CN1884428A - Environment-friendly type heat pump mixed working medium - Google Patents
Environment-friendly type heat pump mixed working medium Download PDFInfo
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- CN1884428A CN1884428A CN 200610052423 CN200610052423A CN1884428A CN 1884428 A CN1884428 A CN 1884428A CN 200610052423 CN200610052423 CN 200610052423 CN 200610052423 A CN200610052423 A CN 200610052423A CN 1884428 A CN1884428 A CN 1884428A
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Abstract
The invention relates the environment-friendly type heat pump mixing working fluid, comprising HFC-125, HFC-134a, the third component and forth component. The third component is HFC-161 or HFC-152a, and the forth component is HC-600a or HC-600 or HC-290. The heat pump mixing working fluid meets the environment protection request, has good thermal parameter and thermodynamic property, and can replace the HCFC-22.
Description
Technical field
The present invention relates to finish in the heat pump working medium of thermodynamic cycle, relating in particular to a kind of ozone layer destroying potential is zero environment-friendly type mixing medium.
Background technology
Heat pump is as a kind of heat lifting gear, and its effect is a draw heat from surrounding environment, and it is passed to heated object.Its adopts the small portion electric energy to drive according to contrary carnot's working cycle principle, promotes compressor working medium is done work, and makes it absorb heat in the surrounding environment in vaporizer, discharges for people to use again through condenser.Heat pump is advantage aspect the energy-conservation and environmental protection at it, and especially the high economic benefit on heat of condensation reclaims causes people's attention, so in that to have refrigeration concurrently gradually many with the application that heats bifunctional heat-pump apparatus.
Heat pump fluid of the prior art is traditional HCFC-22 and some alternative mixing mediums.HCFC-22 (is CHClF
2) be the widely used working medium of present developing country's refrigeration air conditioner heat pump device.Though HCFC-22 has good thermal property, its pressure under the heat pump operating mode is higher, and is higher to the requirement of withstand voltage of system, and its environmental performance is not good.Because HCFC-22 is to the loss effect of ozonosphere and higher Greenhouse effect value, stipulate according to Montreal protocol, developed country advances to the year two thousand twenty to the HCFC end using time, developing country also will stop using the year two thousand thirty, therefore, HCFC will progressively be eliminated in future soon as heat pump fluid.
And the mixing medium that substitutes HCFC-22 mainly is divided into ODP=0 and ODP ≠ 0 two kind.Contain HCFC class material in the mixing medium of ODP ≠ 0, do not meet the environmental requirement of protection ozonosphere, and the mixing medium of ODP=0 is the alternative working medium of compliance with environmental protection requirements.
The alternative mixing medium of ODP=0 mainly contains:
1) R410A, though R410A has the good heat transfer performance, its heat pump operating mode overdraft is too high, even also higher by about 50% than HCFC-22, and is higher than HCFC-22 to the requirement of system, will increase production cost greatly.
2) R407C, though R407C pressure and HCFC-22 are close, its heat transfer property is not good, reach identical heating capacity, need to strengthen two devices, will strengthen production cost equally, and the temperature glide of R407C is bigger, and system reveals the bigger variation that will cause component, is unfavorable for system maintenance.
3) R417A (mix form R125/R134a/R600) and since its have lower system pressure Buddhist monk can heating effect, be the heat pump to replace working medium the most widely of consumption maximum, use range at present.R417A is not flammable, and ODP is zero, can dissolve each other with existing lubricating oil, is fit to typical HCFC-22 direct expansion system.At present, China and other national R417A that used produce air-conditioning and Teat pump boiler in batches.
Though the heat pump operating mode overdraft of the relative HCFC-22 of R417A decreases, and need not the withstand voltage design of raising system, its volume heating capacity descends too much, and its Greenhouse effect are excessive, still needs to improve, and therefore also is not that the best of HCFC-22 substitutes working medium.
In view of taking all factors into consideration many-sided factors such as environmental acceptability, security, power consumption, equipment size and system price, need a kind of environmental performance of searching, thermal property to be better than R417A, pressure is not higher than the novel environment-friendly heat pump fluid of R417A.
Summary of the invention
The present invention's purpose is to provide a kind of environment-friendly type heat pump working medium that meets current protection ozonosphere and suppress the environmental requirement that global warming lays equal stress on; another object of the present invention provide a kind of have be better than R417A or thermal parameter and the thermal performance suitable, can directly charge in R417A system with it, and can be used as the heat pump fluid of the long-term surrogate of HCFC-22.
For achieving the above object, the present invention adopts following technical scheme:
A kind of environment-friendly type heat pump working medium, it is characterized in that this working medium is by pentafluoride ethane (HFC-125), 1,1,1,2-Tetrafluoroethane (HFC-134a), the 3rd component and the 4th component are formed, wherein the 3rd component is fluoroethane (HFC-161) and 1, a kind of in the 1-C2H4F2 C2H4F2 (HFC-152a), and the 4th component is a kind of in Trimethylmethane (HC-600a), normal butane (HC-600) and the propane (HC-290).
Quaternary heat pump mixed working medium provided by the invention, with pentafluoride ethane (HFC-125), 1,1,1,2-Tetrafluoroethane (HFC-134a), the 3rd component and the 4th component, totally four kinds of components are carried out physical mixed under liquid phase state.
Described pentafluoride ethane (HFC-125), 1,1,1,2-Tetrafluoroethane (HFC-134a) with the mass percent of the 3rd component and the 4th component is:
HFC-125：10％-60％
HFC-134a：10％-70％
The 3rd component: 5%-75%
The 4th component: 1%-30%.
Further, the comparatively preferred mass percent of each component is:
HFC-125：20％-60％
HFC-134a：20％-60％
The 3rd component: 5%-35%
The 4th component: 1%-25%.
Experimental results show that its environmental performance and thermal performance are more excellent when HFC-125, HFC-134a mix by following mass percent with the 3rd component and the 4th component:
HFC-125：30％-50％
HFC-134a：30％-50％
The 3rd component: 10%-25%
The 4th component: 3%-10%.
Heat pump mixed working medium of the present invention is compared with the disclosed heat pump of prior art, has the following advantages:
1, environmental performance is good, and depletion potential ODP value is 0, and global warming potential GWP value is less than R417A, compliance with environmental protection requirements.
2, thermal parameter such as evaporating pressure, condensing pressure and pressure ratio and R417A are close, and under the prerequisite that does not change the equipment major parts, unit volume heating capacity, COP value are all greater than R417A.Mixing medium of the present invention can be directly used in the system of former use R417A, and can reduce filling quantity, improves Energy Efficiency Ratio, has the advantage of saving resource, save energy, and is more excellent as the long-term surrogate of HCFC-22 than R417A.
Embodiment
Heat pump fluid provided by the invention, its preparation method is with pentafluoride ethane (HFC-125), 1,1,1,2-Tetrafluoroethane (HFC-134a), the 3rd component is a fluoroethane (HFC-161), 1, a kind of and the 4th component in the 1-C2H4F2 C2H4F2 (HFC-152a) is a kind of in Trimethylmethane (HC-600a), normal butane (HC-600), the propane (HC-290), and totally four kinds of components are carried out physical mixed according to its corresponding mixture ratio under liquid phase state.
Pentafluoride ethane in the said components (HFC-125), its molecular formula are CHF
2CF
3, molecular weight is 120.02, and normal boiling point is-48.1 ℃, and critical temperature is 66.2 ℃, and emergent pressure is 3.63MPa.
In the said components 1,1,1,2-Tetrafluoroethane (HFC-134a), its molecular formula is CH
2FCF
3, molecular weight is 102.03, and normal boiling point is-26.1 ℃, and critical temperature is 101.1 ℃, and emergent pressure is 4.06MPa.
Fluoroethane in the said components (HFC-161), its molecular formula are CH
3CH
2F, molecular weight are 48.06, and normal boiling point is-37.1 ℃, and critical temperature is 102.2 ℃, and emergent pressure is 4.70MPa.
In the said components 1, its molecular formula of 1-C2H4F2 C2H4F2 (HFC-152a) is CH
3CHF
2, molecular weight is 66.05, and normal boiling point is-24.02 ℃, and critical temperature is 113.26 ℃, and emergent pressure is 4.52MPa.
Trimethylmethane in the said components (HC-600a), its molecular formula are CH (CH
3)
2CH
3, molecular weight is 58.12, and normal boiling point is-11.6 ℃, and critical temperature is 134.7 ℃, and emergent pressure is 3.64MPa.
Normal butane in the said components (HC-600), its molecular formula are CH
3CH
2CH
2CH
3, molecular weight is 58.12, and normal boiling point is-0.5 ℃, and critical temperature is 152.0 ℃, and emergent pressure is 3.80MPa.
Propane in the said components (HC-290), its molecular formula are CH
3CH
2CH
3, molecular weight is 44.10, and normal boiling point is-42.1 ℃, and critical temperature is 96.7 ℃, and emergent pressure is 4.25MPa.
The following examples are used for illustrating several embodiment of the present invention, but do not limit the invention to these embodiments.One skilled in the art would recognize that the present invention contained in claims scope all alternativess, improvement project and the equivalents that may comprise.
Embodiment 1: with HFC-125, HFC-134a, HFC-161, HC-600a under liquid phase by 30: 45: 20: 5 mass percent is carried out physical mixed.
Embodiment 2: with HFC-125, HFC-134a, HFC-161, HC-600a under liquid phase by 25: 50: 20: 5 mass percent is carried out physical mixed.
Embodiment 3: with HFC-125, HFC-134a, HFC-152a, HC-600a under liquid phase by 45: 20: 25: 10 mass percent is carried out physical mixed.
Embodiment 4: with HFC-125, HFC-134a, HFC-152a, HC-600a under liquid phase by 30: 50: 19: 1 mass percent is carried out physical mixed.
Embodiment 5: with HFC-125, HFC-134a, HFC-161, HC-600 under liquid phase by 30: 40: 25: 5 mass percent is carried out physical mixed.
Embodiment 6: with HFC-125, HFC-134a, HFC-161, HC-600 under liquid phase by 33: 37: 25: 5 mass percent is carried out physical mixed.
Embodiment 7: with HFC-125, HFC-134a, HFC-161, HC-600 under liquid phase by 25: 45: 25: 5 mass percent is carried out physical mixed.
Embodiment 8: with HFC-125, HFC-134a, HFC-152a, HC-600 under liquid phase by 30: 50: 17: 3 mass percent is carried out physical mixed.
Embodiment 9: with HFC-125, HFC-134a, HFC-161, HC-290 under liquid phase by 30: 50: 19: 1 mass percent is carried out physical mixed.
Embodiment 10: with HFC-125, HFC-134a, HFC-161, HC-600 under liquid phase by 10: 10: 75: 5 mass percent is carried out physical mixed.
Embodiment 11: with HFC-125, HFC-134a, HFC-161, HC-600a under liquid phase by 10: 10: 50: 30 mass percent is carried out physical mixed.
Embodiment 12: with HFC-125, HFC-134a, HFC-161, HC-600a under liquid phase by 60: 15: 22: 3 mass percent is carried out physical mixed.
Embodiment 13: with HFC-125, HFC-134a, HFC-161, HC-600 under liquid phase by 15: 70: 10: 5 mass percent is carried out physical mixed.
Now performance and the R417A with the foregoing description compares, and characteristics of the present invention and effect are described.
A. near azeotropic
The comparison of table 1 temperature glide (unit: ℃)
| Bubble point temperature | Dew-point temperature | Temperature glide | |
| Embodiment 1 | -38.06 | -36.03 | 2.03 |
| Embodiment 2 | -37.40 | -35.37 | 2.03 |
| Embodiment 3 | -37.68 | -32.66 | 5.02 |
| Embodiment 4 | -34.21 | -29.28 | 4.93 |
| Embodiment 5 | -37.71 | -34.77 | 2.95 |
| Embodiment 6 | -38.10 | -35.08 | 3.03 |
| Embodiment 7 | -37.08 | -34.27 | 2.81 |
| Embodiment 8 | -33.79 | -29.09 | 4.70 |
| Embodiment 9 | -40.09 | -35.77 | 4.32 |
| Embodiment 10 | -37.08 | -35.59 | 1.49 |
| Embodiment 11 | -35.60 | -31.36 | 4.24 |
| Embodiment 12 | -42.07 | -40.31 | 1.76 |
| Embodiment 13 | -33.7 | -30.56 | 3.14 |
| R417A | -38.01 | -32.87 | 5.14 |
(annotate: bubble point temperature in the table and dew-point temperature all are the temperature of saturation when standard atmospheric pressure 101.325kPa)
As can be seen from Table 1, the temperature glide of all embodiment is all less than R417A, and wherein the temperature glide of embodiment 1,2,5,6,7,10,12,13 is no more than 3.15 ℃, belongs to near-azeotropic mixture working medium.
B. environmental performance
Table 2 has compared the environmental performance of the foregoing description and R417A.Wherein as benchmark value 1.0, the GWP value is with CO with CFC-11 for the ODP value
2As benchmark value 1.0 (100 years).
Table 2 environmental performance relatively
| Working medium | ODP | GWP |
| Embodiment 1 | 0 | 1428 |
| Embodiment 2 | 0 | 1353 |
| Embodiment 3 | 0 | 1557 |
| Embodiment 4 | 0 | 1517 |
| Embodiment 5 | 0 | 1364 |
| Embodiment 6 | 0 | 1409 |
| Embodiment 7 | 0 | 1289 |
| Embodiment 8 | 0 | 1514 |
| Embodiment 9 | 0 | 1491 |
| Embodiment 10 | 0 | 419 |
| Embodiment 11 | 0 | 421 |
| Embodiment 12 | 0 | 1877 |
| Embodiment 13 | 0 | 1332 |
| R417A | 0 | 1956 |
As can be seen from Table 2, the ozonosphere of the foregoing description consumes potential (ODP) value and is zero, and is identical with R417A, and atmospheric ozone layer is not had destruction.
Moreover, the global warming potential of the foregoing description (GWP) is worth less than R417A, is 21%～96% of R417A GWP value, more meets current protection ozonosphere, reduces the environmental protection requirement that the Global warming effect is laid equal stress on.
C. thermal parameter and thermal performance
Under the heat pump operating mode (being vaporization temperature=10 ℃, condensing temperature=70 ℃, suction temperature=20 ℃, supercooling temperature=60 ℃), the thermal parameter of the foregoing description and R417A (that is: evaporating pressure P
0, condensing pressure P
k, pressure ratio P
k/ P
0, exhaust temperature t
2) and relative thermal performance (that is: relatively COP, relative unit quality heating capacity q
0, relative unit volume heating capacity q
v, relative unit volume wasted work amount w
v) relatively see Table 3.
Above-mentioned relative thermal performance is meant the ratio of each embodiment thermal performance and R417A thermal performance.
The comparison of table 3 thermal parameter and thermal performance
As seen, under heating condition, except that embodiment 9,12, the condensing pressure of all the other embodiment all is lower than R417A from table 3; The pressure ratio of each embodiment is all close with R417A, can directly charge in the system of former use R417A.
Though the exhaust temperature of the various embodiments described above all is higher than R417A, except that embodiment 10, all the other amplitudes are all less, all are in the allowed band.
The unit mass refrigerating duty all is higher than R417A, this means the filling quantity that can reduce systematic working medium.
The COP value is all greater than R417A, and therefore, these embodiment have energy-saving effect.
Except that embodiment 3,4,8,11,13, the unit volume heating capacity of all the other embodiment all is higher than R417A, and this shows can improve the speed of heating.
Except that embodiment 8,11, the unit volume wasted work amount of all the other embodiment is all close with R417A, and this shows that these embodiment can directly use the compressor of R417A, and need not substantially to change.
Claims (4)
1, a kind of environment-friendly type heat pump mixed working medium, it is characterized in that described mixing medium is by pentafluoride ethane (HFC-125), 1,1,1,2-Tetrafluoroethane (HFC-134a), the 3rd component and the 4th component are formed, wherein the 3rd component is fluoroethane (HFC-161) and 1, a kind of in the 1-C2H4F2 C2H4F2 (HFC-152a), and the 4th component is a kind of in Trimethylmethane (HC-600a), normal butane (HC-600) and the propane (HC-290).
2, environment-friendly type heat pump mixed working medium according to claim 1 is characterized in that the mass percent of described HFC-125, HFC-134a, the 3rd component and the 4th component is:
HFC-125：10％～60％
HFC-134a：10％～70％
The 3rd component: 5%～75%
The 4th component: 1%～30%.
3, environment-friendly type heat pump mixed working medium according to claim 1 and 2 is characterized in that the mass percent of described HFC-125, HFC-134a, the 3rd component and the 4th component is:
HFC-125：20％～60％
HFC-134a：20％～60％
The 3rd component: 5%～35%
The 4th component: 1%～25%.
4, environment-friendly type heat pump mixed working medium according to claim 1 and 2 is characterized in that the mass percent of described HFC-125, HFC-134a, the 3rd component and the 4th component is:
HFC-125：30％～50％
HFC-134a：30％～50％
The 3rd component: 10%～25%
The 4th component: 3%～10%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235275B (en) * | 2007-11-09 | 2013-01-02 | 中化蓝天集团有限公司 | Environmental protection type refrigerant |
| CN103436239A (en) * | 2013-09-10 | 2013-12-11 | 浙江永和制冷股份有限公司 | Refrigerant and preparation method thereof |
| CN104610918A (en) * | 2015-03-04 | 2015-05-13 | 天津大学 | Environment-friendly refrigerant suitable for refrigeration and cold storage system |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0568115B1 (en) * | 1990-07-26 | 1996-03-20 | E.I. Du Pont De Nemours & Company Incorporated | Near-azeotropic blends for use as refrigerants |
| WO1993015163A1 (en) * | 1992-02-03 | 1993-08-05 | Allied-Signal Inc. | Novel refrigerant compositions |
| MXPA02003357A (en) * | 1999-09-30 | 2004-09-10 | Rpl Holdings Ltd | Cfc 12 replacement refrigerant. |
| FR2860001B1 (en) * | 2003-09-19 | 2008-02-15 | Arkema | COMPOSITION BASED ON HFCs (HYDROFLUOROCARBONS) AND USE THEREOF |
| CN1285699C (en) * | 2004-09-29 | 2006-11-22 | 浙江蓝天环保高科技股份有限公司 | Environmental protection type refrigerant for replacement of CFC-12 |
| CN100347265C (en) * | 2005-09-16 | 2007-11-07 | 清华大学 | Mixed heat pump work substance with zero ozone layer destroying potential |
-
2006
- 2006-07-10 CN CNB2006100524233A patent/CN100460479C/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235275B (en) * | 2007-11-09 | 2013-01-02 | 中化蓝天集团有限公司 | Environmental protection type refrigerant |
| CN103436239A (en) * | 2013-09-10 | 2013-12-11 | 浙江永和制冷股份有限公司 | Refrigerant and preparation method thereof |
| CN103436239B (en) * | 2013-09-10 | 2016-03-02 | 浙江永和制冷股份有限公司 | Refrigeration agent and preparation method thereof |
| CN104610918A (en) * | 2015-03-04 | 2015-05-13 | 天津大学 | Environment-friendly refrigerant suitable for refrigeration and cold storage system |
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| CN100460479C (en) | 2009-02-11 |
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