working fluid composition is delivered to vaporizer (in this temperature minimum and do not need lubricant) then, working fluid composition then, to steam cold form, turn back in the compressor to repeat this circulation.

When refrigeration working fluid compositions of the present invention is arranged in vaporizer, ester lubricant and the part or all of homogeneous phaseization of HFC refrigeration agent adulterant or miscible, but when working fluid composition is arranged in compressor (temperature high and need lubricant) herein, the ester lubricant that can obtain the form that contracts very much is with lubricate compressors, because ester lubricant and refrigeration agent adulterant are at high temperature promptly about 120 ℃ to 160 ℃ or the complete unmixing of relative superiority or inferiority more.Separating ester lubricant like this in compressor from the refrigeration agent blend is good.

Working fluid composition of the present invention also can be miscible or half homogeneous of part at low temperatures, be that ester and refrigeration agent adulterant can present the partial confounding dissolubility, but this partial confounding dissolubility or half homogeneous phase do not hinder composition in refrigeration equipment application and this class half homogeneous composition at comparatively high temps promptly at about 120 ℃ to 180 ℃ or more also can present substantially completely not mutual solubility under the high temperature, thereby can realize purpose of the present invention.

Therefore, the inventor finds can influence compatibility/unmixability widely by the blending refrigeration agent.But the more important thing is refrigeration agent adulterant such as R125, the temperature of R143a and R134a or R125 and R143a/unmixability relation and conventional known one-component refrigerant and polybasic ester temperature/mutual solubility concerns not opposite.

The inventor finds when special refrigeration agent adulterant of the present invention and polyol ester mix lubricant, at high temperature lubricant becomes immiscible so that can carry out separating of refrigeration agent and lubricant in the operation compressor section of refrigeration system at high temperature, thereby a part of lubricant is stayed in the compressor section and circulated without the whole refrigeration system that does not need lubricant.

On the contrary, thereby one-component refrigerant such as R134a and R143a unmixing refrigeration agent in the vaporizer section of operation refrigeration system at low temperatures at low temperatures separate with lubricant, therefore a part of lubricant is stayed and is not needed the vaporizer of lubricant section, so just the compressor section that more needs lubricant is constituted to hinder (seeing Fig. 3 and Fig. 4).

One-component refrigerant such as R125 also are undesirable, because it all is miscible under all temperature of refrigeration system operation, this make lubricant order ground from evaporator to compressor again to condenser, and do not use concentrating and the benefit (see figure 5) of separating unmixing polyol ester lubricant that refrigeration agent adulterant of the present invention pursued in compressor section.

It is undesirable also having other refrigeration agents such as R32, because their at high temperature miscible and unmixing (see figure 6)s at low temperatures.This class refrigeration agent when working fluid is in the vaporizer, separates lubricant from working fluid composition, thereby has deprived the lubricant that more needs the compressor section of lubricant.

The European Patent Publication No 0536940 that is disclosed on April 14th, 1993 and transfers Imperial Chemical Indus-tries PLC discloses a kind of working fluid that comprises heat-transfer fluid and lubricant, and heat-transfer fluid comprises at least two kinds of mixtures that are selected from the compound of alkane hydrofluoride and fluorine alkane.Heat-transfer fluid can comprise two, three or more is selected from following compound: R32, R134, R134a, R125, R125a, R143a and R143.A kind of suitable fluid comprises the mixture of R32 and R125.

But as shown in FIG. 7, the working fluid composition that comprises R32 and R125 is unmixing at high temperature, but the composition exception of technical grade pentaerythritol, Cekanoic 9 and Cekonic 8 is arranged, and it presents unmixability in 100-130 ℃ of scope.If but referring to the embodiment E of Fig. 1, this lubricant all is being miscible in refrigeration agent adulterant of the present invention under all temperature and is being immiscible at this lubricant of the example I of Fig. 2 in 120-180 ℃ of scope.Therefore, quite clear, not every refrigeration agent adulterant all plays a part identical, and each adulterant of refrigeration agent all shows its unique compatibility and unmixability performance.So to those skilled in the art, as the instruction at adulterant shown in Figure 7, what influence a kind of combination of refrigeration agent adulterant has to the compatibility of specific polyol ester lubricant is not conspicuous according to other refrigeration agent adulterants.

Therefore, because European Patent Publication No 0536940 had not both openly drawn the concrete weight percentage (the particularly percentage ratio of R143a) of the refrigeration agent adulterant of uniqueness in the present invention, do not have open and the concrete lubricant of this class adulterant blended yet, thereby can not think for certain that they will show compatibility and the unmixability identical with refrigeration working fluid compositions of the present invention.Do not have the inventor's deep research comprehensively, people are not easy to determine from the compatibility data of one-component refrigerant and lubricant what influence another kind of refrigeration agent will have to the compatibility of gained working fluid with this one-component refrigerant blending.

Lubricant stayed farthest utilized the effect of lubricant in the compressor and it is stayed the effect that has greatly reduced it in the vaporizer.

Therefore, what be all beyond one's expectations is when refrigeration agent that blending is selected, can improve the lubrication of refrigeration system, and depends merely on refrigeration agent can not make lubricant be immiscible in hot environment such as compressor and be miscible in low temperature environment such as vaporizer.

Summary of the invention

According to the present invention, disclose as the HFC refrigeration agent of the refrigeration working fluid that presents reversible compatibility and the adulterant of some monocarboxylic polyol ester, it has improved the lubrication of the refrigeration equipment that contains this based composition.As follows according to preferred working fluid composition of the present invention:

(a) a kind of refrigeration working fluid compositions, it is miscible during less than 120 ℃ or part is miscible and be at least about 120～180 ℃ for immiscible in temperature in temperature, described refrigeration working fluid comprises:

(i) be base with described working fluid composition, a kind of refrigeration agent of about 65% to 95% (weight), described refrigeration agent comprises pentafluoride ethane, 1,1,1-Halothane and 1,1,1, a kind of adulterant of 2-Tetrafluoroethane, the amount of wherein said Tetrafluoroethane based on the gross weight of refrigeration agent be about 0.5%～10% (weight) and

Be base (ii) with described working fluid composition gross weight, a kind of polyol ester lubricant of about 5%-35% (weight).

(b) a kind of refrigeration working fluid compositions, it when being lower than 120 ℃, be miscible or part miscible, under at least about 120 ℃～180 ℃, be immiscible, described refrigeration working fluid comprises:

(i) be base with described working fluid composition, it is a kind of 1,1 that a kind of refrigeration agent of about 65～95% (weight), described refrigeration agent comprise, the adulterant of 1-Halothane and pentafluoride ethane and

Be base (ii) with described working fluid composition, the polyol ester lubricant of about 5%～35% (weight).

Another object of the present invention is a kind of vaporizer that comprises, the mechanical vapour recompression type cooling system of compressor and condenser, refrigeration working fluid compositions (a) and (b) in this systemic circulation, wherein to be in 120 ℃ the vaporizer be miscible to refrigeration working fluid compositions or part is miscible and be immiscible at least about 120～180 ℃ compressor, whereby, when needing most lubricant, the polyol ester lubricant is separated from refrigeration agent in compressor, and when refrigeration working fluid was in vaporizer, the polyol ester lubricant was miscible in refrigeration agent or part is miscible so that the polyol ester lubricant can be transferred to compressor from vaporizer at an easy rate.

The simple declaration of accompanying drawing

Fig. 1 shows and comprises 44%R125, reversible compatibility that the refrigeration working fluid compositions of the present invention of the lubricant of the refrigeration agent of 52%R143a and 4%R134a and the polyol ester of selection presents and the comparison that does not present the refrigeration working fluid compositions of reversible compatibility.

Fig. 2 shows the refrigeration working fluid compositions of the present invention reversible compatibility that presents and the comparison that does not present the refrigeration working fluid compositions of reversible compatibility of lubricant of the polyol ester of the refrigeration agent that comprises 55%R143a and 45%R125 and selection.

Fig. 3 is illustrated under any temperature the relative unmixability of various polyol ester lubricants in R143a;

Fig. 4 is illustrated under any temperature the relative compatibility of various polyol ester lubricants in R134a;

Fig. 5 show under any temperature in R125 the relative compatibility of various polyol ester lubricants with under any temperature in R125 the relative unmixability of other polyol esters;

Fig. 6 shows the reversible compatibility of various polyol ester lubricants in R32, these lubricants unmixing at low temperatures wherein, and at high temperature miscible, this is opposite fully with the present invention; With

Fig. 7 is illustrated under any temperature the relative compatibility of various polyol ester lubricants in the refrigeration agent adulterant of 60% (weight) R32 and 40% (weight) R125, the working fluid that exception is to use TPE/CK9/CK8 to form, it presents unmixability in about 100-130 ℃ narrow temperature scope.

Detailed description of the present invention

The amount of polyol ester should be able to provide effective lubrication, and it is about 5-35% (weight) based on refrigeration agent working fluid composition gross weight usually.Preferred amount is 10%, 25% and 35% ester

Refrigeration working fluid compositions of the present invention is preferably:

(a) a kind of refrigeration working fluid compositions, said composition is homogeneous phase or half homogeneous, one combined thing at low temperatures basically, and under about 120-180 ℃ temperature, present unmixability, it comprises the R-125 of (i) 44% (weight), the refrigeration agent that the adulterant of the R-134a of the R-143a of 52% (weight) and 4% (weight) is formed and the (ii) polyol ester lubricant of significant quantity, it be (1) a), b) or the ester of TriMethylolPropane(TMP) c): a) 3,5,5-front three caproic acid, b) 2 methyl caproic acid of the positive enanthic acid and 24% (weight) of 67% (weight), the C of the 2-ethyl valeric acid and 2% (weight) of 7% (weight) ₇The mixture of the mixed isomers of paraffinic acid, c) by about 25% (weight) 3,4-dimethyl valeric acid, 51% (weight) 3,4 and the 5-methylhexanoic acid, 8% positive enanthic acid, 5%3-ethyl valeric acid and remaining be the mixture of enanthic acid of mixture composition of the enanthic acid of other branching, or (2) are (a) or the ester of technical grade pentaerythritol (b): (a) C of branching ₇Acid, they are 2-ethyl valeric acids of 27% (weight), the 2 methyl valeric acid of 74% (weight) and remainder are mixed C ₇The isomer of acid or (b) positive valeric acid; Or

(b) a kind of refrigeration agent working fluid, this fluid is essentially homogeneous phase or half homogeneous, one combined thing at low temperatures, and under 120-180 ℃ temperature, present unmixability, it comprises refrigeration agent that (a) is made up of the mixture of the R-125 of the R-143a of 55-50% (weight) and 45-50% (weight) and (b) a kind of polyol ester lubricant of significant quantity, this lubricant is: (1) (a), (b) or the ester of TriMethylolPropane(TMP) (c): (a) 2 ethyl hexanoic acid, (b) 3,5,5-tri-methyl hexanoic acid or (c) by about 25% (weight) 3,4-dimethyl valeric acid, 51%3,4 and the 5-methylhexanoic acid, 8% positive enanthic acid, 5%3-ethyl valeric acid and all the other are the mixture of the branching enanthic acid of other branching enanthic acid mixtures compositions; (2) (a), (b) or the ester of technical grade pentaerythritol (c): (a) 3 of about 75% (weight), 5,5-tri-methyl hexanoic acid and about 25% (weight) by 25% (weight) 3,5-dimethyl caproic acid, 19% (weight) 4,5-dimethyl caproic acid, 17%3,4-dimethyl caproic acid, 11%5-methyl enanthic acid, 5% (weight) 4-methyl enanthic acid are the side chain C that blended methyl enanthic acid and dimethyl caproic acid are formed with all the other ₈Mixture of carboxylic acids, (b) positive valeric acid, or (c) by about 25%3,4-dimethyl valeric acid, 51%3,4 and the 5-methylhexanoic acid, 8% positive enanthic acid, 5%3-ethyl valeric acid and all the other are the mixture of enanthic acid of mixture composition of the enanthic acid of other branching.

The R125 that is used for herein refers to pentafluoride ethane, and R143a refers to 1,1, and 1-Halothane and R134a refer to 1,1,1, the 2-Tetrafluoroethane.

Compatibility and unmixability are measured in the following manner.The ester lubricant of weighing is inclined in the band valve Glass tubing of an internal diameter 12mm.This pipe is linked to R-143a refrigerant charge unit, falls until obtaining desirable refrigerant gas pressure in Glass tubing in this condensation of refrigerant of taking out air and certain volume.The composition of lubricant/refrigerant mixture adds the weight that lubricant weight and pipe add the lubricant refrigerant feeding by measuring tube weight, pipe and calculates.The pipe that contains lubricant/refrigeration agent at room temperature, high temperature is visible bathe in (the temperature thermostatic control is at 180 ℃ at the most) and low temperature is visible bathe in (the temperature thermostatic control is being low to moderate-80 ℃) observe compatibility.If for given temperature observe one clearly the layer mixture is miscible.If observing two separating layer mixtures is unmixing.Part is miscible to be state between miscible and unmixing.

In the data that comprise in an embodiment, the compatibility temperature refers to the observed minimum temperature of given composition.The maximum of these temperature is miscible values that the working fluid composition of ester lubricant is arranged.

Embodiment

With Fig. 1 and 2 the present invention is described, Fig. 1 and 2 shows the reversible compatibility that composition of the present invention shows, and they show every kind of ester the i.e. data that obtain of the ester of 10%, 25% and 35% (weight) compound of 3 compositing ranges.All percentage ratios represent with weight, and temperature is with degree centigrade representing.

These embodiment have produced an interesting phenomenon.Not the unmixing of in single component such as R143a, often seeing in low temperature range, and in the higher temperature scope, tend to unmixing now that this is special hope to cooling system.The following examples have produced various working fluids, and they present compatibility and unmixing at high temperature at low temperatures.The low temperature compatibility means that lubricant is that deleterious cooling system part can not separated in the accumulation of lubricant to performance promptly in the coldest part of cooling system.Equally, the high temperature unmixability means high-temperature zone such as the compressor of lubricant/refrigeration agent at cooling system, speaks by the book to need most isolating place at lubricant/refrigeration agent and will separate.

Fig. 1 and 2 has shown that also the raising compatibility can finish by mix refrigerant, equally also can finish by hybrid lubricant.With the inconsistent R143 of polyol ester as itself and R125, even R125 is less component (promptly less than 50%) when mixing, this uncompatibility almost can be eliminated.

In Fig. 1, the present composition is that Embodiment B, C and D contain following ester:

B:TMP/CK9-3,5, the trihydroxymethylpropanyl ester of 5-tri-methyl hexanoic acid (" Cekanoic9 acid ")

The C:TMP/1770-acid mixture i.e. 67% positive enanthic acid, 24%2-methylhexanoic acid, 7%2-ethyl valeric acid and 2%C ₇The trihydroxymethylpropanyl ester of the mixed isomers of acid.

The trihydroxymethylpropanyl ester of D:TPE/CK7-mixing enanthic acid (" Cekanoic7 acid ").Mixing enanthic acid is 23%2-ethyl valeric acid, and 74%2-methylhexanoic acid and all the other are other C ₇The mixture of acid isomer body.

Comparative composition A and E contain the refrigeration agent adulterant of being made up of 44%R125,52%R143a and 4%R134a with following ester blended.

A:3,5, the DOPCP of 5-tri-methyl hexanoic acid.

E:85% (weight) is (a) and the technical grade pentaerythritol ester of 15% (weight) mixture (b): (a) 3,5,5-tri-methyl hexanoic acid and (b) isocaprylic acid, it be 26% (weight) 3, the 5-dimethyl-, 19%4, the 5-dimethyl-, 17%3,4-dimethyl caproic acid, the 11%5-methyl enanthic acid, 5%4-methyl enanthic acid and all the other are blended methyl enanthic acid and dimethyl caproic acid.

In Fig. 2, the present composition is composition F, G and the I that contains these esters:

F: the trihydroxymethylpropanyl ester that is 2 ethyl hexanoic acid.

G: be with composition B in used identical ester.

I: be with composition E in identical ester, difference is to use the 3,5,5 Trimethylhexanoic acid isocaprylic acid mixture identical with 25% of 75% (weight) here.

Comparative composition H contains the refrigeration agent adulterant with following ester blended 55%R143a and 45%R125:

The trihydroxymethylpropanyl ester of H:TMP/1770-acid mixture, acid mixture are 67% positive enanthic acid, 24%2-methylhexanoic acid, 7%2-ethyl enanthic acid and 2%C ₇The mixed isomers of acid.

All esters are to estimate under 10%, 25% and 35% (weight) (is base with the refrigeration working fluid compositions gross weight) at concentration value all.

Following additive composition is to estimate and obtain similar result under compositing range is the ester of 10%, 25% and 35% (weight):

Composition J: enanthic acid mixture (25%3,4-dimethyl valeric acid, 51%3,4 and the 5-methylhexanoic acid, 8% positive enanthic acid, 5%3-ethyl valeric acid and all the other mixtures for other branching enanthic acid) trihydroxymethylpropanyl ester and the adulterant hybrid concurrency of 44%R-125,52%R143a and 4%R-134a present-50 ℃ to+58 ℃ be miscible at high temperature be immiscible.

Composition K: it is miscible and at high temperature be immiscible now under-50 ℃ to+63 ℃ that the ester of the technical grade pentaerythritol of positive enanthic acid uses the refrigeration agent adulterant identical with ester J to estimate concurrent.

Composition L: the adulterant hybrid concurrency of R-125 that is used for the 143a and 50% (weight) of the identical ester of composition J and 50% (weight) is now miscible under-50 ℃ to+55 ℃ and unmixing at high temperature.

Composition M: the identical refrigeration agent adulterant that is used among the identical ester of composition K and the composition L mixes, and finds that under-50 ℃ and+61 ℃ be miscible, and unmixing at high temperature.

Composition N: the identical refrigeration agent adulterant of the technical grade pentaerythritol ester of the acid mixture of composition J and composition L mixes, and finds under-50 ℃ and+32 ℃ it is miscible and at high temperature be immiscible.

Claims

1. refrigeration working fluid compositions, it is miscible during less than 120 ℃ or part is miscible and be at least about 120～180 ℃ for immiscible in temperature in temperature, described refrigeration working fluid comprises:

2. according to the composition of claim 1, wherein said refrigeration agent comprises the pentafluoride ethane of a kind of 44% (weight), 52% (weight) 1,1,1,1,1 of 1-Halothane and 4% (weight), 2-Tetrafluoroethane.

3. according to the composition of claim 1, wherein said polyol ester lubricant is selected from:

(1) a kind of trishydroxymethyl and be selected from the following at least a acid or the esterification reaction product of acid mixture:

(a) 3,5,5 Trimethylhexanoic acid,

(b) the positive enanthic acid of 67% (weight), the 2 methyl caproic acid of 24% (weight), the C of the 2-ethyl valeric acid and 2% (weight) of 7% (weight) ₇The mixture of the mixed isomers of paraffinic acid and

(c) a kind of mixture of enanthic acid class, by about 25% (weight) 3,4-dimethyl caproic acid, 51% (weight) 3-, the positive enanthic acid of 4-and 5-methylhexanoic acid and 8% (weight), 5% (weight) 3-ethyl valeric acid and all the other be the mixture composition of the enanthic acid of other branching; With

(2) esterification reaction product of technical grade pentaerythritol ester and the mixture that is selected from following at least a acid or acid

(a) C of branching ₇Acid, it is the 2-ethyl valeric acid of 27% (weight), the 2 methyl valeric acid of 74% (weight) and all the other are blended C ₇The mixture that the isomer of acid is formed and

(b) positive valeric acid.

4. refrigeration working fluid compositions, it when being lower than 120 ℃, be miscible or part miscible, under at least about 120 ℃～180 ℃, be immiscible, described refrigeration working fluid comprises:

5. according to the composition of claim 4, wherein said refrigeration agent comprise 50～55% (weight) 1,1, a kind of adulterant of the pentafluoride ethane of 1-Halothane and 45～50% (weight).

6. according to the composition of claim 4, wherein said polyol ester lubricant is selected from:

(i) TriMethylolPropane(TMP) and be selected from the following at least a acid or the esterification reaction product of acid mixture:

(a) 2 ethyl hexanoic acid,

(b) 3,5,5 Trimethylhexanoic acid and

(c) mixture of the enanthic acid class of branching, comprise 25% (weight) 3,4-dimethyl valeric acid, 3,4 and the 5-methylhexanoic acid of 51% (weight), the positive enanthic acid of 8% (weight), the 3-ethyl valeric acid of 5% (weight) and all the other are the mixture of other branching enanthic acid; With

(2) technical grade pentaerythritol ester and be selected from following at least a acid or a kind of esterification reaction product of acid mixture:

(a) the side chain C of the 3,5,5 Trimethylhexanoic acid of about 75% (weight) and about 25% (weight) ₈The mixture of mixture of carboxylic acids, C ₈Mixture of carboxylic acids is by 3 of 25% (weight), 5-dimethyl caproic acid, 19% (weight) 4,5-dimethyl caproic acid, 17% (weight) 3,4-dimethyl enanthic acid, 11% (weight) 5-methyl enanthic acid, the 4-methyl enanthic acid of 5% (weight) and all the other are that the mixing acid of methyl enanthic acid and dimethyl caproic acid is formed

(b) positive enanthic acid and

(c) a kind of mixture of enanthic acid, comprise about 25% (weight) 3,4-dimethyl valeric acid, 3,4 and the 5-methylhexanoic acid of 51% (weight), the positive enanthic acid of 8% (weight), the 3-ethyl valeric acid of 5% (weight) and all the other are the mixture of other branching enanthic acid.

7. mechanical vapour recompression type cooling system, comprise vaporizer, compressor and condenser, wherein said cooling system comprises a round-robin refrigeration working fluid compositions therein, described refrigeration working fluid compositions is miscible during less than 120 ℃ or part is miscible and be at least about 120～180 ℃ for immiscible in temperature in temperature, and described refrigeration working fluid comprises:

Be base (ii) with described working fluid composition gross weight, a kind of polyol ester lubricant of about 5%-35% (weight), whereby when needing most lubricant described polyol ester lubricant in described compressor, from described refrigeration agent, separate and when described refrigeration working fluid mixture is in described vaporizer described polyol ester lubricant in described refrigeration agent, be miscible or part miscible so that described polyol ester lubricant can be transferred to described compressor from described vaporizer at an easy rate.

8. according to the refrigeration system of claim 7, wherein said refrigeration agent comprises the pentafluoride ethane of a kind of 44% (weight), 52% (weight) 1,1,1,1,1 of 1-Halothane and 4% (weight), 2-Tetrafluoroethane.

9. according to the refrigeration system of claim 7, wherein said polyol ester lubricant is selected from:

(a) 3,5,5 Trimethylhexanoic acid,

(b) positive valeric acid.

10. mechanical vapour recompression type cooling system, comprise vaporizer, compressor and condenser, wherein said cooling system comprises a round-robin refrigeration working fluid compositions therein, described refrigeration working fluid compositions when being lower than 120 ℃, be miscible or part miscible, under at least about 120 ℃～180 ℃ is immiscible, and described refrigeration working fluid comprises:

Be base (ii) with described working fluid composition, the polyol ester lubricant of about 5%～35% (weight), whereby when needing most lubricant described polyol ester lubricant in described compressor, from described refrigeration agent, separate and when described refrigeration working fluid mixture is in described vaporizer described polyol ester lubricant in described refrigeration agent, be miscible or part miscible so that described polyol ester lubricant can be transferred to described compressor from described vaporizer at an easy rate.

11. according to the cooling system of claim 10, wherein said refrigeration agent comprise 50～55% (weight) 1,1, a kind of adulterant of the pentafluoride ethane of 1-Halothane and 45～50% (weight).

12. according to the cooling system of claim 10, wherein said polyol ester lubricant is selected from:

(a) 2 ethyl hexanoic acid,

(b) 3,5,5 Trimethylhexanoic acid and

(b) positive enanthic acid and