CN101165136A - Azeotropic refrigerant for single-stage compression refrigeration system - Google Patents
Azeotropic refrigerant for single-stage compression refrigeration system Download PDFInfo
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- CN101165136A CN101165136A CNA2006101138989A CN200610113898A CN101165136A CN 101165136 A CN101165136 A CN 101165136A CN A2006101138989 A CNA2006101138989 A CN A2006101138989A CN 200610113898 A CN200610113898 A CN 200610113898A CN 101165136 A CN101165136 A CN 101165136A
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- c2h4f2
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- azeotropic
- refrigerant
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- 239000003507 refrigerant Substances 0.000 title claims abstract description 34
- 238000005057 refrigeration Methods 0.000 title abstract description 24
- 230000006835 compression Effects 0.000 title abstract 2
- 238000007906 compression Methods 0.000 title abstract 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims abstract description 50
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 abstract description 5
- 239000010687 lubricating oil Substances 0.000 abstract description 4
- 229940051271 1,1-difluoroethane Drugs 0.000 abstract 2
- 239000001282 iso-butane Substances 0.000 abstract 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 25
- 239000000306 component Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000009834 vaporization Methods 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- 238000004378 air conditioning Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012533 medium component Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- -1 methyl chlorofluoride Chemical compound 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to an azeotropic refrigerant for a single-stage compression refrigeration system, which comprises physically mixed 1, 1-difluoroethane and isobutane; the sum of the molar concentrations of all the components in the mixed refrigerant is 100%, wherein the molar concentration range of the 1, 1-difluoroethane is 73-85%, and the balance is isobutane; the efficiency of the mixed refrigerant is higher than that of the traditional excellent working medium R12, the mixed refrigerant has good lubricating oil solubility, and can directly replace the R12 working medium without great change in a refrigeration system; the ODP is zero, and the GWP is far smaller than that of a conventional fluoride working medium and is equivalent to that of a natural working medium.
Description
Technical field
The invention belongs to a kind of mix refrigerant that is used for single stage compressive refrigerating system, particularly a kind of azeotropic refrigerant that is used for single stage compressive refrigerating system of efficient, environmental protection.
Background technology
Single stage compressive refrigerating system all has in systems such as refrigerator, air-conditioning and automative air conditioning widely to be used, because the energy consumption of this type systematic has occupied quite great proportion in social total energy consumption, therefore advocating the today of setting up " conservation-minded society ", thereby the efficient that how to improve single stage compressive refrigerating system is saved the important topic that multipotency source has more become the refrigeration industry development.
Past the most frequently used refrigeration working medium in refrigerator refrigeration system is R12 (methyl chlorofluoride, CF
2Cl
2), it is little that it has toxicity, not flammable, non-explosive, the intrinsic conversion efficiency height, and molten oiliness can well wait overall merit, therefore uses to have very high efficient in single stage compressive refrigerating system.But along with the discovery of depletion of the ozone layer mechanism and Greenhouse effect, R12 is put among the working medium of at first eliminating with its higher ODP and GWP coefficient.
The refrigeration working medium that being most commonly used to of growing up subsequently substitutes 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, therefore can not directly apply to original R12 refrigeration system in use.In addition, R134a refrigerating effect per unit swept volume and cycle efficiency be all not as good as R12, and pressure ratio is higher than R12, therefore also is unfavorable for the efficient operation of compressor.Though and the another kind of working medium R600a cycle efficiency that substitutes is a little more than R12, its pressure ratio is higher equally, and therefore refrigerating effect per unit swept volume will reach same refrigeration capacity much smaller than R12, must select the bigger refrigeration compressor of free air delivery for use.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.
To sum up analyze, original refrigeration working medium R12 and alternative working medium R134a thereof and R600a all have bigger limitation in the refrigerator refrigeration system, therefore, how to select a kind of efficient, environmental protection, and the refrigeration working medium that can directly substitute R12 has become the bottleneck that refrigerator refrigeration system further develops.
Because existing pure substance limited amount, and most screened and part is used for the substitution studies of above-mentioned working medium, and the result is all not satisfactory, and therefore the selection of new working medium being redirect to mixing medium has been trend of the times.Studies show that the azeotropic mixture in the mixing medium has following plurality of advantages, very likely become the optimal selection that substitutes original working medium: 1, azeotropic working medium has with the similar character of pure working medium near its azeotropic district, is easy to obtain stable evaporation operating mode; 2, for positive azeotropic (positive azeotrope) mixing medium, its back pressure is higher than the pure working medium of its single component under same vaporization temperature, therefore 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, near most azeotropic working mediums pure working medium than its single component azeotropic point has higher phase-change heat transfer coefficient; 5, can take into account the similar lubricating oil dissolving properties of certain component; 6, most of azeotropic working mediums help improving the service efficiency of compressor in the pressure ratio in the uniform temp interval pure working medium less than its single component.As seen, azeotropic mixture has great potentiality in substituting working medium research.
Publication number is that the patent application (application number is 94192550.1) of CN1125958A discloses a kind of mechanically refrigerated mixing medium that is used for, and its disclosed working medium has the component identical with patent of the present invention, but concentration is interval different fully.Above-mentioned patent application is based on the early stage research in generation nineteen ninety, the weak point that exists at following critical aspects: not through the research that balances each other accurately, therefore its concentration interval can't cover the azeotropic interval of mixing medium actual operating mode, therefore can not enjoy many advantages that azeotropic mixture has, and the excessive decline that causes system performance of temperature glide; In addition, above-mentioned patent application fails to carry out accurate hot Physical Property Analysis, and therefore in the concentration range of its suggestion, the coefficient of refrigerating performance of working medium may not be the highest; Known patent fails to indicate the molten oily characteristic and the molten oily mechanism of this mixture.
Below summary of the invention will elaborate advantage and the meaning that the concentration interval of the present invention suggestion is had.
Summary of the invention
The object of the present invention is to provide a kind of efficient, environmental protection, the azeotrope refrigerant that is used for single stage compressive refrigerating system that has good mutual solubility with lubricating oil.
Technical scheme of the present invention is as follows:
The azeotrope refrigerant that is used for single stage compressive refrigerating system provided by the invention comprises through 1 of physical mixed, 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, the volumetric molar concentration of 1-C2H4F2 C2H4F2 is 73%～85% (the mass concentration scope is 75.4%～86.6%), remains to be Trimethylmethane.
Above-mentionedly comprise 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-C2H4F2 C2H4F2 volumetric molar concentration is 73%～80% (the mass concentration scope is 75.4%～82.0%), remains to be Trimethylmethane; 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, 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-C2H4F2 C2H4F2 volumetric molar concentration is 73%～77% (the mass concentration scope is 75.4%～79.2%), and all the other are Trimethylmethane.
This mix refrigerant has the azeotropic feature that balances each other, and wherein the azeotropic concentration under 101kPa is 1, and 1-C2H4F2 C2H4F2 volumetric molar concentration is 67.8%, and Trimethylmethane is 32.2%, and corresponding azeotropic temperature is 245.53K (27.62 ℃); Azeotropic concentration under 1500kPa is 1, and 1-C2H4F2 C2H4F2 volumetric molar concentration is 78.5%, and the Trimethylmethane volumetric molar concentration is 21.5%, and corresponding azeotropic temperature is 331.06 (57.91 ℃), sees accompanying drawing 1.Above-mentioned optimum concentration range is positioned within the high-low pressure azeotropic concentration interval, can make this mixture temperature glide in actual moving process less (seeing accompanying drawing 2), and its thermodynamic behavior is equivalent to a pure working medium, and its efficiency of thermal cycle is in the very high scope.Because this azeotropic working medium belongs to positive azeotrope, with its single component 1, the 1-C2H4F2 C2H4F2 is compared with Trimethylmethane has lower boiling point, therefore has higher back pressure under same vaporization temperature, therefore has bigger refrigerating effect per unit swept volume.
Accompanying drawing 3 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.Component 1 in this mixture, the solubleness of 1-C2H4F2 C2H4F2 in plain mineral oil is less, but because the existence of Trimethylmethane component makes this azeotropic working medium also have solubility property preferably in mineral oil, therefore, this azeotropic working medium can directly apply to original R12 refrigeration system and not do big change.
The azeotropic refrigerant that is used for 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 the pure working medium component 1 that contains, the Greenhouse effect coefficient GWP of 1-C2H4F2 C2H4F2 (R152a) and Trimethylmethane (R600a) is all very little, mix refrigerant GWP coefficient provided by the present invention is much smaller than existing R12, serial refrigeration agent such as R134a and near natural medium R600a.Concentration of the present invention interval is near the azeotropic interval of this mixture under actual operating mode, so its temperature glide is little, heat transfer coefficient is high.Another one advantage of the present invention is that this azeotropic working medium has very high intrinsic conversion efficiency, in the concentration interval of suggestion, refrigerating effect per unit swept volume and R12 are quite and coefficient of performance COP is higher than R12, consider the advantages such as heat transfer property that azeotropic working medium is good, the present invention proposes azeotropic working medium efficiency ratio R12 in actual motion will by a relatively large margin raising.In addition, because the temperature and pressure scope of this azeotropic working medium and R12 is approaching, and has good lubricating oil solubility property, therefore, this working medium can directly substitute R12 and be used for original refrigeration system.
Description of drawings
Accompanying drawing 1 is for comprising 1, the phasor of mix refrigerant under 101kPa and 1500kPa of 1-C2H4F2 C2H4F2 (R152a) and Trimethylmethane (R600a).
Accompanying drawing 2 is the embodiment of the invention 1, embodiment 2, embodiment 4, embodiment 6 bubble dew-point temperatures (temperature glide) under different saturation pressures.
Accompanying drawing 3 are embodiment of the invention 1 with the steaming pressure ratio of existing refrigeration agent.
Embodiment
Embodiment 1: get volumetric molar concentration and be 73% 1,1-C2H4F2 C2H4F2 and volumetric molar concentration are 27% 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 75% 1,1-C2H4F2 C2H4F2 and volumetric molar concentration are 25% 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 77% 1,1-C2H4F2 C2H4F2 and volumetric molar concentration are 23% 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 80% 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 5: get volumetric molar concentration and be 82% 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 6: get volumetric molar concentration and be 85% 1,1-C2H4F2 C2H4F2 and volumetric molar concentration are 15% 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 6 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 | Maximum temperature slippage K in 101～1500kPa scope | Pressure ratio | Exhaust temperature ℃ | Relative volume refrigerating capacity compressor | Relative efficiency |
| 1 | 1380 | 122 | 0.17 | 11.34 | 123.25 | 0.961 | 1.002 |
| 2 | 1381 | 122 | 0.30 | 11.36 | 124.16 | 0.965 | 1.005 |
| 3 | 1382 | 121 | 0.43 | 11.40 | 124.97 | 0.968 | 1.008 |
| 4 | 1382 | 121 | 0.63 | 11.45 | 126.23 | 0.972 | 1.012 |
| 5 | 1380 | 120 | 0.76 | 11.49 | 127.09 | 0.974 | 1.016 |
| 6 | 1376 | 119 | 0.91 | 11.57 | 128.46 | 0.974 | 1.021 |
| R12 | 1345 | 132 | / | 10.19 | 125.83 | 1.000 | 1.000 |
| R134a | 1470 | 115 | / | 12.78 | 118.95 | 0.921 | 0.978 |
| R600a | 762 | 63 | / | 12.10 | 102.64 | 0.502 | 1.013 |
Above calculation result shows, along with 1, the increase of 1-C2H4F2 C2H4F2 concentration, refrigerating effect per unit swept volume and cycle efficiency slightly improve, if but 1,1-C2H4F2 C2H4F2 concentration increases and away from the azeotropic interval, temperature glide will increase, and pressure ratio increases thereupon, and will lose the advantages such as high heat transfer coefficient that the azeotropic behavior brings, therefore, based on above consideration, in the concentration range that the present invention proposes 1,1-C2H4F2 C2H4F2 concentration is unsuitable too high, and the suggestion mass concentration is 75.4%～86.6% (volumetric molar concentration 73%～85%).
More than calculate based on the result of the recognized standard Calculation of Physical Properties software REFPROP 7.0 in the world, have very high accuracy, it is 94192550.1 patent that its analytical results is different from application number.(it is thought 1 in the concentration interval that above-mentioned known patent proposes, 1-C2H4F2 C2H4F2 mass concentration had higher coefficient of refrigerating performance at 60%～75% o'clock), through recomputating, its relative volume refrigerating capacity compressor and relative efficiency are respectively: 0.928～0.960,0.992～1.001, equal schemes that proposes not as good as the present invention.
More than show that based on the Theoretical Calculation result of standard condition the raising of certain degree is all arranged except that exhaust temperature than existing alternative working medium R134a and R600a on the refrigeration working medium provided by the invention on all other indexs.Compare with traditional good working medium R12, refrigerating effect per unit swept volume is basic quite and efficient is improved, if considering to conduct heat to strengthen waits other advantage, its actual operating efficiency will be higher than R12 largely.
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. an azeotrope refrigerant that is used for single stage compressive refrigerating system is characterized in that, this mix refrigerant comprises through 1 of physical mixed, 1-C2H4F2 C2H4F2 and Trimethylmethane;
Each component volumetric molar concentration sum is 100% in the described mix refrigerant, and wherein described 1, the volumetric molar concentration scope of 1-C2H4F2 C2H4F2 is 73%～85%, remains to be Trimethylmethane.
2. by the described azeotrope refrigerant that is used for single stage compressive refrigerating system of claim 1, it is characterized in that: described 1,1-C2H4F2 C2H4F2 volumetric molar concentration scope is 73%～80%, remains to be Trimethylmethane.
3. by the described azeotrope refrigerant that is used for single stage compressive refrigerating system of claim 1, it is characterized in that: described 1,1-C2H4F2 C2H4F2 volumetric molar concentration scope is 73%～77%, and all the other are Trimethylmethane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101138989A CN101165136A (en) | 2006-10-20 | 2006-10-20 | Azeotropic refrigerant for single-stage compression refrigeration system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101138989A CN101165136A (en) | 2006-10-20 | 2006-10-20 | Azeotropic refrigerant for single-stage compression refrigeration system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101165136A true CN101165136A (en) | 2008-04-23 |
Family
ID=39333994
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006101138989A Pending CN101165136A (en) | 2006-10-20 | 2006-10-20 | Azeotropic refrigerant for single-stage compression refrigeration system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101165136A (en) |
-
2006
- 2006-10-20 CN CNA2006101138989A patent/CN101165136A/en active Pending
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Open date: 20080423 |