CN110878196B

CN110878196B - Quaternary mixed environment-friendly refrigerant and composition

Info

Publication number: CN110878196B
Application number: CN201910983389.9A
Authority: CN
Inventors: 于艳翠; 赵桓; 梁尤轩; 雷佩玉; 黄宇杰
Original assignee: Gree Electric Appliances Inc of Zhuhai
Current assignee: Gree Electric Appliances Inc of Zhuhai
Priority date: 2019-10-16
Filing date: 2019-10-16
Publication date: 2020-12-22
Anticipated expiration: 2039-10-16
Also published as: CN110878196A

Abstract

The invention provides a quaternary mixed environment-friendly refrigerant, which consists of four components of trifluoroiodomethane (R13I1), 3,3, 3-trifluoropropene (R1243zf), trifluoromethyl methyl ether (RE143a), 2,3,3, 3-tetrafluoropropene (R1234yf), 1-difluoroethane (R152a) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)); the GWP of the composition is 600 or less, and the ODP is 0. The quaternary mixed environment-friendly refrigerant can solve the problems of high GWP and combustibility of the existing refrigerant for replacing R134a, and simultaneously solves the problem of low refrigerating capacity of a system.

Description

Quaternary mixed environment-friendly refrigerant and composition

Technical Field

The invention relates to a refrigerant technology, in particular to a quaternary mixed environment-friendly refrigerant and a composition.

Background

R134a is a widely used refrigerant for automobile air-conditioner in China and internationally, and has been used as a substitute for R12 refrigerant because it has no ozone depletion effect. However, R134a still has a strong greenhouse gas effect (GWP value of 1300). At present, the automobile industry in China is in a high-speed growth stage, and the automobile holding amount in China is expected to increase by 1.9 hundred million in 2030 compared with 2015. Meanwhile, as the installation rate of the air conditioner of the light passenger vehicle approaches 100%, the discharge of the refrigerant of the air conditioner of the automobile will continuously increase along with the economic growth.

In recent years, global warming has been increasing, and countries around the world are increasingly advancing the replacement of Hydrofluorocarbon (HFCs) refrigerants in order to cope with climate change. Research shows that the emission of HFCs refrigerant is limited on the global scale, the global air temperature rise can be slowed down by 0.5 ℃ at the end of the century, and great contribution can be made to the suppression of global warming. Currently, european union countries and the united states have established a clear policy for automotive air conditioning refrigerant management that R134a is forbidden in newly produced light passenger car air conditioners in 2017 and 2021, respectively. At present, China is the largest automobile air conditioner consuming country in the world (the sales amount accounts for about 24 percent of the total amount in the world), and is the largest country in the world which has not regulated R134 a. The reduction and replacement of the automobile air-conditioning refrigerant R134a not only meets the policy trend and background of energy conservation and emission reduction, but also makes an important contribution to the fulfillment of Montreal agreement by China. Therefore, the search for environment-friendly and efficient alternative refrigerants and related technologies has become an urgent task in the automobile air-conditioning industry in China.

International contracts such as the montreal protocol and the kyoto protocol require that contracting countries gradually reduce and eventually disable refrigerant R134a, and at the same time, impose higher environmental requirements on alternatives thereof, in addition to requiring that new refrigerants have no damaging effect on the ozone layer, also require that new refrigerants have as low GWP values as possible.

In the prior art, a chinese patent document CN200810231909.2 discloses an alkane refrigerant consisting of 80-89% of propane and 11-20% of isobutane; patent US2008029733 discloses refrigerant mixtures consisting of pentafluoroethane, tetrafluoropropane and hydrocarbons; KR200500494148 discloses a mixed refrigerant consisting of 71-90% of propane and 10-29% of 1, 1-difluoroethane; chinese patent document CN200810238072.4 discloses a mixture of 45-52% pentafluoroethane, 45-52% 1,1,1, 2-tetrafluoroethane and 3-6% dimethyl ether; patent CN200810097 discloses a ternary azeotropic mixture composed of 1,1,1, 2-tetrafluoroethane, dimethyl ether and propane; chinese patent CN201010198685.7 discloses a mixture of 2,3,3, 3-tetrafluoropropene, trans 1,3,3, 3-tetrafluoropropene and 1, 1-difluoroethane.

The refrigerants disclosed in the above patents have disadvantages of high GWP values or not being directly tank-fillable for R134a system, or having high flammability or small volumetric refrigerating capacity, and thus, there is a need to develop new refrigerants having better refrigerating performance, better compatibility with existing systems, and better environmental protection performance.

Disclosure of Invention

In view of the above, the invention provides a quaternary mixed environment-friendly refrigerant, which has a GWP of 600 or less and an ODP of 0, has obvious environmental protection advantages, and has good thermal performance, and can not only solve the problems of high GWP and combustibility of the existing refrigerant replacing R134a, but also solve the problem of low refrigeration capacity of the system. The capacity and energy efficiency of the unit applying the quaternary mixed environment-friendly refrigerant are equivalent to those of the unit using the R134a refrigerant.

In order to achieve the purpose, the invention adopts the technical scheme that: a quaternary mixed environment-friendly refrigerant, characterized in that the refrigerant is composed of four of trifluoroiodomethane (R13I1), 3,3, 3-trifluoropropene (R1243zf), trifluoromethyl methyl ether (RE143a), 2,3,3, 3-tetrafluoropropene (R1234yf), 1-difluoroethane (R152a), and trans 1,3,3, 3-tetrafluoropropene (R1234ze (E)); the refrigerant has GWP of less than or equal to 600 and ODP of 0, and has obvious environmental protection advantage.

Further optionally, the first component of the four components is trifluoroiodomethane (R13I1) in a mass ratio of 40% -72%; the mass fraction is based on the total mass of the refrigerant substance. The quaternary mixed environment-friendly refrigerant comprising trifluoroiodomethane (R13I1) in the above mass ratio has low flammability or non-flammability.

Further optionally, the second component of the four components is 4-52% by mass of 3,3, 3-trifluoropropene (R1243 zf); the third component and the fourth component are any two of 2,3,3, 3-tetrafluoropropene (R1234yf), 1-difluoroethane (R152a) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) which account for 8-56% of the sum of the mass percentages; the mass fraction is based on the total mass of the refrigerant substance. The quaternary mixed environment-friendly refrigerant has low flammability, low GWP (global warming potential) which is lower than 72.24 and as low as 1, and small temperature slip which is lower than 0.5 ℃ and as low as 0.05 ℃.

Further optionally, the second component of the four components is 4-52% by mass of trifluoromethyl methyl ether (RE143 a); the third component and the fourth component are any two of 2,3,3, 3-tetrafluoropropene (R1234yf), 1-difluoroethane (R152a), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)), and 3,3, 3-trifluoropropene (R1243zf) which account for 8-56% of the sum of the mass percentages; the mass fraction is based on the total mass of the refrigerant substance. The quaternary mixed environment-friendly refrigerant has low flammability, low GWP (global warming potential) which is lower than 277.92 and is as low as 21.88, and the temperature slippage is small and is as low as 0.02 ℃ below 0.5 ℃.

Further optionally, the mass ratio of the first component in the four components is 52% -72%, and the mass ratio of the second component is 4% -40%; the third component and the fourth component have a mass fraction that is 8% to 44% together, wherein the mass fraction is based on the total mass of the refrigerant mass. The quaternary mixed environment-friendly refrigerant has low flammability, low GWP (global warming potential) which is lower than 215.28 and is as low as 1, and has small temperature slip which is lower than 0.5 ℃ and is as low as 0.04 ℃, and the flammability is reduced.

Further optionally, the mass ratio of the first component in the four components is 56-68%, and the mass ratio of the second component is 8-24%; the third component and the fourth component have a mass fraction that is 20% to 40% together, wherein the mass fraction is based on the total mass of the refrigerant mass. The quaternary mixed environment-friendly refrigerant has low flammability, low GWP (lower than 148.2 and lower than 6.48), small temperature slippage (lower than 0.48 ℃ and lower than 0.03 ℃), and volume refrigerating capacity of more than 94 percent of R134a, and is non-flammable.

Further optionally, the third component is 2,3,3, 3-tetrafluoropropene (R1234yf) in a mass fraction of 4-52% and the fourth component is 1, 1-difluoroethane (R152a) in a mass fraction of 4-40%, wherein the mass fractions are based on the total mass of the refrigerant mass. The quaternary mixed environment-friendly refrigerant has low flammability, low GWP (lower than 55.8 and lower than 6.48), small temperature slippage (lower than 0.5 ℃ and lower than 0.03 ℃), and capacity refrigeration capacity of more than 89% of R134 a.

Further optionally, the first component of the four components is trifluoroiodomethane (R13I1) 56-68% by mass, and the second component is trifluoromethyl methyl ether (RE143a) 4-32% by mass; the third component is 4-32% by mass of 2,3,3, 3-tetrafluoropropene (R1234yf) and the fourth component is 4-36% by mass of 1, 1-difluoroethane (R152a), wherein the mass ratios are based on the total mass of the refrigerant material. The quaternary mixed environment-friendly refrigerant has low GWP which is lower than 179 and lower than 32.84, has small temperature slippage which is lower than 0.4 ℃ and lower than 0.05 ℃, and has the volumetric refrigerating capacity of more than 94 percent of R134 a.

Further optionally, a first component of the four components is 64% by mass trifluoroiodomethane (R13I 1); the second component is 4% by mass of 3,3, 3-trifluoropropene (R1243 zf); the third component is 4% by mass of 2,3,3, 3-tetrafluoropropene (R1234 yf); the fourth component is 28 percent by mass of 1, 1-difluoroethane (R152 a); the mass fraction is based on the total mass of the refrigerant substance. The quaternary mixed environment-friendly refrigerant has low GWP of 39.36, low temperature slippage of 0.1 ℃, low flammability and relative efficiency COP of 0.9845 compared with R134 a.

Further optionally, a first component of the four components is 68% by mass trifluoroiodomethane (R13I 1); the second component is trifluoromethyl methyl ether (RE143a) with the mass percentage of 4 percent; the third component is 4% by mass of 2,3,3, 3-tetrafluoropropene (R1234 yf); the fourth component is 24 percent by mass of 1, 1-difluoroethane (R152 a); the mass fraction is based on the total mass of the refrigerant substance. The quaternary mixed environment-friendly refrigerant has low GWP of 54.76, low temperature slippage of 0.24 ℃, non-flammability and relative efficiency COP of 0.9794 compared with R134 a.

Further optionally, the refrigerant is used for a heat transfer medium or a spray propellant or a foaming expansion agent or an electrical insulation medium or a power cycle working medium or a cleaning fluid.

Further alternatively, the refrigerant may be used in any one of refrigerators, freezers, water dispensers, automobile air conditioners, central air conditioners, dehumidifiers, cold stores, commercial refrigeration, water coolers, ice cream machines, and freezing and condensing units.

The invention also provides a composition, the quaternary mixed environment-friendly refrigerant comprises any one of the quaternary mixed environment-friendly refrigerant and at least one of corrosion inhibitor, stabilizer, lubricant, indicator and fluorescent leak detector.

The present invention also provides a method of replacing an existing heat exchange fluid contained in a heat exchange system, comprising: removing at least a portion of said existing heat exchange fluid from said system, said existing heat exchange fluid being R134a, introducing a quaternary mixed environmentally friendly refrigerant of any of the above mentioned systems to replace at least a portion of said existing heat exchange fluid.

Further optionally, the heat exchange system is an HVACR system.

The materials of the present invention are commercially available or can be prepared by methods known in the art. The content ratio of each substance in the invention is obtained by screening a large number of substances, and is a condition for ensuring the excellent performance of the refrigerant harmless to the ozone layer.

The invention has the beneficial effects that:

(1) the trifluoroiodomethane (R13I1) introduced by the invention is a non-flammable substance, the flammability of the residual substance in the refrigerant can be weakened by controlling the change of the mass ratio of the non-flammable substance in the refrigerant, and the quaternary mixed environment-friendly refrigerant with good safety performance is further obtained, and the GWP and ODP are respectively less than or equal to 600 and 0, so that the environment-friendly performance is good.

(2) Compared with the R134a refrigerant, the quaternary mixed environment-friendly refrigerant has the refrigeration capacity of 83-105% of that of R134a, the energy efficiency of 93-100% of that of R134a, and can replace the R134a refrigerant.

(3) In addition to volumetric refrigeration capacity and energy efficiency, the selection of the substance of the quaternary mixed environment-friendly refrigerant of the invention also takes temperature glide into consideration, and the combination with large boiling point difference among members is possible to form a non-azeotropic mixture with large phase change temperature difference (glide temperature), while the glide temperature of the refrigerant of the invention is less than 0.5 ℃ and as low as 0.09 ℃.

Detailed Description

Evaluation standards of the refrigerant generally refer to GWP and ODP in the aspect of environmental protection, volumetric refrigerating capacity and energy efficiency in the aspect of performance, material compatibility, toxicity and flammability in the aspect of safety. In general, the refrigerant is preferably low GWP, ODP is 0, and the refrigerant is non-toxic and non-flammable, has excellent performance and good material compatibility. From an environmental point of view, the GWP of the material chosen must not be too high, and the ODP must be 0. From the safety point of view, the selected substance must be non-toxic, if there is a flammable component in the substance, a flame retardant substance must be added, and the corresponding ratio is adjusted so that the final refrigerant has weak or non-flammable properties.

The invention aims to solve the problems of high GWP, flammability and low system refrigeration capacity in application of the existing R134a alternative refrigerant, and in view of the above, the invention provides six substances with GWP less than 600, namely R13I1, R1243zf, RE143a, R1234yf, R152a and R1234ze (E), and the volumetric refrigeration capacities of the six substances are all more than 70% of R134a, more importantly, R13I1 non-flammable substance, and the weak flammability or flammability of other substances can be reduced by adding the substances. The invention provides the combination mode and the mass ratio of the substances through research and calculation, ensures that the performance of the substances can play a greater synergistic effect, ensures that the GWP of the prepared refrigerant is less than or equal to 600 and the ODP is 0, is non-combustible or weakly combustible, and has obvious environmental protection advantage. The capacity and energy efficiency of the unit using the refrigerant are equivalent to those of the unit using the R134a refrigerant, the refrigerating capacity is 83% -105% of that of R134a, and the energy efficiency is 93% -100% of that of R134 a.

The invention relates to a preparation method of a quaternary mixed environment-friendly refrigerant, which comprises the following steps: the first step is as follows: selected four components of trifluoroiodomethane (R13I1), 3,3, 3-trifluoropropene (R1243zf), trifluoromethyl methyl ether (RE143a), 2,3,3, 3-tetrafluoropropene (R1234yf), 1-difluoroethane (R152a), and trans 1,3,3, 3-tetrafluoropropene (R1234ze (E)) are combined, preferably in a combination and in mass such as shown in table 1:

TABLE 1 refrigerant combination and ratio by mass

Further preferably, the mass ratio of the first component is 52-72%, the mass ratio of the second component is 4-40%, and the mass ratio of the third component and the fourth component is 4-44%.

The second step is that: according to the corresponding mass ratio of the substances, the physical mixing is carried out in a liquid phase state at the temperature of 23-27 ℃ and the pressure of 0.1MPa, and the corresponding refrigerant is obtained after uniform mixing; the trifluoroiodomethane (R13I1) is an incombustible substance, the other substances are A2 combustible and weakly combustible A2L, and the combustibility of the other substances can be weakened by controlling the mass ratio of the incombustible substance, so that the safety requirement is met. The basic parameters of each substance are shown in Table 2.

TABLE 2 basic parameters of substances in quaternary mixed environment-friendly refrigerant

In accordance with the above-described method, a plurality of specific examples and comparative examples are given below, in which the proportions of substances are mass ratios and the sum of the mass percentages of the substances of each refrigerant is 100%. In each of the examples and comparative examples, the substances were physically mixed in a liquid phase at a constant mass ratio under normal temperature and pressure, and the mixture was mixed uniformly to obtain a refrigerant. The comparative examples of the examples are shown in Table 2.

TABLE 2 examples and comparative examples

Examples 1-32 a refrigerant replacing R134a was obtained according to the technical solution provided by the present invention and according to the above preparation method; on the basis of the technical scheme and the preparation method provided by the invention, a parameter is modified, a comparative example is provided, and a refrigerant is obtained. Specific comparative examples 1 to 5 are based on the first combination method provided by the present invention, the mass ratios of the first component, the second component, the third component and the fourth component are respectively modified; comparative examples 6 to 9 on the basis of the second combination of the present invention, the mass ratios of the first component, the second component, the third component and the fourth component were modified, respectively.

Table 3 compares the above examples and comparative examples with basic parameters such as molecular weight, normal boiling point and environmental properties of R134 a.

TABLE 3 basic parameters of the refrigerant

As can be seen from table 3, the GWP of the refrigerant provided by this embodiment is 300 or less, which is much less than the GWP of R134a, and the ODP is 0, which has obvious environmental protection advantages. Meanwhile, the standard boiling point and molecular weight, the critical temperature and the critical pressure of the refrigerant are equivalent to the corresponding values of R134a, and the flammability of part of the formula is A1 which is not flammable.

The present implementation also provides an HVACR system that utilizes the method of the present invention to replace an existing heat exchange fluid R134a contained in the heat exchange system by introducing a quaternary mixed environmentally friendly refrigerant in an embodiment of the HVACR system to replace at least a portion of the HVACR system existing heat exchange fluid R134 a. Preferably, the quaternary mixed environment-friendly refrigerant replaces the existing heat exchange fluid R134a in all HVACR systems.

Preferably, the refrigerants of the above embodiments and comparative examples are applied to an HVACR system, and the refrigerant exchanges heat in the unit, is compressed and throttled, and replaces the R134a refrigerant. Further preferably, the HVACR system comprises an evaporator and a condenser and the structure form is not limited; further preferably, the heat exchange fluid in the HVACR system is the refrigerant and a second medium; further preferably, the second medium may be water, air, coolant.

Table 4 compares the thermodynamic parameters (i.e., compression ratio and exhaust temperature) and relative thermodynamic performance (i.e., relative refrigerating capacity per unit volume and relative efficiency COP) of the refrigerant in the above embodiment with respect to the R134a under the refrigeration condition of the single-stage compression cycle unit (i.e., evaporation temperature of 6 ℃, condensation temperature of 36 ℃, superheat degree of 5 ℃, supercooling degree of 5 ℃, isentropic efficiency of 0.7, taking into account the pressure drop of the suction gas and the exhaust gas).

Table 4 performance comparison of refrigerant with R134a

(slip temperature is the difference between dew point temperature and bubble point temperature under working pressure, maximum value is taken)

For example analysis, from the table above, it can be seen that: the volumetric cooling capacity of the refrigerant in the embodiment 1, the embodiment 4, the embodiment 12, the embodiment 15, the embodiment 16 and the embodiment 18 is larger than that of R134a, and the volumetric cooling capacity of the refrigerant in the other embodiments is smaller than that of R134a, but the relative volumetric cooling capacity is larger than 0.88. The energy efficiency COPs of all examples were less than the energy efficiency COPs of R134a, but greater than 0.9. The capacity and energy efficiency of the refrigerant is higher than that of the refrigerant replacing R134a in the prior art. The temperature glide of some refrigerant examples is less than or equal to 0.2 ℃, which belongs to azeotropic refrigerants, and the temperature glide of other refrigerant examples is less than 0.5 ℃, which belongs to near-azeotropic refrigerants. By combining four factors of volume refrigerating capacity, temperature slippage, energy efficiency COP and flammability grade, the refrigerant obtained according to the mass ratio of 64/4/4/28 by using the combination mode of R13I1, R1243zf and R1234yf and R152a and the refrigerant obtained according to the mass ratio of 60/4/4/32 is the refrigerant with better performance by using the combination mode of R13I1, RE143a and R1234yf and R152a, the volume refrigerating capacity of the refrigerant is more than the volume refrigerating capacity of R134a, the energy efficiency COP is more than 0.98 times of the energy efficiency COP of R134a, the GWP is less than 150, the nonflammable A1 grade is realized, the temperature slippage is less than or equal to 0.1 ℃, and the refrigerant belongs to an azeotropic refrigerant.

Meanwhile, by combining the data of the examples and the comparative examples, when the refrigerant prepared by changing the mass ratio of the substances in each part of the formula disclosed by the invention is changed, the substances cannot well play a synergistic effect, the GWP and/or the slip temperature and/or the flammability of the refrigerant can be increased, and the heat exchange effect and the environmental protection performance of a unit when the refrigerant is used are influenced, for example, the mass ratio of the first component R13I1 is increased and decreased respectively in the comparative examples 1 and 2, namely the mass ratio is lower than 40% and higher than 72% respectively, the temperature slip of the obtained refrigerant is large, and the mass ratio of other substances in the refrigerant can be observed to be changed in other comparative examples, so that the temperature slip of the obtained refrigerant is large, the relative volume refrigerating capacity of the obtained refrigerant is possibly smaller, and the flammability is possibly enhanced. It is comprehensively known that the synergistic effect among the substances is well exerted only when the mass ratio of the substances is in the invention, and the refrigerant capable of replacing R134a is ensured under the condition of ensuring the indexes of the prepared refrigerant such as the sliding temperature and/or the flammability, the GWP, the relative volume refrigerating capacity, the energy efficiency, the temperature sliding and the like, and the refrigerant can maintain good environmental characteristics and solve the problem of low refrigerating capacity of the system using the refrigerant of the embodiment.

Preferably, the refrigerant of the present embodiment has a plurality of uses, including a heat transfer medium, a propellant spray, a foaming expansion agent, an electrical insulating medium, a power cycle working medium, and a cleaning liquid. Preferably, the refrigerant of the embodiment can be used in any one of refrigerators, freezers, water dispensers, automobile air conditioners, central air conditioners, dehumidifiers, cold storages, commercial refrigeration, water coolers, ice cream machines and freezing and condensing units.

The implementation also provides a heat transfer medium which comprises the quaternary mixed environment-friendly refrigerant of any one of the above parts, and at least one of corrosion inhibitor, stabilizer, lubricant, indicator and fluorescent leak detector is added on the refrigerant according to the requirement of the refrigerant system. Preferably, the lubricant is at least one of 8, mineral oil, silicone oil, polyalkyl benzenes (PABs), polyol esters (POEs), polyalkylene glycols (PAGs), polyalkylene glycol esters (PAG esters), polyvinyl ethers (PVEs), poly (alpha-olefins), or a combination of at least two thereof. The lubricant has good compatibility with the refrigerant in the embodiment, ensures the normal operation of the refrigerating system using the heat transfer medium, and has positive influence on the service life of the refrigerating system.

In summary, the four-element mixed environment-friendly refrigerant consists of four components of trifluoroiodomethane (R13I1), 3,3, 3-trifluoropropene (R1243zf), trifluoromethyl methyl ether (RE143a), 2,3,3, 3-tetrafluoropropene (R1234yf), 1-difluoroethane (R152a) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)), not only has the environment-friendly characteristics of low GWP and zero ODP, but also has excellent thermal performance, and under the same refrigeration working condition, the refrigerating device uses the volume capacity and the COP of the four-element mixed environment-friendly refrigerant to be equivalent to those of the refrigerant using R134a, and has small temperature slip, so that the four-element mixed environment-friendly refrigerant can be used for replacing R134 a.

Exemplary embodiments of the present disclosure are specifically illustrated and described above. It is to be understood that the present disclosure is not limited to the precise arrangements, instrumentalities, or instrumentalities described herein; on the contrary, the disclosure is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. The quaternary mixed environment-friendly refrigerant is characterized by comprising four components, wherein the first component is trifluoroiodomethane (R13I1) accounting for 40-68% of the mass ratio; the second component is trifluoromethyl methyl ether (RE143a) with the mass ratio of 4-40%; the third component is 2,3,3, 3-tetrafluoropropene (R1234yf) accounting for 4-32% by mass, and the fourth component is 1, 1-difluoroethane (R152a) accounting for 4-36% by mass; the mass ratio is based on the total mass of the refrigerant substances, the GWP of the refrigerant is less than or equal to 600, and the ODP is 0.

2. The quaternary mixed environment-friendly refrigerant as claimed in claim 1, wherein a first component of the four components is trifluoroiodomethane (R13I1) 56-68% by mass, and a second component is trifluoromethyl methyl ether (RE143a) 4-32% by mass; a third component of 4 to 32 mass% 2,3,3, 3-tetrafluoropropene (R1234yf) and a fourth component of 4 to 36 mass% 1, 1-difluoroethane (R152a), wherein the mass ratios are based on the total mass of the refrigerant material.

3. The quaternary mixed environment-friendly refrigerant as claimed in claim 1, wherein the refrigerant is used for a heat transfer medium or a spray propellant or a foaming expansion agent or an electric insulation medium or a power cycle working medium or a cleaning solution.

4. The quaternary mixed environment-friendly refrigerant as claimed in claim 1, wherein the refrigerant can be used in any one of refrigerators, freezers, drinking water dispensers, automobile air conditioners, central air conditioners, dehumidifiers, freezers, commercial refrigerators, water ices, ice cream machines, and freezing and condensing units.

5. A composition comprising the quaternary mixed environment-friendly refrigerant of any one of claims 1-4, and further comprising at least one of an anti-corrosion agent, a stabilizer, a lubricant, an indicator, and a fluorescent leak detector.

6. A method of replacing an existing heat exchange fluid contained in a heat exchange system, comprising: removing at least a portion of said existing heat exchange fluid from said system, said existing heat exchange fluid being R134a, wherein said system incorporates a quaternary mixed environmentally friendly refrigerant of any one of claims 1 to 4 in place of at least a portion of said existing heat exchange fluid.

7. A method of replacing an existing heat exchange fluid contained in a heat exchange system according to claim 6, wherein the heat exchange system is an HVACR system.