CN101307223B - Ternary near-azeotropic refrigerant containing 1,1,2,2-Ttetrafluoroethane - Google Patents
Ternary near-azeotropic refrigerant containing 1,1,2,2-Ttetrafluoroethane Download PDFInfo
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- CN101307223B CN101307223B CN200810115669XA CN200810115669A CN101307223B CN 101307223 B CN101307223 B CN 101307223B CN 200810115669X A CN200810115669X A CN 200810115669XA CN 200810115669 A CN200810115669 A CN 200810115669A CN 101307223 B CN101307223 B CN 101307223B
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Abstract
The invention relates to an environmental-friendly near-azeotropic mixing refrigerant suitable for a single stage compression refrigeration system. The environmental- friendly near-azeotropic mixing refrigerant is made by mixing 1, 1, 2, 2- tetrafluoro thane, 1, 1-difluoroethane and isobutane physically, wherein, the mass percentage concentration of the 1, 1, 2, 2- tetrafluoro thane is between 1 and 40 percent, the mass percentage concentration of the 1, 1-difluoroethane is between 40 and 84 percent, and the mass percentage concentration of the isobutane is between 15 and 40 percent. The mixing refrigerant has small temperature glide, good lubricating oil dissolving performance, and can directly replace R12 working substance without greatly changing a refrigerating system; and ODP is zero and GWP is much smaller than R12 and R134a working substance.
Description
Technical field
The present invention relates to a kind of mix refrigerant, particularly a kind ofly contain 1,1,2,2-Tetrafluoroethane composition, the ternary near-azeotrope environment friendly refrigerating fluid of single stage compressive refrigerating system be applicable to.
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 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 the theoretical refrigerating efficiency of working medium R600a 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, mixture its back pressure under same vaporization temperature with positive azeotropic feature is higher than the pure working medium of its single component, 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.As seen, the above azeotropic/nearly azeotropic mixture of ternary has great potential in alternative working medium research.
Japanese Patent JP2003148847A discloses a kind of refrigeration working medium that is used for refrigerator chamber, is made up of R134a (1,1,1, the 2-Tetrafluoroethane), R152a and R600a, and wherein the mass concentration of R600a is 1～47%, and all the other are R134a and R152a.Working medium of the present invention other characteristics of phase region with it is not contain R134a, but contains R134 (1,1,2, the 2-Tetrafluoroethane), and has the feature of nearly azeotropic working medium.
The R134 that this patent relates to (1,1,2, the 2-Tetrafluoroethane) is a kind of hydrogen fluorohydrocarbon (HFC) class refrigeration work material, and it is the isomers of R134a (1,1,1, the 2-Tetrafluoroethane), promptly has identical molecular formula with R134a, but the molecular structure difference.Because the difference of molecular structure, R134 and R134a are not a kind of materials, and the two shows the physico-chemical property difference of essence, and the chemical industry synthesis path of its suitability for industrialized production is also different fully.The boiling point of R134 is-23 ℃, and the boiling point of R134a is-26.1 ℃; The critical temperature of R134 is 118.59 ℃, and the critical temperature of R134a is 101.06 ℃, differs 18K; Also difference is very big for same the two emergent pressure; The atmospheric lifetime of R134 and R134a is also different, so its environmental influence characteristic is also inequality, and the former dives than the Global warming of R134a and is worth (GWP) coefficient low about 30%.Because the difference of physico-chemical property causes its thermodynamic cycle performance also to have the difference of highly significant, under same refrigerator cooling condition, the intrinsic conversion efficiency of R134 is higher than R134a, is a kind of very potential alternative refrigerant.
The query display of patent documentation, authorized Chinese patent application CN91110832.7 and Japanese Patent JP308084/1988 to relate to the mixture of relevant R152a and R134 and R134a, be specially the former and related to the mixture of R134 and R152a, the latter is the mixture of R134a and R152a.Wherein carried out setting forth clearly for the difference of R134 and R134a in the application form of patent CN91110832.7: because two carbon atoms of R134 all respectively have combination hydrogen atom thereon, so the chemical structure of R134 is a utmost point equilibrated, and the chemical structure of R134a is unbalanced.Therefore, must not think that according to molecular structure R134 and R134a have similar characteristic.In addition, the saturation vapour pressure of R134a is higher 1.25 to 1.3 times than R134 approximately, and in order to reach identical refrigeration capacity, the use latter's compressor scavenging volume is about 1.2 to 1.25 times of the latter.In addition, the lubricating oil compatibility of R134 and R134a is different, R134a-18 ℃ down with the consistency extreme differences of aliphatic oil, find that it is separated into two-phase this moment, and the R134 when same oil coexists with it is not separated when-40 ℃ or higher temperature.Therefore, from these key technical problems, R134 and R134a have significant difference.This patent will specifically be set forth R134+R152a+R600a and the difference of R134a+R152a+R600a on temperature glide, saturation pressure and environmental protection characteristic in the summary of the invention of back.
Canadian Patent CA2272961A1 discloses multiple frigorific mixture combination, according to the content of its claim, can form the R134 identical with this patent, R152a, R600a tertiary mixture, but concentration is interval different fully with the present invention.Claim 1 according to CA2272961A1 is described, and the concentration of its R600a is 1～10%, and clearly mentions this mixture belong to non-azeotropic working medium in invention is described, and has bigger bubble dew-point temperature, can reach 9K at most.This patent is measured and is analyzed based on accurate phase equilibrium experiment, thinks that this mixture can not form nearly azeotropic mixture in the R600a low strength range, and bigger bubble dew-point temperature will cause the reduction of cyclical stability.The mixture concentration scope that the present invention proposes will form near-azeotropic mixture working medium, therefore have bigger superiority than the described working medium of CA2272961A1.In the summary of the invention of back, will elaborate the present invention and the difference of the described working medium of CA2272961A1 on temperature glide, saturation pressure and environmental protection characteristic.
Summary of the invention
The object of the present invention is to provide a kind of environmental protection, have good mutual solubility, be used for the ternary near-azeotrope refrigerant of single stage compressive refrigerating system with lubricating oil.
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, by 1,1,2,2-Tetrafluoroethane (CHF
2CHF
2Be R134), 1,1-C2H4F2 C2H4F2 (CHF
2CH
3Be R152a) and Trimethylmethane (i-C
4H
10Be R600a) form through physical mixed;
Each constituent mass percentage concentration sum is 100% in the described mix refrigerant, wherein, and described 1,1,2, the mass percent concentration of 2-Tetrafluoroethane is 1%～40%, 1, the mass percent concentration of 1-C2H4F2 C2H4F2 is 40%～84%, and the mass percent concentration of Trimethylmethane is 15%～40%.
Above-mentioned by 1,1,2, the 2-Tetrafluoroethane, 1, the mix refrigerant that 1-C2H4F2 C2H4F2 and Trimethylmethane are formed exists optimizes concentration proportioning: each constituent mass percentage concentration sum is 100% in the mix refrigerant, wherein 1,1,2, the mass percent concentration of 2-Tetrafluoroethane is 1%～25%, 1,1-C2H4F2 C2H4F2 mass percent concentration is 40%～81%, and the mass percent concentration of Trimethylmethane is 18%～35%; The foundation of this optimization concentration mainly is the circulation thermal performance, i.e. COP numerical value is taken all factors into consideration the behavior that balances each other, temperature glide and the working medium problems such as change in concentration in circulation of mixture in addition.
This mix refrigerant has the nearly azeotropic feature that balances each other, wherein the nearly azeotropic concentration interval under 101kPa is: 1,1,2, the mass percent concentration of 2-Tetrafluoroethane is 1%～22%, and 1, the mass percent concentration of 1-C2H4F2 C2H4F2 is 48%～71%, Trimethylmethane is 26%～30%, and corresponding bubble point temperature is 244.43～244.86K; Above-mentioned optimization concentration range has covered the nearly azeotropic concentration interval under the 101kPa, 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 1 gives the temperature glide of the relevant embodiment among patent CA2272961A1 and the JP2003148847A and the contrast of embodiments of the invention.The combination that has only provided R134a/R152a/R600a owing to the embodiment of patent CA2272961A1 does not have the combination of R134/R152a/R600a, therefore in the calculating of accompanying drawing 1, the spy has calculated R134/R152a/R600a in the temperature glide under the 82/12.5/5.5 proportioning (this proportioning is also in its claim scope) according to the densitometer of the embodiment among the CA2272961A1 1.And only provided R134a/R152a/R600a among the patent JP2003148847A is a kind of proportioning of 49.8/26.2/24, so accompanying drawing 1 also calculates according to this concentration.
Accompanying drawing 1 shows that the bubble dew-point temperature of the working medium of the present invention of embodiment 4 representatives much smaller than the described working medium of CA2272961A1, therefore has the various advantages of nearly azeotropic working medium in big pressure range; With the contrast of the described working medium of JP2003148847A, under low pressure less than and under the high pressure a little more than the described working medium of JP2003148847A, its reason is that embodiment 4 belongs to the nearly azeotropic concentration interval under the low pressure.
Accompanying drawing 2 shows, the saturation pressure of the working medium of the present invention of embodiment 4 representative a little less than the described working medium of JP2003148847A a little more than the described working medium of CA2272961A1, three 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 working medium of the present invention, make this mixing medium also have the good solubility energy in mineral oil, therefore, this working medium can directly apply to original R12 refrigeration system and not do big change.
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.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 that the present invention proposes has covered nearly azeotropic interval, so its temperature glide is little.Another one advantage of the present invention is that this nearly azeotropic working medium has higher efficient, and in preferred concentration interval, 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 R134.
Description of drawings
Accompanying drawing 1 is the embodiment of the invention 4 and described working medium of JP2003148847A and the bubble dew-point temperature (temperature glide) of the described working medium of CA2272961A1 under different pressures.
Accompanying drawing 2 is that the temperature-pressure curve of the embodiment of the invention 4, the described working medium of JP2003148847A, the described working medium of CA2272961A1 and R12 compares.
Embodiment
Embodiment 1: get mass percent concentration and be 1% 1,1,2, the 2-Tetrafluoroethane, mass percent concentration be 81% 1,1-C2H4F2 C2H4F2 and mass percent 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 mass percent concentration and be 25% 1,1,2, the 2-Tetrafluoroethane, mass percent concentration be 40% 1,1-C2H4F2 C2H4F2 and mass percent concentration are 35% 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 mass percent concentration and be 8% 1,1,2, the 2-Tetrafluoroethane, mass percent concentration be 66% 1,1-C2H4F2 C2H4F2 and mass percent concentration are 26% 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 mass percent concentration and be 15% 1,1,2, the 2-Tetrafluoroethane, mass percent concentration be 57% 1,1-C2H4F2 C2H4F2 and mass percent 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.
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, above-mentioned 4 described working medium of embodiment, JP2003148847A, the described cycle performances parameter of CA2272961A1 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 MPa | Evaporating pressure MPa | Pressure ratio | Exhaust temperature ℃ | Relative volume refrigerating capacity compressor | Relative efficiency |
| 1 | 1.383 | 0.118 | 11.74 | 126.98 | 0.948 | 1.000 |
| 2 | 1.414 | 0.121 | 11.70 | 117.08 | 0.906 | 0.952 |
| 3 | 1.392 | 0.123 | 11.36 | 121.75 | 0.956 | 0.993 |
| 4 | 1.403 | 0.124 | 11.31 | 119.88 | 0.956 | 0.986 |
| JP2003148847A | 1.501 | 0.132 | 11.38 | 116.12 | 0.982 | 0.959 |
| CA2272961A1 | 1.519 | 0.118 | 12.90 | 121.13 | 0.924 | 0.951 |
| R12 | 1.345 | 0.132 | 10.19 | 125.83 | 1.000 | 1.000 |
| R134a | 1.470 | 0.115 | 12.78 | 118.95 | 0.921 | 0.978 |
| R600a | 0.762 | 0.063 | 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 lower slightly, and exhaust temperature is decrease to some degree then, and this will help the normal operation of compressor.
The COP of all embodiment is better than the described working medium of CA2272961A1, and the COP of 3 embodiment is better than the described working medium of JP2003148847A.
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 4 embodiment and the latent value ODP of the described working medium of JP2003148847A, the described working medium of CA2272961A1 and 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 (2)
1. a ternary environment-friendly type near-azeotrope refrigerant that is applicable to single stage compressive refrigerating system is characterized in that, this mix refrigerant is by 1,1,2, the 2-Tetrafluoroethane, and 1,1-C2H4F2 C2H4F2 and Trimethylmethane form through physical mixed;
Each constituent mass percentage concentration sum is 100% in the described mix refrigerant, wherein, described 1,1,2, the mass percent concentration of 2-Tetrafluoroethane is 1%～25%, described 1, the mass percent concentration of 1-C2H4F2 C2H4F2 is 40%～84%, and the mass percent concentration of described Trimethylmethane is 15%～40%.
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 constituent mass percentage concentration sum is 100% in the mix refrigerant, wherein, described 1,1-C2H4F2 C2H4F2 mass percent concentration is 40%～81%, and the mass percent concentration of described Trimethylmethane is 18%～35%.
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| CN200810115669XA CN101307223B (en) | 2008-06-26 | 2008-06-26 | Ternary near-azeotropic refrigerant containing 1,1,2,2-Ttetrafluoroethane |
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| CN200810115669XA CN101307223B (en) | 2008-06-26 | 2008-06-26 | Ternary near-azeotropic refrigerant containing 1,1,2,2-Ttetrafluoroethane |
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| CN101307223B true CN101307223B (en) | 2010-06-02 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061791A (en) * | 1990-10-19 | 1992-06-10 | 大金工业株式会社 | The mixture of azeotropic and/or azeotropic and they refrigeration or air-conditioning systems as working medium |
| WO1998023702A1 (en) * | 1996-11-28 | 1998-06-04 | Rhodia Limited | Refrigerant composition |
| JP2003148847A (en) * | 2001-11-14 | 2003-05-21 | Sanyo Electric Co Ltd | Refrigerator |
-
2008
- 2008-06-26 CN CN200810115669XA patent/CN101307223B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061791A (en) * | 1990-10-19 | 1992-06-10 | 大金工业株式会社 | The mixture of azeotropic and/or azeotropic and they refrigeration or air-conditioning systems as working medium |
| WO1998023702A1 (en) * | 1996-11-28 | 1998-06-04 | Rhodia Limited | Refrigerant composition |
| JP2003148847A (en) * | 2001-11-14 | 2003-05-21 | Sanyo Electric Co Ltd | Refrigerator |
Non-Patent Citations (7)
| Title |
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| 史琳.《制冷剂使用手册》 第1版.冶金工业出版社,2003,全文. |
| 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),全文. |
| 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),全文. * |
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| 曹德胜;史琳.《制冷剂使用手册》 第1版.冶金工业出版社,2003,全文. * |
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