CN114316904A - Environment-friendly heat transfer composition - Google Patents
Environment-friendly heat transfer composition Download PDFInfo
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- CN114316904A CN114316904A CN202011083525.8A CN202011083525A CN114316904A CN 114316904 A CN114316904 A CN 114316904A CN 202011083525 A CN202011083525 A CN 202011083525A CN 114316904 A CN114316904 A CN 114316904A
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- heat transfer
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- tetrafluoropropene
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Abstract
The invention discloses an environment-friendly heat transfer composition, which comprises the following components in part by weight: 3-25% of (Z) -1-chloro-2, 3,3, 3-tetrafluoropropene by mass percentage; and 75-97 percent by mass of (Z) -1,3,3, 3-tetrafluoropropene; the heat transfer composition has a temperature glide of less than 0.01 ℃, a GWP value of less than 1, and is non-flammable. The heat transfer composition has the advantages of excellent environmental performance, good safety performance, small temperature slippage and high refrigerating capacity/heating capacity per unit volume, and can be used as a heat transfer fluid in an immersed liquid cooling system, a high-temperature heat pump system, a centrifugal refrigerating system and an organic Rankine cycle instead of HFC-245fa, HCFC-123 and the like.
Description
Technical Field
The invention relates to a heat transfer fluid, in particular to an environment-friendly heat transfer composition comprising (Z) -1-chloro-2, 3,3, 3-tetrafluoropropene with the mass percentage of 3-25% and (Z) -1,3,3, 3-tetrafluoropropene with the mass percentage of 75-97%, wherein the heat transfer composition can be used as a heat transfer fluid in an immersed liquid cooling type high-temperature heat pump system, a centrifugal refrigeration system and an organic Rankine cycle.
Background
In recent years, global warming is increasingly intensified, China plans to reduce carbon emission by 40% -50% in 2020, and governments are putting forward various policies beneficial to energy conservation and emission reduction.
In the internet field, the rapid development of the industry pushes the rapid rise of the internet data center, how to solve the heat dissipation problem of the data center under the conditions of low energy consumption and low cost, and the realization of energy conservation and emission reduction is an important subject. At present, the main heat dissipation of a data center usually adopts a room cooling method, but the defects of high energy consumption, low cooling efficiency and the like exist. The immersed liquid cooling has low technical maintenance cost, good refrigeration effect and low operation energy consumption, accords with the technical development direction of a data center, but needs to develop an immersed liquid cooling working medium which is safe, environment-friendly and high in unit refrigerating capacity.
In the industrial field, especially in the petroleum industry, the chemical industry, the sewage treatment industry, the printing and dyeing industry and the like, a large amount of industrial waste heat is often generated, and waste heat can be recovered in a high-temperature heat pump system, an organic Rankine cycle and other modes, so that the comprehensive utilization rate of industrial energy is improved, and energy conservation and emission reduction are facilitated. At present, a heat transfer fluid commonly used in a high-temperature heat pump system and an organic Rankine cycle system is HFC-245fa, but has the defects of high GWP value and poor environmental performance; the heat transfer fluids used in high temperature heat pump systems and organic Rankine cycle systems instead of HFC-245fa currently include HCFO-1233zd (E), HCFO-1224yd (Z) and HFO-1336mzz (Z), but have the defects of ODP not being 0, low volumetric heat production, low efficiency and the like.
In the field of refrigeration, particularly centrifugal refrigeration systems, a large amount of refrigerant is needed, the currently common refrigerant is HCFC-123, but the defect of poor environmental performance (ODP value is not 0) exists, and a heat transfer working medium with good environmental performance and service performance is urgently needed to replace the refrigerant.
Disclosure of Invention
In order to solve the technical problems, the invention provides an environment-friendly heat transfer composition with excellent environmental performance, good safety performance and high unit volume refrigerating capacity/heating capacity.
The physical properties of the components included in the heat transfer composition of the present invention are as follows:
(Z) -1-chloro-2, 33-tetrafluoropropene (HFO-1224yd (Z)) having the molecular formula C3HF4Cl, molecular weight of 148.5, standard boiling point of 14.0 ℃, critical temperature of 156.0 ℃, critical pressure of 3.33MPa, and GWP value of less than 1.
(Z) -1,3,3, 3-tetrafluoropropene (HFO-1234ze (Z)) with the molecular formula C3H2F4Molecular weight of 114.04, standard boiling point of 9.745 deg.C, critical temperature of 150.12 deg.C, critical pressure of 3.55MPa, and GWP value<1。
The purpose of the invention is realized by the following technical scheme:
an environmentally friendly heat transfer composition, said heat transfer composition comprising:
3-25% of (Z) -1-chloro-2, 3,3, 3-tetrafluoropropene by mass percentage; and
75-97% of (Z) -1,3,3, 3-tetrafluoropropene by mass percentage;
the heat transfer composition is non-flammable.
Preferably, the heat transfer composition comprises:
3-15% of (Z) -1-chloro-2, 3,3, 3-tetrafluoropropene by mass percentage; and
(Z) -1,3,3, 3-tetrafluoropropene with the mass percentage of 85-97%.
More preferably, the heat transfer composition comprises:
5-10% of (Z) -1-chloro-2, 3,3, 3-tetrafluoropropene by mass percentage; and
90-95 percent of (Z) -1,3,3, 3-tetrafluoropropene by mass percentage.
The heat transfer composition as described above, the heat transfer composition having a temperature glide of less than 0.01 ℃.
According to the heat transfer composition, the ODP of the environment-friendly heat transfer composition is 0, and the GWP value is less than 1. The ODP value takes CFC-11 as a reference value of 1.0, and the GWP value takes CO2As a reference value of 1.0(100 years).
The heat transfer composition as described above having an enthalpy of vaporization greater than 200KJ/kg at standard atmospheric pressure.
The invention also provides application of any one of the heat transfer compositions as a heat transfer fluid in an immersed liquid cooling system, a high-temperature heat pump system, a centrifugal refrigeration system and an organic Rankine cycle.
The enthalpy of vaporization of the heat transfer composition is higher than that of refrigerating working media such as HCFC-123, HFC-245fa, HCFO-1233zd (E), HFO-1336mzz (Z) and the like, and the heat transfer composition is particularly suitable for being used as a heat transfer fluid of a submerged liquid cooling system of a data center server.
The heat transfer composition is particularly suitable for a single-stage compression type high-temperature heat pump system with the heating temperature of more than or equal to 100 ℃, the high-temperature heat pump system comprises an evaporator, a condenser and a superheater, and the heat transfer composition 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 100-140 ℃. More preferably, the evaporation temperature of the high-temperature heat pump system is 60-80 ℃, and the condensation temperature is 120-140 ℃.
The heat transfer compositions of the present invention are particularly useful in centrifugal refrigeration systems, such as centrifugal air conditioners.
The heat transfer composition has high expansion work, is particularly suitable for an organic Rankine cycle system, and is used for recovering waste heat for power generation.
Compared with the prior art, the invention has the beneficial effects that:
1. the heat transfer composition of the invention is non-flammable and has high safety;
2. the heat transfer composition has zero ODP value, GWP value less than 1 and excellent environmental performance;
3. the heat transfer composition of the present invention has a temperature glide of < 0.01 ℃ and is particularly suitable for use as a heat transfer fluid in place of refrigerants such as HFC-245fa, HCFC-123, HCFO-1233zd (E), HFO-1336mzz (Z), and the like;
4. when the heat transfer composition is used as a heat transfer fluid, the unit volume refrigerating capacity and the unit volume heating capacity are high, the expansion work is large, the service performance is good, and the heat transfer composition can be widely applied to an immersed liquid cooling system, a high-temperature heat pump system, a centrifugal refrigerating system, an organic Rankine cycle 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 present invention provides a refrigeration composition produced by physically mixing (Z) -1-chloro-2, 3,3, 3-tetrafluoropropene (HFO-1224yd (Z)) and (Z) -1,3,3, 3-tetrafluoropropene (R1234ze (Z)) in a liquid phase in terms of the mass percentages of the respective components.
Example 1: r1234ze (Z) and R1224yd (Z) were physically mixed in a liquid phase at 97:3 mass%.
Example 2: r1234ze (Z) and R1224yd (Z) were physically mixed in a liquid phase at a mass ratio of 95: 5.
Example 3: r1234ze (Z) and R1224yd (Z) were physically mixed in a liquid phase at a mass ratio of 90: 10.
Example 4: r1234ze (Z) and R1224yd (Z) were physically mixed in a liquid phase at a mass ratio of 85: 15.
Example 5: r1234ze (Z) and R1224yd (Z) were physically mixed in a liquid phase at a mass ratio of 75: 25.
Comparative example 1: r1234ze (Z) and R1224yd (Z) were physically mixed in a liquid phase at a mass ratio of 70: 30.
Comparative example 2: r1234ze (Z) and R1224yd (Z) were physically mixed in a liquid phase at a mass ratio of 40: 60.
The following examples and comparative examples were compared with the performance of refrigerants HFO-1234ze (Z), HFC-245fa, HCFO-1233zd (E), HFO-1336mzz (Z), HCFO-1224yd (Z) and HCFC-123 available in the corresponding systems.
Mono, flammable
Table 1 shows the combustion grade of each example, comparative example and corresponding refrigerant, specifically as follows:
TABLE 1 flammability
| Examples | Grade of combustion |
| Example 1 | 1 |
| Example 2 | 1 |
| Example 3 | 1 |
| Example 4 | 1 |
| Example 5 | 1 |
| Comparative example 1 | 1 |
| Comparative example 2 | 1 |
| HFO-1234ze(Z) | 2L |
| HFC-245fa | 1 |
| HCFO-1233zd(E) | 1 |
| HFO-1336mzz(Z) | 1 |
| HCFO-1224yd(Z) | 1 |
| HCFC-123 | 1 |
The flammability test adopts the national standard GB/T12474-2008.
As can be seen from the above table, the various embodiments of the present invention are not flammable, and have higher safety performance than single working medium HFO-1234ze (Z).
Temperature glide, evaporation enthalpy and environmental performance
Table 2 shows data of temperature glide, density, evaporation enthalpy, environmental performance, and the like of each example, comparative example, and common single working medium refrigerant, specifically as follows:
TABLE 2 temperature glide, enthalpy of vaporization and environmental Properties
As can be seen from the above table, the heat transfer compositions of the examples had very little temperature glide, all less than 0.01 ℃. Even if gas phase leakage of the heat transfer fluid occurs during use, the influence on the component ratio is extremely small. The heat transfer compositions of the examples had ODP values of 0 and GWP values of less than 1, and were excellent in environmental properties. The heat transfer compositions of the examples have densities comparable to HFO-1234ze (Z), lower than those of the comparative examples and common single-working-medium refrigerants, and allow for reduced charge in system applications.
The enthalpy of vaporization of the heat transfer compositions of the examples at standard atmospheric pressure is comparable to HFO-1234ze (Z), but higher than that of the comparative examples and the common single-working-medium refrigerants. Therefore, when the heat transfer composition of each example is used in an immersed liquid cooling system of a data center server, the phase change heat exchange amount under the same working condition is higher than that of each comparative example and each common single working medium refrigerant (HFO-1234ze (Z)), and the cooling efficiency is higher than that of each comparative example and each common single working medium refrigerant. In particular, the heat transfer compositions of the various embodiments of the present invention have significant environmental performance advantages over the HCFO-1233zd (E) and HCFO-1224yd (Z) currently used in submerged liquid cooling systems, and greatly reduce the charge of heat transfer fluid.
Third, heating performance
Table 3 shows performance data of each example, comparative example, and common single working medium refrigerant under different heating conditions, specifically as follows:
TABLE 3 heating Performance under different working conditions
As can be seen from the above table, in the working condition range of the high-temperature heat pump (such as the working condition ranges of the evaporation temperature of 40-80 ℃, the condensation temperature of 10-140 ℃, the suction temperature of 45-85 ℃ and the supercooling temperature of 95-135 ℃), the heat production quantity per unit volume of the heat transfer composition of each embodiment is equivalent to that of HFO-1234ze (Z), and is obviously higher than that of a comparative example and a common single-working-medium refrigerant. The energy efficiency ratio of the heat transfer compositions of the examples is comparable to HFO-1234ze (Z), slightly lower than HCFO-1233zd (E) and HFO-1336mzz (Z), and higher than that of the comparative examples and common single-working-medium coolants. The heat transfer composition of the embodiments of the invention has the comprehensive advantages that the heat transfer composition is obviously higher than the HFC-245fa and substitutes thereof commonly used at present.
Fourth, refrigeration performance
Table 4 shows the performance data of each example, comparative example and common refrigerant with single working medium under the standard air conditioning conditions (evaporation temperature 7.2 ℃, condensation temperature 54.4 ℃, suction temperature 18.3 ℃, and supercooling temperature 46.1 ℃), which are as follows:
TABLE 4 refrigeration performance under standard air-conditioning conditions
As can be seen from the above table, the heat transfer compositions of the examples have a refrigeration capacity per unit volume comparable to HFO-1234ze (Z) and significantly higher than the comparative examples and the common single-working-medium refrigerants under air conditioning conditions. The energy efficiency ratios of the heat transfer compositions of the examples were comparable to HFO-1234ze (Z), HCFO-1233zd (E), slightly lower than HCFC-123, and higher than the comparative examples and the common single-refrigerant coolants. The heat transfer composition of the embodiments of the invention has comprehensive advantages obviously higher than that of the heat transfer media HCFC-123, HFC-245fa and substitutes thereof which are commonly used at present.
Fifth, organic Rankine cycle performance
Table 5 shows the performance data of the organic rankine cycle of each example, comparative example, and common single working medium refrigerant under different working conditions, which is as follows:
TABLE 5 ORC Performance under different conditions
As can be seen from the table above, in the working condition range of the organic Rankine cycle (such as the working condition ranges of the condensation temperature of 30-40 ℃, the evaporation temperature of 80-120 ℃, the superheat temperature of 5 ℃, the pump efficiency of 1 and the expander efficiency of 1), the expansion work of the heat transfer composition of each embodiment is equivalent to that of HFO-1234ze (Z), and is higher than that of a comparative example and other working media; the efficiency is equivalent to HFO-1234ze (Z) and HCFO-1233zd (E), which is obviously higher than that of comparative example and common single-working medium refrigerant. The heat transfer compositions of the examples are comparable in efficiency to HFO-1234ze (Z), HCFO-1233zd (E), and higher than the comparative examples and common single-working-medium coolants. The expansion work, the efficiency and the safety are comprehensively considered, the application effect of the heat transfer composition of each embodiment is obviously better than that of other working media, particularly the application in an organic Rankine cycle, and the comprehensive advantages of the heat transfer composition of each embodiment of the invention are obviously higher than that of HFC-245fa and substitutes thereof commonly used at present.
Claims (10)
1. An environment-friendly heat transfer composition characterized by: the heat transfer composition comprises:
3-25% of (Z) -1-chloro-2, 3,3, 3-tetrafluoropropene by mass percentage; and
75-97% of (Z) -1,3,3, 3-tetrafluoropropene by mass percentage;
the heat transfer composition is non-flammable.
2. An environmentally friendly heat transfer composition according to claim 1, wherein: the heat transfer composition has a temperature glide of less than 0.01 ℃.
3. An environmentally friendly heat transfer composition according to claim 1, wherein: the heat transfer composition comprises:
3-15% of (Z) -1-chloro-2, 3,3, 3-tetrafluoropropene by mass percentage; and
(Z) -1,3,3, 3-tetrafluoropropene with the mass percentage of 85-97%.
4. An environmentally friendly heat transfer composition according to claim 3, wherein: the heat transfer composition comprises:
5-10% of (Z) -1-chloro-2, 3,3, 3-tetrafluoropropene by mass percentage; and
90-95 percent of (Z) -1,3,3, 3-tetrafluoropropene by mass percentage.
5. An environmentally friendly heat transfer composition according to any one of claims 1-4, wherein: the GWP value of the environment-friendly heat transfer composition is less than 1.
6. An environmentally friendly heat transfer composition according to any one of claims 1-4, wherein: the heat transfer composition has an enthalpy of vaporization greater than 200KJ/kg at standard atmospheric pressure.
7. Use of an environmentally friendly heat transfer composition as claimed in any of claims 1 to 6, wherein: the heat transfer compositions are useful as heat transfer fluids in submerged liquid cooling systems, high temperature heat pump systems, centrifugal refrigeration systems, and organic rankine cycles.
8. Use of an environmentally friendly heat transfer composition according to claim 7, wherein: the heat transfer composition is used for submerged cooling of data center servers.
9. Use of an environmentally friendly heat transfer composition according to claim 7, wherein: the heat transfer composition is used for a high-temperature heat pump system with the heating temperature more than or equal to 100 ℃.
10. Use of an environmentally friendly heat transfer composition according to claim 9, wherein: the evaporation temperature of the high-temperature heat pump system is 40-80 ℃, and the condensation temperature is 100-140 ℃.
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| CN115572579A (en) * | 2022-10-12 | 2023-01-06 | 澳江(无锡)网络能源有限公司 | Perfluorinated compound composition for liquid cooling and application thereof in immersion cooling |
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