CN101275067B - Ternary near-azeotrope refrigerant - Google Patents
Ternary near-azeotrope refrigerant Download PDFInfo
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- CN101275067B CN101275067B CN2008100973937A CN200810097393A CN101275067B CN 101275067 B CN101275067 B CN 101275067B CN 2008100973937 A CN2008100973937 A CN 2008100973937A CN 200810097393 A CN200810097393 A CN 200810097393A CN 101275067 B CN101275067 B CN 101275067B
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- molar percentage
- percentage concentration
- dme
- propane
- mix refrigerant
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Abstract
The present invention provides a ternary near-azeotropic refrigerant, including a ternary mixture composed of 1, 1, 2, 2-tetrafluoro thane, dimethyl ether and propane, wherein the molar percentage of 1, 1, 2, 2-tetrafluoro thane is 1%-20%, the molar percentage of dimethyl ether is 1-40%, the molar percentage of propane is 40-90%. The invention also provides a method of preparing the mixing refrigerant. The invention further provides a use of the mixing refrigerant. The mixing refrigerant is fit for a single-stage com-pression refrigeration system, substituting the traditional R502 and R22, having higher efficiency and less pressure ratio, having lower flammability; the ODP is zero, the GWP is less than the GWP of R502 and R404A.
Description
Technical field
The invention belongs to refrigerant art.The present invention relates to a kind of mix refrigerant, particularly a kind of efficient, environmental protection, can be used for substituting the mix refrigerant of traditional R502, R22 operation material.The invention still further relates to a kind of method for preparing described mix refrigerant.The present invention relates to a kind of purposes of described mix refrigerant in addition.
Background technology
The refrigeration equipment of-40 ℃ of warm areas is being brought into play increasing effect at commercial refrigerating field.For example, the biological activity of medical field stores, and the deep cooling of sea going fisheries is fresh-keeping, and the cryogenic quick-freezing chamber of high end home refrigerator etc., all need to obtain-40 ℃ even lower refrigeration temperature, this also is minimum effective refrigeration temperature that single stage compressive refrigerating system can reach.
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 high back pressure, 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.
International monopoly WO2006038766 discloses the mix refrigerant of a series of alternative R502 and R22, 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 dme 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.
R134 (1,1,2, the 2-Tetrafluoroethane) is a kind of HFC class refrigeration work material that newly emerges, 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.Dme (DME) molecular formula is CH
3OCH
3, atmospheric boiling point-24.8 ℃ experimental results show that its refrigerating efficiency under the refrigerator work situation is suitable with R134a, its atmospheric lifetime is 0.015, so the GWP coefficient is about 1 only, is the very high operation material of a kind of environmental-protecting performance.It is the very high operation material of a kind of intrinsic conversion efficiency that propane (R290) uses at-40 ℃ of warm areas, still owing to the combustibility of alkane, is filled in the refrigeration equipment seldom separately and uses.Because R290 and DME can form positive azeotrope, use the refrigeration performance of the pure operation material of raising that can be by a relatively large margin at-40 ℃ of warm areas.This patent proposes R134 is added into the ternary near-azeotrope refrigerant of forming among the R290+DME, not only has higher refrigerating efficiency, and has suppressed the combustibility of DME and R290 largely, is the refrigeration agent of a kind of efficient, environmental protection, safety.
International monopoly WO9715637 discloses multiple frigorific mixture combination, described by its claim 2, might be combined into the R134 identical with this patent, DME, R290 tertiary mixture, but described according to its claim 3, the concentration of the R134 that it may contain is up to 40～95%.According to the phase equilibrium of admixture analysis, the temperature glide of R134+DME+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 more superior azeotropic/nearly azeotropic working medium, therefore have bigger superiority than WO9715637.
Summary of the invention
The object of the present invention is to provide a kind of complete ozone free damage layer, freezer compartment effect, alternative traditional R502, R22 operation material, 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:
The invention provides a kind of mix refrigerant, described refrigeration agent is by 1,1,2, the tertiary mixture that 2-Tetrafluoroethane, dme and three kinds of materials of propane are formed, each component molar percentage concentration sum is 100% in the described mix refrigerant, wherein, described 1,1,2, the molar percentage concentration of 2-Tetrafluoroethane is 1%～20%, the molar percentage concentration of dme is 1%～40%, and the molar percentage concentration of propane is 40%～90%.
Preferably, described 1,1,2, the molar percentage concentration of 2-Tetrafluoroethane is 1%～15%, and the molar percentage concentration of dme is 5%～30%, and the molar percentage concentration of propane is 55%～80%.
Preferably, described 1,1,2, the molar percentage concentration of 2-Tetrafluoroethane is 1%～10%, and the molar percentage concentration of dme is 10%～25%, and the molar percentage concentration of propane is 65%～80%.
Preferably, described 1,1,2, the molar percentage concentration of 2-Tetrafluoroethane is 5%, and the molar percentage concentration of dme is 20%, and the molar percentage concentration of propane is 75%.
Preferably, each component is made through physical mixed in the described mix refrigerant.
Preferably, described mix refrigerant can be only by 1,1,2, and 2-Tetrafluoroethane, dme and three kinds of materials of propane are formed.
As mentioned above, this comprises 1,1,2, the 2-Tetrafluoroethane, the mix refrigerant of dme and propane exists optimizes concentration proportioning: each component molar percentage concentration sum is 100% in the mix refrigerant, described 1,1,2, the molar percentage concentration of 2-Tetrafluoroethane is 1%～15%, and the molar percentage concentration of described dme is 5%～30%, and the molar percentage concentration of propane is 55%～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, also there is optimum concentration range in the mix refrigerant of dme and propane: each component molar percentage concentration sum is 100% in the mix refrigerant, described 1,1,2, the molar percentage concentration of 2-Tetrafluoroethane is 1%～10%, the molar percentage concentration of described dme is 10%～25%, and the molar percentage concentration of propane is 65%～80%.
This mix refrigerant has the nearly azeotropic feature that balances each other, and adopts the temperature glide of this mixture in certain pressure range of nearly azeotropic proportioning very little, and its thermodynamic behavior is equivalent to a pure operation material, and its efficiency of thermal cycle is in the very high scope.
On the other hand, the present invention also provides a kind of method for preparing described mix refrigerant, and described method comprises that with 1,1,2,2-Tetrafluoroethane, three kinds of materials of dme and propane physical mixed at normal temperatures prepare.
Another aspect, the present invention also provides a kind of described mix refrigerant to be used for the purposes of the near-azeotrope refrigerant of single stage compressive refrigerating system in preparation.
The technique effect that mix refrigerant of the present invention produces is:
The near azeotropic mixed refrigerant of single stage compressive refrigerating system that is applicable to provided by the invention 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 propane and dme, mix refrigerant Global warming provided by the present invention is dived, and GWP is very little 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, and the reducing of pressure ratio can effectively be improved compressor efficiency.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 molar percentage concentration and be 1% 1,1,2, the 2-Tetrafluoroethane, molar percentage concentration is the propane physical mixed at normal temperatures of 40% dme and molar percentage concentration 59%, obtains a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 2: get molar percentage concentration and be 20% 1,1,2, the 2-Tetrafluoroethane, molar percentage concentration is the propane physical mixed at normal temperatures of 40% dme and molar percentage concentration 40%, obtains a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 3: get molar percentage concentration and be 9% 1,1,2, the 2-Tetrafluoroethane, molar percentage concentration is the propane physical mixed at normal temperatures of 1% dme and molar percentage concentration 90%, obtains a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 4: get molar percentage concentration and be 1% 1,1,2, the 2-Tetrafluoroethane, molar percentage concentration is the propane physical mixed at normal temperatures of 30% dme and molar percentage concentration 69%, obtains a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 5: get molar percentage concentration and be 15% 1,1,2, the 2-Tetrafluoroethane, molar percentage concentration is the propane physical mixed at normal temperatures of 5% dme and molar percentage concentration 80%, obtains a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 6: get molar percentage concentration and be 15% 1,1,2, the 2-Tetrafluoroethane, molar percentage concentration is the propane physical mixed at normal temperatures of 30% dme and molar percentage concentration 55%, obtains a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 7: get molar percentage concentration and be 1% 1,1,2, the 2-Tetrafluoroethane, molar percentage concentration is the propane physical mixed at normal temperatures of 25% dme and molar percentage concentration 74%, obtains a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 8: get molar percentage concentration and be 10% 1,1,2, the 2-Tetrafluoroethane, molar percentage concentration is the propane physical mixed at normal temperatures of 10% dme and molar percentage concentration 80%, obtains a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 9: get molar percentage concentration and be 10% 1,1,2, the 2-Tetrafluoroethane, molar percentage concentration is the propane physical mixed at normal temperatures of 25% dme and molar percentage concentration 65%, obtains a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 10: get molar percentage concentration and be 5% 1,1,2, the 2-Tetrafluoroethane, molar percentage concentration is the propane physical mixed at normal temperatures of 20% dme and molar percentage concentration 75%, obtains a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
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 10 embodiment and the results are shown in the following table 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.
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/DME/R290 among the international monopoly WO9715637 be 40/10/50 mixture to WO9715637.
Table 1: among the embodiment mix refrigerant performance gather and with existing refrigerant performance comparison sheet
| Embodiment | Pressure ratio | Exhaust temperature ℃ | Relative volume refrigerating capacity compressor | Relative efficiency |
| 1 | 14.65 | 108.20 | 0.840 | 1.087 |
| 2 | 17.27 | 113.46 | 0.727 | 1.038 |
| 3 | 12.79 | 99.42 | 0.946 | 1.067 |
| 4 | 13.59 | 104.52 | 0.898 | 1.096 |
| 5 | 12.91 | 99.94 | 0.956 | 1.058 |
| 6 | 14.77 | 107.01 | 0.845 | 1.060 |
| 7 | 13.22 | 103.06 | 0.919 | 1.010 |
| 8 | 12.88 | 100.47 | 0.950 | 1.075 |
| 9 | 13.68 | 103.99 | 0.904 | 1.079 |
| 10 | 13.09 | 102.12 | 0.932 | 1.091 |
| Embodiment | Pressure ratio | Exhaust temperature ℃ | Relative volume refrigerating capacity compressor | Relative efficiency |
| WO9715637 | 13.07 | 99.20 | 0.986 | 1.008 |
| R502 | 13.20 | 100.71 | 1.0 | 1.0 |
| R404A | 14.17 | 95.16 | 0.921 | 0.890 |
| R22 | 14.79 | 138.02 | 1.086 | 1.175 |
More than be based on the Theoretical Calculation result of standard operation situation.Be in each embodiment of optimizing in the concentration range on refrigerating efficiency far above R502 and existing alternative operation material R404A thereof, volume refrigerating capacity compressor and R502 are suitable.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 mix refrigerant that is applicable to single stage compressive refrigerating system that the present invention proposes has good environmental protection characteristic, and following table has provided embodiment 10 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.
Table 2: embodiment 12 dives value GWP relatively with existing refrigeration agent ozone depletion latent value ODP and Global warming
* existing refrigeration agent and pure prime number are according to drawing from " refrigeration agent service manual, 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, the tertiary mixture that 2-Tetrafluoroethane, dme and three kinds of materials of propane are formed, it is characterized in that: each component molar percentage concentration sum is 100% in the described mix refrigerant, wherein, described 1,1,2, the molar percentage concentration of 2-Tetrafluoroethane is 1%～20%, and the molar percentage concentration of dme is 1%～40%, and the molar percentage concentration of propane is 40%～90%.
2. mix refrigerant according to claim 1 is characterized in that: wherein, and described 1,1,2, the molar percentage concentration of 2-Tetrafluoroethane is 1%～15%, the molar percentage concentration of dme is 5%～30%, and the molar percentage concentration of propane is 55%～80%.
3. mix refrigerant according to claim 1 and 2 is characterized in that: wherein, and described 1,1,2, the molar percentage concentration of 2-Tetrafluoroethane is 1%～10%, the molar percentage concentration of dme is 10%～25%, and the molar percentage concentration of propane is 65%～80%.
4. mix refrigerant according to claim 1 and 2 is characterized in that: described 1,1,2, the molar percentage concentration of 2-Tetrafluoroethane is 5%, and the molar percentage concentration of dme is 20%, and the molar percentage concentration of propane is 75%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100973937A CN101275067B (en) | 2007-08-17 | 2008-05-14 | Ternary near-azeotrope refrigerant |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710120437.9 | 2007-08-17 | ||
| CN200710120437 | 2007-08-17 | ||
| CN2008100973937A CN101275067B (en) | 2007-08-17 | 2008-05-14 | Ternary near-azeotrope refrigerant |
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| Publication Number | Publication Date |
|---|---|
| CN101275067A CN101275067A (en) | 2008-10-01 |
| CN101275067B true CN101275067B (en) | 2010-06-09 |
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| CN103965836B (en) * | 2014-04-02 | 2017-04-19 | 浙江大学 | Environment-friendly refrigerant for automobile air conditioner and preparation method of refrigerant |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006038766A1 (en) * | 2004-08-25 | 2006-04-13 | Yoon-Sik Ham | R502, r12 or r22 substitute mixed refrigerant and refrigeration system using thereof |
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2008
- 2008-05-14 CN CN2008100973937A patent/CN101275067B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (4)
| Title |
|---|
| 吴兆立.《新型制冷剂R134、R134-R134a及R134-R22的热力学性质》.高校化学工程学报第11卷 第3期.1997,第11卷(第3期),238-243. |
| 宋锡瑾 |
| 宋锡瑾;张未星;吴兆立.《新型制冷剂R134、R134-R134a及R134-R22的热力学性质》.高校化学工程学报第11卷 第3期.1997,第11卷(第3期),238-243. * |
| 张未星 |
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