CN102229794A - Refrigerant composition with low GWP (Global Warming Potential) value - Google Patents
Refrigerant composition with low GWP (Global Warming Potential) value Download PDFInfo
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- CN102229794A CN102229794A CN2011101170218A CN201110117021A CN102229794A CN 102229794 A CN102229794 A CN 102229794A CN 2011101170218 A CN2011101170218 A CN 2011101170218A CN 201110117021 A CN201110117021 A CN 201110117021A CN 102229794 A CN102229794 A CN 102229794A
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- refrigerant composition
- tetrafluoeopropene
- fluoroethane
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Abstract
The invention provides a refrigerant composition with low GWP (Global Warming Potential) value, and the refrigerant composition consists of fluoroethane(R161) and 2,3,3,3-tetrafluoropropene (HFO-1234yf). The preparation method of the refrigerant composition is as follows: physically mixing the components under liquid phase based on corresponding proportions. The refrigerant composition provided by the invention, which has zero ODP (Ozone Deplete Potential) value and quite low GWP value, can be applied to directly replacing R22 in a household air conditioners/heat pump systems and the like.
Description
Technical field
The invention belongs to refrigerant art, relate to a kind of refrigerant composition, relate in particular to and a kind ofly be applied to substitute in the refrigerated air-conditioning system such as domestic air conditioning/heat pump difluorochloromethane (R22) and have the dive refrigerant composition of value (GWP) of low Global warming.
Background technology
The Montreal protocol conference of contracting party that hold at Montreal, CAN in September, 2007, reached new resolution, wherein stipulate, developed country will stop the R22 production and consumption of non-feedstock property fully in the year two thousand twenty, the developing country that comprises China, be frozen on the mean level (ML) of 2009 and 2010 the production and consumption amounts with non-feedstock property HCFCs (wherein about 70% is R22) in 2013, the year two thousand thirty finishes comprehensively and eliminates.Compare original superseded timetable, whole superseded process shifts to an earlier date greatly, and about 80% systems such as domestic air conditioning/heat pump of domestic production at present and application adopt R22 to make refrigeration agent, this shows, the alternative situation of the R22 very research and development of sternness and substitute is extremely urgent.
Except protection ozonosphere problem; the Greenhouse effect problem that highlights also is one of current main environmental problem that faces; countries in the world all face very severe energy-saving and emission-reduction pressure challenge, and the energy-saving and emission-reduction topic becomes necessity of head of State's meeting and various forms meeting link is discussed.United Nations Environment Programme (UNEP) (UNEP) tentatively classifies to material with GWP value size, the GWP value greater than 1000 be high GWP material, it be middle GWP material between 300 and 1000 that the GWP value is situated between, GWP value less than 300 for hanging down the GWP material, the GWP value less than 100 be extremely to hang down the GWP material.At present, some countries and regions has begun to limit the application of high GWP value material, also plan progressively to eliminate the application of high GWP value and middle GWP value material in the medium-term and long-term development program, encourage growth hangs down the application of GWP value, especially extremely low GWP value material, therefore, low GWP value, refrigeration agent substitute energy-efficient, that cost is low will be the targets of next step development and pursuit.
In addition, when being applied to systems such as Teat pump boiler as R22, because its exhaust temperature is higher, make draw the hot water temperature can only be below 55 ℃, influenced its normal market sale and application, if can reduce exhaust temperature more than 10 ℃, then can correspondingly improve and about 10 ℃ of hot water temperatures, reach 65 ℃ of left and right sides hot water, so then can satisfy normal production or the resident living demand better.
Current, the main substitute of R22 comprises R407C (R32/125/134a) and R410A (R32/125) etc. on the domestic and international market, but these substitutes are still undesirable, and for example, the efficiency of R407C is lower, and its slip temperature is bigger, has restricted its market and has used; R410A and R22 system are incompatible, compressor that the alternative R22 of use R410A must more renew and two devices etc., and these two kinds of substitutes are direct filling to substitute R 22 all, needs system component or lubricated wet goods are done to change or change in alternative Process, has increased alternative cost greatly; Existing directly R417A of filling to substitute R 22 (R125/134a/600) or R422A (R125/134a/600a) etc., when direct filling to substitute R 22, though have lower exhaust temperature, show shortcomings such as efficient reduction, cold reduction or pressure increase, substitution effect is unsatisfactory.And they all belong to the refrigeration agent substitute of high GWP value, are still the progressively category of restriction in the long run.
In the prior art, U.S. Patent application US 20060022166, US 7534366, european patent application WO 2004037913 and Chinese patent file CN1732243A (200380107462.3) disclose the composition of five fluorine propylene and tetrafluoeopropene; Five fluorine propylene and 3,3 are disclosed among U.S. Patent application US 20040127383, the european patent application WO 2004037752,3-trifluoro propene, 1,1-C2H4F2 C2H4F2,1,1,1, the one or more combination thing in the 3-tetrafluoeopropene.It is the mixture of component that U.S. Patent application US20050245421, european patent application WO 2005108522 and Chinese patent file CN 101014680A (200580013536.6) disclose with tetrafluoeopropene and one or more fluoric ethers; The mixture of forming with tetrafluoeopropene and fluorocarbon (HFCs) is disclosed among U.S. Patent application US 7524805, the US 7767638; Chinese patent file CN 1977023A (200580019019.X) discloses five fluorine propylene (HFO-1225yeZ) and 2,3,3, the composition of 3-tetrafluoeopropene (HFO-1234yf); U.S. Patent application US7413674, US7465698, European patent WO2005103191 and Chinese patent file CN 101124288A (200580019196.8) disclose 1,1-C2H4F2 C2H4F2,2,3,3, the Azeotrope-like compositions of 3-tetrafluoeopropene and CF3I; U.S. Pat 6969701, european patent application WO2005103190 and Chinese patent file CN 1969028A (200580019197.2) disclose 2,3,3, the mixture of 3-tetrafluoeopropene and CF3I; It is the mixture of component that Chinese patent file CN1973016A (200580021136.X) discloses with tetrafluoeopropene and carbonic acid gas; U.S. Patent application US 20080075673, european patent application WO 2009005854 and Chinese patent file CN 101796154A (200880105818.2) disclose the mixture of tetrafluoeopropene and one or more hydrocarbon stable hydrocarbon; The mixture that 4-seven fluorine butylene and tetrafluoeopropene are formed is disclosed with 1,1,1,2,4,4 in the U.S. Pat 7563384; The mixture of forming with tetrafluoeopropene and bromine fluorine propylene is disclosed among U.S. Pat 7563384, the Chinese patent CN 101668796A (200880013714.9); Disclose a kind of composition among U.S. Pat 7708903, the Chinese patent CN 101415793A (200680054110.x), comprised fluoroolefin and at least a other component; Disclose the composition that contains methylene fluoride and fluorine substituted olefins among the Chinese patent file CN101665681 (200910163337.3), wherein fluorine substituted olefins comprises 1,1,1,3-tetrafluoeopropene and 2,3,3,3-tetrafluoeopropene etc.; Disclose with 2,3,3 in the U.S. Pat 20100123095, one or more are the mixture of component in 3-tetrafluoeopropene and cyclopropane, propylene, propane, C2H4F2 C2H4F2, the Tetrafluoroethane; One or more composition is disclosed in the U.S. Pat 20100122545 in tetrafluoeopropene and methylene fluoride, C2H4F2 C2H4F2, Tetrafluoroethane, the pentafluoride ethane; Disclose with 2,3,3 in the U.S. Pat 20100119460,3-tetrafluoeopropene and 3,3,3-trifluoro propene are the mixture of component.Though these compositions all are the lower compositions of GWP, exist or starting material are difficult to obtain and price is higher or slip temperature is big or performance is lower or not directly charge and be applied to R22 system or the more high deficiency of exhaust temperature.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of low GWP refrigerant composition, the direct refrigeration agent of filling to substitute R 22, be used for systems such as domestic air conditioning/heat pump, especially be applied in the Teat pump boiler, have characteristics such as safe and reliable, that refrigerating efficiency is high, need not more oil change, need not to change or change existing systems parts and production line, the transition cost is low, but also have low-down GWP value and lower exhaust temperature.
Technical scheme of the present invention is as follows:
A kind of refrigerant composition, the GWP value of this refrigeration agent (100 years) is lower than 12, and by fluoroethane (R161) and 2,3,3,3-tetrafluoeopropene (HFO-1234yf) is formed, and each constituent mass per-cent is as follows:
Fluoroethane: 30～90%
2,3,3,3-tetrafluoeopropene: 70～10%
Preferably, refrigerant composition component of the present invention is as follows, is mass percent:
Fluoroethane 50～90%, 2,3,3,3-tetrafluoeopropene 50～10%.
Further preferred, refrigerant composition component of the present invention is as follows, is mass percent:
Fluoroethane 60～80%, 2,3,3,3-tetrafluoeopropene 40～20%.
Optimized technical scheme of the present invention is as follows:
A kind of refrigerant composition, component is as follows, is mass percent: fluoroethane 60%, 2,3,3,3-tetrafluoeopropene 40%.
Another optimized technical scheme of the present invention is as follows:
A kind of refrigerant composition, component is as follows, is mass percent: fluoroethane 70%, 2,3,3,3-tetrafluoeopropene 30%.
Another optimized technical scheme of the present invention is as follows:
A kind of refrigerant composition, component is as follows, is mass percent: fluoroethane 80%, 2,3,3,3-tetrafluoeopropene 20%.
Fluoroethane in the said components (R161), its molecular formula are CH
3CH
2F, molar mass is 48.06, and normal boiling point is-37.6 ℃, and critical temperature is 102.2 ℃, and emergent pressure is 5.09MPa.
In the said components 2,3,3,3-tetrafluoeopropene (HFO-1234yf), its molecular formula is CH
2CFCF
3, molar mass is 114.04g/mol, and normal boiling point is-29.35 ℃, and critical temperature is 94.7 ℃, and emergent pressure is 3.375MPa.
The invention provides the preparation method of above-mentioned refrigeration agent, with fluoroethane and 2,3,3, the 3-tetrafluoeopropene carries out physical mixed by its corresponding mixture ratio and gets final product under liquid phase state.
Refrigerant composition of the present invention, be to be used for the directly refrigeration agent of filling to substitute R 22 of system such as domestic air conditioning/heat pump, be particularly useful in the heat pump water heater system directly filling to substitute R 22, need not more oil change, need not to change or change existing systems parts and production line.
Beneficial effect of the present invention is as follows:
A. environmental performance
The environmental performance that table 1 has been listed the present invention and R22 compares, as can be seen, ozone layer destroying potential value of the present invention (ODP) is zero, can not destroy atmospheric ozone layer, and the GWP value is very low, belong to ultralow GWP value substitute, satisfy current domestic and international environment-friend substitution requirement fully, representing the developing direction of next step refrigeration agent substitute environmental performance index R22.
Table 1 environmental performance relatively
B. thermal parameter:
The thermal parameter that table 2 has provided the present invention and R22 compares, under the air conditioning condition of ARI Standard 520 international standards, the force value of vaporizer, condenser inner refrigerant and R22 are close and a little less than R22, exhaust temperature is better than R22, can realize directly charging, and useful to the compressor long-time running.
Table 2 thermal parameter relatively
C. thermal property
The thermal property that table 3 has provided the present invention and R22 compares, and COP value of the present invention is slightly high than R22, has certain energy-saving effect; The unit mass refrigerating duty is better than R22, can corresponding minimizing system refrigerant charging amount; Refrigerating effect per unit swept volume and R22 are suitable, can satisfy the workload demand that substitutes refrigeration air-conditioner behind the R22 fully.
Table 3 thermal property relatively
D. directly charge performance
Basic thermal parameter of the present invention and R22 are very approaching, and through meeting the material compatibility experimental verification of international standard regulation, metallic substance, plastic material and resilient material etc. in the present invention and the former R22 system all are compatible, needn't transform or change the parts and the pipeline of former R22 system during replacement, thereby, the present invention can directly charge in the R22 system, need not to change any pipeline component.
In sum, ODP value of the present invention is zero, and the GWP value is very low, satisfies current domestic and international environment-friend substitution requirement to R22 fully, is representing the developing direction of next step refrigeration agent substitute environmental performance index; Pressure and R22 are close and a little less than R22, exhaust temperature is better than R22, and be useful to the compressor long-time running; COP is slightly high than R22, has certain energy-saving effect, and the unit mass refrigerating duty is better than R22, can corresponding minimizing system refrigerant charging amount, and refrigerating effect per unit swept volume and R22 are suitable, can satisfy the workload demand of refrigeration air-conditioner behind the alternative R22; Need not to change the equipment and the parts of existing R22 refrigerated air-conditioning system, can realize directly charging, is a kind of ideal substitute of R22.
Embodiment
For helping understanding, enumerate several specific embodiments below, but protection scope of the present invention is not limited to this to refrigeration agent of the present invention and advantage thereof.
The ratio of each component is mass percent in the embodiment of the invention, wherein, fluoroethane (R161), its molecular formula is CH
3CH
2F, molar mass is 48.06, and normal boiling point is-37.6 ℃, and critical temperature is 102.2 ℃, and emergent pressure is 5.09Mpa; 2,3,3,3-tetrafluoeopropene (HFO-1234yf), its molecular formula is CH
2CFCF
3, molar mass is 114.04g/mol, and normal boiling point is-29.35 ℃, and critical temperature is 94.7 ℃, and emergent pressure is 3.375MPa.
Embodiment 1: a kind of low GWP refrigerant composition, the fluoroethane by 30% and 70% 2,3,3, the 3-tetrafluoeopropene is formed.
The preparation method: with fluoroethane and 2,3,3, two kinds of materials of 3-tetrafluoeopropene carry out physical mixed by the respective quality proportioning and make refrigeration agent under liquid phase.
Embodiment 2: a kind of low GWP refrigerant composition, the fluoroethane by 40% and 60% 2,3,3, the 3-tetrafluoeopropene is formed.
The preparation method is with embodiment 1.
Embodiment 3: a kind of low GWP refrigerant composition, the fluoroethane by 50% and 50% 2,3,3, the 3-tetrafluoeopropene is formed.
The preparation method is with embodiment 1.
Embodiment 4: a kind of low GWP refrigerant composition, the fluoroethane by 60% and 40% 2,3,3, the 3-tetrafluoeopropene is formed.
The preparation method is with embodiment 1.
Embodiment 5: a kind of low GWP refrigerant composition, the fluoroethane by 70% and 30% 2,3,3, the 3-tetrafluoeopropene is formed.
The preparation method is with embodiment 1.
Embodiment 6: a kind of low GWP refrigerant composition, the fluoroethane by 80% and 20% 2,3,3, the 3-tetrafluoeopropene is formed.
The preparation method is with embodiment 1.
Embodiment 7: a kind of low GWP refrigerant composition, the fluoroethane by 90% and 10% 2,3,3, the 3-tetrafluoeopropene is formed.
The preparation method is with embodiment 1.
Under the air conditioning condition of ARI Standard 520 international standards, be that vaporization temperature is that 7.2 ℃, condensing temperature are that 54.4 ℃, temperature of superheat are that 11.1 ℃, supercooling temperature are that 8.3 ℃ 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 85% the operating mode.
The environmental parameter of table 4 refrigeration agent, physical parameter and thermal property
Remarks: * represents the corresponding ratio with R22, and wherein COP is the coefficient of performance.
Claims (7)
1. a refrigerant composition is characterized in that, by fluoroethane (R161) and 2,3,3,3-tetrafluoeopropene (HFO-1234yf) is formed, and the mass percent of each component is as follows:
Fluoroethane: 30～90%
2,3,3,3-tetrafluoeopropene: 70～10%
2. refrigerant composition as claimed in claim 1 is characterized in that component is as follows, is mass percent:
Fluoroethane 50～90%, 2,3,3,3-tetrafluoeopropene 50～10%.
3. refrigerant composition as claimed in claim 1 is characterized in that component is as follows, is mass percent:
Fluoroethane 60～80%, 2,3,3,3-tetrafluoeopropene 40～20%.
4. refrigerant composition as claimed in claim 1 is characterized in that component is as follows, is mass percent: fluoroethane 60%, 2,3,3,3-tetrafluoeopropene 40%.
5. refrigerant composition as claimed in claim 1 is characterized in that component is as follows, is mass percent: fluoroethane 70%, 2,3,3,3-tetrafluoeopropene 30%.
6. refrigerant composition as claimed in claim 1 is characterized in that component is as follows, is mass percent: fluoroethane 80%, 2,3,3,3-tetrafluoeopropene 20%.
7. the preparation method of each described refrigerant composition of claim 1-7 is with fluoroethane and 2,3,3, and the 3-tetrafluoeopropene carries out physical mixed by its corresponding mixture ratio under liquid phase state.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103820082B (en) * | 2014-03-02 | 2017-04-12 | 上海海洋大学 | Environmental protection refrigerant for ultralow-temperature refrigeration system |
| CN110373157A (en) * | 2019-07-22 | 2019-10-25 | 珠海格力电器股份有限公司 | Refrigerant composition and preparation method thereof |
| CN113480978A (en) * | 2021-07-07 | 2021-10-08 | 国节新辉科技(浙江)有限公司 | Refrigerant replacing R22, and preparation method and application thereof |
| CN115975602A (en) * | 2023-03-17 | 2023-04-18 | 北京星宇环试科技有限公司 | Non-combustible mixed refrigerant suitable for low-temperature system |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101297016A (en) * | 2005-03-04 | 2008-10-29 | 纳幕尔杜邦公司 | Compositions comprising a fluoroolefin |
-
2011
- 2011-05-06 CN CN2011101170218A patent/CN102229794A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101297016A (en) * | 2005-03-04 | 2008-10-29 | 纳幕尔杜邦公司 | Compositions comprising a fluoroolefin |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103820082B (en) * | 2014-03-02 | 2017-04-12 | 上海海洋大学 | Environmental protection refrigerant for ultralow-temperature refrigeration system |
| CN110373157A (en) * | 2019-07-22 | 2019-10-25 | 珠海格力电器股份有限公司 | Refrigerant composition and preparation method thereof |
| CN113480978A (en) * | 2021-07-07 | 2021-10-08 | 国节新辉科技(浙江)有限公司 | Refrigerant replacing R22, and preparation method and application thereof |
| CN115975602A (en) * | 2023-03-17 | 2023-04-18 | 北京星宇环试科技有限公司 | Non-combustible mixed refrigerant suitable for low-temperature system |
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Application publication date: 20111102 |