CN101235274A - Ternary near azeotropy mixture refrigerant adapted for single-stage compression refrigerating system - Google Patents
Ternary near azeotropy mixture refrigerant adapted for single-stage compression refrigerating system Download PDFInfo
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- CN101235274A CN101235274A CNA2007100635457A CN200710063545A CN101235274A CN 101235274 A CN101235274 A CN 101235274A CN A2007100635457 A CNA2007100635457 A CN A2007100635457A CN 200710063545 A CN200710063545 A CN 200710063545A CN 101235274 A CN101235274 A CN 101235274A
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Abstract
The invention relates to environment-friendly near-azeotropic mixture refrigerant which is suitable to use on a single-stage compression refrigerating system, which is prepared through conducting physical mixture for 1, 1, 1, 2- tetrafluoro ethane, 1, 1-difluoroethane and isobutene, wherein the molar concentration of 1, 1, 1, 2- tetrafluoro ethane is 2%-47%, the molar concentration of 1, 1-difluoroethane is 35%-80%, and the molar concentration of isobutene is 18%-63%. The mixture refrigerant has smaller temperature glide and excellent lubricating oil dissolving property, can directly replace R12 working medium without making large modification in the refrigerating system, wherein ODP is zero, and GWP is far smaller than conventional HFC working medium.
Description
Technical field
The present invention relates to a kind of mix refrigerant, particularly a kind of ternary near azeotropic mixed refrigerant that is applicable to single stage compressive refrigerating system of environment-friendly type.
Background technology
Single stage compressive refrigerating system is widely used in fields such as family expenses refrigerator, air-conditionings, and is of close concern to each other with people's the modern life.But along with the enhancing of social enviroment protection consciousness and the requirement of energy saving, the exploitation of " green working medium " has become a big important topic of refrigeration industry to efficiently.
Past the most frequently used refrigeration working medium in refrigerator refrigeration system is R12 (methyl chlorofluoride, CF
2Cl
2), though that it has toxicity is little, not flammable, non-explosive, overall merits such as intrinsic conversion efficiency height, it has higher ODP and GWP coefficient, therefore is put among the working medium of at first eliminating.In existing refrigerator system, the refrigeration working medium that is most commonly used to substitute R12 mainly contain R134a (1,1,1,2-Tetrafluoroethane, CH
2FCF
3) and R600a (Trimethylmethane, i-C
4H
10) these two kinds of pure working medium.Compare with R12, R134a has better transport property and higher gas and heat of liquid conductance, and exhaust temperature is lower slightly.But R134a is immiscible with conventional mineral oil, and R134a refrigerating effect per unit swept volume and refrigerating efficiency be all not as good as R12, and pressure ratio is higher than R12, so also is unfavorable for the efficient operation of compressor.Though and another kind substitutes working medium R600a refrigerating efficiency a little more than R12, its pressure ratio is higher equally, and refrigerating effect per unit swept volume is much smaller than R12.In addition, the R600a boiling point is higher, and in most of the cases, the R600a in the vaporizer is in negative pressure state, and materials such as entrained air and water vapour cause the decline of system performance easily.
From substituting the research situation of working medium, the selection of working medium mainly concentrates on pure substance and binary mixture aspect, and the above multicomponent mixture of ternary also compares rarely, and major cause is the shortcoming of the rerum natura research of multicomponent mixture.Because the azeotropic mixture more than the ternary is quite rare, therefore, the less nearly azeotropic mixture of bubble dew-point temperature also is a pretty good selection.Polynary azeotropic/nearly azeotropic mixture has some tangible advantages: 1, near azeotropic/nearly azeotropic working medium temperature glide its azeotropic district is less, has with the similar character of pure working medium, is easy to obtain stable evaporation operating mode; 2, its back pressure is higher than the pure working medium of its single component under same vaporization temperature, so has higher refrigerating effect per unit swept volume; 3, avoid the change in concentration of non-azeotropic working medium in full cycle, therefore can keep the stability and the reliability of refrigeration cycle; 4, the pure working medium than its single component has higher phase-change heat transfer coefficient near azeotropic point; 5, the mixture that has added alkane has better lubricating oil dissolving properties.As seen, the above azeotropic/nearly azeotropic mixture of ternary has great potential in alternative working medium research.
Summary of the invention
What the object of the present invention is to provide a kind of environmental protection has good mutual solubility with lubricating oil, is used for the ternary near-azeotrope refrigerant of single stage compressive refrigerating system.
Technical scheme of the present invention is as follows:
The ternary near-azeotrope refrigerant that is applicable in the single stage compressive refrigerating system provided by the invention comprises through 1,1,1 of physical mixed, 2-Tetrafluoroethane (CH
2FCF
3Be R134a), 1,1-C2H4F2 C2H4F2 (CHF
2CH
3Be R152a) and Trimethylmethane (i-C
4H
10Be R600a);
Each component volumetric molar concentration sum is 100% in the described mix refrigerant, and wherein described 1,1,1, the volumetric molar concentration of 2-Tetrafluoroethane is 2%～47%, 1, and the volumetric molar concentration of 1-C2H4F2 C2H4F2 is 35%～80%, and the volumetric molar concentration of Trimethylmethane is 18%～63%.
Above-mentionedly comprise 1,1,1, the 2-Tetrafluoroethane, 1, the mix refrigerant of 1-C2H4F2 C2H4F2 and Trimethylmethane exists optimizes concentration proportioning: each component volumetric molar concentration sum is 100% in the mix refrigerant, wherein 1,1,1, the volumetric molar concentration of 2-Tetrafluoroethane is 4%～40%, 1,1-C2H4F2 C2H4F2 volumetric molar concentration is 40%～60%, and the volumetric molar concentration of Trimethylmethane is 20%～56%; The foundation of this optimization concentration mainly is the circulation thermal performance, i.e. COP numerical value is taken all factors into consideration the problems such as heat transfer in the behavior that balances each other, temperature glide and the azeotropic interval of mixture in addition.
Above-mentionedly comprise 1,1,1, the 2-Tetrafluoroethane, 1, also there is optimum concentration range in the mix refrigerant of 1-C2H4F2 C2H4F2 and Trimethylmethane: each component volumetric molar concentration sum is 100% in the mix refrigerant, wherein 1,1,1, the volumetric molar concentration of 2-Tetrafluoroethane is 5.4%～26.5%, 1,1-C2H4F2 C2H4F2 volumetric molar concentration is 49.5%～72.5%, and the volumetric molar concentration of Trimethylmethane is 22.1%～33.1%.
This mix refrigerant has the nearly azeotropic feature that balances each other, wherein the nearly azeotropic concentration interval under 101kPa is: 1,1,1, the volumetric molar concentration of 2-Tetrafluoroethane is 5.4%～11.5%, and 1, the volumetric molar concentration of 1-C2H4F2 C2H4F2 is 55.4%～62.3%, Trimethylmethane is 32.3%～33.1%, and corresponding bubble point temperature is 244.89～245.21K (27.62～-28.26 ℃); Nearly azeotropic concentration interval under 1500kPa is: 1,1,1, the volumetric molar concentration of 2-Tetrafluoroethane is 5.4%～26.5%, 1, the volumetric molar concentration of 1-C2H4F2 C2H4F2 is 49.5%～72.5%, and Trimethylmethane is 22.1%～24.0%, and corresponding bubble point temperature is 328.85～330.65K (55.70～57.50 ℃).Above-mentioned optimum concentration range has covered the nearly azeotropic concentration interval under the high-low pressure, can make this mixture temperature glide in actual moving process less (seeing accompanying drawing 1), its thermodynamic behavior is equivalent to a pure working medium, and its efficiency of thermal cycle is in the very high scope.
Accompanying drawing 2 shows that the temperature-pressure curve of this azeotropic working medium and R12 are very approaching, therefore can use with the identical compressor of R12 and carry out work.In addition, owing to contain the Trimethylmethane component in the mixture, make this mixing medium also have solubility property preferably in mineral oil, therefore, this working medium can directly apply to original R12 refrigeration system and not do big change.
The azeotropic 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.Because two kinds of components 1 containing, the Greenhouse effect coefficient GWP of 1-C2H4F2 C2H4F2 (R152a) and Trimethylmethane (R600a) is all very little, and mix refrigerant GWP coefficient provided by the present invention is much smaller than existing R12, serial refrigeration agent such as R134a.The concentration interval of the present invention's suggestion has covered the nearly azeotropic interval under the high-low pressure, so its temperature glide is little.Another one advantage of the present invention is that this azeotropic working medium has higher intrinsic conversion efficiency, and in the concentration interval of suggestion, coefficient of performance COP and R12 are suitable, and refrigerating effect per unit swept volume is higher than R134a.In addition,, therefore reduced the combustibility of this mixture to a certain extent, improved than the security of existing working medium R600a because this azeotropic working medium contains not flammable component R134a.
Description of drawings
Accompanying drawing 1 is the embodiment of the invention 7, embodiment 8, embodiment 9, the embodiment 10 bubble dew-point temperature (temperature glide) under different saturation pressures.
Accompanying drawing 2 are embodiment of the invention 10 with the steaming pressure ratio of existing refrigeration agent.
Embodiment
Embodiment 1: get volumetric molar concentration and be 2% 1,1,1, the 2-Tetrafluoroethane, volumetric molar concentration be 80% 1,1-C2H4F2 C2H4F2 and volumetric molar concentration are 18% Trimethylmethane physical mixed at normal temperatures, obtain a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 2: get volumetric molar concentration and be 47% 1,1,1, the 2-Tetrafluoroethane, volumetric molar concentration be 35% 1,1-C2H4F2 C2H4F2 and volumetric molar concentration are 18% Trimethylmethane physical mixed at normal temperatures, obtain a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 3: get volumetric molar concentration and be 2% 1,1,1, the 2-Tetrafluoroethane, volumetric molar concentration be 35% 1,1-C2H4F2 C2H4F2 and volumetric molar concentration are 63% Trimethylmethane physical mixed at normal temperatures, obtain a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 4: get volumetric molar concentration and be 4% 1,1,1, the 2-Tetrafluoroethane, volumetric molar concentration be 60% 1,1-C2H4F2 C2H4F2 and volumetric molar concentration are 36% Trimethylmethane physical mixed at normal temperatures, obtain a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 5: get volumetric molar concentration and be 40% 1,1,1, the 2-Tetrafluoroethane, volumetric molar concentration be 40% 1,1-C2H4F2 C2H4F2 and volumetric molar concentration are 20% Trimethylmethane physical mixed at normal temperatures, obtain a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 6: get volumetric molar concentration and be 4% 1,1,1, the 2-Tetrafluoroethane, volumetric molar concentration be 40% 1,1-C2H4F2 C2H4F2 and volumetric molar concentration are 56% Trimethylmethane physical mixed at normal temperatures, obtain a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 7: get volumetric molar concentration and be 5.4% 1,1,1, the 2-Tetrafluoroethane, volumetric molar concentration be 72.5% 1,1-C2H4F2 C2H4F2 and volumetric molar concentration are 22.1% Trimethylmethane physical mixed at normal temperatures, obtain a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 8: get volumetric molar concentration and be 26.5% 1,1,1, the 2-Tetrafluoroethane, volumetric molar concentration be 49.5% 1,1-C2H4F2 C2H4F2 and volumetric molar concentration are 24% Trimethylmethane physical mixed at normal temperatures, obtain a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 9: get volumetric molar concentration and be 11.5% 1,1,1, the 2-Tetrafluoroethane, volumetric molar concentration be 55.4% 1,1-C2H4F2 C2H4F2 and volumetric molar concentration are 33.1% Trimethylmethane physical mixed at normal temperatures, obtain a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 10. get volumetric molar concentration be 5.4% 1,1,1, the 2-Tetrafluoroethane, volumetric molar concentration be 62.3% 1,1-C2H4F2 C2H4F2 and volumetric molar concentration are 32.3% Trimethylmethane physical mixed at normal temperatures, obtain a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 11: get volumetric molar concentration and be 8.8% 1,1,1, the 2-Tetrafluoroethane, volumetric molar concentration be 58.2% 1,1-C2H4F2 C2H4F2 and volumetric molar concentration are 33% Trimethylmethane physical mixed at normal temperatures, obtain a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 12: get volumetric molar concentration and be 5.4% 1,1,1, the 2-Tetrafluoroethane, volumetric molar concentration be 65.5% 1,1-C2H4F2 C2H4F2 and volumetric molar concentration are 29.1% Trimethylmethane physical mixed at normal temperatures, obtain a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 13: get volumetric molar concentration and be 10.8% 1,1,1, the 2-Tetrafluoroethane, volumetric molar concentration be 59.9% 1,1-C2H4F2 C2H4F2 and volumetric molar concentration are 29.3% Trimethylmethane physical mixed at normal temperatures, obtain a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 14: get volumetric molar concentration and be 17.4% 1,1,1, the 2-Tetrafluoroethane, volumetric molar concentration be 52.6% 1,1-C2H4F2 C2H4F2 and volumetric molar concentration are 30% Trimethylmethane physical mixed at normal temperatures, obtain a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 15: get volumetric molar concentration and be 5.4% 1,1,1, the 2-Tetrafluoroethane, volumetric molar concentration be 67.5% 1,1-C2H4F2 C2H4F2 and volumetric molar concentration are 27.1% Trimethylmethane physical mixed at normal temperatures, obtain a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 16: get volumetric molar concentration and be 13% 1,1,1, the 2-Tetrafluoroethane, volumetric molar concentration be 59% 1,1-C2H4F2 C2H4F2 and volumetric molar concentration are 28% Trimethylmethane physical mixed at normal temperatures, obtain a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 17: get volumetric molar concentration and be 21.5% 1,1,1, the 2-Tetrafluoroethane, volumetric molar concentration be 50.3% 1,1-C2H4F2 C2H4F2 and volumetric molar concentration are 28.2% Trimethylmethane physical mixed at normal temperatures, obtain a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
Embodiment 18: get volumetric molar concentration and be 16% 1,1,1, the 2-Tetrafluoroethane, volumetric molar concentration be 60.9% 1,1-C2H4F2 C2H4F2 and volumetric molar concentration are 23.1% Trimethylmethane physical mixed at normal temperatures, obtain a kind of mix refrigerant that can be applicable to single stage compressive refrigerating system.
According to the relevant regulations among " use in refrigerator totally-enclosedmotor---compressor " standard GB 9098-88, determine that design conditions are vaporization temperature-23.3 ℃, 32.2 ℃ of suction temperatures, 54.4 ℃ of condensing temperatures, 32.2 ℃ of supercooling temperatures, 32.2 ℃ of envrionment temperatures.According to cycle calculations, the cycle performance parameter of above-mentioned 18 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 R12 relatively.
Among the embodiment mix refrigerant performance gather and with existing refrigerant performance comparison sheet
| Embodiment | Condensing pressure kPa | Evaporating pressure kPa | Pressure ratio | Exhaust temperature ℃ | Relative volume refrigerating capacity compressor | Relative efficiency |
| 1 | 1384.4 | 116.61 | 11.87 | 127.86 | 0.943 | 0.999 |
| 2 | 1501.7 | 121.71 | 12.34 | 121.29 | 0.942 | 0.955 |
| 3 | 1251.4 | 91.46 | 13.68 | 117.28 | 0.691 | 0.899 |
| 4 | 1377.3 | 121.88 | 11.30 | 119.56 | 0.939 | 0.986 |
| 5 | 1487.5 | 122.28 | 12.16 | 121.33 | 0.946 | 0.960 |
| 6 | 1303.8 | 99.68 | 13.08 | 117.83 | 0.751 | 0.913 |
| 7 | 1395.1 | 119.28 | 11.70 | 125.20 | 0.950 | 0.995 |
| 8 | 1455.1 | 123.27 | 11.80 | 121.27 | 0.955 | 0.972 |
| 9 | 1407.4 | 124.43 | 11.31 | 119.35 | 0.956 | 0.984 |
| 10 | 1388.7 | 123.01 | 11.29 | 120.51 | 0.953 | 0.991 |
| 11 | 1398.6 | 123.78 | 11.30 | 119.78 | 0.954 | 0.987 |
| 12 | 1392.8 | 122.50 | 11.37 | 121.83 | 0.956 | 0.993 |
| 13 | 1408.8 | 123.54 | 11.40 | 120.96 | 0.958 | 0.987 |
| 14 | 1429.2 | 125.17 | 11.42 | 119.73 | 0.962 | 0.981 |
| 15 | 1394.4 | 121.81 | 11.45 | 122.72 | 0.956 | 0.994 |
| 16 | 1416.1 | 123.41 | 11.47 | 121.23 | 0.959 | 0.986 |
| 17 | 1442.6 | 125.19 | 11.52 | 119.97 | 0.962 | 0.977 |
| 18 | 1423.5 | 121.00 | 11.76 | 123.19 | 0.951 | 0.983 |
| R12 | 1344.8 | 132.28 | 10.19 | 125.83 | 1.000 | 1.000 |
| R134a | 1469.8 | 114.84 | 12.78 | 118.95 | 0.921 | 0.978 |
| R600a | 761.6 | 62.65 | 12.10 | 102.64 | 0.502 | 1.013 |
More than show that based on the Theoretical Calculation result of standard condition most embodiment of refrigeration working medium provided by the invention all have the raising of certain degree than existing alternative working medium R134a except that exhaust temperature on all other indexs; Compare with alternative working medium R600a, refrigerating effect per unit swept volume and pressure ratio have advantage largely; Compare with traditional good working medium R12, refrigerating effect per unit swept volume and efficient are suitable, and exhaust temperature then has reduction largely, and this will help the normal operation of compressor.
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 3 embodiment and the latent value ODP of existing refrigeration agent ozone depletion and Global warming and dived value GWP relatively.The mixed refrigerant of the present invention's proposition has reduced the GWP value greatly as can be seen.
*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 (3)
1. one kind is applicable to the ternary environment-friendly type near-azeotrope refrigerant in the single stage compressive refrigerating system, it is characterized in that, this mix refrigerant comprises through 1,1,1 of physical mixed, 2-Tetrafluoroethane, 1,1-C2H4F2 C2H4F2 and Trimethylmethane;
Each component volumetric molar concentration sum is 100% in the described mix refrigerant, and wherein described 1,1,1, the volumetric molar concentration of 2-Tetrafluoroethane is 2%～47%, 1, and the volumetric molar concentration of 1-C2H4F2 C2H4F2 is 35%～80%, and the volumetric molar concentration of Trimethylmethane is 18%～63%.
2. by the described near azeotropic mixed refrigerant that is applicable in the single stage compressive refrigerating system of claim 1, it is characterized in that: each component volumetric molar concentration sum is 100% in the mix refrigerant, wherein 1,1,1, the volumetric molar concentration of 2-Tetrafluoroethane is 4%～40%, 1,1-C2H4F2 C2H4F2 volumetric molar concentration is 40%～60%, and the volumetric molar concentration of Trimethylmethane is 20%～56%.
3. by the described azeotropic refrigerant that is applicable in the single stage compressive refrigerating system of claim 1, it is characterized in that: each component volumetric molar concentration sum is 100% in the mix refrigerant, wherein 1,1,1, the volumetric molar concentration of 2-Tetrafluoroethane is 5.4%～26.5%, 1,1-C2H4F2 C2H4F2 volumetric molar concentration is 49.5%～72.5%, and the volumetric molar concentration of Trimethylmethane is 22.1%～33.1%.
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106762645A (en) * | 2016-11-16 | 2017-05-31 | 西安交通大学 | The rotary compressor for main refrigerant and application using R600a or R600 |
| CN107513372A (en) * | 2017-02-22 | 2017-12-26 | 唐建 | A kind of ternary mixed refrigerant |
| WO2023098779A1 (en) * | 2021-12-03 | 2023-06-08 | 青岛海尔特种电冰柜有限公司 | Ternary mixed refrigerant, refrigeration system, and refrigeration device |
-
2007
- 2007-02-02 CN CNA2007100635457A patent/CN101235274A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106762645A (en) * | 2016-11-16 | 2017-05-31 | 西安交通大学 | The rotary compressor for main refrigerant and application using R600a or R600 |
| CN106762645B (en) * | 2016-11-16 | 2020-06-26 | 西安交通大学 | Method for determining viscosity grade of lubricating oil of rotary compressor |
| CN107513372A (en) * | 2017-02-22 | 2017-12-26 | 唐建 | A kind of ternary mixed refrigerant |
| WO2023098779A1 (en) * | 2021-12-03 | 2023-06-08 | 青岛海尔特种电冰柜有限公司 | Ternary mixed refrigerant, refrigeration system, and refrigeration device |
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