A heat transfer composition to replace R123 and its application

Abstract

This invention discloses a heat transfer composition to replace R123, comprising 30–98 wt% Z-1-chloro-3,3,3-trifluoropropylene, 1–65 wt% Z-1,3,3,3-tetrafluoropropylene, and 1–5 wt% n-butane. The heat transfer composition has an enthalpy of vaporization >250 KJ / kg at standard atmospheric pressure, and the average relative deviation (AAD) of the saturated vapor pressure at any temperature within the range of 15–145°C is <50%. The heat transfer composition of this invention has advantages such as excellent environmental performance, good safety performance, high heating / cooling capacity per unit volume, high latent heat of vaporization, good heat transfer performance, and large expansion work.

Description

Technical Field

[0001] This invention relates to the field of heat transfer compositions, and more specifically to a heat transfer composition that replaces R123 and its application. Background Technology

[0002] In the industrial sector, especially in industries such as petrochemicals, wastewater treatment, and printing and dyeing, a large amount of industrial waste heat is often generated. It is necessary to recover the waste heat through heat pump systems or organic Rankine cycle systems to improve the comprehensive utilization rate of industrial energy and promote energy conservation and emission reduction.

[0003] R123 (trifluorodichloroethane) has a critical temperature of 183.68℃, a critical pressure of 3.6618MPa, and a boiling point of 27.823℃. It is the most commonly used working fluid in systems such as heat pumps and organic Rankine cycles. However, R123 contains chlorine (Cl), belongs to the HCFC class, and has ozone-depleting capabilities. It is also classified as a Group B1 refrigerant in the ASHRAE classification, making it a toxic refrigerant, and therefore faces the risk of being phased out.

[0004] Using R123 as a circulating working fluid in heat pumps and chillers results in a high COP, which can save electricity under the same operating conditions. However, in chillers, due to the high boiling point of R123, the system operates under negative pressure.

[0005] In order to find a heat transfer medium to replace R123 and achieve in-situ replacement of the original system, the following efforts have been made in the existing technology:

[0006] CN104662121A discloses a composition containing 1-42 wt% Z-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz) and 99-58 wt% R123. This composition can replace R123 in refrigeration, air conditioning, heat pump or power cycle systems. However, this composition still contains a large mass percentage of R123 and faces the risk of being phased out in the long term.

[0007] CN104946206A discloses a non-azeotropic composition containing 89-97 wt% difluoromethane (R32) and 3-11 wt% R123. This composition exhibits good thermal performance, environmental performance, safety performance, and market availability. Furthermore, it demonstrates good compatibility with the existing system, effectively improving system cycle performance and serving as a replacement for R123. However, the boiling point of R32 is -51.7℃, significantly different from that of R123, resulting in a large temperature glide. In the event of a leak, the composition changes drastically, requiring retesting and refilling, which is cumbersome. Additionally, due to the significant difference in boiling point between the mixture and R123, its performance within the existing system will differ considerably from that of R123.

[0008] CN107810247A discloses a refrigerant composition containing 61.5–67.5 wt% R1336mzz(Z), 20.5–22.5 wt% R1130(E), and 10–18 wt% R1233zd(E), which exhibits a small temperature glide and is a suitable substitute for R123. However, component R1130(E) is a highly flammable substance, and its vapor can easily form an explosive mixture with air. It also has a certain degree of toxicity, posing a safety hazard during use.

[0009] CN110945100A discloses refrigerant compositions containing FO-1216 and hydrofluoroolefins (such as HFO-1234ze, HFO-1243zf), refrigerant compositions containing FO-1216 and halogenated ethylenes (such as HCFO-1122a, FO-1114, HFO-1123, HFO-1132(E), HFO-1132(Z), HFO-1132a, HFO-1141), and refrigerant compositions containing FO-1216 and hydrofluorocarbons (HFC-125, HFC-143a, HFC-32, HFC-134, HFC-134a, HFC-152a, HFC-227ea). These refrigerant compositions have low GWP values, are non-flammable or slightly flammable, and can be used as alternative refrigerants such as R134a, R410A, R123, or R404A. However, this composition also suffers from a significant difference in boiling point compared to R123. Specifically, the key component FO-1216 has a boiling point of -30.34°C and a critical temperature of 87.75°C. Therefore, this type of alternative is not suitable for high-temperature heat pump systems and organic Rankine cycle systems.

[0010] In summary, existing heat transfer compositions that can replace R123 either have significant performance differences, pose safety issues, or cannot be replaced in some systems, necessitating the development of new heat transfer compositions to replace R123. Summary of the Invention

[0011] To address the aforementioned technical problems, this invention proposes a heat transfer composition that replaces R123, exhibiting excellent environmental performance, good safety performance, high heating / cooling capacity per unit volume, and large expansion work. This heat transfer composition has a boiling point close to that of R123, moderate temperature glide, and good system versatility, and can be used in medium-temperature heat pump systems, high-temperature heat pump systems, chillers, heat pipe systems, or inflatable plate systems.

[0012] The physical properties of the components involved in this invention are as follows:

[0013] Z-1-chloro-3,3,3-trifluoropropene (R1233zd(Z)) has the molecular formula C3H2F3Cl and a molecular weight of 130.5. Its standard boiling point was obtained by static method experiment by measuring the saturated phase pressure at a selected temperature group to obtain the saturated vapor pressure equation. Substituting a standard atmosphere (0.101325MPa) into the equation, we get 36.44℃. The critical temperature is 200.52℃, the critical pressure is 3.647MPa, and the GWP < 1.

[0014] Z-1,3,3,3-Tetrafluoropropylene (R1234ze(Z)) has the molecular formula C3H2F4, a molecular weight of 114.04, a standard boiling point of 9.73℃, a critical temperature of 150.12℃, a critical pressure of 3.5306MPa, and a GWP < 1.

[0015] n-Butane (R600), its molecular formula is C4H 10 It has a molecular weight of 58.122, a standard boiling point of -0.49℃, a critical temperature of 151.98℃, a critical pressure of 3.796MPa, and a GWP < 1.

[0016] The objective of this invention is achieved through the following technical solution:

[0017] A heat transfer composition to replace R123, the heat transfer composition comprising 30-98 wt% Z-1-chloro-3,3,3-trifluoropropene, 1-65 wt% Z-1,3,3,3-tetrafluoropropene and 1-5 wt% n-butane, the heat transfer composition having an enthalpy of vaporization of >250 kJ / kg at standard atmospheric pressure, and the average relative deviation (AAD) of the saturated vapor pressure of the heat transfer composition at any temperature within the range of 15-145 °C being <50%.

[0018] Furthermore, the heat transfer composition comprises 35-80 wt% Z-1-chloro-3,3,3-trifluoropropylene, 15-60 wt% Z-1,3,3,3-tetrafluoropropylene and 1-5 wt% n-butane.

[0019] Furthermore, the heat transfer composition comprises 45–76 wt% Z-1-chloro-3,3,3-trifluoropropylene, 19–50 wt% Z-1,3,3,3-tetrafluoropropylene, and 1–5 wt% n-butane.

[0020] Furthermore, the heat transfer composition comprises 60-70 wt% Z-1-chloro-3,3,3-trifluoropropylene, 25-35 wt% Z-1,3,3,3-tetrafluoropropylene, and 1-5 wt% n-butane.

[0021] Further, the heat transfer composition comprises 60-90 wt% Z-1-chloro-3,3,3-trifluoropropene, 5-35 wt% Z-1,3,3,3-tetrafluoropropene, and 1-5 wt% n-butane, and the average relative deviation (AAD) of the saturated vapor pressure of the heat transfer composition at any temperature within the range of 15-145°C is <20%.

[0022] Furthermore, the heat transfer composition comprises 70–90 wt% Z-1-chloro-3,3,3-trifluoropropene, 5–25 wt% Z-1,3,3,3-tetrafluoropropene, and 1–5 wt% n-butane, and the average relative deviation (AAD) of the saturated vapor pressure of the heat transfer composition at any temperature point within the range of 15–145 °C is <10%.

[0023] The analysis and screening of the heat transfer composition that replaces R123 described in this invention was obtained through objective function weight analysis, namely:

[0024]

[0025] In equation (1), S k This represents the objective function; a larger value indicates a greater advantage of the heat transfer composition in replacing R123. i This represents the i-th performance parameter, including: enthalpy of evaporation, saturated vapor pressure, system cooling / heating capacity, system COP, etc. i This represents the weight of the i-th performance attribute, which is determined by the importance of the performance attribute in the system operation.

[0026] The heat transfer composition that replaces R123 according to the present invention is non-flammable, with an ODP value of approximately 0 and a GWP value of <1. The ODP value is based on CFC-11 as a reference value of 1.0, and the GWP value is based on CO2 as a reference value of 1.0 (100 years).

[0027] The heat transfer composition that replaces R123 according to the present invention has an enthalpy of vaporization greater than 250 KJ / kg under standard atmospheric pressure, and can reduce the amount of heat transfer medium required compared with R123.

[0028] The heat transfer composition of the present invention, which replaces R123, has an average relative deviation (AAD) of saturated vapor pressure of less than 50% at any temperature point within the range of 15 to 145°C compared with R123. Preferably, the AAD is less than 20%, and more preferably, the AAD is less than 10%.

[0029] The average relative deviation of the saturated vapor pressure is calculated as shown in equation (2):

[0030]

[0031] In equation (2), AAD represents the average relative deviation of the saturated vapor pressure, n represents the number of temperature points, and p R123represents the saturated vapor pressure of R123 at different temperatures, and p represents the saturated vapor pressure of the alternative heat transfer composition at the same temperature.

[0032] The average relative deviation of the saturated vapor pressure represents the magnitude of the deviation between the saturated vapor pressure of the alternative heat transfer composition and R123. The smaller the average relative deviation of the saturated vapor pressure, the closer the saturated vapor pressure of the alternative heat transfer composition is to that of R123, and the less modification to the system equipment is required when replacing the heat transfer composition.

[0033] Based on extensive testing of the physical properties of R1233zd(Z) and R1234ze(Z), this invention creatively introduces R600 and controls its content to improve heat transfer capacity while ensuring safety. The result is a heat transfer composition with a boiling point and critical performance close to that of R123. This allows for in-situ replacement of R123 without altering the main equipment in existing R123 systems, thus mitigating the toxicity risks associated with R123 leaks. Simultaneously, it reduces the charge amount and significantly increases the cooling / heating capacity per unit volume.

[0034] The present invention also provides an application of the heat transfer composition that replaces R123, wherein the heat transfer composition that replaces R123 is used as a heat transfer medium in a medium-temperature heat pump system, a high-temperature heat pump system, a chiller, a heat pipe system, or a blown plate system.

[0035] The heat transfer composition that replaces R123 is used as a heat transfer medium in a medium-temperature heat pump system, a high-temperature heat pump system, or a chiller unit. Compared with R123, the compressor pressure in the system is reduced by more than 2%.

[0036] The heat transfer composition that replaces R123 is used as a heat transfer medium in a medium-high temperature heat pump system, wherein the evaporation temperature of the medium-high temperature heat pump system is 20-80°C and the condensation temperature is 60-130°C.

[0037] The heat transfer composition that replaces R123 is used as a heat transfer medium in a chiller unit, wherein the evaporation temperature of the chiller unit is 1-10°C and the condensation temperature is 30-50°C.

[0038] The heat transfer composition that replaces R123 is used as a heat transfer medium in a medium-temperature heat pump system, a high-temperature heat pump system, or a chiller unit. It needs to be used with a lubricating oil. The lubricating oil is selected from at least one of diester oil, polyol carbonate oil, perfluoropolyether oil, fluorinated silicone oil, naphthenic mineral oil, polyalphaolefin, alkylbenzene, or alkylnaphthalene. Preferably, the lubricating oil is a naphthenic mineral oil that is miscible with R123, such as 3GS or T68.

[0039] To improve the compatibility of the heat transfer composition replacing R123 with lubricating oil and enhance the circulating heat transfer effect, the heat transfer composition replacing R123 further includes an additive selected from at least one of 1-butyne, 1-pentene, 2,2-dimethylbutane, cis-butene, trans-butene, pentane, cyclopentane, isopentane, and neopentane. The content of the additive accounts for 1-3% of the total mass of the heat transfer composition replacing R123. Preferably, the additive is selected from at least one of 1-pentene, pentane, or isopentane.

[0040] The heat transfer composition that replaces R123 is used as a heat transfer medium in heat pipe systems or blown plate systems, and the heat transfer capacity of the heat transfer composition increases by more than 50% compared with R123.

[0041] In one embodiment, the heat transfer composition that replaces R123 is used as a heat transfer medium in a medium-temperature heat pump system, with an evaporation temperature of 20-50°C and a condensation temperature of 60-100°C, and the heating capacity per unit volume is increased by 16.2-73.76% compared to R123.

[0042] In one embodiment, the heat transfer composition that replaces R123 is used as a heat transfer medium in a high-temperature heat pump system, with an evaporation temperature of 40-80°C, a condensation temperature of 100-130°C, and a heating capacity per unit volume that is 15.3-69.1% higher than that of R123.

[0043] In one embodiment, the heat transfer composition that replaces R123 is used as a heat transfer medium in a cooling unit system, with an evaporation temperature of 1-10°C, a condensation temperature of 30-50°C, and a volumetric cooling capacity that is 24-90.6% higher than that of R123.

[0044] The medium-temperature heat pump system, high-temperature heat pump system, or cooling unit system described in this invention includes a condenser, an evaporator, a compressor, and a throttling valve.

[0045] When the heat transfer composition of the present invention, which replaces R123, is used in medium- and high-temperature heat pump systems, especially in high-temperature heat pump systems with condensation temperatures above 80°C, it can ensure that the compressor outlet is always in the gas phase, thus avoiding the presence of liquid phase at the compressor outlet, which could cause liquid slugging and damage the compressor.

[0046] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0047] 1. The heat transfer composition of the present invention has an ODP value of approximately 0 and a GWP < 1, exhibiting excellent environmental performance.

[0048] 2. The boiling point and critical performance of the heat transfer composition of the present invention are close to those of R123, and it can replace R123 in situ in heating systems, refrigeration systems, heat dissipation systems, etc. that originally used R123.

[0049] 3. During the operation of the heating / cooling system, the overall heat exchange capacity is significantly improved, with an average increase of 40.9% in heating capacity per unit volume and an average increase of 54.9% in cooling capacity per unit volume.

[0050] 4. During the operation of the cooling system, the system's heat dissipation capacity is improved by an average of 50.15% compared to R123. Attached Figure Description

[0051] Figure 1 The saturated vapor pressure curves of the heat transfer compositions of Examples 1-5 of this invention and R123 are shown.

[0052] Figure 2 The saturated vapor pressure curves of the heat transfer compositions of Examples 6-10 of this invention and R123 are shown.

[0053] Figure 3 The saturated vapor pressure curves of the heat transfer compositions of Examples 11-15 of this invention and R123 are shown.

[0054] Figure 4 This is a schematic diagram of the working principle of a heat pump / refrigeration system, where 1 is the expansion valve, 2 is the subcooler, 3 is the condenser, 4 is the compressor, 5 is the superheater, and 6 is the evaporator.

[0055] Figure 5 This is a schematic diagram of the working principle of a heat pipe cooling system, where 1 represents vapor, 2 represents the wick, 3 represents the liquid, 4 represents the tube shell, 5 represents the condensation section, 6 represents the insulation section, 7 represents the heat absorption section, and 8 represents the cross-section. Detailed Implementation

[0056] The present invention will be further described below with reference to specific embodiments, but the invention is not limited to these specific embodiments. Those skilled in the art should recognize that the present invention covers all alternatives, improvements, and equivalents that may be included within the scope of the claims.

[0057] The heating system used in this embodiment of the invention is a heat pump system, the cooling system is a chiller unit, and the heat dissipation system is a heat pipe system and a blown plate system. Both the heat pump system and the chiller unit are equipped with supercoolers and superheaters at the outlets of the condenser and evaporator.

[0058] Table 1 shows the thermophysical properties of R1233zd(Z), R1234ze(Z), R600, R1233zd(E), R1234ze(E), and R123.

[0059]

[0060] The standard boiling points in Table 1 were determined by static method experiments.

[0061] heat transfer composition

[0062] The method for preparing the heat transfer composition in this embodiment of the invention involves physically mixing Z-1-chloro-3,3,3-trifluoropropylene, Z-1,3,3,3-tetrafluoropropylene, and n-butane in a liquid phase according to the mass percentage of each component.

[0063] Example 1: R1233zd(Z), R1234ze(Z) and R600 were physically mixed in the liquid phase at a mass percentage of 35:60:5.

[0064] Example 2: R1233zd(Z), R1234ze(Z) and R600 were physically mixed in the liquid phase at a mass percentage of 40:55:5.

[0065] Example 3: R1233zd(Z), R1234ze(Z) and R600 were physically mixed in the liquid phase at a mass percentage of 45:50:5.

[0066] Example 4: R1233zd(Z), R1234ze(Z) and R600 were physically mixed in the liquid phase at a mass percentage of 50:45:5.

[0067] Example 5: R1233zd(Z), R1234ze(Z) and R600 were physically mixed in the liquid phase at a mass percentage of 55:40:5.

[0068] Example 6: R1233zd(Z), R1234ze(Z) and R600 were physically mixed in the liquid phase at a mass percentage of 60:35:5.

[0069] Example 7: R1233zd(Z), R1234ze(Z) and R600 were physically mixed in the liquid phase at a mass percentage of 65:30:5.

[0070] Example 8: R1233zd(Z), R1234ze(Z) and R600 were physically mixed in the liquid phase at a mass percentage of 70:25:5.

[0071] Example 9: R1233zd(Z), R1234ze(Z) and R600 were physically mixed in the liquid phase at a mass percentage of 73:22:5.

[0072] Example 10: R1233zd(Z), R1234ze(Z) and R600 were physically mixed in the liquid phase at a mass percentage of 76:19:5.

[0073] Example 11: R1233zd(Z), R1234ze(Z) and R600 were physically mixed in the liquid phase at a mass percentage of 79:16:5.

[0074] Example 12: R1233zd(Z), R1234ze(Z) and R600 were physically mixed in the liquid phase at a mass percentage of 82:13:5.

[0075] Example 13: R1233zd(Z), R1234ze(Z) and R600 were physically mixed in the liquid phase at a mass percentage of 85:10:5.

[0076] Example 14: R1233zd(Z), R1234ze(Z) and R600 were physically mixed in the liquid phase at a mass percentage of 87:8:5.

[0077] Example 15: R1233zd(Z), R1234ze(Z) and R600 were physically mixed in the liquid phase at a mass percentage of 90:5:5.

[0078] Comparative Example 1: R1233zd(Z) and R1234ze(Z) were physically mixed in the liquid phase at a mass percentage of 40:60.

[0079] Comparative Example 2: R1233zd(Z) and R1234ze(Z) were physically mixed in the liquid phase at a mass percentage of 50:50.

[0080] Comparative Example 3: R1233zd(Z) and R1234ze(Z) were physically mixed in the liquid phase at a mass percentage of 60:40.

[0081] Comparative Example 4: R1233zd(Z) and R1234ze(Z) were physically mixed in the liquid phase at a mass percentage of 70:30.

[0082] Comparative Example 5: R1233zd(Z) and R1234ze(Z) were physically mixed in the liquid phase at a mass percentage of 80:20.

[0083] Comparative Example 6: R1233zd(E) and R1234ze(E) were physically mixed in the liquid phase at a mass percentage of 40:60.

[0084] Comparative Example 7: R1233zd(E), R1234ze(E) and R600 were physically mixed in the liquid phase at a mass percentage of 60:35:5.

[0085] Basic physical properties of heat transfer compositions

[0086] (a) Flammability

[0087] Table 2 below provides the flammability rating data for the heat transfer compositions and R123 in each embodiment and comparative example, as follows:

[0088] Table 2 Flammability Rating Data

[0089]

[0090]

[0091] The flammability tests above were conducted according to the national standard GB / T 12474-2008. As shown in Table 2 above, the heat transfer compositions of each embodiment of the present invention are weakly flammable or non-flammable; in particular, the heat transfer compositions of Examples 8-15 are non-flammable.

[0092] (II) Temperature glide, enthalpy of vaporization and environmental performance

[0093] Table 3 below provides data on temperature glide, density, enthalpy of vaporization, and environmental performance of the heat transfer compositions and R123 in each embodiment and comparative example, as detailed below:

[0094] Table 3 Temperature glide, enthalpy of vaporization, and environmental performance

[0095]

[0096]

[0097] The heat transfer compositions of each embodiment exhibit an enthalpy of vaporization of more than 50% higher than that of R123 under standard atmospheric pressure. The comparative examples also show an increase in enthalpy of vaporization compared to R123, but the maximum increase is only 27%, significantly inferior to the aforementioned embodiments. Furthermore, comparative examples 6 and 7 show a temperature slip exceeding 10°C, which can lead to substantial changes in system performance in the event of leakage. Therefore, when the heat transfer compositions of each embodiment are applied to a heat dissipation system, the phase change heat transfer under the same operating conditions is far higher than that of R123, resulting in higher cooling efficiency. The heat transfer compositions of the present invention possess superior performance at the same charge amount, making them particularly suitable for heat dissipation systems such as heat pipes and blown plates.

[0098] Saturated vapor pressure characterizes the system pressure of a fluid in a gas-liquid coexistence phase. It is one of the fundamental thermodynamic properties of fluids, and it determines the actual pressure of the system equipment. Therefore, the closer the saturated vapor pressure of the alternative working fluid is to R123, the less modification is required to the new working fluid equipment system. It is one of the important physical property indicators of concern for heat pump systems and chiller systems. Figure 1-3 The saturated vapor pressure curves for R123 and Examples 1-15 are given. Figures 1-3As can be seen from the formula for average relative deviation (AAD), the vapor pressures of the heat transfer compositions in each embodiment of the present invention are similar to those of R123, with deviations not exceeding 50%. Specifically, the average relative deviation (AAD) of the saturated vapor pressures of the heat transfer compositions in Examples 6-15 from R123 is <20%, and the average relative deviation (AAD) of the saturated vapor pressures in Examples 8-15 is <10%. In particular, the saturated vapor pressures of Examples 10-12 are very close to those of R123, with an average relative deviation (AAD) of <5%.

[0099] As can be seen from the saturated vapor pressure curve and enthalpy of vaporization, under the same phase change pressure, the heat dissipation capacity of the heat transfer composition of the present invention exceeds that of R123 by 50%. That is, under the same material pressure rating and the same phase change heat transfer system structure, the efficiency of the heat transfer composition of the present invention is 50% higher than that of R123.

[0100] Application of heat transfer compositions in medium-temperature heat pumps, high-temperature heat pumps and chillers

[0101] Cycle performance (coefficient of performance (COP)) and volumetric heating / cooling capacity (Q) of medium-temperature heat pumps, high-temperature heat pumps, and chillers v It is used to evaluate the heating / cooling performance of the entire system during operation.

[0102] Appendix Figure 4 The diagram illustrates the working principle of heat transfer compositions 1-15 in a heat pump / refrigeration system according to embodiments of the present invention. During operation, the vapor of the heat transfer composition is compressed into a high-temperature, high-pressure gas by the compressor. The high-temperature, high-pressure gas discharged from the compressor releases heat through the condenser, achieving the heating effect of the heat pump system. The gaseous working fluid condenses into a low-temperature, high-pressure liquid after passing through the condenser, and then passes through the subcooler to form an even lower-temperature subcooled liquid. The low-temperature, high-pressure liquid flashes through the expansion valve to become a low-temperature, low-pressure gas-liquid mixture. This gas-liquid mixture absorbs heat through the evaporator and superheater, achieving the cooling effect of the refrigeration system. Finally, it returns to a high-temperature, low-pressure gas and enters the compressor. This cycle repeats continuously.

[0103] In a heat pump / refrigeration cycle system, the coefficient of performance (COP) is expressed as the ratio of the heat released by the condenser and subcooler to the heat absorbed by the evaporator and superheater, and the power consumed by the compressor. The higher the COP, the higher the system efficiency.

[0104] Volumetric heating / cooling capacity is expressed as the amount of heat released / absorbed per unit volume of working fluid. A larger volumetric heating / cooling capacity results in superior system performance and enables system miniaturization.

[0105] (I) Heating performance of heat pump system

[0106] This invention presents experimental studies on medium-temperature and high-temperature heat pump systems in different temperature zones. Table 4 shows the design conditions for each group of heat pump experiments, as detailed below:

[0107] Table 4 Experimental Design Conditions for Medium-Temperature and High-Temperature Heat Pumps

[0108]

[0109] Table 5 presents the performance data of Examples 1-15, Comparative Examples, and R123 under medium-temperature and high-temperature heat pump conditions, as detailed below:

[0110] Table 5 Heating performance under different operating conditions

[0111]

[0112]

[0113]

[0114]

[0115]

[0116] As shown in Table 5 above, the volumetric heating capacity of each embodiment in the medium-temperature heat pump system is significantly higher than that of R123, averaging 42.8% higher, with a maximum exceeding of 73.76% and a minimum exceeding of 16.2%. In terms of energy efficiency ratio (COP), it is lower than that of R123, averaging a decrease of 2.37%, with the largest decrease being 5% and the smallest being 0.8%. In the comparative examples, the volumetric heating capacity of the medium-temperature heat pump systems in Comparative Examples 1-5 is only 22.2% higher than that of R123 on average, and the COP decrease is comparable to that of the embodiments, averaging a decrease of 2.07%. Comparative Examples 6-7 can bring a significant increase in volumetric heating capacity, but the system pressure is more than twice that of the original R123 working fluid, making direct replacement of the original system impossible. The experimental results and analysis of the medium-temperature heat pump system show that the energy efficiency ratio of each embodiment of the present invention decreases slightly, but the volumetric heating capacity can be significantly improved. Furthermore, the pressure ratio between the condensing pressure and the evaporating pressure in embodiments 6-15 is not significantly different from that of the original R123 working fluid, and is slightly lower than that of R123 (an average reduction of 3.6%). The results indicate that the heat transfer composition of the present invention is particularly suitable for replacing R123 in medium-temperature heat pump systems and can bring significant benefits.

[0117] In the high-temperature heat pump system, the volumetric heating capacity of each embodiment is significantly higher than that of R123, averaging 39% higher, with a maximum exceeding it by 69.1% and a minimum by 15.3%. Regarding the energy efficiency ratio (EER), it is significantly lower than R123, averaging a decrease of 11%, with the largest decrease being 14.9% and the smallest being 6.9%. In the comparative examples, the volumetric heating capacity of the high-temperature heat pump systems in Comparative Examples 1-5 is only 22.2% higher than that of R123 on average, and the COP is also significantly lower, averaging a decrease of 10.8%. Similarly, while Comparative Examples 6-7 bring a significant increase in volumetric heating capacity, the system pressure also more than doubles. From the experimental results and analysis of the high-temperature heat pump system, it can be seen that the volumetric heating capacity gain of each embodiment is almost the same as that of the medium-temperature heat pump system, but the EER loss is greater. Therefore, overall, the benefits of replacing R123 in high-temperature heat pumps are not as great as in medium-temperature heat pump systems. However, compared with the original R123 system, its heating performance is still improved. Moreover, when replacing R123 in a high-temperature heat pump system with a condensation temperature above 80°C, it can ensure that the compressor outlet is always in the gas phase, avoiding the presence of liquid phase at the compressor outlet, which could cause liquid slugging and damage the compressor.

[0118] Considering volumetric heating capacity, energy efficiency ratio, and safety, the application effects of each embodiment are significantly better than R123, especially in medium-temperature heat pumps. Therefore, the heat transfer composition of the embodiments of the present invention can replace R123 in heat pump systems and offers significant benefits.

[0119] (II) Cooling performance of water chiller units

[0120] This invention also includes experimental studies on various heat transfer compositions in the refrigeration cycle system of a chiller unit. Table 6 presents the design conditions for the chiller unit experiments, as follows:

[0121] Table 6 Experimental Design Conditions for Chiller Units

[0122] Condensation temperature (°C) Evaporation temperature (°C) Supercooling temperature (°C) Superheat temperature (°C) 40 3 38 5

[0123] Table 7 presents the performance data of Examples 1-15, Comparative Examples, and R123 under chiller unit operating conditions, as detailed below:

[0124] Table 7 Cooling performance of chiller units under operating conditions

[0125]

[0126]

[0127] As shown in Table 7 above, the volumetric cooling capacity of the heat transfer compositions in each embodiment is significantly higher than that of R123, averaging 54.9% higher, with the highest exceeding R123 by 90.6% and the lowest by 24%. The average energy efficiency ratio is 99.6% of that of R123. In the comparative examples, the increase in volumetric cooling capacity in Comparative Examples 1-5 is not significant, averaging 48.2%, but the COP in the comparative examples is higher than that of R123, averaging 15.3%. Furthermore, Comparative Examples 6-7 are inferior to the original R123 working fluid in terms of both volumetric heating capacity and COP. In each embodiment, a high volumetric cooling capacity gain (an increase of 54.9%) is achieved at the cost of a minimal loss in energy efficiency ratio (0.5%). At the same time, the compressor pressure ratio required under the same cooling conditions is reduced by an average of 9.02% compared to the original R123 working fluid. Taking into account volumetric cooling capacity, energy efficiency ratio, and safety, the application effect of each embodiment in the chiller system is significantly better than that of R123, and can replace R123 in the chiller system. At the same time, the evaporation pressure of each embodiment is higher than that of R123, resulting in a lower evaporator vacuum degree in the system and greater safety.

[0128] Weighting advantage of heat transfer composition

[0129] The heat transfer composition analysis and screening were obtained through objective function weighting analysis:

[0130]

[0131] The heat transfer composition described in this invention relates to applications in refrigeration / heating systems and heat dissipation systems. Key parameters of the refrigeration / heating system include: volumetric cooling / heating capacity, COP, etc. Key parameters of the heat dissipation system include: saturated vapor pressure, enthalpy of vaporization, etc.

[0132] In the formula, S k This represents the objective function; a larger value indicates a greater advantage of the composition in replacing R123. i This represents the i-th performance parameter, including: enthalpy of evaporation, saturated vapor pressure, system volumetric cooling / heating capacity, system COP, etc. i This represents the weight of the i-th performance attribute, which is determined by the importance of the performance attribute in the system operation.

[0133] Table 8. Examples, Comparative Examples, and R123 Weighted Objective Function Values

[0134] working medium <![CDATA[S k ]]> working medium <![CDATA[S k ]]> Example 1 81.38 Example 13 66.67 Example 2 84.24 Example 14 59.30 Example 3 86.56 Example 15 48.08 Example 4 88.33 Comparative Example 1 13.20 Example 5 89.55 Comparative Example 2 15.14 Example 6 90.38 Comparative Example 3 14.89 Example 7 90.50 Comparative Example 4 12.50 Example 8 90.10 Comparative Example 5 -15.28 Example 9 89.48 Comparative Example 6 -170.69 Example 10 88.79 Comparative Example 7 -215.11 Example 11 84.47 R123 0 Example 12 76.65

[0135] As can be seen from the weighted objective function, considering the advantages and disadvantages of the cooling / heating and heat dissipation systems, all embodiments show significant performance improvements compared to R123, with an average weighted objective function value of 80.96. Among them, embodiments 6-8 exhibit the best advantage. In contrast, the average weighted objective function value of comparative examples 1-4 is only 13.93. In particular, the weight values ​​of comparative examples 5-7 are <0, indicating that comparative examples 5-7 are inferior to R123 under comprehensive consideration.

[0136] In summary, the heat transfer composition described in this invention, when used as a heat transfer medium in heat pipes, inflated plate systems, heat pump systems, and chillers, exhibits superior overall performance compared to R123. Furthermore, because the saturated vapor pressure of the replacement heat transfer composition is similar to that of R123, the system itself requires minimal modification. Moreover, compared to R123, the heat transfer composition described in this invention offers superior environmental and safety performance. Therefore, the heat transfer composition proposed in this invention, replacing R123 in refrigeration / heating systems and heat dissipation systems, has significant practical implications and feasibility.

Claims

1. A heat transfer composition which is a replacement for R123 characterised in that: The heat transfer composition comprises 45–76 wt% Z-1-chloro-3,3,3-trifluoropropene, 19–50 wt% Z-1,3,3,3-tetrafluoropropene, and 1–5 wt% n-butane. The heat transfer composition has an enthalpy of vaporization of >250 KJ / kg at standard atmospheric pressure, and the average relative deviation (AAD) of the saturated vapor pressure of the heat transfer composition at any temperature within the range of 15–145 °C is <50%.

2. The heat transfer composition of claim 1 which is a replacement for R123. The heat transfer composition comprises 60-70 wt% Z-1-chloro-3,3,3-trifluoropropylene, 25-35 wt% Z-1,3,3,3-tetrafluoropropylene, and 1-5 wt% n-butane.

3. Use of a heat transfer composition according to any of claims 1-2 as a replacement for R123, characterized in that: The heat transfer composition is used as a heat transfer medium in one of the following systems: medium-temperature heat pump system, high-temperature heat pump system, chiller unit, heat pipe system, or blown plate system.

4. The application of the heat transfer composition according to claim 3 as a substitute for R123, characterized in that: The heat transfer composition is used as a heat transfer medium in a medium-temperature heat pump system, a high-temperature heat pump system, or a chiller unit. Compared with R123, the compressor pressure in the system is reduced by more than 2%.

5. The application of the heat transfer composition according to claim 4 as a substitute for R123, characterized in that: The evaporation temperature of the medium-temperature heat pump system is 20–50°C, and the condensation temperature is 60–100°C; the evaporation temperature of the high-temperature heat pump system is 40–80°C, and the condensation temperature is 100–130°C; the evaporation temperature of the chiller unit is 1–10°C, and the condensation temperature is 30–50°C.

6. The application of the heat transfer composition according to claim 3 as a substitute for R123, characterized in that: The heat transfer composition is used as a heat transfer medium in heat pipe systems or blown plate systems. Compared with R123, the heat transfer capacity of the heat transfer composition increases by more than 50%.

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