CN101892033A - Hydrocarbon-containing medium-high temperature heat pump mixture - Google Patents
Hydrocarbon-containing medium-high temperature heat pump mixture Download PDFInfo
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- CN101892033A CN101892033A CN2010102228654A CN201010222865A CN101892033A CN 101892033 A CN101892033 A CN 101892033A CN 2010102228654 A CN2010102228654 A CN 2010102228654A CN 201010222865 A CN201010222865 A CN 201010222865A CN 101892033 A CN101892033 A CN 101892033A
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Abstract
The invention discloses a set of hydrocarbon-containing medium-high temperature heat pump mixture, which is suitable for serving as a low-temperature organic Rankine cycle system refrigerant the evaporation temperature of which is 60-100 DEG C. The set of mixed working fluid can be a binary, tertiary or quaternary mixture prepared from eight substances (R600, R600a, R290, R245fa, R13I1, R152a, R124 and R142b) according to different mass ratios. The preparation method comprises the step of physically mixing the various components according to a specific proportion at ordinary temperature to obtain the corresponding mixed working fluid. The working fluid does not cause damage to the ozonosphere, and the greenhouse effect potential is lower, thereby meeting the environmental requirements. The thermal parameters are eligible and the cycle performance is fine, so the working fluid can be directly filled in an HFC134a air conditioning compressor, thereby avoiding specially designing a compressor for the working fluid. Besides, COP under design conditions is 4 or so, and the output net work per unit mass is above 150kJ/kg.
Description
Technical field
The invention belongs to the refrigeration agent in heat pump or the air-conditioning system, being specifically related to as condensing temperature is refrigeration working medium in 60-100 ℃ the moderate and high temperature heat system.
Background technology
For produce and life in a large amount of that exist, to heat energy grade requirement relatively low (temperature is 60-100 ℃) with alleviating, adopt the heat pump heat supply technology that the total energy utilising efficiency higher than conventional energy-provision way not only arranged, reduce the CO2 discharging, can also effectively utilize the low grade heat energy that contains in industrial exhaust heat, Geothermal energy, sun power and the environment (air, soil, surface water or shallow ground water), reduce the thermal pollution that the waste heat discharging causes.Current, high temperature in the heat pump techniques forward (condensing temperature 80-100 ℃), high temperature (condensing temperature is higher than 100 ℃) heat pump direction develop, and restrict one of key issue of its development, are exactly to lack the cycle fluid that is fit to.The material that in the past once was used as high temperature heat pump system working medium has CFC11, CFC113, CFC114 etc., they are CFC class material, its depletion of the ozone layer gesture (ODP) and global warming potential (GWP) are all very big, and developed country is in forbidding in 1996, and developing country also will be in forbidding in 2010.Using at present more is to be the air-conditioning-heat pump of working medium with HCFC22 or its surrogate R407C etc., and the hot water top temperature that can provide is 50-55 ℃, and the heat energy of higher temperature level can't be provided.Development environment close friend, the good novel working medium of thermal performance are most important to the development of moderate and high temperature heat technology.
Mixing medium provided by the invention is for condensing temperature is that 60-100 ℃ moderate and high temperature heat system applies is developed, and also can be used as centrifugal refrigerating, air conditioning unit working medium.
Summary of the invention
The objective of the invention is, provide one group to contain the new working medium that hydrocarbon polymer is suitable for the application of moderate and high temperature heat unit, make its environmental characteristics and environmental performance all good.
Content introduction of the present invention: carry out the constituent element combination according to the principle of having complementary advantages, screening obtains the moderate and high temperature heat mixing medium of following excellent property.Specifically comprise: butane (R600), Trimethylmethane (R600a), propane (R290), 1,1,1,3,3-pentafluoropropane (R245fa), CF3I (R13I1), 1,1-C2H4F2 C2H4F2 (R152a), a chloro-1,2,2, a 2-Tetrafluoroethane (R124) and a chloro-1,1-C2H4F2 C2H4F2 (R142b).The basic parameter of each constituent element material is as shown in table 1.
The moderate and high temperature heat mixing medium that contains HC600, HC600a and HC290 that the present invention proposes, by butane (R600) and 1,1,1,3,3-pentafluoropropane (R245fa) is formed; Or by Trimethylmethane (R600a) and 1,1,1,3,3-pentafluoropropane (R245fa); Trimethylmethane (R600a) is formed, or by 1,1,1,3,3-pentafluoropropane (R245fa) and CF3I (R13I1) are formed; Or by butane (R600), 1,1,1,3,3-pentafluoropropane (R245fa) and 1,1-C2H4F2 C2H4F2 (R152a) is formed; Or by Trimethylmethane (R600a), 1,1,1,3,3-pentafluoropropane (R245fa) and 1,1-C2H4F2 C2H4F2 (R152a) is formed; Or by a chloro-1,1-C2H4F2 C2H4F2 (R142b), a chloro-1,2,2,2-Tetrafluoroethane (R124), Trimethylmethane (R600a) and 1,1,1,3,3-pentafluoropropane (R245fa) is formed; Or by a Trimethylmethane (R600a) and a chloro-1,1-C2H4F2 C2H4F2 (R142b) is formed; Or form by Trimethylmethane (R600a) and CF3I (R13I1); Or form by butane (R600) and CF3I (R13I1); Or by propane (R290) and 1,1,1,3,3-pentafluoropropane (R245fa) is formed; Or by a propane (R290) and a chloro-1,2,2,2-Tetrafluoroethane (R124) is formed; Or by a propane (R290) and a chloro-1,1-C2H4F2 C2H4F2 (R142b) is formed.
The concrete proportioning (mass percent) of above-mentioned each constituent element material is:
R600/R245fa 2-97/3-98%,
R600a/R245fa 3-98/2-97%,
R600a/R245fa/R13I1 3-97/2-96/1-95%,
R600/R245fa/R152a 4-90/5-91/5-91%,
R600a/R245fa/R152a 3-93/4-94/3-93%,
R142b/R124/R600a/R245fa 2-94/3-95/2-94/1-93%,
R600a/R142b 2-97/3-98%,
R600a/R13I1 2-97/3-98%,
R600/R13I1 2-97/3-98%,
R290/R245fa 2-97/3-98%,
R290/R124 2-97/3-98%,
R290/R142b 2-97/3-98%,
More than each constituent element material mass percentage ratio sum of every kind of mixing medium be 100%.
The preparation method of above-mentioned mixing medium is each constituent element material to be carried out physical mixed at normal temperatures by its specified quality proportioning get final product.More than each constituent element material mass percentage ratio sum of every kind of mixing medium be 100%.
The present invention has the following advantages and beneficial effect:
(1) environmental performance: ODP of the present invention equals zero or is lower, and environmental characteristics is good.
(2) thermal parameter is suitable: under moderate and high temperature heat system design operating mode, stress level is not higher than the stress level of HFC134a under the standard air conditioning condition, and row's temperature is lower than the exhaust temperature restriction of HFC134a compressor.Therefore, can directly working medium of the present invention be poured into the compressor of air conditioner of HFC134a, need not to be working medium otherwise designed compressor of the present invention.
(3) cycle performance is good: the present invention is heating that COP is about 4, more than 150kJ/kg, the unit volume heating capacity is at 3000kJ/m substantially for the unit mass heat supplied under the above-mentioned design conditions
3More than, cycle performance is good.
The basic parameter of contained constituent element in the table 1 moderate and high temperature heat mixing medium
T
b: normal boiling point, T
c: critical temperature, P
c: emergent pressure
Embodiment
Embodiment 1: get 20
Mass%R600 and 80
Mass%R245fa carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 2: get 55
Mass%R600 and 45
Mass%R245fa carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 3: get 75
Mass%R600 and 25
Mass%R245fa carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 4: get 25
Mass%R600a and 75
Mass%R245fa carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 5: get 50
Mass%R600a and 50
Mass%R245fa carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 6: get 70
Mass%R600a and 30
Mass%R245fa carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 7: get 20
Mass%R600a, 70
Mass%R245fa and 10
Mass%R13I1 carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 8: get 30
Mass%R600a, 10
Mass%R245fa and 60
Mass%R13I1 carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 9: get 70
Mass%R600a, 20
Mass%R245fa and 10
Mass%R13I1 carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 10: get 10
Mass%R600,70
Mass%R245fa and 20
Mass%R152a carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 11: get 30
Mass%R600,20
Mass%R245fa and 50
Mass%R152a carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 12: get 70
Mass%R600,20
Mass%R245fa and 10
Mass%R152a carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 13: get 25
Mass%R600a, 65
Mass%R245fa and 10
Mass%R152a carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 14: get 30
Mass%R600a, 10
Mass%R245fa and 60
Mass%R152a carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 15: get 70
Mass%R600a, 20
Mass%R245fa and 10
Mass%R152a carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 16: get 20
Mass%R142b, 60
Mass%R124,10
Mass%R600a and 10
Mass%R245fa carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 17: get 30
Mass%R142b, 10
Mass%R124,50
Mass%R600a and 10
Mass%R245fa carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 18: get 70
Mass%R142b, 10
Mass%R124,10
Mass%R600a and 10
Mass%R245fa carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 19: get 30
Mass%R600a and 70
Mass%R142b carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 20: get 50
Mass%R600a and 50
Mass%R142b carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 21: get 75
Mass%R600a and 25
Mass%R142b carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 22: get 25
Mass%R600a and 75
Mass%R13I1 carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 23: get 50
Mass%R600a and 50
Mass%R13I1 carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 24: get 95
Mass%R600a and 5
Mass%R13I1 carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 25: get 20
Mass%R600 and 80
Mass%R13I1 carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 26: get 50
Mass%R600 and 50
Mass%R13I1 carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 27: get 90
Mass%R600 and 10
Mass%R13I1 carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 28: get 30
Mass%R290 and 70
Mass%R245fa carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 29: get 55
Mass%R290 and 45
Mass%R245fa carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 30: get 80
Mass%R290 and 20
Mass%R245fa carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 31: get 2
Mass%R290 and 98
Mass%R124 carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 32: get 45
Mass%R290 and 55
Mass%R124 carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 33: get 85
Mass%R290 and 15
Mass%R124 carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 34: get 6
Mass%R290 and 94
Mass%R142b carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 35: get 30
Mass%R290 and 70
Mass%R142b carries out after the physical mixed at normal temperatures as refrigeration agent.
Embodiment 36: get 80
Mass%R290 and 20
Mass%R142b carries out after the physical mixed at normal temperatures as refrigeration agent.
The design conditions of heat pump are taken as: average vaporization temperature is 45 ℃, 90 ℃ of average condensing temperatures, and 2 ℃ of suction superheat (, avoiding wet compression with assurance) with suitable exhaust superheating temperature to some working medium, condensate depression is 0 ℃.With closed piston compressor is example, and compressor heat efficient gets 0.9, and electrical efficiency, mechanical efficiency are 0.75, and the clearance volume coefficient gets 0.03.
According to cycle calculations, above-mentioned 36 embodiment have related parameter and cycle performance index as shown in table 2.
Table 2 embodiment of the invention performance
Parameter and performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
Evaporating pressure MPa | 0.35 | 0.39 | 0.41 | 0.41 | 0.48 | 0.54 |
Condensing pressure MPa | 1.11 | 1.19 | 1.22 | 1.26 | 1.43 | 1.53 |
Pressure ratio | 3.2 | 3.01 | 2.95 | 3.11 | 2.95 | 2.85 |
Exhaust temperature ℃ | 96.7 | 97 | 97 | 98 | 98 | 97.5 |
COP h | 4.34 | 4.35 | 4.36 | 4.25 | 4.20 | 4.16 |
Heat supplied kJ/kg | 141 | 181 | 204 | 140 | 159 | 173 |
Unit volume heating capacity kJ/m 3 | 2019 | 2185 | 2248 | 2244 | 2487 | 2624 |
Parameter and performance | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 |
Evaporating pressure MPa | 0.41 | 0.63 | 0.56 | 0.45 | 0.64 | 0.45 |
Condensing pressure MPa | 1.28 | 1.75 | 1.58 | 1.45 | 1.9 | 1.34 |
Pressure ratio | 3.11 | 2.78 | 2.8 | 3.2 | 3.0 | 2.97 |
Exhaust temperature ℃ | 98.8 | 102 | 97.8 | 105 | 110 | 99.7 |
COP h | 4.26 | 4.15 | 4.15 | 4.29 | 4.23 | 4.34 |
Heat supplied kJ/kg | 130 | 105 | 16 | 149 | 189 | 207 |
Unit volume heating capacity kJ/m 3 | 2281 | 3000 | 2703 | 2625 | 3383 | 2452 |
Parameter and performance | Embodiment 13 | Embodiment 14 | Embodiment 15 | Embodiment 16 | Embodiment 17 | Embodiment 18 |
Evaporating pressure MPa | 0.46 | 0.79 | 0.59 | 0.60 | 0.58 | 0.58 |
Condensing pressure MPa | 1.44 | 2.26 | 1.66 | 1.75 | 1.64 | 1.68 |
Pressure ratio | 3.1 | 2.8 | 2.8 | 2.9 | 2.8 | 2.9 |
Exhaust temperature ℃ | 101 | 110 | 99 | 102 | 99 | 104 |
COP h | 4.23 | 4.06 | 4.14 | 4.12 | 4.17 | 4.25 |
Heat supplied kJ/kg | 149 | 175 | 179 | 108 | 156 | 130 |
Unit volume heating capacity kJ/m 3 | 2546 | 3785 | 2837 | 2963 | 2827 | 2989 |
Parameter and performance | Embodiment 19 | Embodiment 20 | Embodiment 21 | Embodiment 22 | Embodiment 23 | Embodiment 24 |
Evaporating pressure MPa | 0.61 | 0.61 | 0.61 | 0.70 | 0.65 | 0.60 |
Condensing pressure MPa | 1.71 | 1.69 | 1.67 | 1.89 | 1.76 | 1.66 |
Pressure ratio | 2.8 | 2.8 | 2.8 | 2.7 | 2.7 | 2.7 |
Exhaust temperature ℃ | 102 | 100 | 98 | 103 | 100 | 97 |
COP h | 4.22 | 4.18 | 4.14 | 4.13 | 4.12 | 4.11 |
Heat supplied kJ/kg | 147 | 160 | 177 | 91 | 125 | 187 |
Unit volume heating capacity kJ/m 3 | 3001 | 2919 | 2836 | 3212 | 2979 | 2784 |
Parameter and performance | Embodiment 25 | Embodiment 26 | Embodiment 27 | Embodiment 28 | Embodiment 29 | Embodiment 30 |
Evaporating pressure MPa | 0.61 | 0.50 | 0.44 | 0.68 | 0.99 | 1.30 |
Condensing pressure MPa | 1.70 | 1.43 | 1.28 | 2.13 | 2.83 | 3.41 |
Pressure ratio | 2.8 | 2.9 | 2.9 | 3.1 | 2.8 | 2.6 |
Exhaust temperature ℃ | 106 | 101 | 97 | 112 | 113 | 111 |
COP h | 4.27 | 4.33 | 4.36 | 3.99 | 3.67 | 3.33 |
Heat supplied kJ/kg | 94 | 147 | 215 | 155 | 160 | 149 |
Unit volume heating capacity kJ/m 3 | 3056 | 2610 | 2350 | 3489 | 4137 | 4301 |
Parameter and performance | Embodiment 31 | Embodiment 32 | Embodiment 33 | Embodiment 34 | Embodiment 35 | Embodiment 36 |
Evaporating pressure MPa | 0.71 | 1.19 | 1.46 | 0.68 | 0.93 | 1.38 |
Condensing pressure MPa | 2.03 | 3.13 | 3.65 | 1.93 | 2.55 | 3.50 |
Pressure ratio | 2.9 | 2.6 | 2.5 | 2.8 | 2.7 | 2.5 |
Exhaust temperature ℃ | 103 | 109 | 109 | 108 | 111 | 109 |
COP h | 3.92 | 3.44 | 3.12 | 4.22 | 3.92 | 3.30 |
Heat supplied kJ/kg | 84 | 114 | 128 | 133 | 145 | 142 |
Unit volume heating capacity kJ/m 3 | 3218 | 4125 | 4148 | 3407 | 4075 | 4330 |
Claims (2)
1. the moderate and high temperature heat mixing medium that contains hydrocarbon polymer is characterized in that by butane (R600) and 1,1,1,3, and 3-pentafluoropropane (R245fa) is formed; Or by Trimethylmethane (R600a) and 1,1,1,3,3-pentafluoropropane (R245fa); Trimethylmethane (R600a) is formed, or by 1,1,1,3,3-pentafluoropropane (R245fa) and CF3I (R13I1) are formed; Or by butane (R600), 1,1,1,3,3-pentafluoropropane (R245fa) and 1,1-C2H4F2 C2H4F2 (R152a) is formed; Or by Trimethylmethane (R600a), 1,1,1,3,3-pentafluoropropane (R245fa) and 1,1-C2H4F2 C2H4F2 (R152a) is formed; Or by a chloro-1,1-C2H4F2 C2H4F2 (R142b), a chloro-1,2,2,2-Tetrafluoroethane (R124), Trimethylmethane (R600a) and 1,1,1,3,3-pentafluoropropane (R245fa) is formed; Or by a Trimethylmethane (R600a) and a chloro-1,1-C2H4F2 C2H4F2 (R142b) is formed; Or form by Trimethylmethane (R600a) and CF3I (R13I1); Or form by butane (R600) and CF3I (R13I1); Or by propane (R290) and 1,1,1,3,3-pentafluoropropane (R245fa) is formed; Or by a propane (R290) and a chloro-1,2,2,2-Tetrafluoroethane (R124) is formed; Or by a propane (R290) and a chloro-1,1-C2H4F2 C2H4F2 (R142b) is formed.
2. according to the described moderate and high temperature heat mixing medium that contains hydrocarbon polymer of claim 1, it is characterized in that the concrete proportioning (mass percent) of described each constituent element material is:
R600/R245fa 2-97/3-98%,
R600a/R245fa 3-98/2-97%,
R600a/R245fa/R13I1 3-97/2-96/1-95%,
R600/R245fa/R152a 4-90/5-91/5-91%,
R600a/R245fa/R152a 3-93/4-94/3-93%,
R142b/R124/R600a/R245fa 2-94/3-95/2-94/1-93%,
R600a/R142b 2-97/3-98%,
R600a/R13I1 2-97/3-98%,
R600/R13I1 2-97/3-98%,
R290/R245fa 2-97/3-98%,
R290/R124 2-97/3-98%,
R290/R142b 2-97/3-98%,
More than each constituent element material mass percentage ratio sum of every kind of mixing medium be 100%.
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CN201210452792.7A Division CN102925111B (en) | 2010-07-09 | 2010-07-09 | Low-high-temperature heat pump mixed working medium containing hydrocarbon butane |
CN2012104557585A Division CN102925112A (en) | 2010-07-09 | 2010-07-09 | Medium-high temperature heat pump mixed refrigerants containing hydrocarbon trifluoro-iodomethane |
CN201210353683XA Division CN102911642A (en) | 2010-07-09 | 2010-07-09 | Medium-and-high temperature heat pump refrigerant mixture containing iso-butane (R600a) |
CN201210353059XA Division CN102911641A (en) | 2010-07-09 | 2010-07-09 | Medium-high temperature heat pump mixed refrigerant containing propane (R290) |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN105733514A (en) * | 2016-04-08 | 2016-07-06 | 中国建筑科学研究院 | Medium-high temperature heat pump mixed working medium containing R13I1 and used for large-cycle temperature rise |
CN114149791A (en) * | 2021-11-18 | 2022-03-08 | 湖北瑞能华辉能源管理有限公司 | Energy-saving environment-friendly heat pump working medium capable of realizing high-temperature heating and application thereof |
CN114752359A (en) * | 2022-04-13 | 2022-07-15 | 华中科技大学 | Energy-saving environment-friendly working medium capable of replacing HFC245fa for heat pump boiler |
CN114752358A (en) * | 2022-04-13 | 2022-07-15 | 华中科技大学 | Energy-saving environment-friendly working medium for heat pump boiler |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1821681A (en) * | 2004-12-14 | 2006-08-23 | 三洋电机株式会社 | Freezer unit |
-
2010
- 2010-07-09 CN CN2010102228654A patent/CN101892033A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1821681A (en) * | 2004-12-14 | 2006-08-23 | 三洋电机株式会社 | Freezer unit |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105733514A (en) * | 2016-04-08 | 2016-07-06 | 中国建筑科学研究院 | Medium-high temperature heat pump mixed working medium containing R13I1 and used for large-cycle temperature rise |
CN105733514B (en) * | 2016-04-08 | 2019-04-23 | 中国建筑科学研究院 | Medium-high temperature heat pump mixed working medium containing R13I1 and used for large-cycle temperature rise |
CN114149791A (en) * | 2021-11-18 | 2022-03-08 | 湖北瑞能华辉能源管理有限公司 | Energy-saving environment-friendly heat pump working medium capable of realizing high-temperature heating and application thereof |
CN114149791B (en) * | 2021-11-18 | 2023-12-29 | 湖北瑞能华辉能源管理有限公司 | Energy-saving environment-friendly heat pump working medium capable of realizing high-temperature heating and application thereof |
CN114752359A (en) * | 2022-04-13 | 2022-07-15 | 华中科技大学 | Energy-saving environment-friendly working medium capable of replacing HFC245fa for heat pump boiler |
CN114752358A (en) * | 2022-04-13 | 2022-07-15 | 华中科技大学 | Energy-saving environment-friendly working medium for heat pump boiler |
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Application publication date: 20101124 |