CN101270275B - Mixed refrigerant - Google Patents

Mixed refrigerant Download PDF

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CN101270275B
CN101270275B CN2008100945551A CN200810094555A CN101270275B CN 101270275 B CN101270275 B CN 101270275B CN 2008100945551 A CN2008100945551 A CN 2008100945551A CN 200810094555 A CN200810094555 A CN 200810094555A CN 101270275 B CN101270275 B CN 101270275B
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c2h4f2
tetrafluoroethane
mass concentration
propane
mix refrigerant
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CN101270275A (en
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公茂琼
吴剑峰
张宇
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Qingdao Zhongke Future Health Research Institute Co ltd
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Technical Institute of Physics and Chemistry of CAS
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Abstract

The invention provides a ternary near-azeotropic refrigerant, which comprises a ternary mixture consisting of 1, 1, 2, 2-tetrafluoroethane, 1-difluoroethane and propane, wherein the sum of the mass percent concentrations of all components in the mixed refrigerant is 100%, the mass percent concentration of the 1, 1, 2, 2-tetrafluoroethane is 1-20%, the mass percent concentration of dimethyl ether is 1-50%, and the mass percent concentration of propane is 30-90%. The invention also provides a method for preparing the mixed refrigerant. The invention further provides the application of the mixed refrigerant. The mixed refrigerant has higher efficiency and high evaporation pressure, and has larger refrigerating capacity under the same compressor displacement; the ODP is zero, and the GWP is greatly reduced compared with R502 and R404A.

Description

A kind of mix refrigerant
Technical field
The invention belongs to refrigerant art.The present invention relates to a kind of mix refrigerant, particularly a kind of efficient and environmental protection, be used for the mix refrigerant of single stage compressive refrigerating system.The invention still further relates to a kind of method for preparing described mix refrigerant.The invention still further relates to a kind of purposes of described mix refrigerant.
Background technology
The single-stage compression Refrigeration Technique is a most widely used technology of civilian refrigerating field, as central air-conditioning in the refrigerator in the household electrical appliance, air-conditioning and the office buildings etc.Along with the development of social production life, more and more for the demand of lower refrigeration temperature (as-40 ℃ of warm areas), as the activity of biomaterial store, the quick-freeze low-temperature of food is fresh-keeping etc.In general, because the restriction of compressor, must make the refrigeration work material when evaporation and condensing temperature differ greatly, can also satisfy the requirement that evaporating pressure is only low, condensing pressure is not too high, minimum effective refrigeration temperature of single stage compressive refrigerating system can only reach about-40 ℃, and the performance of this class refrigeration equipment depends on the characteristic of operation material to a great extent.
Be usually used in-40 ℃ of operation materials in the warm area single stage compressive refrigerating system in the past and mainly contain R502, R22 etc.Wherein R502 is by R22 (CHClF 2) and R115 (CClF 2CF 3) with the azeotropic operation material that the mass ratio of 48.8/51.2 is formed, atmospheric boiling point is-45.3 ℃, because two constituent element all contains the chlorine atom, therefore has very high ozone layer destroying effect.R22 (CHClF 2) atmospheric boiling point be-40.8 ℃, the theoretical efficiency of this operation material is higher, but excessive discharge temperature when it is applied to-40 ℃ of working conditions, be unfavorable for the long-time running of compressor, therefore this operation material generally only uses in the air-conditioning system of higher warm area, and, belong to the refrigeration agent that " Montreal Protocol book " middle quilt of stipulating is progressively eliminated because it has certain ozone layer destroying effect.The main substitute R404A of R502 is by R125 (CHF 2CF 3), R143a (CH 3CF 3) and R134a (CH 2FCF 3) with the zeotrope that 44/52/4 mass ratio is formed, atmospheric boiling point be-46.6 ℃, its maximum characteristics are not flammable and do not contain the depletion of the ozone layer material, but it is bigger to steep dew-point temperature, and operation material efficient is not high.
The mix refrigerant of a series of alternative R502 and R22 is disclosed among the international monopoly WO2006038766, be characterized in around HFC class operation material R134a (1,1,1, the 2-Tetrafluoroethane), R152a (1, the 1-C2H4F2 C2H4F2) and HC class operation material R290 (propane), R1270 (third is rare), R600a (Trimethylmethane), and combinations of substances such as dme multiple mix refrigerant.Because R152a, R290, R1270, R600a and dme all are combustiblesubstances, the mixture that these several materials are formed has stronger combustibility; Though the interpolation of R134a has suppressed its combustibility to a certain extent, it is very low that the R134a operation material is applied to-40 ℃ of its intrinsic conversion efficiencies of warm area, and the multicomponent mixture of forming is non-azeotropic operation material, has bigger bubble dew-point temperature.
U.S. Pat 6843930 discloses a series of azeotropic mixture that is applied to high back pressure working condition (air conditioning condition), and its technical field and this patent have certain difference.The nucleus of this patent also is made up of R152a and R290, suppresses its combustibility by adding CF3I or carbonic acid gas.Equally, because that CF3I or carbonic acid gas are used for the efficient of-40 ℃ of warm areas is lower, so multicomponent mixture efficient descends to some extent.
The R134 that this patent relates to (1,1,2, the 2-Tetrafluoroethane) is a kind of HFC class refrigeration work material that emerges recently, and it belongs to the isomer of R134a (1,1,1, the 2-Tetrafluoroethane), promptly has identical molecular formula with R134a, but the molecular structure difference.R134 is not flammable, and is low more about 30% than the Global warming of R134a value (GWP) coefficient of diving, and intrinsic conversion efficiency is higher than R134a, is a kind of very potential alternative refrigerant.The ternary near-azeotrope refrigerant that comprises R134, R152a, R290 that this patent proposes not only can suppress the combustibility of R152a and R290 largely, and refrigerating efficiency will have raising by a relatively large margin.
International monopoly WO9715637 discloses multiple frigorific mixture combination, according to the content of its claim, can form the R134 identical with this patent, R152a, R290 tertiary mixture, and described according to its claim 3, the concentration of its R134 is up to 40~95%.According to the phase equilibrium of admixture analysis, the temperature glide of R134+R152a+R290 mixture (bubble dew-point temperature) increases along with the increase of R134 ratio, and the refrigerating efficiency of mixture is also along with reduction.This patent is based on accurate Phase Equilibrium Calculation and analysis of refrigeration cycle, and the R134 concentration range of proposition will form superior azeotropic/nearly azeotropic working medium, therefore have bigger superiority than WO9715637.
International monopoly WO9417153 discloses class frigorific mixture combination, it is made up of the low boiling working fluid of plurality of optional and the high boiling point working medium of plurality of optional, though the described R290 of this patent is in its optional low boiling working fluid, described R134, R152a are in its optional high boiling point working medium, but summary of the invention and claim according to WO9417153 are described, and the boiling point of its low boiling component and high boiling component differs 20 ℃ at least.And the boiling point of R290 is-42.2 ℃, the boiling point of R134 is-23 ℃, the boiling point of R152a is-24 ℃, and (pure prime number is according to drawing from " refrigeration agent service manual ", and Cao Desheng, Shi Lin write, Beijing, metallurgical industry press, 2003), 20 ℃ of the equal less thaies of boiling-point difference are if illustrate that promptly low boiling working fluid is selected R290 in WO9417153, then high boiling point working medium can not be selected R134, R152a, therefore can't form the described R134+R152a+R290 mixture of this patent.
Summary of the invention
The object of the present invention is to provide a kind of complete ozone free damage layer, freezer compartment effect, be used for single stage compressive refrigerating system, near-azeotrope refrigerant with greater efficiency.The present invention also aims to provide a kind of method for preparing described mix refrigerant, and the purposes that a kind of described mix refrigerant is provided.
At the foregoing invention purpose, the invention provides following technical scheme:
On the one hand, the invention provides a kind of mix refrigerant, it is by 1,1,2,2-Tetrafluoroethane, 1, the tertiary mixture that three kinds of materials of 1-C2H4F2 C2H4F2 and propane are formed, the mass percent concentration sum of each component is 100% in the described mix refrigerant, wherein, described 1,1,2, the mass percent concentration of 2-Tetrafluoroethane is 1%~20%, 1, the mass percent concentration of 1-C2H4F2 C2H4F2 is 1%~50%, and the mass percent concentration of propane is 30%~90%.
Preferably, described 1,1,2 in the described mix refrigerant, the mass percent concentration of 2-Tetrafluoroethane is 1%~15%, 1, and the mass percent concentration of 1-C2H4F2 C2H4F2 is 10%~40%, and the mass percent concentration of propane is 45%~80%.
Preferably, described 1,1,2, the mass concentration of 2-Tetrafluoroethane is 1%~10%, 1, and the mass concentration of 1-C2H4F2 C2H4F2 is 20%~40%, and the mass concentration of propane is 50%~75%.
Preferably, described 1,1,2 in the described mix refrigerant, the mass concentration of 2-Tetrafluoroethane is 5%, 1, and the mass concentration of 1-C2H4F2 C2H4F2 is 25%, and the mass concentration of propane is 70%.
Preferably, each component is made through physical mixed in the described mix refrigerant.
Preferably, this refrigeration agent can be only by 1,1,2, the 2-Tetrafluoroethane, and 1, three kinds of materials of 1-C2H4F2 C2H4F2 and propane are formed.
As mentioned above, describedly comprise 1,1,2,2-Tetrafluoroethane, 1, the mix refrigerant of 1-C2H4F2 C2H4F2 and propane exists optimizes concentration proportioning: each constituent mass concentration sum is 100% in the mix refrigerant, described 1,1,2, the mass concentration of 2-Tetrafluoroethane is 1%~15%, described 1, the mass concentration of 1-C2H4F2 C2H4F2 is 10%~40%, and the mass concentration of propane is 45%~80%.The foundation of this optimization concentration mainly is the circulation thermal performance, i.e. COP numerical value, take all factors into consideration the behavior that balances each other of mixture in addition and dissolve each other with lubricating oil after change in concentration problem etc.
Above-mentionedly comprise 1,1,2, the 2-Tetrafluoroethane, 1, also there is optimum concentration range in the mix refrigerant of 1-C2H4F2 C2H4F2 and propane: each constituent mass concentration sum is 100% in the mix refrigerant, described 1,1,2, the mass concentration of 2-Tetrafluoroethane is 1%~10%, described 1, the mass concentration of 1-C2H4F2 C2H4F2 is 20%~40%, and the mass concentration of propane is 50%~75%.
On the other hand, the invention provides a kind of method for preparing described mix refrigerant, described method comprises, with 1,1,2, and 2-Tetrafluoroethane, 1, the physical mixed preparation at normal temperatures of three kinds of materials of 1-C2H4F2 C2H4F2 and propane.
Another aspect the invention provides a kind of described mix refrigerant is used for clicking the near-azeotrope refrigerant of compression refrigerating system in preparation purposes.
The technique effect that the present invention obtains is:
Mix refrigerant of the present invention has the nearly azeotropic feature that balances each other, adopt the temperature glide of this mixture in certain pressure range of nearly azeotropic proportioning very little, its thermodynamic behavior is equivalent to a pure operation material, and its efficiency of thermal cycle is in the very high scope.
The near azeotropic mixed refrigerant that is applicable to single stage compressive refrigerating system that the present invention proposes has following plurality of advantages: the latent value ODP of its ozone depletion is zero, and life-time service can not cause damage to atmospheric ozone layer.Owing to contain nature operation material propane (R290), mix refrigerant Global warming provided by the present invention is dived, and GWP is less for value.Another one advantage of the present invention is that nearly azeotropic refrigeration work material has very little bubble dew-point temperature, therefore can keep stable evaporation working condition, and is that filling with the maintenance of refrigeration system of refrigeration agent provided convenience.In addition, this hybrid working material has less pressure ratio, the reducing of pressure ratio can effectively be improved compressor efficiency, especially the raising of evaporating pressure, make refrigerator be in operation and avoid system under vacuum, to move, under the situation of identical compressor free air delivery, actual refrigerating duty obtains increasing in addition.In addition, therefore mix refrigerant provided by the present invention has higher security owing to contain noncombustibles matter R134.
Embodiment
Further specify detailed content of the present invention and relevant effect thereof below in conjunction with embodiment, but should be understood that these embodiment only are for illustrating the present invention, and not in office where face constitutes limitation of the scope of the invention.
Embodiment 1: get mass concentration and be 1% 1,1,2, the 2-Tetrafluoroethane, mass concentration be 50% 1, the propane of 1-C2H4F2 C2H4F2 and mass concentration 49% is physical mixed at normal temperatures, obtains a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 2: get mass concentration and be 20% 1,1,2, the 2-Tetrafluoroethane, mass concentration be 50% 1, the propane of 1-C2H4F2 C2H4F2 and mass concentration 30% is physical mixed at normal temperatures, obtains a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 3: get mass concentration and be 9% 1,1,2, the 2-Tetrafluoroethane, mass concentration be 1% 1, the propane of 1-C2H4F2 C2H4F2 and mass concentration 90% is physical mixed at normal temperatures, obtains a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 4: get mass concentration and be 1% 1,1,2, the 2-Tetrafluoroethane, mass concentration be 40% 1, the propane of 1-C2H4F2 C2H4F2 and mass concentration 59% is physical mixed at normal temperatures, obtains a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 5: get mass concentration and be 10% 1,1,2, the 2-Tetrafluoroethane, mass concentration be 10% 1, the propane of 1-C2H4F2 C2H4F2 and mass concentration 80% is physical mixed at normal temperatures, obtains a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 6: get mass concentration and be 15% 1,1,2, the 2-Tetrafluoroethane, mass concentration be 40% 1, the propane of 1-C2H4F2 C2H4F2 and mass concentration 45% is physical mixed at normal temperatures, obtains a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 7: get mass concentration and be 10% 1,1,2, the 2-Tetrafluoroethane, mass concentration be 40% 1, the propane of 1-C2H4F2 C2H4F2 and mass concentration 50% is physical mixed at normal temperatures, obtains a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 8: get mass concentration and be 5% 1,1,2, the 2-Tetrafluoroethane, mass concentration be 20% 1, the propane of 1-C2H4F2 C2H4F2 and mass concentration 75% is physical mixed at normal temperatures, obtains a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 9: get mass concentration and be 1% 1,1,2, the 2-Tetrafluoroethane, mass concentration be 30% 1, the propane of 1-C2H4F2 C2H4F2 and mass concentration 69% is physical mixed at normal temperatures, obtains a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 10: get mass concentration and be 2% 1,1,2, the 2-Tetrafluoroethane, mass concentration be 30% 1, the propane of 1-C2H4F2 C2H4F2 and mass concentration 68% is physical mixed at normal temperatures, obtains a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 11: get mass concentration and be 5% 1,1,2, the 2-Tetrafluoroethane, mass concentration be 25% 1, the propane of 1-C2H4F2 C2H4F2 and mass concentration 70% is physical mixed at normal temperatures, obtains a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Below table 1 and table 2 good and bad contrast of performance that specifically shown mix refrigerant of the present invention and existing refrigeration agent, wherein to represent the concentration proportioning of R134/R152a/R290 among the international monopoly WO9715637 be 40/10/50 mixture to WO9715637.
According to ARI 540 LBP of U.S. air conditioner refrigerating institute 3 standards, determine that the design effort situation is a vaporization temperature-40 ℃, 4.4 ℃ of suction temperatures, 40.6 ℃ of condensing temperatures, 0 ℃ of condensate depression.According to cycle calculations, the cycle performance parameter of above-mentioned 11 embodiment and the results are shown in the following table 1 with the performance comparison of existing refrigeration agent, wherein refrigerating duty and relative efficiency all are to be the correlative value of benchmark with R502 relatively.
Table 1: the mix refrigerant performance gathers and compares with existing refrigerant performance among the embodiment
Embodiment Pressure ratio Exhaust temperature ℃ Relative volume refrigerating capacity compressor Relative efficiency
1 14.96 108.9 0.863 1.035
2 19.36 117.12 0.684 0.966
3 12.81 99.15 0.942 1.057
Embodiment Pressure ratio Exhaust temperature ℃ Relative volume refrigerating capacity compressor Relative efficiency
4 13.37 104.03 0.952 1.065
5 12.82 99.87 0.962 1.053
6 15.53 108.72 0.837 1.005
7 14.52 106.6 0.888 1.030
8 12.76 100.63 0.973 1.065
9 12.82 101.73 0.977 1.073
10 12.84 101.76 0.977 1.071
11 12.80 101.15 0.978 1.066
WO9715637 13.07 99.2 0.986 1.008
R502 13.29 101.11 1.0 1.0
R404A 14.17 95.17 0.921 0.887
R22 14.79 138.02 1.086 1.170
More than be based on the Theoretical Calculation result of standard operation situation.The refrigeration agent that is in the optimum concentration range of embodiment 8 to embodiment 11 representatives is higher than R502 and existing alternative operation material R404A thereof on refrigerating efficiency, volume refrigerating capacity compressor is a little less than R502.In actual moving process, the pressure ratio of considering refrigeration work material provided by the invention reduces and the raising of the compressor efficiency that brings, and good phase-change heat transfer performance, therefore the actual efficiency of refrigeration work material provided by the invention should with suitable (the R22 excessive discharge temperature of R22, can not be used for-40 ℃ of actual commercial refrigeration), be a kind of very excellent alternative refrigerant.
The described refrigeration agent of contrast WO9715637, from theoretical analysis, it is excessive to cause steeping dew-point temperature owing to its R134 concentration is higher, so pressure ratio increases and refrigerating efficiency decline is obvious, forms far below refrigeration agent of the present invention.
The mix refrigerant that is applicable to single stage compressive refrigerating system that the present invention proposes has good environmental protection characteristic, and following table 2 has provided embodiment 11 and dived value GWP relatively with latent value ODP of existing refrigeration agent ozone depletion and Global warming.The mixed refrigerant of the present invention's proposition has reduced the GWP value greatly as can be seen, has better environmental protection characteristic than the described working medium of WO9715637.
Table 2: embodiment 11 dives value GWP relatively with existing refrigeration agent ozone depletion latent value ODP and Global warming
Figure G2008100945551D00071
Figure G2008100945551D00081
* existing refrigeration agent and pure prime number are according to drawing from " refrigeration agent service manual ", and Cao Desheng, Shi Lin write, Beijing, metallurgical industry press, 2003;
* according to pure component ODP value according to mass concentration weighted calculation gained.

Claims (4)

1. a mix refrigerant is characterized in that, described refrigeration agent is by 1,1,2,2-Tetrafluoroethane, 1, the tertiary mixture that three kinds of materials of 1-C2H4F2 C2H4F2 and propane are formed, the mass percent concentration sum of each component is 100% in the described mix refrigerant, wherein, described 1,1,2, the mass percent concentration of 2-Tetrafluoroethane is 1%~20%, 1, the mass percent concentration of 1-C2H4F2 C2H4F2 is 1%~50%, and the mass percent concentration of propane is 30%~90%.
2. mix refrigerant according to claim 1, it is characterized in that: in the described mix refrigerant, described 1,1,2, the mass percent concentration of 2-Tetrafluoroethane is 1%~15%, 1, the mass percent concentration of 1-C2H4F2 C2H4F2 is 10%~40%, and the mass percent concentration of propane is 45%~80%.
3. mix refrigerant according to claim 1 and 2 is characterized in that: in the described mix refrigerant, and described 1,1,2, the mass concentration of 2-Tetrafluoroethane is 1%~10%, 1, the mass concentration of 1-C2H4F2 C2H4F2 is 20%~40%, and the mass concentration of propane is 50%~75%.
4. according to each described mix refrigerant among the claim 1-3, it is characterized in that: in the described mix refrigerant, described 1,1,2, the mass concentration of 2-Tetrafluoroethane is 5%, 1, the mass concentration of 1-C2H4F2 C2H4F2 is 25%, and the mass concentration of propane is 70%.
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CN102766438B (en) * 2010-04-06 2014-11-12 中国科学院理化技术研究所 Mixed refrigerant containing trifluoroiodomethane
CN102994052B (en) * 2012-11-30 2015-09-09 徐超 A kind of air-conditioning refrigeration agent
CN106281231B (en) * 2016-07-18 2019-02-12 合肥凯利光电科技有限公司 Refrigerant used in the detection of digestive tract power detector job stability
CN106967388A (en) * 2017-03-06 2017-07-21 唐建 A kind of environment-protecting mixed refrigerating agent preparation method for substituting monochlorodifluoromethane
CN115287042A (en) * 2022-07-21 2022-11-04 北京大学南昌创新研究院 Mixed refrigerant replacing R404A and preparation method thereof

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WO2006038766A1 (en) * 2004-08-25 2006-04-13 Yoon-Sik Ham R502, r12 or r22 substitute mixed refrigerant and refrigeration system using thereof

Non-Patent Citations (3)

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Title
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Assignee: ZHONGKE MEILING CRYOGENICS Ltd.

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Contract record no.: 2011340000237

Denomination of invention: Mixed refrigerant

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Address before: 100190 No. 2, north of Haidian District, Beijing, Zhongguancun

Patentee before: Technical Institute of Physics and Chemistry Chinese Academy of Sciences