CN1148613A - Refrigerant substituted for freon-12 for long time - Google Patents
Refrigerant substituted for freon-12 for long time Download PDFInfo
- Publication number
- CN1148613A CN1148613A CN 95117039 CN95117039A CN1148613A CN 1148613 A CN1148613 A CN 1148613A CN 95117039 CN95117039 CN 95117039 CN 95117039 A CN95117039 A CN 95117039A CN 1148613 A CN1148613 A CN 1148613A
- Authority
- CN
- China
- Prior art keywords
- hfc
- freon
- substituted
- refrigeration agent
- long time
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 235000019404 dichlorodifluoromethane Nutrition 0.000 title claims abstract description 11
- 239000003507 refrigerant Substances 0.000 title description 2
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 claims abstract description 21
- YFMFNYKEUDLDTL-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)C(F)(F)F YFMFNYKEUDLDTL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005057 refrigeration Methods 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 15
- 231100000749 chronicity Toxicity 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000001282 iso-butane Substances 0.000 description 7
- 235000013847 iso-butane Nutrition 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004378 air conditioning Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- UPLPHRJJTCUQAY-WIRWPRASSA-N 2,3-thioepoxy madol Chemical compound C([C@@H]1CC2)[C@@H]3S[C@@H]3C[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@](C)(O)[C@@]2(C)CC1 UPLPHRJJTCUQAY-WIRWPRASSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- UKACHOXRXFQJFN-UHFFFAOYSA-N heptafluoropropane Chemical compound FC(F)C(F)(F)C(F)(F)F UKACHOXRXFQJFN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010412 perfusion Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- VPAYJEUHKVESSD-UHFFFAOYSA-N trifluoroiodomethane Chemical compound FC(F)(F)I VPAYJEUHKVESSD-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a cryogen substituted for freon-12 for a long period, which is composed of two substances of FC-1311 and R290 or is composed of the both said substances and one substance of HFC-152a and HFC-227ea or is composed of one of FC-1311 and R290 and HFC-152a and HFC-227ea. Said invented cryogen is a non-toxic non-inflammable hypoazeotropic mixture, not only possesses good thermodynamic property, but also doesn't damage ozonosphere (ODP-0), and doesn't affect greenhouse effect, and has no need of changing existent equipment and production line, and is superior to existent other substitutes in properties.
Description
The invention belongs to the refrigeration agent that uses in the equipment such as refrigeration, air-conditioning, heat pump.
In the prior art, the refrigeration agent as devices such as refrigerator, refrigerator-freezer, automative air conditionings mostly uses F-12 (CFC-12) for a long time.Since it have hypotoxicity, not flammable, do not have a corrosion, with other material characteristics such as compatibility mutually, be widely used in refrigeration system and some other fields for many years.But since finding that CFC class material had a havoc effect to atmospheric ozone layer in 1974, caused increasingly extensive in the world attention, and decision production and the use of CFCs have progressively been limited.
At present, the main refrigeration of F-12 is made as HHC-134a as an alternative, and its advantage is not damage the ozone layer, thermal property and F-12 are close, its utilisation technology also reaches its maturity, but when promoting the use of HFC-134a, has but brought a series of requirements different with F-12.For example the aspects such as some major equipments, refrigeration oil and technology in the refrigeration system have all been proposed a series of new requirements, thereby the inconvenience part has been arranged in actual use.In addition, its Greenhouse effect GWP value is also higher.So it is still undesirable.In recent years, Germany uses some hydrocarbon polymer such as Trimethylmethane to replace F-12, and its advantage is that thermal property is good, but it is flammable, explosion hazard becomes the major obstacle of applying all the time.For carrying out explosion-proof processing, expensive bigger, and the optical haze reaction is arranged.For overcoming above-mentioned defective, the binary mixture HCFC22/HFC152a better performances of Tsing-Hua University's research and development, but HCFC22 wherein also will belong to the row of forbidding, and therefore also can only be as transitional surrogate.
The present invention is intended to develop new refrigeration agent, is inferior azeotropic mixture not only, and thermal property is good, and compliance with environmental protection requirements is safe, reliable, efficient, and need not change existing equipment and refrigeration oil; And can directly charge, be a kind of refrigeration agent (being called THR02) of substituted for freon-12 for long time
The refrigeration agent of this substituted for freon-12 for long time provided by the invention is characterized in that this refrigeration agent is made up of FC-131 and two kinds of materials of R290, and its component concentration (weight percent) is:
HFC-1311：80-95％
R290: 5-20% or form by FC-1311, R290 and three kinds of materials of HFC-152a, its content (weight percent) is:
FC-1311?：60-90％
R290????：3-10％
HFC-152a：5-35％
Also can change above-mentioned HFC-152a into HFC-227ea, promptly be made up of FC-1311, R290 and three kinds of materials of HFC-227ea, its content (weight percent) is:
FC-1311??：??55-85％
R290?????：?5-20％
HFC-227ea：?5-25％
Above-mentioned refrigeration agent, can also with a kind of material among FC-1311 and the R290 respectively with HFC-152a and two kinds of combinations of substances of HFC-227ea.
If during with FC-1311 and HFC-152a and three kinds of combinations of substances of HFC-227ea, its content (weight percent) is:
FC-1311??：??40-85％
HFC-152a?：??7-50％
HFC-227ea：??3-30％
If during with R290 and HFC-152a and three kinds of combinations of substances of RFC-227ea, its content (weight percent) is:
R290????：??5-15％
HFC-152a：??30-45％
HFC-227ea：?40-65％
Refrigeration agent provided by the invention, its preparation method are above-mentioned each component to be carried out physical mixed by its corresponding mixture ratio get final product under liquid phase state.
FC-1311 in the said components promptly is called CF3I, and its molecular formula is CF
8I, molecular weight are 195.91, normal boiling point-22.5 ℃, and critical temperature is 121.9 ℃, emergent pressure is 4.04MPa.
R290 also claims propane, and molecular formula is C
3H
8, molecular weight is 44.01, and normal boiling point is-42.1 ℃, and critical temperature is 113.3 ℃, and emergent pressure is 4.52MPa.
HFC-152a, its molecular formula is CH
3CHF
2, molecular weight is 66.05, and normal boiling point is-24 ℃, and critical temperature is that 96.8 ℃ of emergent pressures are 4.25MPa
HFC-227ea also claims heptafluoro-propane, and its molecular formula is CF
3CHFCF
3, molecular weight is 170.03, and normal boiling point is-18.3 ℃, and critical temperature is 103.5 ℃, and emergent pressure is 2.95MPa.
Embodiment:
Embodiment 1: the FC-1311 (CF with 80%
3I) and 20% R290 under liquid phase, carry out physical mixed.
Embodiment 2: the FC-1311 (CF with 70%
3I) and three kinds of materials of the HFC-152a of 10% R290 and 20% under liquid phase, mix.
Embodiment 3: the FC-1311 (CF with 70%
3I) and 20% R290 (C
3H
8) and three kinds of material liquid-phase mixing of HFC-227ea of 10%.
Embodiment 4: three kinds of material liquid-phase mixing of the HFC-227ea of the FC-1311 with 50% and 40% HFC-152a and 10%.
Embodiment 5: with the HFC-152a of 100R290 and 40% and three kinds of material liquid-phase mixing of HFC-227ea of 500%.
Under the design conditions of refrigerator, the thermal property of the foregoing description refrigeration agent is listed in the table 1.
Table 1 embodiment thermal property relatively
Annotate: be corresponding ratio with F-12.
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Evaporating pressure MPa | ????0.14 | ????0.13 | ????0.13 | ?????0.11 | ?????0.13 |
| Condensing pressure MPa | ????1.42 | ????1.43 | ????1.41 | ?????1.34 | ?????0.5 |
| Pressure ratio | ????10.5 | ????11.0 | ????10.6 | ?????12.0 | ?????11.3 |
| Exhaust temperature ℃ | ????141.3 | ????146.8 | ????136.1 | ?????147.0 | ?????127.4 |
| ????COP* | ????1.01 | ????1.01 | ????1.00 | ?????1.02 | ?????0.96 |
| Cold * | ????1.05 | ????1.12 | ????0.94 | ?????1.21 | ?????1.31 |
| Volume refrigerating capacity compressor * | ????1.05 | ????1.04 | ????1.01 | ?????0.93 | ?????0.99 |
| ????ODP | ????0 | ????0 | ????0 | ?????0 | ?????0 |
| ????GWP | ????＜10 | ????＜50 | ????＜350 | ????＜400 | ????＜1700 |
The present invention compared with prior art has the following advantages and beneficial effect (with among the present invention a kind of for example):
A, environmental performance:
This cold-producing medium ozone layer destroying potential (ODP) is zero, its greenhouse effects coefficient (GWP)＜50, baze-free reaction (VOC). This shows that the present invention meets Ozonosphere protection fully, do not affect greenhouse effects, the environmental protection requirement of baze-free reaction, table 1 has provided the comparison with the environmental performance of F-12 and other substitute.
The comparison of table 2 environmental performance
| Cold-producing medium | F-12 | HCF-134a | Iso-butane | The present invention |
| ODP | 1.0 | 0 | 0 | 0 |
| GWP (100 years) | 8500 | 1300 | 0 | ＜50 |
| VOC | 0.1 | 0.6 | 200 | Nothing |
B, thermal parameter:
Under the design conditions of refrigerator, the force value of the cold-producing medium in evaporimeter, the condenser, the pressure ratio of compressor and delivery temperature and F-12 are very close, and except delivery temperature is omited height, other all is better than used substitute HFC-134a and iso-butane, for example the evaporating pressure of iso-butane is in the vacuum operation less than 1 atmospheric pressure, and air easily bleeds; Therefore the pressure ratio of HFC-134a and iso-butane all is higher than the present invention, uses when of the present invention, and the volumetric efficiency of compressor is than they height.
The comparison of table 3 thermal parameter
| Cold-producing medium | F-12 | HCF-134a | Iso-butane 600a | The present invention |
| Evaporating pressure MPa | 0.129 | 0.115 | 0.039 | 0.12 |
| Condensing pressure | 1.352 | 1.475 | 0.556 | 1.35 |
| Pressure ratio | 10.46 | 12.85 | 14.1 | 11.6 |
| Delivery temperature ℃ | 145.7 | 134.9 | 118.8 | 151.5 |
C, thermal property
The thermal property of this cold-producing medium (COP and refrigerating capacity) is better than F-12, referring to table 4. Volume refrigerating capacity compressor approximates F-12, and this shows, this cold-producing medium can directly use the compressor of former F-12 and need not change, and the volume refrigerating capacity compressor of iso-butane is very little, and former compressor must be transformed.
Table 4 thermal property relatively
| Cold-producing medium | F-12 | HCF-134a | Iso-butane | The present invention |
| COP | 1.0 | 0.98 | 1.04 | 1.02 |
| Cold | 1.0 | 1.25 | 2.43 | 1.16 |
| Volume refrigerating capacity compressor | 1.0 | 0.93 | 0.35 | 0.97 |
In sum, it is good that the present invention not only has thermal property, and do not damage the ozone layer, and do not affect greenhouse effects, and the baze-free reaction meets environmental requirement fully. Be a kind of nontoxic, non-flammable inferior azeotropic mixture (slip temperature is less than 1 ℃), applicable to former refrigeration oil and directly perfusion, the critical piece in its compressor and the system need not changed, and production line need not transformed. Be better than existing other substitute in performance, can be used as the cold-producing medium of substituted for freon-12 for long time fully. The refrigerator Thermal Performance Test shows that the thermal properties such as its cooling rate, starting performance, refrigerating chamber and storeroom temperature all meet China's national standard fully, and than the energy-conservation 15-20% that reaches of former F-12; Filling quantity of refrigerant reduces about 20%.
Claims (5)
1, a kind of refrigeration agent of substituted for freon-12 for long time is characterized in that this refrigeration agent is made up of FC-1311 and two kinds of materials of R290, and its content (weight percent) is:
HFC-1311：80-95％
R290????：5-20％
2, a kind of refrigeration agent of chronicity replacement fluorine-12 is characterized in that this refrigeration agent is made up of FC-1311, R290 and three kinds of materials of HFC-152a, and its content (weight percent) is:
FC-1311?：60-90％
R290????：3-10％
HFC-152a：5-35％
3, a kind of refrigeration agent of substituted for freon-12 for long time is characterized in that this refrigeration agent is made up of FC-1311, R290 and three kinds of materials of HFC-227ea, and its content (weight percent) is:
FC-1311?：??55-85％
R290????：??5-20％
HFC-152a：??5-25％
4, a kind of refrigeration agent of substituted for freon-12 for long time is characterized in that this refrigeration agent is made up of FC-1311, HFC-152a and three kinds of materials of HFC-227ea, and its content (weight percent) is:
FC-131??：??40-85％
HFC-152a：??7-50％
HFC-227ea：?3-30％
5, a kind of refrigeration agent of substituted for freon-12 for long time is characterized in that this refrigeration agent is made up of R290, HFC-152a and three kinds of materials of HFC-227ea, and its content (weight percent) is:
R290????：??5-15％
HFC-152a：?30-45％
HFC-227ea：40-65％
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95117039A CN1053211C (en) | 1995-10-20 | 1995-10-20 | Refrigerant substituted for freon-12 for long time |
| PCT/CN1996/000093 WO1997015637A1 (en) | 1995-10-20 | 1996-10-18 | Refrigerant |
| AU72769/96A AU7276996A (en) | 1995-10-20 | 1996-10-18 | Refrigerant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95117039A CN1053211C (en) | 1995-10-20 | 1995-10-20 | Refrigerant substituted for freon-12 for long time |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1148613A true CN1148613A (en) | 1997-04-30 |
| CN1053211C CN1053211C (en) | 2000-06-07 |
Family
ID=5081110
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95117039A Expired - Fee Related CN1053211C (en) | 1995-10-20 | 1995-10-20 | Refrigerant substituted for freon-12 for long time |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1053211C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824305A (en) * | 2010-04-06 | 2010-09-08 | 中国科学院理化技术研究所 | Trifluoroiodomethane-containing mixed refrigerant |
| CN102876295A (en) * | 2004-04-16 | 2013-01-16 | 霍尼韦尔国际公司 | Azeotrope-like compositions of tetrafluoropropene and pentafluoropropene |
| CN102925108A (en) * | 2010-04-06 | 2013-02-13 | 中国科学院理化技术研究所 | Mixed refrigerant containing trifluoroiodomethane |
| CN102925109A (en) * | 2010-04-06 | 2013-02-13 | 中国科学院理化技术研究所 | Mixed refrigerant containing iodotrifluoromethane |
| CN107118746A (en) * | 2017-05-25 | 2017-09-01 | 华南理工大学 | A kind of environmentally friendly mix refrigerant and preparation method thereof |
| CN110157383A (en) * | 2019-05-22 | 2019-08-23 | 山西省工业设备安装集团有限公司 | It is a kind of for heat driven heat pump ternary mix working medium |
| CN110746936A (en) * | 2019-10-11 | 2020-02-04 | 金华永和氟化工有限公司 | Environment-friendly mixed refrigerant |
| CN111423854A (en) * | 2020-05-13 | 2020-07-17 | 全球能源互联网研究院有限公司 | Mixed cold storage medium and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992016597A1 (en) * | 1991-03-18 | 1992-10-01 | Allied-Signal Inc. | Non-azeotropic refrigerant compositions comprising difluoromethane; 1,1,1-trifluoroethane; or propane |
| JPH04323294A (en) * | 1991-04-22 | 1992-11-12 | Daikin Ind Ltd | Fluid for heat transfer |
-
1995
- 1995-10-20 CN CN95117039A patent/CN1053211C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102876295A (en) * | 2004-04-16 | 2013-01-16 | 霍尼韦尔国际公司 | Azeotrope-like compositions of tetrafluoropropene and pentafluoropropene |
| CN102876295B (en) * | 2004-04-16 | 2016-08-17 | 霍尼韦尔国际公司 | Difluoromethane and the Azeotrope-like compositions of CF3I |
| CN102925108B (en) * | 2010-04-06 | 2015-03-18 | 中国科学院理化技术研究所 | Mixed refrigerant containing trifluoroiodomethane |
| CN102925108A (en) * | 2010-04-06 | 2013-02-13 | 中国科学院理化技术研究所 | Mixed refrigerant containing trifluoroiodomethane |
| CN102925109A (en) * | 2010-04-06 | 2013-02-13 | 中国科学院理化技术研究所 | Mixed refrigerant containing iodotrifluoromethane |
| CN102925109B (en) * | 2010-04-06 | 2014-09-03 | 中国科学院理化技术研究所 | Mixed refrigerant containing iodotrifluoromethane |
| CN101824305A (en) * | 2010-04-06 | 2010-09-08 | 中国科学院理化技术研究所 | Trifluoroiodomethane-containing mixed refrigerant |
| CN101824305B (en) * | 2010-04-06 | 2012-11-21 | 中国科学院理化技术研究所 | Trifluoroiodomethane-containing mixed refrigerant |
| CN107118746A (en) * | 2017-05-25 | 2017-09-01 | 华南理工大学 | A kind of environmentally friendly mix refrigerant and preparation method thereof |
| CN110157383A (en) * | 2019-05-22 | 2019-08-23 | 山西省工业设备安装集团有限公司 | It is a kind of for heat driven heat pump ternary mix working medium |
| CN110746936A (en) * | 2019-10-11 | 2020-02-04 | 金华永和氟化工有限公司 | Environment-friendly mixed refrigerant |
| CN110746936B (en) * | 2019-10-11 | 2021-05-04 | 金华永和氟化工有限公司 | Environment-friendly mixed refrigerant |
| CN111423854A (en) * | 2020-05-13 | 2020-07-17 | 全球能源互联网研究院有限公司 | Mixed cold storage medium and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1053211C (en) | 2000-06-07 |
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