A heat transfer composition replacing R123 and its application

Abstract

The present invention discloses a heat transfer composition for replacing R123. The heat transfer composition comprises: 1% to 98% by weight of Z-1-chloro-2,3,3,3-tetrafluoropropene, 1% to 98% by weight of Z-1-chloro-2,3,3-trifluoropropene, and 1% to 30% by weight of 1,1,2,2,3-pentafluoropropane. The heat transfer composition is non-flammable, has a global warming potential (GWP) of less than 150, and an organic thermal conductivity (ODP) of approximately 0. The heat transfer composition of the present invention offers advantages such as environmental friendliness, excellent safety performance, and a high heating capacity per unit volume. It can be used as a heat transfer fluid in systems such as medium- and high-temperature heat pumps, chillers, heat pipes, and organic Rankine cycles.

Description

Technical Field

[0001] The present invention relates to a heat transfer fluid, in particular to a heat transfer composition replacing R123, and its application in medium- and high-temperature heat pump systems, heat pipe systems, organic Rankine cycle systems, and chiller systems. Background Art

[0002] In recent years, global warming has become increasingly serious, and the government is implementing various policies that are conducive to energy conservation and emission reduction.

[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 (dichlorotrifluoroethane) 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 refrigerant in systems such as heat pumps and organic Rankine cycles. However, R123 contains the element Cl, making it a HCFC with ozone-depleting properties. It is also classified as Class B1 in the ASHRAE classification, making it a toxic refrigerant and facing the risk of being phased out.

[0005] DuPont patent 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 pumps, or power cycle systems. However, this composition still contains a significant proportion of R123 by weight, and faces the risk of long-term obsolescence.

[0006] Beijing University of Technology patent CN104946206A discloses a non-azeotropic composition containing 89-97 wt% difluoromethane (R32) and 3-11 wt% R123. The composition exhibits excellent thermal, environmental, and safety properties, as well as market availability. Furthermore, the composition exhibits good compatibility with existing systems, effectively improving system cycle performance and enabling its use as an alternative to R123. However, R32 has a boiling point of -51.7°C, significantly different from that of R123. This mixture exhibits a significant temperature glide, and due to the significant difference in boiling point between the mixture and R123, performance can differ significantly during system operation.

[0007] Trane International Patent CN107810247A discloses a refrigerant composition of 61.5-67.5 wt% R1336mzz(Z), 20.5-22.5 wt% R1130(E), and 10-18 wt% R1233zd(E). This composition exhibits minimal temperature glide and is a suitable replacement for R123. However, the R1130(E) component is highly flammable, and its vapor can easily form an explosive mixture with air. It also possesses a certain degree of toxicity, posing a safety hazard during use.

[0008] Daikin patent CN110945100A discloses refrigerant compositions comprising FO-1216 and hydrofluoroolefins (such as HFO-1234ze and HFO-1243zf), refrigerant compositions comprising FO-1216 and vinyl halides (such as HCFO-1122a, FO-1114, HFO-1123, HFO-1132(E), HFO-1132(Z), HFO-1132a, and HFO-1141), and refrigerant compositions comprising FO-1216 and hydrofluorocarbons (HFC-125, HFC-143a, HFC-32, HFC-134, HFC-134a, HFC-152a, and HFC-227ea). These compositions have low GWP values, are non-flammable or slightly flammable, and can be used as alternative refrigerants to R134a, R410A, R123, or R404A. However, this composition also suffers from a significant difference in boiling point from R123. The key component, FO-1216, has a boiling point of -30.34°C and a critical temperature of 87.75°C. Therefore, this alternative is unsuitable for high-temperature heat pump systems and organic ORC systems.

[0009] In summary, the heat transfer fluids used in the existing technology to replace R123 have significant performance differences, safety issues, or cannot be replaced in some systems. It is necessary to develop new heat transfer fluids to replace R123. Summary of the Invention

[0010] In order to solve the above technical problems, the present invention proposes an environmentally friendly heat transfer composition with excellent environmental performance, good safety performance and high heating capacity per unit volume, which is used to replace R123 in medium and high temperature heat pumps, heat pipes, organic Rankine cycles, chillers and other systems.

[0011] The physical properties of the components included in the heat transfer composition of the present invention are as follows:

[0012] Z-1-chloro-2,3,3,3-tetrafluoropropene (R1224yd(Z)), with a molecular formula of C3HF4Cl, a molecular weight of 148.49, a standard boiling point of 14.62°C, a critical temperature of 155.54°C, a critical pressure of 3.337 MPa, and a GWP of <1.

[0013] Z-1-chloro-2,3,3-trifluoropropene (R1233yd(Z)), whose molecular formula is C3H2F3Cl, molecular weight is 130.5, standard boiling point is 54°C, critical temperature is 224.43°C, critical pressure is 3.916MPa, and GWP is <1.

[0014] 1,1,2,2,3-pentafluoropropane (R245ca), whose molecular formula is C3H3F5, molecular weight is 134.05, standard boiling point is 25.26℃, critical temperature is 174.42℃, critical pressure is 3.9407MPa, and GWP is 716.

[0015] The physical properties of R1224yd(Z) and R245ca can be obtained by consulting existing technologies. As for R1233yd(Z), a new type of heat transfer fluid, its standard boiling point is measured by the boiling method, and its critical temperature and critical pressure are calculated by the Marrero-Pardillo group contribution method:

[0016] The critical temperature calculation formula is as follows:

[0017]

[0018] Where, T b is the standard boiling point, tcbk is the contribution of the kth type of atoms to the critical temperature obtained by regression, N k is the number of atom pairs of type k.

[0019] The critical pressure calculation formula is as follows:

[0020]

[0021] Where N atoms is the number of atoms, and pcbk is the contribution of the kth type of atoms to the critical pressure obtained by regression.

[0022] In the present invention, other relevant physical properties of R1233yd(Z) are calculated using the semi-empirical PR equation:

[0023]

[0024] in:

[0025] a=a c α(T r ,ω)

[0026]

[0027]

[0028] The auxiliary ideal gas constant pressure specific heat capacity is derived from the Planck-Einstein equation:

[0029]

[0030] Other physical properties such as enthalpy and entropy are calculated by combining the PR equation and Maxwell relation.

[0031] The purpose of the present invention is achieved through the following technical solutions:

[0032] A heat transfer composition for replacing R123, comprising: 1% to 98% by mass of Z-1-chloro-2,3,3,3-tetrafluoropropene, 1% to 98% by mass of Z-1-chloro-2,3,3-trifluoropropene, and 1% to 30% by mass of 1,1,2,2,3-pentafluoropropane.

[0033] Preferably, the heat transfer composition comprises:

[0034] The mass percentage of Z-1-chloro-2,3,3,3-tetrafluoropropene is 20% to 80%, the mass percentage of Z-1-chloro-2,3,3-trifluoropropene is 10% to 70%, and the mass percentage of 1,1,2,2,3-pentafluoropropane is 1% to 20%.

[0035] More preferably, the heat transfer composition comprises:

[0036] The mass percentage of Z-1-chloro-2,3,3,3-tetrafluoropropene is 40% to 80%, the mass percentage of Z-1-chloro-2,3,3-trifluoropropene is 10% to 40%, and the mass percentage of 1,1,2,2,3-pentafluoropropane is 5% to 20%.

[0037] Most preferably, the heat transfer composition comprises:

[0038] The mass percentage of Z-1-chloro-2,3,3,3-tetrafluoropropene is 40% to 60%, the mass percentage of Z-1-chloro-2,3,3-trifluoropropene is 20% to 40%, and the mass percentage of 1,1,2,2,3-pentafluoropropane is 10% to 20%.

[0039] The heat transfer composition of the present invention is non-flammable, has an ODP of approximately 0, and a GWP of less than 150. The ODP is based on CFC-11 as a reference value of 1.0, and the GWP is based on CO2 as a reference value of 1.0 (100 years).

[0040] When the heat transfer composition of the present invention is used in place of R123, to improve its circulation efficiency, the composition further comprises at least one of 1-butyne, 1-pentene, 2,2-dimethylbutane, cis-butene, trans-butene, pentane, cyclopentane, isopentane, and neopentane. Preferably, when the heat transfer composition is used in place of R123, 1% to 3% of 1-butyne, 1-pentene, 2,2-dimethylbutane, cis-butene, trans-butene, pentane, cyclopentane, isopentane, or neopentane is added to the composition to improve its oil solubility.

[0041] The heat transfer composition of the present invention has an evaporation enthalpy greater than 180 kJ / kg at standard atmospheric pressure, and compared with R123, the filling amount of the heat transfer composition can be reduced.

[0042] The present invention measures and calculates the relevant physical properties of R1233yd(Z), comprehensively considers the physical properties of R1224yd(Z) and R245ca, and ultimately calculates a heat transfer composition with a boiling point close to that of R123 and similar critical properties. This allows the replacement of R123 without changing the main equipment of the original R123 system.

[0043] Therefore, the present invention also provides a use of any of the above-mentioned heat transfer compositions, wherein the heat transfer composition replaces R123 and is used in medium and high temperature heat pump systems, heat pipe systems, organic Rankine cycle systems, chiller systems, etc.

[0044] Preferably, the heat transfer composition is suitable for a single-stage compression medium- and high-temperature heat pump system with a heating temperature ≥ 60°C. The medium- and high-temperature heat pump system includes a compressor, an evaporator, a condenser, and a superheater, and is used for industrial waste heat recovery. Furthermore, by adjusting the ratio of the heat transfer composition, the heat transfer composition can be better adapted to a medium-temperature heat pump system or a high-temperature heat pump system. Preferably, the evaporation temperature of the medium-temperature heat pump system using the heat transfer composition is 30-40°C, and the condensation temperature is 60-100°C; the evaporation temperature of the high-temperature heat pump system using the heat transfer composition is 60-80°C, and the condensation temperature is 100-140°C.

[0045] In particular, when the heat transfer composition is used to replace R123 in a medium- and high-temperature heat pump system, the heating capacity per unit volume is increased by more than 20%, or even more than 30%, compared with R123.

[0046] The heat transfer composition of the present invention has large expansion work and is particularly suitable for an organic Rankine cycle system for recovering waste heat to generate electricity.

[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 approximately zero and a GWP value of <150, and has excellent environmental performance.

[0049] When the heat transfer composition of the present invention is used as a heat transfer fluid instead of R123, it has high heating capacity per unit volume, large expansion work, and good performance, and can be widely used in systems such as heat pipes, medium and high temperature heat pumps, chillers, and organic Rankine cycles. DETAILED DESCRIPTION

[0050] The present invention will be further described below with reference to 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.

[0051] The refrigeration composition provided by the present invention is prepared by physically mixing Z-1-chloro-2,3,3,3-tetrafluoropropene, Z-1-chloro-2,3,3-trifluoropropene and 1,1,2,2,3-pentafluoropropane in a liquid phase according to the mass percentage of each component.

[0052] Example 1: R1224yd(Z), R1233yd(Z) and R245ca were physically mixed in a liquid phase at a mass percentage of 70:20:10.

[0053] Example 2: R1224yd(Z), R1233yd(Z) and R245ca were physically mixed in a liquid phase at a mass percentage of 80:10:10.

[0054] Example 3: R1224yd(Z), R1233yd(Z) and R245ca were physically mixed in a liquid phase at a mass percentage of 60:25:15.

[0055] Example 4: R1224yd(Z), R1233yd(Z) and R245ca were physically mixed in a liquid phase at a mass percentage of 50:35:15.

[0056] Example 5: R1224yd(Z), R1233yd(Z) and R245ca were physically mixed in a liquid phase at a mass percentage of 40:40:20.

[0057] Example 6: R1224yd(Z), R1233yd(Z) and R245ca were physically mixed in a liquid phase at a mass percentage of 45:35:20.

[0058] Example 7: R1224yd(Z), R1233yd(Z) and R245ca were physically mixed in a liquid phase at a mass percentage of 50:30:20.

[0059] Example 8: R1224yd(Z), R1233yd(Z) and R245ca were physically mixed in a liquid phase at a mass percentage of 55:25:20.

[0060] Example 9: R1224yd(Z), R1233yd(Z) and R245ca were physically mixed in a liquid phase at a mass percentage of 60:20:20.

[0061] Comparative Example 1: R1224yd(Z) and R1233yd(Z) were physically mixed in a liquid phase at a mass percentage of 50:50.

[0062] Comparative Example 2: R1224yd(Z) and R245ca were physically mixed in a liquid phase at a mass percentage of 80:20.

[0063] Comparative Example 3: R1233yd(Z) and R245ca were physically mixed in a liquid phase at a mass percentage of 80:20.

[0064] Comparative Example 4: R1233yd(Z) and R245fa were physically mixed in a liquid phase at a mass percentage of 82:18.

[0065] Comparative Example 5: R1224yd(Z), R1233yd(Z) and R245fa were physically mixed in a liquid phase at a mass percentage of 41:41:18.

[0066] The following is a comparison of the various properties of the heat transfer compositions of the embodiments of the present invention, comparative examples, and R123, as well as their performance in corresponding systems.

[0067] 1. Flammability

[0068] Table 1 shows the combustion levels of the heat transfer compositions of various embodiments and comparative examples and R123, as follows:

[0069] Table 1 Flammability

[0070] Example Combustion level Example 1 1 Example 2 1 Example 3 1 Example 4 1 Example 5 1 Example 6 1 Example 7 1 Example 8 1 Example 9 1 Comparative Example 1 1 Comparative Example 2 1 Comparative Example 3 1 Comparative Example 4 1 Comparative Example 5 1 R123 1

[0071] The above flammability test adopts the national standard GB / T 12474-2008. As can be seen from Table 1 above, all embodiments of the present invention are non-flammable.

[0072] 2. Temperature Glide, Evaporation Enthalpy and Environmental Performance

[0073] Table 2 shows the temperature glide, density, evaporation enthalpy and environmental performance data of the heat transfer compositions of various embodiments and comparative examples and R123, as follows:

[0074] Table 2 Temperature glide, evaporation enthalpy and environmental performance

[0075]

[0076]

[0077] As shown in Table 2 above, the addition of R245fa in Comparative Examples 4 and 5 significantly increases the temperature glide of the compositions, making them unsuitable for mixing with R1224yd(Z) and R1233yd(Z) of the present invention. The heat transfer compositions in each example have an ODP value of approximately 0 and a GWP value of less than 150, demonstrating excellent environmental performance. The density of the heat transfer compositions in each example is slightly higher than that of R123, and the charge amount does not significantly differ in system applications.

[0078] The heat transfer compositions of each embodiment have a higher enthalpy of vaporization at standard atmospheric pressure than R123. Therefore, when used in a heat pipe system, the heat transfer compositions of each embodiment exhibit higher phase change heat capacity and cooling efficiency than R123 under the same operating conditions. The heat transfer compositions of each embodiment of the present invention exhibit superior performance at the same charge level.

[0079] 3. Heating performance (heat pump)

[0080] Table 3 shows the performance data of various embodiments, comparative examples and R123 under different heating conditions, as follows:

[0081] Table 3 Heating performance under different working conditions

[0082]

[0083]

[0084]

[0085]

[0086] As can be seen from Table 3 above, under the above-mentioned heat pump operating conditions, the performance of Comparative Example 1 is similar to that of the embodiments in all aspects, but due to the lack of the R245ca component, the temperature glide of the mixture is higher than that of the embodiments. Comparative Example 2 has superior cycle performance, but the system pressure is relatively high, which is particularly obvious in the condenser, and the demand for condensing equipment is relatively high, increasing the system cost. Comparative Example 3 is inferior to R123 and the above-mentioned embodiments in terms of unit volume heating capacity and COP. When the condensing temperature is less than 120°C, the COP of the heat transfer composition of each embodiment is similar to that of R123. When the condensing temperature exceeds 120°C, the COP of the heat transfer composition of each embodiment decreases significantly, but the unit volume heating capacity of the heat transfer composition of each embodiment is greater than that of R123. Therefore, the heat transfer composition of the present application is better suitable for medium and high temperature working conditions, and the heating performance is much higher than that of R123, with an improvement of at least 20%. Taking into account the volumetric heating capacity, energy efficiency ratio and safety, the application effect of each embodiment is significantly better than R123, especially the application effect on medium and high temperature heat pumps. The comprehensive advantages of the heat transfer composition of each embodiment of the present invention are significantly higher than the currently commonly used R123 and its substitutes.

[0087] 4. Organic Rankine Performance

[0088] The Organic Rankine Cycle (ORC) system uses an organic working fluid to absorb high-temperature industrial waste heat, converting it into steam at a certain temperature and pressure. This steam then passes through a turbine to generate power. The ORC system effectively recovers waste heat.

[0089] Table 4 shows the performance data of various embodiments, comparative examples and R123 under different organic Rankine cycle system operating conditions, as follows:

[0090] Table 4 Performance of organic Rankine cycle system under working conditions

[0091]

[0092]

[0093]

[0094]

[0095] As shown in Table 4, under organic Rankine cycle system conditions, Comparative Example 1 similarly performs comparable to the examples. Comparative Example 2, in addition to higher evaporation and condensation pressures, also suffers from low expansion work. Comparative Example 3 performs significantly better across all operating conditions, outperforming both R123 and the examples. The cycle efficiency of the heat transfer compositions of the examples is similar to that of R123, with some compositions exceeding this efficiency. Furthermore, the work output of each composition exceeds that of R123 under all of the aforementioned operating conditions, averaging approximately 15% higher than R123 and reaching a maximum of 17% higher. Taking into account work output, cycle efficiency, and safety, the examples significantly outperform R123 in organic Rankine cycle systems. The comprehensive advantages of the heat transfer compositions of the present invention significantly surpass those of currently commonly used R123 and its alternatives.

[0096] 5. Chiller Performance

[0097] Table 5 shows the performance data of various embodiments, comparative examples and R123 under chiller working conditions, as follows:

[0098] Table 5 Refrigeration performance under standard air-conditioning conditions

[0099]

[0100]

[0101] As shown in Table 5, similarly, in a chiller, the evaporator and condenser pressures of Comparative Example 2 were higher than those of R123, while Comparative Example 3 was inferior to R123 and the various Examples in terms of unit volumetric cooling capacity. The unit volumetric cooling capacity of the heat transfer compositions of each Example was higher than that of R123, and their energy efficiency ratios were comparable to that of R123. The unit volumetric cooling capacity of the compositions of each Example exceeded that of R123 by an average of 20%, with the highest exceeding that by 44%. Taking into account the comprehensive considerations of volumetric cooling capacity, energy efficiency, and safety, the various Examples clearly outperformed R123 in chiller systems.

[0102] Comparative examples of each binary component exhibit significant drawbacks in various application scenarios, resulting in poor overall performance. However, the heat transfer compositions of the present invention effectively combine the advantages of each working medium while overcoming their shortcomings. Their overall advantages are significantly superior to those of the currently commonly used heat transfer medium R123 and its alternatives.

Claims

1. A heat transfer composition for replacing R123, characterized in that: The heat transfer composition is composed of 40% to 80% by mass of Z-1-chloro-2,3,3,3-tetrafluoropropene, 10% to 40% by mass of Z-1-chloro-2,3,3-trifluoropropene, and 5% to 20% by mass of 1,1,2,2,3-pentafluoropropane; The heat transfer composition has an enthalpy of vaporization greater than 180 kJ / kg at standard atmospheric pressure; The composition realizes the replacement of R123 without changing the main equipment of the original R123 system.

2. The heat transfer composition according to claim 1, wherein: The heat transfer composition consists of 40% to 60% by mass of Z-1-chloro-2,3,3,3-tetrafluoropropene, 20% to 40% by mass of Z-1-chloro-2,3,3-trifluoropropene and 10% to 20% by mass of 1,1,2,2,3-pentafluoropropane.

3. The heat transfer composition according to any one of claims 1-2, characterized in that: The heat transfer composition further comprises at least one of 1-butyne, 1-pentene, 2,2-dimethylbutane, cis-butene, trans-butene, pentane, cyclopentane, isopentane, and neopentane.

4. The heat transfer composition according to claim 1, wherein: The heat transfer composition is non-flammable and has a GWP value of <150.

5. Use of the heat transfer composition according to any one of claims 1 to 4, characterized in that: The heat transfer composition can replace R123 and be used in medium and high temperature heat pump systems, heat pipe systems, organic Rankine cycle systems, and chiller systems.

6. The use of the heat transfer composition according to claim 5, characterized in that: The heat transfer composition is suitable for medium and high temperature heat pump systems with a heating temperature of ≥60°C.

7. The use of the heat transfer composition according to claim 6, characterized in that: The evaporation temperature of the medium-temperature heat pump system using the heat transfer composition is 30-40°C, and the condensation temperature is 60-100°C; the evaporation temperature of the high-temperature heat pump system using the heat transfer composition is 60-80°C, and the condensation temperature is 100-140°C.

8. The use of the heat transfer composition according to claim 7, characterized in that: When the heat transfer composition is used in a medium- and high-temperature heat pump system instead of R123, the heating capacity per unit volume is increased by more than 20% compared with R123.

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