Heat transfer composition replacing R123 and application thereof

Abstract

The invention discloses a heat transfer composition for replacing R123, the heat transfer composition comprises 30-98 wt% of Z-1-chloro-3, 3, 3-trifluoropropene, 1-65 wt% of Z-1, 3, 3, 3-tetrafluoropropene and 1-5 wt% of n-butane, the evaporation enthalpy of the heat transfer composition under standard atmospheric pressure is greater than 250 KJ / kg, and the average relative deviation AAD of saturated vapor pressure of the heat transfer composition at any temperature within 15-145 DEG C is less than 50%. The heat transfer composition has the advantages of being excellent in environmental performance, good in safety performance, high in unit volume heating / refrigerating capacity, high in latent heat of vaporization, good in heat transfer performance, large in expansion work and the like.

Description

Technical Field

[0001] The invention relates to the field of heat transfer compositions, and in particular to a heat transfer composition replacing R123 and application thereof. Background Art

[0003] In the industrial field, especially in the petrochemical, sewage treatment, printing and dyeing industries, 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.

[0004] R123 (trifluoroethylene dichloroethane) has a critical temperature of 183.68°C, a critical pressure of 3.6618 MPa, and a boiling point of 27.823°C. It is the most commonly used working fluid in heat pumps, organic Rankine cycles, and other systems. However, R123 contains the Cl element, belongs to the HCFC class, has ozone destruction capabilities, and is classified as Class B1 in the ASHRAE classification, which is a toxic refrigerant and faces the risk of being phased out.

[0005] Using R123 as a circulating working fluid in heat pumps and chillers has a higher COP and can save electricity under the same working conditions. However, in chillers, due to the high boiling point of R123, the system operates at negative pressure.

[0006] In order to find a heat transfer medium to replace R123 and realize the in-situ replacement of the original system, the existing technology has made the following efforts:

[0007] CN104662121A discloses a composition comprising 1 to 42 wt% of Z-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz) and 99 to 58 wt% of R123. The composition can replace R123 for refrigeration, air conditioning, heat pump or power cycle systems. However, the composition still contains a large mass proportion of R123 and still faces the risk of elimination in the long run.

[0008] CN104946206A discloses a non-azeotropic composition containing 89-97wt% of difluoromethane (R32) and 3-11wt% of R123, which has good thermal performance, environmental performance, safety performance and market availability, and the non-azeotropic composition has good compatibility with the original system, can effectively improve the cycle performance of the system, and can replace R123. However, the boiling point of R32 is -51.7°C, which is quite different from the boiling point of R123, so that the composition has a large temperature glide. Once a leak occurs, the composition changes too much, and it needs to be re-tested and refilled, which is troublesome to operate; at the same time, due to the large difference between the boiling point of the mixture and R123, the performance of the operation in the original system will be quite different from that of R123.

[0009] CN107810247A discloses a refrigerant composition of 61.5-67.5wt% R1336mzz(Z), 20.5-22.5wt% R1130(E) and 10-18wt% R1233zd(E), which has a small temperature glide and is a suitable substitute for R123. However, the component R1130(E) is a highly flammable substance, and its vapor easily forms an explosive mixture with air, and it also has certain toxicity, which poses a safety hazard during use.

[0010] CN110945100A discloses a refrigerant composition comprising FO-1216 and a hydrofluoroolefin (such as HFO-1234ze, HFO-1243zf), a refrigerant composition comprising FO-1216 and a halogenated vinyl (such as HCFO-1122a, FO-1114, HFO-1123, HFO-1132(E), HFO-1132(Z), HFO-1132a, HFO-1141), and a refrigerant composition comprising FO-1216 and a hydrofluorocarbon (HFC-125, HFC-143a, HFC-32, HFC-134, HFC-134a, HFC-152a, HFC-227ea), which have a small GWP value, are non-flammable or slightly flammable, and can be used as a substitute refrigerant such as R134a, R410A, R123 or R404A. However, the composition also has the problem of a large difference in boiling point from R123. Among them, the boiling point of FO-1216, the key component, is -30.34°C and the critical temperature is 87.75°C. Therefore, this type of substitute is not suitable for high-temperature heat pump systems and organic Rankine cycle systems.

[0011] In summary, the heat transfer compositions used in the prior art to replace R123 have either large performance differences, or have safety issues, or cannot be replaced in some systems, and it is necessary to develop new heat transfer compositions to replace R123. Summary of the invention

[0012] In order to solve the above technical problems, the present invention proposes a heat transfer composition for replacing R123 with excellent environmental performance, good safety performance, high heating / cooling capacity per unit volume, and large expansion work. The boiling point of the heat transfer composition is close to that of R123, the temperature glide is moderate, and the system universality is good. It can be used in medium-temperature heat pump systems, high-temperature heat pump systems, chillers, heat pipe systems or blown plate systems.

[0013] The physical properties of the components involved in the present invention are as follows:

[0014] Z-1-chloro-3,3,3-trifluoropropene (R1233zd(Z)), with a molecular formula of C3H2F3Cl and a molecular weight of 130.5, has a standard boiling point. The saturated vapor pressure equation is obtained by measuring the saturated phase pressure under a selected temperature group in a static method experiment. The standard atmospheric pressure (0.101325MPa) is 36.44°C, the critical temperature is 200.52°C, the critical pressure is 3.647MPa, and the GWP is <1.

[0015] Z-1,3,3,3-tetrafluoropropylene (R1234ze(Z)), with molecular formula of C3H2F4, molecular weight of 114.04, standard boiling point of 9.73°C, critical temperature of 150.12°C, critical pressure of 3.5306MPa, GWP<1.

[0016] n-Butane (R600), whose molecular formula is C4H 10 , molecular weight is 58.122, standard boiling point is -0.49℃, critical temperature is 151.98℃, critical pressure is 3.796MPa, GWP<1.

[0017] The objective of the present invention is achieved through the following technical solutions:

[0018] A heat transfer composition for replacing R123, comprising 30-98 wt% of Z-1-chloro-3,3,3-trifluoropropene, 1-65 wt% of Z-1,3,3,3-tetrafluoropropene and 1-5 wt% of n-butane, wherein the evaporation enthalpy of the heat transfer composition under standard atmospheric pressure is greater than 250 kJ / kg, 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 less than 50%.

[0019] Furthermore, the heat transfer composition comprises 35 to 80 wt % of Z-1-chloro-3,3,3-trifluoropropene, 15 to 60 wt % of Z-1,3,3,3-tetrafluoropropene and 1 to 5 wt % of n-butane.

[0020] Furthermore, the heat transfer composition comprises 45-76 wt % of Z-1-chloro-3,3,3-trifluoropropene, 19-50 wt % of Z-1,3,3,3-tetrafluoropropene and 1-5 wt % of n-butane.

[0021] Still further, the heat transfer composition comprises 60-70 wt % of Z-1-chloro-3,3,3-trifluoropropene, 25-35 wt % of Z-1,3,3,3-tetrafluoropropene and 1-5 wt % of n-butane.

[0022] Furthermore, the heat transfer composition comprises 60-90 wt% of Z-1-chloro-3,3,3-trifluoropropene, 5-35 wt% of Z-1,3,3,3-tetrafluoropropene and 1-5 wt% of 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 less than 20%.

[0023] Furthermore, the heat transfer composition comprises 70-90 wt% of Z-1-chloro-3,3,3-trifluoropropene, 5-25 wt% of Z-1,3,3,3-tetrafluoropropene and 1-5 wt% of 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 less than 10%.

[0024] The analysis and screening of the heat transfer composition replacing R123 of the present invention is obtained by objective function weight analysis, namely:

[0025]

[0026] In formula (1), S k Represents the objective function, and the larger its value is, the greater the advantage of the heat transfer composition in replacing R123. i Indicates the i-th performance parameter, including: evaporation enthalpy, saturated vapor pressure, system cooling / heating capacity, system COP, etc. i It represents the weight of the ith performance, which is determined by the importance of the performance in the system operation.

[0027] The heat transfer composition replacing R123 of the present invention is non-flammable, has an ODP value of about 0, and a GWP value of less than 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).

[0028] The heat transfer composition replacing R123 of the present invention has an evaporation enthalpy greater than 250 KJ / kg at standard atmospheric pressure, and compared with R123, the filling amount of the heat transfer medium can be reduced.

[0029] The heat transfer composition replacing R123 of the present invention, compared with R123, has an average relative deviation AAD of saturated vapor pressure at any temperature point within the range of 15 to 145° C. of less than 50%, preferably, AAD less than 20%, and more preferably, AAD less than 10%.

[0030] The calculation of the average relative deviation of the saturated vapor pressure is shown in formula (2):

[0031]

[0032] In formula (2), AAD represents the average relative deviation of 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.

[0033] The average relative deviation of saturated vapor pressure represents the deviation of saturated vapor pressure between the alternative heat transfer composition and R123. The smaller the average relative deviation of saturated vapor pressure, the closer the saturated vapor pressure of the alternative heat transfer composition is to that of R123, and the smaller the modification to the system equipment is when the heat transfer composition is replaced.

[0034] The present invention creatively introduces R600 and controls the content based on a large number of tests on the physical properties related to R1233zd (Z) and R1234ze (Z), improves the heat transfer capacity while ensuring safety, and finally obtains a heat transfer composition with a boiling point similar to that of R123 and a critical performance close to that of R123. On the basis of not changing the main equipment of the original R123 system, the in-situ replacement of R123 can be achieved, and the toxicity risk caused by leakage of the R123 system can be solved. At the same time, the filling amount can be reduced, and the refrigeration / heating capacity per unit volume can be greatly improved.

[0035] The present invention also provides an application of the heat transfer composition replacing R123, wherein the heat transfer composition replacing R123 is used as a heat transfer working fluid in a medium-temperature heat pump system, a high-temperature heat pump system, a chiller, a heat pipe system or a blown plate system.

[0036] The heat transfer composition replacing R123 is used as a heat transfer working medium in a medium-temperature heat pump system, a high-temperature heat pump system or a chiller. Compared with R123, the pressure of the compressor in the system is reduced by more than 2%.

[0037] The heat transfer composition replacing R123 is used as a heat transfer working 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.

[0038] The heat transfer composition replacing R123 is used as a heat transfer medium in a water chiller, and the evaporation temperature of the water chiller is 1-10°C and the condensation temperature is 30-50°C.

[0039] The heat transfer composition replacing R123 is used as a heat transfer working fluid in a medium-temperature heat pump system, a high-temperature heat pump system or a chiller, and needs to be used together with a lubricating oil. The lubricating oil is selected from at least one of dibasic acid ester oil, polyol carbonate oil, perfluoropolyether oil, fluorinated silicone oil, cycloparaffin mineral oil, poly-α-olefin, alkylbenzene or alkylnaphthalene. Preferably, the lubricating oil is a cycloparaffin mineral oil miscible with R123, such as 3GS, T68, etc.

[0040] In order to improve the compatibility of the heat transfer composition replacing R123 with lubricating oil and improve the cyclic heat transfer effect, the heat transfer composition replacing R123 also includes an auxiliary agent, which is selected from at least one of 1-butyne, 1-pentene, 2,2-dimethylbutane, cis-butene, trans-butene, pentane, cyclopentane, isopentane and neopentane, and the content of the auxiliary agent accounts for 1-3% of the total mass of the heat transfer composition replacing R123. Preferably, the auxiliary agent is selected from at least one of 1-pentene, pentane or isopentane.

[0041] The heat transfer composition replacing R123 is used as a heat transfer medium in a heat pipe system or a blown plate system. Compared with R123, the heat transfer capacity increment of the heat transfer composition is greater than 50%.

[0042] As an embodiment, the heat transfer composition replacing R123 is used as a heat transfer medium in a medium-temperature heat pump system, with an evaporation temperature of 20 to 50°C, a condensation temperature of 60 to 100°C, and a heating capacity per unit volume increased by 16.2 to 73.76% compared to R123.

[0043] As an embodiment, the heat transfer composition replacing R123 is used as a heat transfer medium in a high-temperature heat pump system, with an evaporation temperature of 40 to 80°C, a condensation temperature of 100 to 130°C, and a heating capacity per unit volume increased by 15.3 to 69.1% compared to R123.

[0044] As an embodiment, the heat transfer composition replacing R123 is used as a heat transfer medium in a cooling unit system, with an evaporation temperature of 1 to 10°C, a condensation temperature of 30 to 50°C, and a unit volume refrigeration capacity increased by 24 to 90.6% compared with R123.

[0045] The medium-temperature heat pump system, high-temperature heat pump system or cooling unit system of the present invention comprises a condenser, an evaporator, a compressor and a throttle valve.

[0046] When the heat transfer composition replacing R123 of the present invention is used in a medium- and high-temperature heat pump system, especially when replacing R123 in a high-temperature heat pump system with a condensing temperature above 80°C, it can ensure that the compressor outlet is all gas phase, avoiding the presence of liquid phase at the compressor outlet, causing liquid hammer and damaging the compressor.

[0047] Compared with the prior art, the present invention has the following beneficial effects:

[0048] 1. The heat transfer composition of the present invention has an ODP value of about 0, a GWP value of <1, and excellent environmental performance.

[0049] 2. The boiling point of the heat transfer composition of the present invention is close to that of R123, and the critical performance is close to that of R123. It can replace R123 in situ and be used in heating systems, refrigeration systems, heat dissipation systems, etc. that originally used R123.

[0050] 3. During the operation of the heating / cooling system, the overall heat exchange capacity is significantly improved, with the heating capacity per unit volume increased by an average of 40.9% and the cooling capacity per unit volume increased by an average of 54.9%.

[0051] 4. During the operation of the cooling system, the cooling capacity of the system is increased by an average of 50.15% compared with R123. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1 The saturated vapor pressure curves of the heat transfer compositions of Examples 1 to 5 of the present invention and R123;

[0053] Figure 2 The saturated vapor pressure curves of the heat transfer compositions of Examples 6 to 10 of the present invention and R123;

[0054] Figure 3 The saturated vapor pressure curves of the heat transfer compositions of Examples 11 to 15 of the present invention and R123;

[0055] Figure 4 This is the working principle diagram of the heat pump / refrigeration system, where 1 is the throttle valve, 2 is the subcooler, 3 is the condenser, 4 is the compressor, 5 is the superheater, and 6 is the evaporator.

[0056] Figure 5 The working principle diagram of the heat pipe cooling system, where 1 is steam, 2 is the liquid absorption core, 3 is liquid, 4 is the tube shell, 5 is the condensation section, 6 is the insulation section, 7 is the heat absorption section, and 8 is the cross section. DETAILED DESCRIPTION

[0057] The present invention is further described below in conjunction with specific embodiments, but the present invention is not limited to these specific embodiments. Those skilled in the art should recognize that the present invention covers all possible alternatives, improvements and equivalents within the scope of the claims.

[0058] The heating system used in the embodiment of the present invention is a heat pump system, the refrigeration system is a chiller, and the heat dissipation system is a heat pipe system and a blowing plate system. The heat pump system and the chiller are equipped with subcoolers and superheaters at the outlets of the condenser and the evaporator.

[0059] Table 1 shows the thermophysical properties of R1233zd(Z), R1234ze(Z), R600, R1233zd(E), R1234ze(E), and R123

[0060]

[0061] The standard boiling points in Table 1 are measured by static method experiments.

[0062] Heat transfer composition

[0063] The method for preparing the heat transfer composition of the embodiment of the present invention is to physically mix Z-1-chloro-3,3,3-trifluoropropene, Z-1,3,3,3-tetrafluoropropene and n-butane in a liquid phase according to the mass percentage of each component.

[0064] Example 1: R1233zd(Z), R1234ze(Z) and R600 were physically mixed in a liquid phase at a mass percentage of 35:60:5.

[0065] Example 2: R1233zd(Z), R1234ze(Z) and R600 were physically mixed in a liquid phase at a mass percentage of 40:55:5.

[0066] Example 3: R1233zd(Z), R1234ze(Z) and R600 were physically mixed in a liquid phase at a mass percentage of 45:50:5.

[0067] Example 4: R1233zd(Z), R1234ze(Z) and R600 were physically mixed in a liquid phase at a mass percentage of 50:45:5.

[0068] Example 5: R1233zd(Z), R1234ze(Z) and R600 were physically mixed in a liquid phase at a mass percentage of 55:40:5.

[0069] Example 6: R1233zd(Z), R1234ze(Z) and R600 were physically mixed in a liquid phase at a mass percentage of 60:35:5.

[0070] Example 7: R1233zd(Z), R1234ze(Z) and R600 were physically mixed in a liquid phase at a mass percentage of 65:30:5.

[0071] Example 8: R1233zd(Z), R1234ze(Z) and R600 were physically mixed in a liquid phase at a mass percentage of 70:25:5.

[0072] Example 9: R1233zd(Z), R1234ze(Z) and R600 were physically mixed in a liquid phase at a mass percentage of 73:22:5.

[0073] Example 10: R1233zd(Z), R1234ze(Z) and R600 were physically mixed in a liquid phase at a mass percentage of 76:19:5.

[0074] Example 11: R1233zd(Z), R1234ze(Z) and R600 are physically mixed in a liquid phase at a mass percentage of 79:16:5.

[0075] Example 12: R1233zd(Z), R1234ze(Z) and R600 were physically mixed in a liquid phase at a mass percentage of 82:13:5.

[0076] Example 13: R1233zd(Z), R1234ze(Z) and R600 were physically mixed in a liquid phase at a mass percentage of 85:10:5.

[0077] Example 14: R1233zd(Z), R1234ze(Z) and R600 were physically mixed in a liquid phase at a mass percentage of 87:8:5.

[0078] Example 15: R1233zd(Z), R1234ze(Z) and R600 were physically mixed in a liquid phase at a mass percentage of 90:5:5.

[0079] Comparative Example 1: R1233zd(Z) and R1234ze(Z) were physically mixed in a liquid phase at a mass percentage of 40:60.

[0080] Comparative Example 2: R1233zd(Z) and R1234ze(Z) were physically mixed in a liquid phase at a mass percentage of 50:50.

[0081] Comparative Example 3: R1233zd(Z) and R1234ze(Z) were physically mixed in a liquid phase at a mass percentage of 60:40.

[0082] Comparative Example 4: R1233zd(Z) and R1234ze(Z) were physically mixed in a liquid phase at a mass percentage of 70:30.

[0083] Comparative Example 5: R1233zd(Z) and R1234ze(Z) were physically mixed in a liquid phase at a mass percentage of 80:20.

[0084] Comparative Example 6: R1233zd (E) and R1234ze (E) were physically mixed in a liquid phase at a mass percentage of 40:60.

[0085] Comparative Example 7: R1233zd (E), R1234ze (E) and R600 were physically mixed in a liquid phase at a mass percentage of 60:35:5.

[0086] Basic physical properties of heat transfer compositions

[0087] (I) Flammability

[0088] Table 2 below gives the combustion grade data of the heat transfer compositions of various embodiments and comparative examples and R123, as follows:

[0089] Table 2 Combustion grade data

[0090]

[0091]

[0092] The above flammability test adopts the national standard GB / T 12474-2008. As can be seen from Table 2 above, the heat transfer compositions of various embodiments of the present invention are weakly flammable or non-flammable, and in particular, the heat transfer compositions of embodiments 8-15 are non-flammable.

[0093] (II) Temperature glide, evaporation enthalpy and environmental performance

[0094] Table 3 below gives the data of temperature glide, density, evaporation enthalpy and environmental performance of the heat transfer composition and R123 of each embodiment and comparative example, as follows:

[0095] Table 3 Temperature glide, evaporation enthalpy and environmental performance

[0096]

[0097]

[0098] The evaporation enthalpy of the heat transfer composition of each embodiment at standard atmospheric pressure is higher than that of R123 by more than 50%. The evaporation enthalpy of each comparative example is also improved compared with R123, but the highest increase is only 27%, and the effect is obviously inferior to the above-mentioned embodiment, and the temperature glide of comparative examples 6 to 7 exceeds 10°C, which will bring about a significant change in system performance when a leak occurs. Therefore, when the heat transfer composition of each embodiment is applied to a heat dissipation system, the phase change heat under the same working conditions is much higher than that of R123, and the cooling efficiency is higher than that of R123. The heat transfer composition of each embodiment of the present invention has more excellent performance at the same filling amount, and is particularly suitable for heat dissipation systems such as heat pipes and inflation plates.

[0099] Saturated vapor pressure characterizes the system pressure of the fluid in the gas-liquid coexistence phase. It is one of the basic thermodynamic properties of the fluid. The saturated vapor pressure 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 changes will be made to the new working fluid equipment system. It is one of the important physical property indicators that heat pump systems and chiller systems pay attention to. Figure 1-3 The saturated vapor pressure curves of R123 and Examples 1 to 15 are given. Figures 1 to 3It can be seen that according to the formula of average relative deviation AAD, the vapor pressure of the heat transfer composition of each embodiment of the present invention is close to that of R123, and the deviation does not exceed 50%. Among them, the average relative deviation AAD of the saturated vapor pressure of the heat transfer composition of Examples 6 to 15 and R123 is <20%, and the average relative deviation AAD of the saturated vapor pressure of Examples 8 to 15 is <10%. In particular, the saturated vapor pressure of Examples 10 to 12 is very close to that of R123, and its average relative deviation AAD is <5%.

[0100] It can be seen from the saturated vapor pressure curve and evaporation enthalpy that at 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, at the same material pressure resistance level of the equipment 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.

[0101] Application of heat transfer compositions in medium temperature heat pumps, high temperature heat pumps and chillers

[0102] Medium temperature heat pump, high temperature heat pump, chiller cycle performance (coefficient of performance (COP), volumetric heating / cooling capacity (Q v )) is used to evaluate the heating / cooling performance during the operation of the entire system.

[0103] Attached Figure 4 The working principle diagram of the heat transfer composition 1 to 15 of the embodiments of the present invention in the heat pump / refrigeration system is given. When the heat pump and refrigeration system are working, the heat transfer composition vapor is compressed into a high-temperature and high-pressure gas by the compressor, and the high-temperature and high-pressure gas discharged by the compressor releases heat to the outside through the condenser to achieve the heating effect of the heat pump system. The gas working fluid condenses into a low-temperature and high-pressure liquid after passing through the condenser, and then passes through the subcooler to form a supercooled liquid with a lower temperature. The low-temperature and high-pressure liquid flashes through the throttle valve to become a low-temperature and low-pressure gas-liquid phase mixture. The gas-liquid phase mixture absorbs heat through the evaporator and superheater to achieve the refrigeration effect of the refrigeration system, and finally becomes a high-temperature and low-pressure gas again and enters the compressor. This reciprocating cycle is formed.

[0104] In the heat pump / refrigeration cycle system, the coefficient of performance COP is expressed as: the ratio of the heat released by the condenser and subcooler / the heat absorbed by the evaporator and superheater to the power consumption of the compressor. The higher the COP, the higher the efficiency of the system.

[0105] Volumetric heating / cooling capacity is expressed as the amount of heat that can be released / absorbed per unit volume of working fluid. The larger the volumetric heating / cooling capacity, the better the system performance and the more miniaturized the system can be.

[0106] (I) Heating performance of heat pump system

[0107] The present invention conducts experimental research on medium-temperature and high-temperature heat pump systems in different temperature zones. Table 4 gives the design conditions of each group of heat pump experiments, as follows:

[0108] Table 4 Design conditions for medium and high temperature heat pump experiments

[0109]

[0110] Table 5 gives the performance data of Examples 1 to 15, Comparative Examples and R123 under medium and high temperature heat pump conditions, as follows:

[0111] Table 5 Heating performance under different working conditions

[0112]

[0113]

[0114]

[0115]

[0116]

[0117] As can be seen from Table 5 above, the volumetric heating capacity of each embodiment in the medium-temperature heat pump system is much higher than that of R123, with an average excess of 42.8% over the volumetric heating capacity of R123, a maximum excess of 73.76%, and a minimum excess of 16.2%. In terms of energy efficiency ratio, it has decreased compared to R123, with an average decrease of 2.37%, of which the maximum decrease is 5% and the minimum decrease is 0.8%. In the comparative examples, the volumetric heating capacity of the medium-temperature heat pump systems of comparative examples 1 to 5 is only 22.2% higher than that of R123 on average, and the COP decrease is equivalent to that of each embodiment, with an average decrease of 2.07%. Comparative examples 6 to 7 can bring about a significant increase in volumetric heating capacity, but the system pressure is more than twice that of the original R123 working fluid, and it is impossible to directly replace the original system. From the experimental results and analysis of the medium-temperature heat pump system, it can be seen that the energy efficiency ratio of each embodiment of the present invention is slightly reduced, but the volumetric heating capacity can be greatly improved, and the pressure ratio between the condensing pressure and the evaporation pressure in Examples 6 to 15 is not much different from that of the original R123 working fluid, and is slightly lower than R123 (an average reduction of 3.6%). The results show that the heat transfer composition of the present invention is particularly suitable for replacing R123 for use in medium-temperature heat pump systems, and can bring greater benefits.

[0118] The volumetric heating capacity of each embodiment in the high-temperature heat pump system is also much higher than that of R123, with an average of 39% higher than that of R123, a maximum of 69.1% higher, and a minimum of 15.3% higher. In terms of energy efficiency ratio, the decline is more obvious compared with R123, with an average decline of 11%, of which the maximum decline is 14.9% and the minimum decline is 6.9%. In the comparative examples, the volumetric heating capacity of the high-temperature heat pump system of comparative examples 1 to 5 is only 22.2% higher than that of R123 on average, and the COP also declines significantly, with an average decline of 10.8%. Similarly, although comparative examples 6 to 7 can bring a large increase in volumetric heating capacity, the system pressure has also increased by more than doubled. From the experimental results and analysis of the high-temperature heat pump system, it can be seen that the volumetric heating capacity benefits of each embodiment are almost the same as those of the medium-temperature heat pump system, but the energy efficiency loss is greater than that of the medium-temperature heat pump system. Therefore, the overall benefits of replacing R123 for high-temperature heat pumps are not as good as those of medium-temperature heat pump systems. However, compared with the original R123 system, its heating effect is still improved. Moreover, when replacing R123 in a high-temperature heat pump system with a condensing temperature above 80°C, it can ensure that the compressor outlet is all gas phase, avoiding the presence of liquid phase at the compressor outlet, causing liquid hammer and damaging the compressor.

[0119] In terms of volumetric heating capacity, energy efficiency ratio and safety, the application effects of each embodiment are significantly better than those of R123, especially in medium-temperature heat pumps. Therefore, the heat transfer composition of the embodiment of the present invention can replace R123 and be applied to heat pump systems, and has great benefits.

[0120] (II) Refrigeration performance of chiller

[0121] The present invention also conducts experimental research on various heat transfer compositions in the refrigeration cycle system of a chiller. Table 6 shows the design conditions of the chiller experiment, which are as follows:

[0122] Table 6 Experimental design conditions of chiller

[0123] Condensation temperature (℃) Evaporation temperature(℃) Subcooling temperature(℃) Overheat temperature(℃) 40 3 38 5

[0124] Table 7 gives the performance data of Examples 1 to 15, the comparative example and R123 under the working conditions of the chiller, as follows:

[0125] Table 7 Refrigeration performance under chiller operating conditions

[0126]

[0127]

[0128] As can be seen from Table 7 above, the unit volume refrigeration capacity of the heat transfer composition of each embodiment is much higher than that of R123, with an average excess of 54.9% over the unit volume refrigeration capacity of R123, a maximum excess of 90.6% over the unit volume refrigeration capacity of R123, and a minimum excess of 24% over the unit volume refrigeration capacity of R123, and an average energy efficiency ratio of 99.6% of R123. In the comparative examples, the increase in unit volume refrigeration capacity of comparative examples 1 to 5 is not obvious, with an average increase of 48.2%, but the COP in the comparative examples is improved relative to R123, with an average increase of 15.3%. In addition, comparative examples 6 to 7 are not as good as the original R123 working fluid in terms of both volumetric heating capacity and COP. In each embodiment, a high volumetric refrigeration capacity benefit (increased by 54.9%) is obtained at the cost of a very small energy efficiency ratio loss (0.5%). At the same time, the required compressor pressure ratio under the same refrigeration conditions is reduced by an average of 9.02% compared with the original R123 working fluid. Taking into account the volumetric cooling capacity, energy efficiency ratio and safety, the application effect of each embodiment in the chiller system is obviously better than R123, and it can replace R123 in the chiller. At the same time, the evaporation pressure of each embodiment is higher than R123, so that the vacuum degree of the system evaporator is smaller and safer.

[0129] Weighted Advantages of Heat Transfer Compositions

[0130] The heat transfer composition analysis and screening was obtained through objective function weight analysis:

[0131]

[0132] The heat transfer composition of the present invention is applicable to cooling / heating systems and heat dissipation systems. The main parameter indicators of cooling / heating systems include volumetric cooling / heating capacity, COP, etc. The main indicators of heat dissipation systems include saturated vapor pressure, evaporation enthalpy, etc.

[0133] In the formula, S k Represents the objective function, and the larger its value is, the greater the advantage of the composition in replacing R123. i Indicates the i-th performance parameter, including: evaporation enthalpy, saturated vapor pressure, system volumetric cooling / heating capacity, system COP, etc. i It represents the weight of the ith performance, which is determined by the importance of the performance in the system operation.

[0134] Table 8 Example, comparative example and R123 weight objective function value

[0135] Working fluid <![CDATA[S k ]]> Working fluid <![CDATA[S k ]]> Example 1 81.38 Embodiment 13 66.67 Example 2 84.24 Embodiment 14 59.30 Example 3 86.56 Embodiment 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 Embodiment 11 84.47 R123 0 Example 12 76.65

[0136] It can be seen from the weighted objective function that, considering the advantages and disadvantages of the use of the refrigeration / heating and heat dissipation systems, each embodiment has a significant performance improvement compared to the R123 working fluid, and the average value of the weighted objective function is 80.96, among which embodiments 6 to 8 have the best advantage. In contrast, the average value of the weighted objective function of comparative examples 1 to 4 is only 13.93. In particular, the weight values ​​of comparative examples 5 to 7 are <0, indicating that comparative examples 5 to 7 are inferior to R123 under comprehensive consideration.

[0137] In summary, the heat transfer composition of the present invention as a heat transfer medium is applied to heat pipes, inflation plate systems, heat pump systems, and chillers, and its comprehensive operating performance is better than that of R123 medium. At the same time, since the saturated vapor pressure of the alternative heat transfer composition is similar to that of R123, the system itself does not need to be modified too much, and compared with R123, the environmental performance and safety performance of the heat transfer composition of the present invention are more excellent. Therefore, the heat transfer composition proposed by the present invention is applied to refrigeration / heating systems and heat dissipation systems instead of R123, which has great practical significance and feasibility.

Claims

1. A heat transfer composition for replacing R123, characterized in that: The heat transfer composition comprises 30-98 wt% of Z-1-chloro-3,3,3-trifluoropropene, 1-65 wt% of Z-1,3,3,3-tetrafluoropropene and 1-5 wt% of n-butane, the evaporation enthalpy of the heat transfer composition under standard atmospheric pressure is greater than 250 KJ / kg, 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 less than 50%.

2. The heat transfer composition for replacing R123 according to claim 1, characterized in that: The heat transfer composition comprises 35-80 wt % of Z-1-chloro-3,3,3-trifluoropropene, 15-60 wt % of Z-1,3,3,3-tetrafluoropropene and 1-5 wt % of normal butane.

3. The heat transfer composition for replacing R123 according to claim 2, characterized in that: The heat transfer composition comprises 45-76 wt % of Z-1-chloro-3,3,3-trifluoropropene, 19-50 wt % of Z-1,3,3,3-tetrafluoropropene and 1-5 wt % of normal butane.

4. The heat transfer composition for replacing R123 according to claim 3, characterized in that: The heat transfer composition comprises 60-70 wt % of Z-1-chloro-3,3,3-trifluoropropene, 25-35 wt % of Z-1,3,3,3-tetrafluoropropene and 1-5 wt % of normal butane.

5. The heat transfer composition for replacing R123 according to claim 1, characterized in that: The heat transfer composition comprises 60-90 wt% of Z-1-chloro-3,3,3-trifluoropropene, 5-35 wt% of Z-1,3,3,3-tetrafluoropropene and 1-5 wt% of 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 less than 20%.

6. The heat transfer composition for replacing R123 according to claim 5, characterized in that: The heat transfer composition comprises 70-90 wt% of Z-1-chloro-3,3,3-trifluoropropene, 5-25 wt% of Z-1,3,3,3-tetrafluoropropene and 1-5 wt% of 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 less than 10%.

7. An application of a heat transfer composition for replacing R123 as claimed in any one of claims 1 to 6, 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, a chiller, a heat pipe system or a blown plate system.

8. The use of the heat transfer composition as a substitute for R123 according to claim 7, 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. Compared with R123, the pressure of the compressor in the system is reduced by more than 2%.

9. The use of the heat transfer composition as a substitute for R123 according to claim 8, 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 is 1-10°C, and the condensation temperature is 30-50°C.

10. The use of the heat transfer composition as a substitute for R123 according to claim 7, characterized in that: The heat transfer composition is used as a heat transfer medium in a heat pipe system or a blown plate system. Compared with R123, the heat transfer capacity increment of the heat transfer composition is greater than 50%.

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