CN114907816A - Heat transfer composition for replacing HFC-245fa - Google Patents
Heat transfer composition for replacing HFC-245fa Download PDFInfo
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- CN114907816A CN114907816A CN202110168515.2A CN202110168515A CN114907816A CN 114907816 A CN114907816 A CN 114907816A CN 202110168515 A CN202110168515 A CN 202110168515A CN 114907816 A CN114907816 A CN 114907816A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
- C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/122—Halogenated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/126—Unsaturated fluorinated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/40—Replacement mixtures
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Abstract
The present invention discloses a heat transfer composition for replacing HFC-245fa, which comprises: 1) 1,1, 2-trifluoroethane with the mass percentage of 6-45 percent; 2) a second component with the mass percentage of 55-94 percent, wherein the second component is selected from (Z) -1-chloro-2, 3,3, 3-tetrafluoropropene and/or (E) -1-chloro-3, 3, 3-trifluoropropene; 3) optionally, the mass percentage content is 1-15% (E) -1,1,1,4,4, 4-hexafluoro-2-butene. The heat transfer composition is non-flammable or weakly flammable, has a temperature glide of less than 3 ℃, and has a GWP value of less than 150. The heat transfer composition has the advantages of safety, environmental protection, strong phase-change heat exchange capacity, high heat production/refrigerating capacity per unit volume and the like, and can be used for replacing HFC-245fa in heat pipe systems, high-temperature heat pump systems, compression refrigerating systems and organic Rankine cycle power generation systems (ORC).
Description
Technical Field
The present invention relates to heat transfer fluids, and in particular to applications in heat pipe systems, high temperature heat pump systems, compression refrigeration systems, and organic rankine cycle power generation systems (ORC).
Background
In recent years, global warming is increasingly intensified, and governments are pushing policies beneficial to energy conservation and emission reduction. HFC-245fa is used as a common heat transfer fluid and can be used in the fields of data center heat pipe systems, high-temperature heat pump systems, organic Rankine cycle systems and the like, but the GWP value of the heat transfer fluid is high, the environmental performance is poor, and the heat transfer fluid faces gradually reduced fate; and the phase change heat exchange capacity is insufficient, the heat exchange efficiency is low, and the heat exchange requirement of the internet data center under huge data processing capacity cannot be met.
The Kemu patent CN108699921A discloses a method for using 2-perfluoroheptene and/or 3-perfluoroheptene to replace HFC-245fa in an ORC system, but the boiling point of the method is between 60 and 75 ℃, the boiling point is far higher than that of HFC-245fa, the applicable waste heat range is small, and the method is not suitable for recycling low-grade energy.
The cobmu patent CN107923266A discloses a method of replacing HFC-245fa in power cycle equipment (ORC) with HFO-1336ze-Z or HFO-1336ze-E or a combination of HFC-245fa and HFO-1336ze, but HFO-1336ze has less prior disclosures, lacks thermophysical data and safety performance data, and is not currently reported commercially, and its practical use is limited.
Dupont patent CN103906821A discloses a method of replacing HFC-245fa in power cycle systems with a composition of HFO-1336mzz (z) and HFO-1336mzz (e) that, while achieving GWP values of less than about 35, requires higher evaporation temperatures, i.e., higher grade waste heat, suitable for use in supercritical ORC systems.
Disclosure of Invention
In order to solve the technical problems, the invention provides a heat transfer composition which is safe and environment-friendly, has strong phase-change heat exchange capacity and high unit volume heating capacity/refrigerating capacity and is used for replacing HFC-245 fa.
The physical properties of the components included in the heat transfer compositions of the present invention and the comparative examples are as follows:
1,1, 2-trifluoroethane (HFC-143) of the formula C 2 H 3 F 3 The molecular weight is 84.04, the normal boiling point is 5 ℃, the critical temperature is 157.8 ℃, the critical pressure is 4.233MPa, and the GWP value is 328.
(Z) -1-chloro-2, 3,3, 3-tetrafluoropropene (HCFO-1224yd (Z)) with the molecular formulaC 3 HF 4 Cl, molecular weight of 148.49, standard boiling point of 14.62 ℃, critical temperature of 155.54 ℃, critical pressure of 3.337MPa, and GWP value of less than 1.
(E) -1-chloro-3, 3, 3-trifluoropropene (HCFO-1233zd (E)) of formula C 3 H 2 F 3 Cl, molecular weight of 130.5, standard boiling point of 18.263 deg.C, critical temperature of 166.45 deg.C, critical pressure of 3.624MPa, and GWP value<1。
(E) -1,1,1,4,4, 4-hexafluoro-2-butene (HFO-1336mzz (E)), of formula C 4 H 2 F 6 The molecular weight is 148.49, the standard boiling point is 7.43 ℃, the critical temperature is 130.22 ℃, the critical pressure is 2.766MPa, and the GWP value is 7.
1,1,1,2,3, 3-hexafluoropropane (HFC-236ea), the molecular formula of which is C3H2F6, the molecular weight of which is 152.04, the standard boiling point of which is 6.172 ℃, the critical temperature of which is 139.29 ℃, the critical pressure of which is 3.42MPa and the GWP value of which is 1330.
1,1,1,2, 2-pentafluoro-2-methoxyethane (HFE-245cb2), which has the molecular formula of C3H3F5O, the molecular weight of 150.05, the normal boiling point of 5.61 ℃, the critical temperature of 133.66 ℃, the critical pressure of 2.8864MPa and the GWP value of 654.
(Z) -1-chloro-3, 3, 3-trifluoropropene (HCFO-1233zd (Z)) having a molecular formula of C 3 H 2 F 3 Cl, molecular weight 130.5, normal boiling point 39.0 deg.C, GWP value<1。
The purpose of the invention is realized by the following technical scheme:
a heat transfer composition that replaces HFC-245fa, said heat transfer composition comprising:
1) 1,1, 2-trifluoroethane with the mass percentage of 6-45 percent;
2) a second component with the mass percentage of 55-94 percent, wherein the second component is selected from (Z) -1-chloro-2, 3,3, 3-tetrafluoropropene and/or (E) -1-chloro-3, 3, 3-trifluoropropene;
the heat transfer composition is non-flammable or weakly flammable.
Preferably, the heat transfer composition comprises:
10-45% of 1,1, 2-trifluoroethane; and a second component with the mass percentage of 55-90 percent.
More preferably, the heat transfer composition comprises:
1,1, 2-trifluoroethane with the mass percentage of 17-45 percent; and 55-83% of a second component by mass.
The present invention also provides a heat transfer composition as a replacement for HFC-245fa, the heat transfer composition comprising:
1) 17-45% of 1,1, 2-trifluoroethane;
2) (Z) -1-chloro-2, 3,3, 3-tetrafluoropropane and/or (E) -1-chloro-trifluoropropane with the mass percentage of 40-82%;
3) 1-15 percent of (E) -1,1,1,4,4, 4-hexafluoro-2-butene.
Preferably, the heat transfer composition comprises:
1) 30-45% of 1,1, 2-trifluoroethane;
2) (Z) -1-chloro-2, 3,3, 3-tetrafluoropropane and/or (E) -1-chloro-trifluoropropane with the mass percentage of 40-60%;
3) 5-15 percent of (E) -1,1,1,4,4, 4-hexafluoro-2-butene.
Any of the heat transfer compositions of the present invention described above has a small temperature glide, all less than 3 ℃, can form azeotropic or near azeotropic compositions, and has little effect on compositional proportions even if gas phase leakage of the heat transfer fluid occurs during use.
The heat transfer composition of any of the above is excellent in environmental properties, has an ODP of 0 and a GWP value<150. The ODP value takes CFC-11 as a reference value and is 1.0(100 years), and the GWP value takes CO 2 As a reference value of 1.0(100 years).
The heat transfer composition has higher evaporation enthalpy, the evaporation enthalpy is more than 200kJ/kg and higher than HFC-245fa under the standard atmospheric pressure, and the heat transfer composition is applied to systems such as a data center server heat pipe and the like, has strong phase change heat exchange capacity, high heat exchange efficiency and high heat exchange amount per unit mass.
The invention also provides application of any one of the heat transfer compositions in place of HFC-245fa, and the heat transfer composition is applied to a heat pipe system, a high-temperature heat pump system, a compression refrigeration system, an organic Rankine cycle power generation system (ORC) or a foaming system.
In one embodiment, the heat transfer composition is used in a heat pipe system for a data center server in place of HFC-245 fa.
In another embodiment, the heat transfer composition is used in a high temperature heat pump system having a heating temperature greater than or equal to 100 ℃ in place of HFC-245 fa.
Further, the high-temperature heat pump system is a single-stage compression type high-temperature heat pump system, comprises an evaporator, a condenser and a superheater and is used for industrial waste heat recovery. Preferably, the evaporation temperature of the high-temperature heat pump system is 40-80 ℃, and the condensation temperature is 90-140 ℃. More preferably, the evaporation temperature of the high-temperature heat pump system is 50-70 ℃, and the condensation temperature is 120-140 ℃.
Any of the heat transfer compositions described above of the present invention has a large expansion work, is suitable for an Organic Rankine Cycle (ORC) power generation system, is used for power generation by recovering waste heat, and has a large applicable waste heat range.
Compared with the prior art, the invention has the following beneficial effects:
1. the heat transfer composition of the invention not only has excellent environmental performance (ODP is 0, GWP value is less than 150), but also has temperature glide less than 3 ℃, and is suitable for replacing HFC-245fa refrigerant to be used as heat transfer fluid.
2. When the heat transfer composition is applied as a heat transfer fluid instead of HFC-245fa, the heat transfer composition has the advantages of high heat exchange efficiency, strong heat exchange capacity per unit mass, high heat production/refrigeration capacity per unit volume, large expansion work and good use performance, and can be used for replacing HFC-245fa and used for heat pipe systems, high-temperature heat pump systems, compression refrigeration systems, organic Rankine cycle power generation systems (ORC) or foaming systems and the like.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
The refrigeration composition is prepared by physically mixing 1,1, 2-trifluoroethane, a second component, and/or (E) -1,1,1,4,4, 4-hexafluoro-2-butene in a liquid phase according to the mass percentage of the components.
Example 1: r143 and R1224yd (Z) were physically mixed in a liquid phase at a mass ratio of 17: 83.
Example 2: and (3) physically mixing the R143 and the R1233zd (E) in a liquid phase according to the mass percent of 25: 75.
Example 3: r143 and R1224yd (Z) were physically mixed at a mass ratio of 29:71 in a liquid phase.
Example 4: and (3) physically mixing R143 and R1233zd (E) in a liquid phase according to the mass percent of 35: 65.
Example 5: r143 and R1224yd (Z) were physically mixed in a liquid phase at a mass ratio of 45: 55.
Example 6: r143 and R1233zd (E) were physically mixed in a liquid phase at a ratio of 45:55 by mass.
Example 7: r143, R1224yd (Z) and R1233zd (E) were physically mixed in the liquid phase at a mass ratio of 27:35: 38.
Example 8: r143, R1224yd (Z) and R1336mzz (E) were physically mixed in a liquid phase at a mass ratio of 34:55: 11.
Example 9: r143, R1224yd (Z) and R1336mzz (E) were physically mixed in a liquid phase at 37:56:7 mass%.
Example 10: r143, R1233zd (E) and R1336mzz (E) were physically mixed in a liquid phase at a mass ratio of 39:56: 5.
Example 11: r143, R1233zd (E) and R1336mzz (E) were physically mixed in a liquid phase at a mass ratio of 41:45: 14.
Example 12: r143, R1224yd (Z), R1233zd (E) and R1336mzz (E) were physically mixed in a liquid phase at a mass ratio of 32:35:23: 10.
Comparative example 1: and (3) physically mixing R143 and R236ea in a liquid phase according to the mass percent of 25: 75.
Comparative example 2: r143 and RE245cb2 were physically mixed in a liquid phase at 25:75 mass%.
Comparative example 3: r143 and R1233zd (Z) in liquid phase according to 30: 70 percent by mass.
Comparative example 4: HFC-245fa is used as the heat transfer system.
The following is a comparison of various performances of refrigerant HFC-245fa used in the examples and comparative examples of the present invention and corresponding systems.
Combustibility of
The combustion ratings for each example and comparative example are given in table 1, specifically as follows:
TABLE 1 flammability
| Examples/comparative examples | Composition comprising a fatty acid ester and a fatty acid ester | Grade of combustion |
| Example 1 | R143:R1224yd(Z)＝17:83 | 1 |
| Example 2 | R143:R1233zd(E)＝25:75 | 1 |
| Example 3 | R143:R1224yd(Z)＝29:71 | 1 |
| Example 4 | R143:R1233zd(E)＝35:65 | 1 |
| Example 5 | R143:R1224yd(Z)＝45:55 | 2L |
| Example 6 | R143:R1233zd(E)＝45:55 | 2L |
| Example 7 | R143:R1224yd(Z):R1233zd(E)＝27:35:38 | 1 |
| Example 8 | R143:R1224yd(Z):R1336mzz(E)＝34:55:11 | 1 |
| Example 9 | R143:R1224yd(Z):R1336mzz(E)＝37:56:7 | 1 |
| Example 10 | R143:R1233zd(E):R1336mzz(E)＝39:56:5 | 2L |
| Example 11 | R143:R1233zd(E):R1336mzz(E)＝41:45:14 | 2L |
| Example 12 | R143:R1233zd(E):R1233zd(E)R1336mzz(E)＝32:35:23:10 | 1 |
| Comparative example 1 | R143:R236ea＝25:75 | 1 |
| Comparative example 2 | R143:RE245cb2＝25:75 | 2/2L |
| Comparative example 3 | R143:R1233zd(Z)＝30:70 | 1 |
| Comparative example 4 | R245fa | 1 |
The flammability test adopts the national standard GB/T12474-2008.
As can be seen from the above table, each of the examples of the present invention is non-flammable or weakly flammable.
Temperature glide, evaporation enthalpy and environmental performance
Table 2 gives the temperature glide, density, enthalpy of vaporization, and environmental performance data for each example, comparative example, and HFC-245fa, as follows:
TABLE 2 temperature glide, enthalpy of vaporization and environmental Properties
As can be seen from the above table, the temperature slips for each example were small, all less than 3 ℃. Even if gas phase leakage of the heat transfer fluid occurs during use, the influence on the component ratio is small. The ODP value of each example is 0, the GWP value is less than 150, and the environmental performance is excellent. The density of the various embodiments is less than HFC-245fa and can reduce the charge in system applications.
The evaporation enthalpy of each embodiment under the standard atmospheric pressure is higher than HFC-245fa, when the method is applied to a heat pipe system of a data center server, the phase change heat exchange quantity under the same working condition is higher than HFC-245fa, and the cooling efficiency is higher than HFC-245 fa.
While comparative examples 1 and 2, which have evaporation enthalpies comparable to the individual examples, have significantly higher GWP values than the examples and poor environmental performance. In contrast, comparative example 3, although the environmental performance and the vaporization enthalpy were comparable to those of the examples, had a large temperature glide, and once used in each system, was liable to cause the secondary fractionation phenomenon, and was not suitable for practical use.
Third, heating performance
Table 3 shows the performance data of each example, comparative example and HFC-245fa under different heating conditions, which are as follows:
TABLE 3 heating Performance under Heat Pump operating conditions
As can be seen from the above table, the heat production per unit volume of each example is higher than 3000kJ/m 3 A heat production per unit volume greater than HFC-245 fa; the energy efficiency ratio is equivalent to HFC-245fa, and the energy efficiency ratio of part of the composition is higher than that of HFC-245 fa. The comprehensive advantages of the embodiments of the invention are obviously higher than that of HFC-245fa and substitutes thereof commonly used at present.
Fourth, refrigeration performance
Table 4 gives the performance data for each example, comparative example and HFC-245fa under standard air conditioning conditions (evaporation temperature 7.2 ℃, condensation temperature 54.4 ℃, suction temperature 18.3 ℃ and subcooling temperature 46.1 ℃), in particular as follows:
TABLE 4 refrigeration performance under standard air-conditioning conditions
As can be seen from the above table, under the air conditioning condition, the refrigerating capacity per unit volume of each embodiment is higher than HFC-245fa, and the energy efficiency ratio is equivalent to HFC-245 fa. The heat transfer composition of the embodiments of the invention has the comprehensive advantages that the heat transfer composition is obviously higher than the heat transfer medium HFC-245fa and the substitute thereof commonly used at present, and the heat transfer composition is particularly applied to a centrifugal refrigerating system.
In conclusion, the composition disclosed by the invention can simultaneously have excellent environmental performance and service performance (safety, heat exchange efficiency, heat exchange capacity per unit mass, heating capacity per unit volume, refrigerating capacity per unit volume and the like), can be widely used for replacing HFC-245fa in various fields, and is easy to realize industrialization.
Claims (11)
1. A heat transfer composition that replaces HFC-245fa, said heat transfer composition comprising:
1) 1,1, 2-trifluoroethane with the mass percentage of 6-45 percent;
2) a second component with the mass percentage of 55-94 percent, wherein the second component is selected from (Z) -1-chloro-2, 3,3, 3-tetrafluoropropene and/or (E) -1-chloro-3, 3, 3-trifluoropropene;
3) optionally, 1-15% by weight of (E) -1,1,1,4,4, 4-hexafluoro-2-butene;
the heat transfer composition is non-flammable or weakly flammable.
2. A heat transfer composition as recited in claim 1 which replaces HFC-245fa, wherein: the heat transfer composition comprises:
10-45% of 1,1, 2-trifluoroethane; and 55-90% of a second component by mass percent.
3. The HFC-245fa replacement heat transfer composition of claim 2, wherein: the heat transfer composition comprises:
1,1, 2-trifluoroethane with the mass percentage of 17-45 percent; and 55-83% of a second component by mass.
4. The HFC-245fa replacement heat transfer composition of claim 1, wherein: the heat transfer composition comprises:
1) 17-45% of 1,1, 2-trifluoroethane;
2) (Z) -1-chloro-2, 3,3, 3-tetrafluoropropane and/or (E) -1-chloro-trifluoropropane with the mass percentage of 40-82%;
3) 1-15 percent of (E) -1,1,1,4,4, 4-hexafluoro-2-butene.
5. The HFC-245fa replacement heat transfer composition of claim 4, wherein: the heat transfer combination comprises:
1) 30-45% of 1,1, 2-trifluoroethane;
2) (Z) -1-chloro-2, 3,3, 3-tetrafluoropropane and/or (E) -1-chloro-trifluoropropane with the mass percentage of 40-60%;
3) 5-15 percent of (E) -1,1,1,4,4, 4-hexafluoro-2-butene.
6. A heat transfer composition as recited in any of claims 1-5 which replaces HFC-245fa wherein: the heat transfer composition has a temperature glide of less than 3 ℃.
7. A heat transfer composition as recited in any of claims 1-5 which replaces HFC-245fa wherein: the GWP of the heat transfer composition is less than 150.
8. The HFC-245fa replacement heat transfer composition of any of claims 1-5, wherein: the heat transfer composition has an enthalpy of vaporization greater than 200KJ/kg at standard atmospheric pressure.
9. Use of a heat transfer composition as claimed in any of claims 1 to 5 in place of HFC-245fa, characterised in that: the heat transfer composition is useful as a heat pipe system, a high temperature heat pump system, a compression refrigeration system, an organic Rankine cycle power generation system (ORC), or a foaming system.
10. Use of an environmentally friendly heat transfer composition according to claim 9, wherein: the heat transfer composition is used for a heat pipe system of a data center server or a high-temperature heat pump system with the heating temperature more than or equal to 100 ℃.
11. The use of a heat transfer composition as recited in claim 10 in place of HFC-245fa, wherein: the evaporation temperature of the high-temperature heat pump system is 40-80 ℃, and the condensation temperature is 90-140 ℃.
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