CN101020812A - Environment protection refrigerant composition - Google Patents
Environment protection refrigerant composition Download PDFInfo
- Publication number
- CN101020812A CN101020812A CN 200710013386 CN200710013386A CN101020812A CN 101020812 A CN101020812 A CN 101020812A CN 200710013386 CN200710013386 CN 200710013386 CN 200710013386 A CN200710013386 A CN 200710013386A CN 101020812 A CN101020812 A CN 101020812A
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- CN
- China
- Prior art keywords
- c2h4f2
- dme
- trimethylmethane
- refrigerant composition
- refrigeration agent
- 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.)
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- 239000000203 mixture Substances 0.000 title claims abstract description 27
- 239000003507 refrigerant Substances 0.000 title claims abstract description 23
- 239000007791 liquid phase Substances 0.000 claims abstract description 10
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 42
- 238000002360 preparation method Methods 0.000 claims description 2
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 abstract description 10
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 abstract 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 abstract 2
- 229940051271 1,1-difluoroethane Drugs 0.000 abstract 1
- 238000005057 refrigeration Methods 0.000 description 29
- 239000003795 chemical substances by application Substances 0.000 description 22
- 238000004378 air conditioning Methods 0.000 description 15
- 230000007613 environmental effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- VPAYJEUHKVESSD-UHFFFAOYSA-N trifluoroiodomethane Chemical compound FC(F)(F)I VPAYJEUHKVESSD-UHFFFAOYSA-N 0.000 description 5
- 239000001273 butane Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- UHCBBWUQDAVSMS-UHFFFAOYSA-N fluoroethane Chemical compound CCF UHCBBWUQDAVSMS-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
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- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The refrigerant composition for replacing R134a in automobile air conditioner consists of dimethyl ether DME or RE170, 1, 1-difluoro ethane R152a and isobutene R600a; and is prepared through liquid phase mixing the said components in certain proportion physically. The present invention has environment friendship, zero ODP, GWP lower than 150, heat engineering performance similar to that of R134a and high efficiency. The refrigerant composition is used for replacing R134a in automobile air conditioner.
Description
Technical field
The invention belongs to refrigerant art, relate to a kind of refrigerant composition, relate in particular to a kind of being applied to and substitute 1,1,1 in the automotive air-conditioning system, the refrigerant composition of 2-Tetrafluoroethane (R134a).
Background technology
Because 1,1,1,2-Tetrafluoroethane (R134a) has characteristics such as nontoxicity, not flammable, no burn into material compatibility be better, is widely used in fields such as automative air conditioning and some other refrigeration system.But because its chamber effect potential value (GWP value) too high (reaching 1300), the requirement of fluorine-containing greenhouse gases (F-gas) the control rules of having passed through according to European Union: from January 1st, 2011, European Union will forbid that the automative air conditioning of new production uses the GWP value greater than 150 refrigeration agent; On January 1st, 1 day 1 January in 2011 six in the period of, the vehicle in use air-conditioning will be in proportion progressively eliminated the GWP value greater than 150 refrigeration agent; From on January 1st, 2017, will forbid that all automative air conditionings use GWP values greater than 150 refrigeration agent.Therefore, automative air conditioning uses the refrigeration agent of low GWP value to become trend and inevitable, and the R134a that uses in the automative air conditioning will progressively eliminate, and does not also have both at home and abroad at present a kind ofly can be directly used in the alternative refrigerants that has automative air conditioning now and need not reforming equipment.
In patent application CN 200610049650.0, disclose a kind of with fluoroethane (R161) and 1, the mixture that 1-C2H4F2 C2H4F2 (R152a) is formed; In patent application CN 200610052120.1, the mixture that 1-C2H4F2 C2H4F2 (R152a) and Trimethylmethane (R600a) or butane (R600) etc. are formed is disclosed by fluoroethane (R161), 1; In patent application CN 98101170.5, disclose a kind of by 1, the mixture that 1-C2H4F2 C2H4F2 (R152a), butane (R600) and Trimethylmethane (R600a) are formed; The mixture of forming with CF3I (R13I1), butane (R600) and Trimethylmethane (R600a) is disclosed in patent application CN 200510119566.7; In patent application US 2003178597, disclose a kind of by Trimethylmethane (R600a), 1,1-C2H4F2 C2H4F2 (R152a) and carbonic acid gas (CO
2) mixture refrigerant formed; In patent application US 20060116310 and US 20060025322, the mixture refrigerant that 1-C2H4F2 C2H4F2 (R152a) and CF3I (R1311) are formed is disclosed by 1; In patent application US 20060043330 and US 20060019857, the mixture of being made up of CF3I (R13I1) and tetrafluoeopropene (R1234yf) is disclosed; In patent application JP 11199863, CF3I (R1311), butane (R600), Trimethylmethane (R600a) and 1 are disclosed, the mixture that 1-C2H4F2 C2H4F2 (R152a) is formed; In patent application WO 9529210, disclose a kind of by 1, the mixture refrigerant that 1-C2H4F2 C2H4F2 (R152a) and Trimethylmethane (R600a) are formed.These mix refrigerants are compared with R134a all has lower GWP value, but these mixtures or stronger combustibility is arranged, or have bigger slip temperature, bad with existing automotive air-conditioning system compatibility, or efficient is lower, costs an arm and a leg or the like.
Shanghai Communications University's machinery has been studied dme as automobile air-conditioning refrigeration agent (Liu Jinghui with power engineering institute; Chen Jiangping; Lu Xuesheng; Chen Zhijiu, automobile engineering, 2006 07 phases), analyze according to the refrigeration cycle performance of the thermal physical characteristic confrontation dme of dme, and the refrigeration performance to dme is tested on the R134a automotive air-conditioning system.The result shows: because the gas phase and the liquid phase viscosity of dme is all smaller, use dme can reduce the resistance of system as refrigeration agent, help the raising of system's refrigeration performance.Dme directly filling type substitutes R134a, but can cause the evaporator outlet superheating temperature to reduce.On the basis that the dme thermophysical property is analyzed, refrigeration performance to dme has carried out experimental study, and compare with the refrigeration performance of refrigerant R134a commonly used, the result shows: on same experimental installation, the refrigerating duty of the dme under identical condensing temperature, different vaporization temperature is lower approximately by 10%～15% than R134a, and coefficient of refrigerating performance (COP) is than low about 3%～9% (Liu Jinghui of R134a; Chen Jiangping; Lu Xuesheng; Chen Zhijiu, refrigeration journal, 2006 01 phases).
Summary of the invention
The present invention is intended to research and develop a kind of refrigeration agent that automotive air-conditioning system substitutes R134a that is used for, make alternative refrigerants newly developed should meet environmental protection requirement, again safety, reliable, refrigerating efficiency is high, but also need not to change existing equipment and production line, can directly charge.
The invention provides a kind of refrigerant composition, by dme (DME or RE170), 1,1-C2H4F2 C2H4F2 (R152a) and Trimethylmethane (R600a) are formed, and wherein each component is as follows, is mass percent:
Dme: 25～70
1,1-C2H4F2 C2H4F2: 25～70
Trimethylmethane: 1～5
Preferably, refrigerant composition of the present invention, component is as follows:
Dme 35～60%, 1,1-C2H4F2 C2H4F2 35～60%, Trimethylmethane 1～5% is mass percent.
Dme in the said components (DME or RE170), its molecular formula is CH
3OCH
3, molar mass is 46.07, and normal boiling point is-24.8 ℃, and critical temperature is 127.2 ℃, and emergent pressure is 5.34MPa.
1, the 1-C2H4F2 C2H4F2, its molecular formula is CF
2HCH
3, molar mass is 66.05, and normal boiling point is-24.0 ℃, and critical temperature is 113.3 ℃, and emergent pressure is 4.52MPa.
Trimethylmethane (R600a), its molecular formula are CH (CH
3)
3, molar mass is 58.12, and normal boiling point is-11.7 ℃, and critical temperature is 134.7 ℃, and emergent pressure is 3.63MPa.
The preparation method of refrigeration agent provided by the invention is above-mentioned various components to be carried out physical mixed by its corresponding mixture ratio get final product under liquid phase state.
The purposes of refrigerant composition of the present invention is used for the refrigeration agent that automotive air-conditioning system substitutes R134a.Alternative refrigerants newly developed had both met environmental protection requirement, again safety, reliable, refrigerating efficiency is high, but also need not to change existing equipment and production line, can directly charge.
The present invention has the following advantages and beneficial effect:
A. environmental performance
The environmental performance that table 1 has provided the present invention and R134a compares, and as can be seen, (ODP) is the same with R134a for ozone layer destroying potential of the present invention, is zero, can not destroy atmospheric ozone layer; And the Greenhouse effect potential (GWP) of R134a is 1300, and GWP value of the present invention only is 2.5～6.6% of R134a all less than 150, meets the environmental requirement of European Union to novel refrigerant fully, can significantly reduce the discharging of greenhouse gases.
Table 1 environmental performance relatively
| Refrigeration agent | R134a | The present invention |
| ODP | 0 | 0 |
| GWP (100 years) | 1300 | 32～86 |
B. thermal parameter:
The thermal parameter that table 2 has provided the present invention and R134a compares, and under aforementioned operating mode, the force value of vaporizer, condenser inner refrigerant and exhaust temperature are very approaching with R134a's, can realize directly charging, and condensing pressure is low useful to prolonging the compressor life-span; Slip temperature of the present invention is very little, is nearly azeotropic mixture, leaks very little to constituent element composition and Effect on Performance.
Table 2 thermal parameter relatively
| Refrigeration agent | R134a | The present invention |
| Evaporating pressure (kPa) | 283 | 271～282 |
| Condensing pressure (kPa) | 1780 | 1581～1659 |
| Exhaust temperature (℃) | 89.17 | 97.63～99.08 |
| Slip temperature (℃) | 0 | 0.03～0.3 |
C. thermal property
The thermal property that table 3 has provided the present invention and R134a compares, and COP of the present invention is bigger by 8～11% than R134a, and is more energy-efficient than R134a; Cold is also big than R134a, can be corresponding the refrigerant charging loading amount of minimizing system; Refrigerating effect per unit swept volume is also big by 6～9% than R134a, and air outlet temperature is lower, and cooling rate is faster.
Table 3 thermal property relatively
| Refrigeration agent | R134a | The present invention |
| COP | 1 | 1.08～1.11 |
| Cold | 1 | 1.87～2.26 |
| Volume refrigerating capacity compressor | 1 | 1.06～1.09 |
In sum, the present invention meets the environmental requirement of European Union to the automobile air-conditioning refrigeration agent fully, the ODP value is zero, the GWP value is very low, thermal property and R134a are very approaching, need not to change existing system equipment and parts, can realize directly charging, and it is more energy-efficient to compare R134a, is a kind of ideal substitute of R134a in the automative air conditioning.
Embodiment
In order to help understanding to refrigeration agent of the present invention and advantage thereof, enumerate several specific embodiments below, wherein the ratio of each component is mass percent.Dme among the embodiment (DME or RE170), its molecular formula is CH
3OCH
3, molar mass is 46.07, and normal boiling point is-24.8 ℃, and critical temperature is 127.2 ℃, and emergent pressure is 5.34MPa.1, the 1-C2H4F2 C2H4F2, its molecular formula is CF
2HCH
3, molar mass is 66.05, and normal boiling point is-24.0 ℃, and critical temperature is 113.3 ℃, and emergent pressure is 4.52MPa.Trimethylmethane (R600a), its molecular formula are CH (CH
3)
3, molar mass is 58.12, and normal boiling point is-11.7 ℃, and critical temperature is 134.7 ℃, and emergent pressure is 3.63MPa.
Embodiment 1: the dme with 70%, 25% 1,1-C2H4F2 C2H4F2 and three kinds of materials of Trimethylmethane of 5% carry out under liquid phase after the physical mixed as refrigeration agent.
Embodiment 2: the dme with 60%, 36% 1,1-C2H4F2 C2H4F2 and three kinds of materials of Trimethylmethane of 4% carry out under liquid phase after the physical mixed as refrigeration agent.
Embodiment 3: the dme with 50%, 47% 1,1-C2H4F2 C2H4F2 and three kinds of materials of Trimethylmethane of 3% carry out under liquid phase after the physical mixed as refrigeration agent.
Embodiment 4: the dme with 40%, 58% 1,1-C2H4F2 C2H4F2 and three kinds of materials of Trimethylmethane of 2% carry out under liquid phase after the physical mixed as refrigeration agent.
Embodiment 5: the dme with 30%, 69% 1,1-C2H4F2 C2H4F2 and three kinds of materials of Trimethylmethane of 1% carry out under liquid phase after the physical mixed as refrigeration agent.
Embodiment 6: the dme with 25%, 70% 1,1-C2H4F2 C2H4F2 and three kinds of materials of Trimethylmethane of 5% carry out under liquid phase after the physical mixed as refrigeration agent.
In vaporization temperature is that 62 ℃, temperature of superheat are that 10 ℃, supercooling temperature are that 5 ℃ and compressor efficiency are that the environmental parameter of the foregoing description refrigeration agent, physical parameter and thermal property are listed in the table 4 under 80% the operating mode for-1 ℃, condensing temperature.
Environmental parameter, physical parameter and the thermal property of table 4 embodiment refrigeration agent
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | R134a |
| ODP | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| GWP | ～32 | ～45 | ～58 | ～70 | ～84 | ～86 | 1300 |
| Molar mass g/mol | 50.40 | 52.19 | 54.10 | 56.16 | 58.38 | 59.22 | 102.03 |
| Evaporating pressure kPa | 271 | 276 | 281 | 282 | 280 | 280 | 283 |
| Condensing pressure kPa | 1581 | 1614 | 1639 | 1655 | 1659 | 1649 | 1780 |
| Exhaust temperature ℃ | 97.63 | 97.84 | 98.12 | 98.52 | 99.08 | 97.29 | 89.17 |
| Slip temperature ℃ | 0.3 | 0.2 | 0.1 | 0.03 | 0.04 | 0.05 | 0 |
| COP * | 1.11 | 1.10 | 1.10 | 1.09 | 1.09 | 1.08 | 1 |
| Cold * | 2.26 | 2.17 | 2.08 | 2.0 | 1.93 | 1.87 | 1 |
| Volume refrigerating capacity compressor * | 1.06 | 1.07 | 1.08 | 1.09 | 1.08 | 1.07 | 1 |
Remarks:
*The corresponding ratio of expression and R134a.Wherein COP is the coefficient of performance.
Claims (3)
1. an environment protection refrigerant composition is characterized in that, by dme, 1,1-C2H4F2 C2H4F2 and Trimethylmethane are formed, and wherein each component is as follows, is mass percent:
Dme: 25～70
1,1-C2H4F2 C2H4F2: 25～70
Trimethylmethane: 1～5.
2. environment protection refrigerant composition as claimed in claim 1 is characterized in that component is as follows:
Dme 35～60%, 1,1-C2H4F2 C2H4F2 35～60%, Trimethylmethane 1～5%; Be mass percent.
3. the preparation method of environment protection refrigerant composition as claimed in claim 1 is with dme, 1, and 1-C2H4F2 C2H4F2 and Trimethylmethane carry out physical mixed by its corresponding mixture ratio under liquid phase state.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710013386XA CN101020812B (en) | 2007-03-14 | 2007-03-14 | Environment protection refrigerant composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710013386XA CN101020812B (en) | 2007-03-14 | 2007-03-14 | Environment protection refrigerant composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101020812A true CN101020812A (en) | 2007-08-22 |
| CN101020812B CN101020812B (en) | 2011-12-28 |
Family
ID=38708692
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710013386XA Active CN101020812B (en) | 2007-03-14 | 2007-03-14 | Environment protection refrigerant composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101020812B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103045174A (en) * | 2012-12-24 | 2013-04-17 | 广州市香港科大霍英东研究院 | Environment-friendly medium-high temperature heat pump working medium containing dimethyl ether and iodotrifluoromethane |
| CN103289648A (en) * | 2013-05-06 | 2013-09-11 | 陈振乐 | Environmentally-friendly energy-saving refrigerant capable of substituting R134a |
| CN110843457A (en) * | 2019-10-16 | 2020-02-28 | 珠海格力电器股份有限公司 | Automobile air conditioner heat pump system adopting environment-friendly refrigerant |
| CN110845997A (en) * | 2019-10-16 | 2020-02-28 | 珠海格力电器股份有限公司 | Heat transfer medium and composition suitable for cooler |
| CN114989783A (en) * | 2022-05-28 | 2022-09-02 | 哈尔滨工业大学 | Environment-friendly mixed refrigerant and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL106132A0 (en) * | 1992-06-25 | 1993-10-20 | Great Lakes Chemical Corp | Refrigerant composition containing 1,1,1,2,3,3,3-heptafluoropropane and methods utilizing the same |
| CN1431271A (en) * | 2003-01-08 | 2003-07-23 | 苏州联氟化学有限公司 | Cross blend refrigerant used to substitute freon R-12 |
| US20090261289A1 (en) * | 2004-08-25 | 2009-10-22 | Yoon-Sik Ham | R502, R12 or R22 Substitute Mixed Refrigerant and Refrigeration System Using Thereof |
-
2007
- 2007-03-14 CN CN200710013386XA patent/CN101020812B/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103045174A (en) * | 2012-12-24 | 2013-04-17 | 广州市香港科大霍英东研究院 | Environment-friendly medium-high temperature heat pump working medium containing dimethyl ether and iodotrifluoromethane |
| CN103289648A (en) * | 2013-05-06 | 2013-09-11 | 陈振乐 | Environmentally-friendly energy-saving refrigerant capable of substituting R134a |
| CN110843457A (en) * | 2019-10-16 | 2020-02-28 | 珠海格力电器股份有限公司 | Automobile air conditioner heat pump system adopting environment-friendly refrigerant |
| CN110845997A (en) * | 2019-10-16 | 2020-02-28 | 珠海格力电器股份有限公司 | Heat transfer medium and composition suitable for cooler |
| CN114989783A (en) * | 2022-05-28 | 2022-09-02 | 哈尔滨工业大学 | Environment-friendly mixed refrigerant and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101020812B (en) | 2011-12-28 |
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Effective date of registration: 20240115 Address after: 1399 Gongye Road, Tangshan Town, Huantai County, Zibo City, Shandong Province, 256400 Patentee after: Shandong Dongyue Green Cold Technology Co.,Ltd. Address before: 256401 Tangshan Town, Huantai County, Shandong Province Patentee before: SHANDONG DONGYUE CHEMICAL Co.,Ltd. |
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