CN104974718A - Refrigerant and applications thereof - Google Patents

Abstract

The invention discloses a low GWP (Greenhouse Effect Potential) value, high-efficiency refrigerator mixed refrigerant, including 1,1,1,3,3-pentafluoropropane (C ₃ H ₃ F ₅ , R245fa), fluoroethane (C ₂ H ₅ F, R161) and dimethyl ether (C ₂ H ₆ O, DME), the mass percentage of which is: 1,1,1,3,3-pentafluoropropane: 2%~15%; Fluoroethane: 0%~20%; Dimethyl ether: 65%~98%. The ODP (Ozone Destruction Potential) of the mixed refrigerant is 0, the GWP value is less than 120, and the environmental protection performance is excellent, and the cooling capacity per unit mass and unit volume is equivalent to R12 (dichlorodifluoromethane, Freon), and the COP (refrigeration coefficient of performance) It is slightly higher than R12, and has the evaporation and condensation pressure closer to R12. It can be directly charged into the refrigeration system that originally used R12. It has the advantages of low replacement cost, energy saving and environmental protection.

Description

A kind of refrigerant and its application

technical field

The invention relates to a refrigerant, in particular to a refrigerant mixture in a household refrigerator system that does not destroy the atmospheric ozone layer (ODP is 0), has extremely low greenhouse effect and has excellent thermodynamic properties.

Background technique

Refrigerant is the carrier of energy conversion and utilization in the refrigeration system, and its thermodynamic performance plays a crucial role in the energy utilization efficiency of the system. In recent years, the two major environmental problems of ozone layer depletion and greenhouse effect have aroused global attention. Dichlorodifluoromethane (CCl ₂ F ₂ , R12), as a refrigerant that has been used in refrigerator refrigeration systems for a long time and has high refrigeration efficiency, destroys the ozone layer because it contains chlorine atoms, and at the same time has high The greenhouse effect potential, has been banned production and use.

The new environment-friendly and energy-saving working fluid requires better environmental performance. First, the ozone destruction potential (ODP) is 0, and the greenhouse effect potential (GWP) is small; second, the safety performance is good, that is, low flammability or non-flammability; third, the toxicity is small, in line with relevant national regulations; fourth, thermodynamics Excellent performance and high cycle efficiency. Generally, existing pure refrigerants are difficult to meet all the requirements of alternative refrigerants, and mixed refrigerants may concentrate the advantages of each component to form a new type of refrigerant that meets many requirements such as environmental protection, safety and performance. At the same time, the cost of mixed refrigerants is low, which will help alleviate the pressure faced by my country in dealing with the elimination of CFCs and HCFCs refrigerants and industrial upgrading.

However, the main components of the current mixed refrigerants are all HFCs, and the ODP value is 0, but they have a high GWP value, so they cannot be used as long-term replacement refrigerants. The invention patent with the publication number CN101671544A proposes a mixed refrigerant whose components are R22, R142b and R21 to replace R12. All components of this mixed refrigerant contain chlorine atoms, and its ODP value is not zero, so it cannot be called an environmentally friendly refrigerant. The invention patent with the publication number CN1740262A proposes a mixed refrigerant whose components are R290, R600a and THT (tetrahydrothiophene), and the mass ratio when used to replace R12 is: 61%, 38.5% and 0.5%. Among them, the components R290 and R600a are both flammable and explosive substances and account for 99.5% by mass, which limits the charging amount of the mixed refrigerant. The invention patent with the publication number CN101307223A proposes a mixed refrigerant whose components are R134, R152a and R600a, and its optimized mass ratio is 1% to 25%, 40% to 81% and 18% to 35%. This refrigerant has a small condensation and evaporation glide temperature, and its thermodynamic performance is slightly lower than that of R12, but because it contains a large mass ratio of R134a and R152a, and the GWP of these two refrigerants is high, the environmental performance is poor. . The invention patent with publication number CN101003723A discloses a mixed refrigerant whose components are R152a, R227ea and R125. All three components have high GWP values, so they do not have good environmental performance.

The refrigerant mixtures proposed in existing patents often have disadvantages such as high GWP value, or flammability, or small volumetric cooling capacity, or large temperature glide, so the development of refrigerants with higher refrigeration performance and better compatibility with Refrigerator refrigerants that are compatible with existing systems and have better environmental performance are particularly urgent.

Contents of the invention

The present invention aims to provide a mixed refrigerant whose environmental protection performance and thermodynamic performance are close to or better than R12, which can be directly replaced without changing any parts in the system using R12, and is a low replacement cost. Refrigerant.

A kind of refrigerant provided by the present invention comprises the raw material of following mass percentage:

1,1,1,3,3-Pentafluoropropane: 2% ~ 15%;

Fluoroethane: 0% ~ 20%;

Dimethyl ether: 65% ~ 98%;

The sum of the mass percentages of each component is 100%.

As a preferred version, the above-mentioned refrigerant includes the following raw materials in mass percentage:

1,1,1,3,3-Pentafluoropropane: 2% ~ 14%;

Dimethyl ether: 86% ~ 98%;

The sum of the mass percentages of each component is 100%.

Further, the above-mentioned refrigerant includes the following raw materials in mass percentage:

1,1,1,3,3-Pentafluoropropane: 7% ~ 12%;

Dimethyl ether: 88% ~ 93%;

The sum of the mass percentages of each component is 100%.

As another preferred solution, the above-mentioned refrigerant includes the following raw materials in mass percentage:

1,1,1,3,3-Pentafluoropropane: 8% ~ 10%;

Fluoroethane: 10% ~ 20%;

Dimethyl ether: 70% ~ 82%;

The sum of the mass percentages of each component is 100%.

The invention provides the application of the refrigerant to replace R12 in household refrigerators.

The mixed refrigerant provided by the invention is suitable for replacing R12, especially suitable for replacing R12 in household refrigerators. When used in a household refrigerator to replace R12, the household refrigerator system may directly charge the mixed refrigerant to replace R12 without changing any equipment components.

Beneficial effects of the present invention:

(1) Excellent environmental performance, ODP value is 0, GWP value is less than 120;

(2) Adding the flame retardant component 1,1,1,3,3-pentafluoropropane can weaken the flammability of the mixed refrigerant, improve safety, and increase the refrigerant charge;

(3) The evaporating pressure, condensing pressure, pressure ratio and cooling capacity per unit volume are all equivalent to R12, the temperature glide is small, and the COP value is close to or better than R12;

(4) On the premise of not changing any parts of the equipment, it can be directly charged to the original household refrigerator system using R12.

Detailed ways

The present invention is further illustrated by the following examples, but not limited to the following examples.

The refrigerant provided by the invention is prepared by physically mixing 1,1,1,3,3-pentafluoropropane, fluoroethane and dimethyl ether in a liquid state according to their corresponding mass proportions.

The 1,1,1,3,3-pentafluoropropane (flame retardant) in the above components has a molecular weight of 134.05 g·mol ^-1 , a standard boiling point of -15.14°C, a critical temperature of 154.01°C, and a critical pressure of 3.651 MPa, GWP value is 858.

Fluoroethane in the above components has a molecular weight of 46.06 g·mol ^-1 , a standard boiling point of -34.55°C, a critical temperature of 102.15°C, a critical pressure of 5.091 MPa, and a GWP of 4.

The dimethyl ether in the above components has a molecular weight of 46.07g·mol ^-1 , a standard boiling point of -24.78°C, a critical temperature of 127.15°C, a critical pressure of 5.337 MPa, and a GWP value of 0.

Several examples are listed below to illustrate the specific implementation process of the present invention, but the present invention is not limited to the following examples, all of which include the components and proportions of the present invention, as well as the screening ideas and concepts of mixed refrigerants in the present invention. The implementation modes all belong to the protection scope of the present invention.

Example 1: 1,1,1,3,3-pentafluoropropane and dimethyl ether were physically mixed in a liquid state at a mass percentage of 5:95.

Example 2: 1,1,1,3,3-pentafluoropropane and dimethyl ether were physically mixed in a liquid state at a mass percentage of 7:93.

Example 3: 1,1,1,3,3-pentafluoropropane and dimethyl ether were physically mixed in a liquid state at a mass percentage of 9:91.

Example 4: 1,1,1,3,3-pentafluoropropane and dimethyl ether were physically mixed in a liquid state at a mass percentage of 11:89.

Example 5: 1,1,1,3,3-pentafluoropropane and dimethyl ether were physically mixed in a liquid state at a mass percentage of 13:87.

Example 6: 1,1,1,3,3-pentafluoropropane, fluoroethane and dimethyl ether were physically mixed in a liquid state at a mass percentage of 8:10:82.

Example 7: 1,1,1,3,3-pentafluoropropane, fluoroethane and dimethyl ether were physically mixed in a liquid state at a mass percentage of 8:20:72.

Example 8: 1,1,1,3,3-pentafluoropropane, fluoroethane and dimethyl ether were physically mixed in a liquid state at a mass percentage of 10:10:80.

Example 9: 1,1,1,3,3-pentafluoropropane, fluoroethane and dimethyl ether were physically mixed in a liquid state at a mass percentage of 10:20:70.

By analyzing the above embodiment and comparing it with the performance of R12, the characteristics and effects of the present invention can be found. The environmental protection performance and thermal performance of the above-mentioned embodiment and R12 are analyzed through specific data below.

1. Environmental performance

Table 1 compares the environmental protection performance of the above-mentioned embodiments and R12. The ODP value takes R12 as the benchmark value and takes 1.0; the GWP value takes _CO2 as the benchmark value and takes 1.0.

Table 1 Environmental Performance Comparison

It can be seen from the data in the table that the ODP values of the present invention are all 0, and the GWP values are all less than 120, which has more remarkable environmental performance compared with R12.

2. Temperature glide and thermal performance

Table 2 Temperature slip table

It can be seen from the table that the temperature glide of each embodiment is relatively small, which is conducive to improving the thermodynamic performance of the household refrigerator system.

The standard operating conditions of the domestic refrigerator used in the calculation of the present invention are: evaporation temperature -23.3°C, condensation temperature 54.4°C, superheat degree 11.1°C, and supercooling degree 5°C. Under this working condition, thermodynamic calculations are carried out on the above examples to obtain thermodynamic performance (evaporating pressure p _e , condensing pressure p _con , pressure ratio π = p _con / p _e ) and relative thermodynamic performance (relative COP _R , relative refrigeration per unit mass Quantity q _m , relative unit volume refrigerating capacity q _v ), and compared with the thermal performance of R12, see Table 3. The relative thermal performance refers to the ratio of the thermal performance of each embodiment to the thermal performance of R12 under the above working conditions.

Table 3 Comparison of thermal parameters and thermal performance

It can be seen that the evaporating pressure, condensing pressure and pressure ratio of the above embodiment are all close to those of R12; at the same time, the cooling capacity per unit mass is about 2.8 times that of R12, and the COP value is greater than that of R12. Embodiments 1-5 are binary pure substances, and their cooling capacity per unit volume is slightly lower than that of R12; Examples 6-9 are ternary pure substances, and their cooling capacity per unit volume is equivalent to that of R12.

In general, the mixed refrigerant obtained in the embodiment of the present invention has excellent environmental performance, high safety and economy, and can be used as a long-term substitute refrigerant for R12.

Claims (6)

1. A kind of refrigerant is characterized in that: comprise the raw material of following mass percentage: 1,1,1,3,3-Pentafluoropropane: 2% ~ 15%; Fluoroethane: 0% ~ 20%; Dimethyl ether: 65% ~ 98%; The sum of the mass percentages of each component is 100%. 2. The refrigerant according to claim 1, characterized in that: it comprises the following raw materials in mass percentage: 1,1,1,3,3-Pentafluoropropane: 2% ~ 14%; Dimethyl ether: 86% ~ 98%; The sum of the mass percentages of each component is 100%. 3. The refrigerant according to claim 2, characterized in that: it comprises the following raw materials in mass percentage: 1,1,1,3,3-Pentafluoropropane: 7% ~ 12%; Dimethyl ether: 88% ~ 93%; The sum of the mass percentages of each component is 100%. 4. The refrigerant according to claim 1, characterized in that: it comprises the following raw materials in mass percentage: 1,1,1,3,3-Pentafluoropropane: 8% ~ 10%; Fluoroethane: 10% ~ 20%; Dimethyl ether: 70% ~ 82%; The sum of the mass percentages of each component is 100%. 5. An application of the refrigerant according to any one of claims 1 to 4 to replace R12 in household refrigerators. 6. The application according to claim 5, characterized in that the household refrigerator system can be directly filled with the refrigerant to replace R12 without changing any equipment components.