CN110878195A - Coolant containing trifluoroiodomethane, mixture containing coolant and heat exchange system - Google Patents

Coolant containing trifluoroiodomethane, mixture containing coolant and heat exchange system Download PDF

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CN110878195A
CN110878195A CN201910983387.XA CN201910983387A CN110878195A CN 110878195 A CN110878195 A CN 110878195A CN 201910983387 A CN201910983387 A CN 201910983387A CN 110878195 A CN110878195 A CN 110878195A
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refrigerant
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trifluoroiodomethane
mass ratio
heat exchange
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CN110878195B (en
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黄宇杰
于艳翠
赵桓
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Gree Electric Appliances Inc of Zhuhai
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Gree Electric Appliances Inc of Zhuhai
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract

The invention provides a refrigerant containing trifluoroiodomethane, which comprises three components, wherein the three components comprise 36-80% of a first component, 8-60% of a second component and 4-24% of a third component in percentage by mass; the mass ratio is based on the total mass of the refrigerant substances; wherein the first component is trifluoroiodomethane (R13I 1); the second component is any two of trifluoromethyl methyl ether (RE143a), 1-difluoroethane (R152a), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)), 3,3, 3-trifluoropropene (R1243zf), 2,3,3, 3-tetrafluoropropene (R1234yf), isobutane (R600a), dimethylether (RE170) and fluoroethane (R161); the third component is one of dimethyl ether (RE170) and cyclopropane (RC 270); the refrigerant has a GWP of 150 or less. The refrigerant not only can solve the problems of high GWP and low refrigerating capacity of the refrigerant replacing R134a in the conventional automobile air-conditioning system, but also solves the problem of low heat exchange efficiency caused by large temperature slippage.

Description

Coolant containing trifluoroiodomethane, mixture containing coolant and heat exchange system
Technical Field
The invention relates to a refrigerant technology, in particular to a trifluoroiodomethane-containing refrigerant, a mixture containing the trifluoroiodomethane-containing refrigerant and a heat exchange system.
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 1550). With the trend of environmental protection becoming more severe, and with respect to the "greenhouse effect" of HFCs, the montreal protocol amendment requires a refrigerant with a low GWP value without destroying the ozone layer to replace the current high GWP refrigerant, and is effectively applied to air conditioning systems. In the F-gas act of the european union, the GWP of a refrigerant for an automotive air conditioning system is required to be less than 150, but a perfect alternative to R134a (GWP of 1300) is not found at present, and since the refrigerant has the characteristic of balancing the physical properties of the refrigerant, the research on the refrigerant becomes a hot spot for researchers and enterprises at home and abroad, and although some refrigerants in the prior art meet lower GWP values, the thermal performance often cannot meet the requirements, and a good refrigerating and heating effect cannot be achieved. 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. It is therefore imperative to find a refrigerant that simultaneously meets the lower GWP and has good thermal performance.
Disclosure of Invention
In view of the above, the present invention provides a refrigerant containing trifluoroiodomethane, wherein the GWP of the refrigerant is less than or equal to 150, the temperature glide is less than 1 ℃, and adverse effects caused by the temperature glide are eliminated. The automobile system using the refrigerant has obvious environmental protection advantage and good thermal performance, and has performance equivalent to that of an R134a automobile air conditioning system, so that the R134a automobile air conditioning system is replaced.
In order to achieve the purpose, the invention adopts the technical scheme that: a refrigerant containing trifluoroiodomethane comprises three components, wherein the three components comprise 36-80% of a first component, 8-60% of a second component and 4-24% of a third component in percentage by mass; the mass ratio is based on the total mass of the refrigerant substances; wherein the first component is trifluoroiodomethane (R13I 1); the second component is any two of trifluoromethyl methyl ether (RE143a), 1-difluoroethane (R152a), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)), 3,3, 3-trifluoropropene (R1243zf), 2,3,3, 3-tetrafluoropropene (R1234yf), isobutane (R600a), dimethylether (RE170) and fluoroethane (R161); the third component is one of dimethylether (RE170) and cyclopropane (RC 270); the refrigerant has GWP of less than or equal to 150, is a near-azeotropic substance, has thermal performance equivalent to that of R134a, and can completely replace R134a refrigerant for use.
Further optionally, the mass ratio of the first component is 48% to 64%, the second component is 36% to 60%, and the third component is 4% to 12%, wherein the mass ratio is based on the total mass of the refrigerant material. The refrigerant has GWP of less than or equal to 150, is a near azeotropic substance and has better refrigerating capacity per unit volume and COP.
Further optionally, the mass ratio of the first component is 48% to 80%, the mass ratio of the second component is 36% to 44%, and the mass ratio of the third component is 4% to 12%, wherein the mass ratio is based on the total mass of the refrigerant material. The refrigerant has GWP of less than or equal to 150, is a near azeotropic substance and has better refrigerating capacity per unit volume and COP.
Further optionally, the second component is composed of two substances, namely a first substance and a second substance, wherein the mass ratio of the first substance is 4% -56%, and the mass ratio of the second substance is 4% -44%, wherein the mass ratio is based on the total mass of the refrigerant substances.
Further optionally, the third component is dimethylether (RE 170). The refrigerant containing dimethylether (RE170) has a better COP than the refrigerant containing cyclopropane (RC 270).
Further optionally, the first component is 52% trifluoroiodomethane (R13I1), the second component is 4% isobutane (R600a) and 36% trans 1,3,3, 3-tetrafluoropropene (R1234ze (E)), and the third component is 8% dimethylether (RE170), in mass percent; the mass ratio is based on the total mass of the refrigerant substance. The quaternary refrigerant has better unit volume refrigerating capacity and COP.
The invention also provides a mixture which comprises lubricating oil and any one of the coolants containing trifluoroiodomethane. The lubricating oil has good compatibility with the refrigerant, ensures the normal operation of an automobile air-conditioning system using the mixture, and has positive influence on the service life of the automobile air-conditioning system.
Further optionally, the lubricating oil is selected from at least one of mineral oil, silicone oil, polyalkyl benzenes (PABs), polyol esters (POEs), polyalkylene glycols (PAGs), polyalkylene glycol esters (PAG esters), polyvinyl ethers (PVEs), poly (α -olefins), or a combination of at least two thereof.
Further optionally, it further comprises a stabilizer. The stabilizer is not higher than 1% by mass based on the total mass of the mixture, so that the stability of a refrigerant in the stabilizer is improved, and the heat exchange efficiency is improved.
Further optionally, the stabilizer is selected from: one of a diene-based compound, a phosphate, a phenol compound and an epoxide, and mixtures thereof.
The invention provides a heat exchange system which comprises a compressor, a condenser and an evaporator which are communicated with each other through fluid, an expansion device and a heat transfer composition for realizing the fluid communication, wherein the heat transfer composition is any one of the refrigerant or mixture containing trifluoroiodomethane.
Further optionally, the heat exchange system is an automotive air conditioning system.
Further optionally, the compressor is any one of a scroll compressor, a rotary compressor and a reciprocating compressor.
Further optionally, the compressor is a scroll compressor. The machine has high efficiency, energy conservation and environmental protection.
Further optionally, the condenser is an indoor side heat exchanger in the vehicle air conditioning system, and the evaporator is an outdoor side heat exchanger in the vehicle air conditioning system. Condensing the refrigerant into medium-temperature and medium-pressure liquid in an indoor heat exchanger; evaporated into low-temperature and low-pressure gas by an outdoor heat exchanger
Further optionally, the indoor side heat exchanger and the outdoor side heat exchanger are microchannel heat exchangers. The micro-channel heat exchanger has compact structure and can reduce the filling amount.
Further optionally, the expansion device is an electronic expansion valve, so that the supercooling and the superheat degree of the refrigerant can be more accurately adjusted, and the cycle performance of the system is improved.
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 the existing heat exchange fluid from the heat exchange system, the existing heat exchange fluid being R134a, and replacing at least a portion of the existing heat exchange fluid by introducing any of the trifluoroiodomethane-containing refrigerants described above, to ensure a refrigeration capacity of 81% to 107% of that of the R134a refrigerant.
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 refrigerant is obtained by screening a large number of substances, and the refrigerant 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 refrigerant containing the trifluoroiodomethane has the GWP value lower than 150, and meets the requirements of environmental protection regulations in various regions of the world on automobile air-conditioning systems.
(2) The trifluoroiodomethane (R13I1) introduced by the invention is a non-flammable substance, and 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, so that the refrigerant with good safety performance is obtained, the GWP is less than or equal to 150, and the thermodynamic performance is good.
(3) Compared with the R134a working medium, the refrigerant has obvious environmental protection advantages, and simultaneously has good thermal performance, and the capacity and the energy efficiency of an automobile air conditioning system using the refrigerant are equivalent to those of the automobile air conditioning system using the R134a working medium, so that the refrigerant can replace the R134a working medium.
(4) In addition to the capacity refrigeration capacity and energy efficiency, the selection of the refrigerant material also considers the temperature slippage, the combination with larger boiling point difference between the members of the group can form a non-azeotropic mixture with larger phase change temperature difference (slippage temperature), and the refrigerant slippage temperature of the invention is less than 1 ℃ and as low as 0.02 ℃, thereby eliminating the adverse effect caused by the temperature slippage. The heat pump system of the automobile air conditioner adopting the refrigerant does not need to be provided with a coping scheme to prevent the heat exchange efficiency reduction caused by temperature slippage in the compressor.
Drawings
The above and other objects, features and advantages of the present disclosure will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings. The drawings described below are merely some embodiments of the present disclosure, and other drawings may be derived from those drawings by those of ordinary skill in the art without inventive effort.
FIG. 1 is a diagram of an automotive air conditioning heat pump system in accordance with an embodiment of the present invention;
in the figure:
1-a compressor; 2-indoor heat exchanger; 3-an expansion device; 4-outdoor heat exchanger;
detailed description of the preferred embodiments
Evaluation standards of the refrigerant generally refer to GWP and ODP in the aspect of environmental protection, volumetric refrigeration 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, non-toxic, non-flammable, excellent in performance, and good in 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 the substance has combustible components, a flame-retardant substance must be added, and the corresponding proportion is adjusted, so that the final refrigerant has the property of weak combustibility or non-combustibility.
According to the requirements of the automobile air conditioning system on the refrigerant, the refrigerant is required to have low GWP, zero ODP and high safety, in order to meet the performance, the refrigerant has the advantages of good environmental protection and good thermal performance, and one of two of the substances of the second component, namely trifluoromethyl methyl ether (RE143a), 1-difluoroethane (R152a), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)), 3,3, 3-trifluoropropene (R1243zf), 2,3,3, 3-tetrafluoropropene (R1234yf), isobutane (R600a), dimethylether (RE170), fluoroether (R161) and one of the substances of the third component, namely dimethylether (RE170) and cyclopropane (RC270), is added into the formula, so that the refrigerant has good environmental protection and good thermal performance. However, the substances provided by the second component and the third component are flammable, and the safety performance of the prepared refrigerant is poor, so that the substance of the first component, namely trifluoroiodomethane (R13I1), is added in the formula of the refrigerant to play a role of a flame retardant, so that the refrigerant provided by the invention has the advantages that the GWP is lower than 150, the thermal performance and the slip temperature are lower than 1 ℃, and the safety performance is good.
The invention relates to a method for preparing a refrigerant containing trifluoroiodomethane, which comprises the following steps: the refrigerant is prepared by physically mixing trifluoroiodomethane (R13I1) serving as a first component, trifluoromethyl methyl ether (RE143a), 1-difluoroethane (R152a), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)), any two of 3,3, 3-trifluoropropene (R1243zf), 2,3,3, 3-tetrafluoropropene (R1234yf), isobutane (R600a), dimethyl ether (RE170) and fluoroethane (R161) serving as a second component and one of dimethyl ether (RE170) and cyclopropane (RC270) serving as a third component in mass ratio, wherein the mass ratio of the first component is 36-80%, the second component is 8-60% and the third component is 4-24%, and the mass ratios of the first component, the second component and the third component are different substances, and are physically mixed in a normal-temperature and normal-pressure liquid phase state, mixing them uniformly to obtain refrigerant. The basic parameters of each component substance are shown in the table 1:
TABLE 1 basic parameters of the substances in the refrigerant
Figure BDA0002235940530000061
Figure BDA0002235940530000071
According to the method, a plurality of specific examples and comparative examples are given below, wherein the mass ratio of the substances is the mass ratio, and the sum of the mass percentage of each refrigerant is 100%. In each embodiment and the comparative example, all the substances are subjected to liquid-phase physical mixing according to a fixed mass ratio under a normal-temperature normal-pressure liquid-phase state, and are uniformly mixed to obtain a refrigerant.
In example 1, trifluoroiodomethane (R13I1), 1-difluoroethane (R152a), trifluoromethyl methyl ether (RE143a), and dimethylether (RE170) were physically mixed at a mass ratio of 48:40:4:8 in a normal-temperature and normal-pressure liquid phase, and a refrigerant was obtained by uniformly mixing the components.
In example 2, four substances, that is, trifluoroiodomethane (R13I1), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)), trifluoromethyl ether (RE143a) and dimethylether (RE170), were physically mixed at a mass ratio of 60:4:20:16 in a liquid phase at normal temperature and pressure, and were uniformly mixed to obtain a refrigerant.
In example 3, trifluoroiodomethane (R13I1), 3,3, 3-trifluoropropene (R1243zf), trifluoromethyl methyl ether (RE143a), and dimethylether (RE170) were physically mixed at a mass ratio of 68:4:8:20 in a liquid phase at normal temperature and pressure, and a refrigerant was obtained by uniformly mixing the components.
In example 4, trifluoroiodomethane (R13I1), 2,3,3, 3-tetrafluoropropene (R1234yf), trifluoromethyl methyl ether (RE143a), and dimethylether (RE170) were physically mixed at room temperature and normal pressure in a mass ratio of 36:48:8:8 to obtain a refrigerant.
In example 5, trifluoroiodomethane (R13I1), 2,3,3, 3-tetrafluoropropene (R1234yf), trifluoromethyl methyl ether (RE143a), and dimethylether (RE170) were physically mixed at room temperature and normal pressure in a mass ratio of 36:56:4:4, and uniformly mixed to obtain a refrigerant.
Example 6, trifluoroiodomethane (R13I1), 1-difluoroethane (R152a), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and dimethylether (RE170) were physically mixed at room temperature and normal pressure in a mass ratio of 52:32:4:12, and uniformly mixed to obtain a refrigerant.
Example 7, a refrigerant was obtained by physically mixing, at normal temperature and pressure, four substances of trifluoroiodomethane (R13I1), 2,3,3, 3-tetrafluoropropene (R1234yf), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)), and dimethylether (RE170) at a mass ratio of 60:16:4: 20.
In example 8, trifluoroiodomethane (R13I1), 1-difluoroethane (R152a), 3,3, 3-trifluoropropene (R1243zf), and dimethylether (RE170) were physically mixed at a mass ratio of 48:4:44:4 in a liquid phase at normal temperature and pressure, and uniformly mixed to obtain a refrigerant.
In example 9, trifluoroiodomethane (R13I1), 1-difluoroethane (R152a), 3,3, 3-trifluoropropene (R1243zf), and dimethylether (RE170) were physically mixed at a mass ratio of 64:8:4:24 in a liquid phase at normal temperature and pressure, and uniformly mixed to obtain a refrigerant.
In example 10, trifluoroiodomethane (R13I1), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)), 3,3, 3-trifluoropropene (R1243zf), and dimethylether (RE170) were physically mixed at a mass ratio of 48:4:44:4 in a liquid phase at normal temperature and pressure, and were uniformly mixed to obtain a refrigerant.
Example 11, trifluoroiodomethane (R13I1), 2,3,3, 3-tetrafluoropropene (R1234yf), 3,3, 3-trifluoropropene (R1243zf), and dimethylether (RE170) were physically mixed at a mass ratio of 80:4:4:12 in a normal temperature and pressure liquid phase, and a refrigerant was obtained by uniformly mixing.
In example 12, trifluoroiodomethane (R13I1), trifluoromethyl methyl ether (RE143a), dimethylether (RE170), and cyclopropane (RC270) were physically mixed at a mass ratio of 68:4:24:4 in a normal temperature and pressure liquid phase, and were uniformly mixed to obtain a refrigerant.
In example 13, trifluoroiodomethane (R13I1), trifluoromethyl methyl ether (RE143a), dimethyl ether (RE170), and cyclopropane (RC270) were physically mixed at a mass ratio of 60:24:12:4 under normal temperature and pressure, and uniformly mixed to obtain a refrigerant.
Example 14, trifluoroiodomethane (R13I1), 1-difluoroethane (R152a), trans-form 1,3,3, 3-tetrafluoropropene (R1234ze (E)), and cyclopropane (RC270) were physically mixed at normal temperature and pressure in a liquid phase at a mass ratio of 56:4:36:4, and uniformly mixed to obtain a refrigerant.
In example 15, trifluoroiodomethane (R13I1), 1-difluoroethane (R152a), 3,3, 3-trifluoropropene (R1243zf), and cyclopropane (RC270) were physically mixed at a mass ratio of 48:16:32:4 in a liquid phase at normal temperature and pressure, and were uniformly mixed to obtain a refrigerant.
In example 16, trifluoroiodomethane (R13I1), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)), dimethylether (RE170), and cyclopropane (RC270) were physically mixed at a mass ratio of 48:24:16:12 in a liquid phase at normal temperature and pressure, and uniformly mixed to obtain a refrigerant.
In example 17, trifluoroiodomethane (R13I1), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)), dimethylether (RE170), and cyclopropane (RC270) were physically mixed at a mass ratio of 72:8:16:4 in a liquid phase at normal temperature and pressure, and uniformly mixed to obtain a refrigerant.
In example 18, trifluoroiodomethane (R13I1), 3,3, 3-trifluoropropene (R1243zf), trifluoromethyl methyl ether (RE143a), and cyclopropane (RC270) were physically mixed at normal temperature and pressure in a liquid phase at a mass ratio of 48:20:24:8, and uniformly mixed to obtain a refrigerant.
In example 19, trifluoroiodomethane (R13I1), 3,3, 3-trifluoropropene (R1243zf), isobutane (R600a), and cyclopropane (RC270) were physically mixed at a mass ratio of 40:52:4:4 in a normal-temperature normal-pressure liquid phase, and a refrigerant was obtained by uniformly mixing.
In example 20, trifluoroiodomethane (R13I1), 3,3, 3-trifluoropropene (R1243zf), dimethylether (RE170), and cyclopropane (RC270) were physically mixed at a mass ratio of 64:4:28:4 under normal temperature and pressure, and uniformly mixed to obtain a refrigerant.
In example 21, trifluoroiodomethane (R13I1), 2,3,3, 3-tetrafluoropropene (R1234yf), trifluoromethyl methyl ether (RE143a), and cyclopropane (RC270) were physically mixed at room temperature and normal pressure in a liquid phase at a mass ratio of 48:24:24:4, and uniformly mixed to obtain a refrigerant.
In example 22, trifluoroiodomethane (R13I1), 2,3,3, 3-tetrafluoropropene (R1234yf), 1-difluoroethane (R152a), and cyclopropane (RC270) were physically mixed at room temperature and pressure in a liquid phase at a mass ratio of 52:4:36:8, and uniformly mixed to obtain a refrigerant.
In example 23, trifluoroiodomethane (R13I1), 2,3,3, 3-tetrafluoropropene (R1234yf), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and cyclopropane (RC270) were physically mixed at room temperature and normal pressure in a liquid phase at a mass ratio of 48:32:16:4, and uniformly mixed to obtain a refrigerant.
In example 24, trifluoroiodomethane (R13I1), 2,3,3, 3-tetrafluoropropene (R1234yf), 3,3, 3-trifluoropropene (R1243zf), and cyclopropane (RC270) were physically mixed at a mass ratio of 44:48:4:4 in a normal temperature and pressure liquid phase, and were uniformly mixed to obtain a refrigerant.
In example 25, trifluoroiodomethane (R13I1), 2,3,3, 3-tetrafluoropropene (R1234yf), 3,3, 3-trifluoropropene (R1243zf), and cyclopropane (RC270) were physically mixed at a mass ratio of 48:4:44:4 in a normal temperature and pressure liquid phase, and were uniformly mixed to obtain a refrigerant.
Example 26, trifluoroiodomethane (R13I1), 2,3,3, 3-tetrafluoropropene (R1234yf), dimethylether (RE170), and cyclopropane (RC270) were physically mixed at normal temperature and pressure in a liquid phase at a mass ratio of 68:4:24:4, and uniformly mixed to obtain a refrigerant.
Example 27, a refrigerant was obtained by physically mixing, at normal temperature and pressure, trifluoroiodomethane (R13I1), 2,3,3, 3-tetrafluoropropene (R1234yf), fluoroethane (R161), and dimethylether (RE170) at a mass ratio of 40:52:4: 4.
In example 28, trifluoroiodomethane (R13I1), trifluoromethyl methyl ether (RE143a), isobutane (R600a), and dimethylether (RE170) were physically mixed at room temperature and normal pressure in a mass ratio of 64:16:4:16, and mixed uniformly to obtain a refrigerant.
In example 29, trifluoroiodomethane (R13I1), trifluoromethyl methyl ether (RE143a), isobutane (R600a), and dimethylether (RE170) were physically mixed at a mass ratio of 60:28:4:8 in a normal temperature and pressure liquid phase, and a refrigerant was obtained by uniformly mixing.
In example 30, trifluoroiodomethane (R13I1), 1-difluoroethane (R152a), iso-butane (R600a), and dimethylether (RE170) were physically mixed at room temperature and normal pressure in a mass ratio of 48:44:4:4, and uniformly mixed to obtain a refrigerant.
In example 31, trifluoroiodomethane (R13I1), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)), isobutane (R600a), and dimethylether (RE170) were physically mixed at a mass ratio of 52:36:4:8 in a normal temperature and pressure liquid phase, and uniformly mixed to obtain a refrigerant.
In example 32, trifluoroiodomethane (R13I1), 2,3,3, 3-tetrafluoropropene (R1234yf), isobutane (R600a) and dimethylether (RE170) were physically mixed at room temperature and normal pressure in a liquid phase at a mass ratio of 72:4:4:20, and uniformly mixed to obtain a refrigerant.
In example 33, trifluoroiodomethane (R13I1), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)), isobutane (R600a), and dimethylether (RE170) were physically mixed at a mass ratio of 68:8:4:20 in a normal temperature and pressure liquid phase, and uniformly mixed to obtain a refrigerant.
Comparative example 1, three substances of trifluoroiodomethane (R13I1), 2,3,3, 3-tetrafluoropropene (R1234yf), isobutane (R600a) and dimethylether (RE170) are physically mixed according to the mass ratio of 30:15:31:24 under normal temperature and pressure liquid phase, and the mixture is uniformly mixed to obtain a refrigerant.
Comparative example 2, trifluoroiodomethane (R13I1), 2,3,3, 3-tetrafluoropropene (R1234yf), 3,3, 3-trifluoropropene (R1243zf) and cyclopropane (RC270) were physically mixed at a mass ratio of 82:4:4:10 in a normal temperature and pressure liquid phase, and uniformly mixed to obtain a refrigerant.
Comparative example 3, trifluoroiodomethane (R13I1), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)), dimethylether (RE170) and cyclopropane (RC270) were physically mixed at room temperature and normal pressure in a liquid phase at a mass ratio of 36:30:30:4, and uniformly mixed to obtain a refrigerant.
Comparative example 4, three substances of trifluoroiodomethane (R13I1), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)), isobutane (R600a) and dimethylether (RE170) are physically mixed in a mass ratio of 40:10:20:30 at normal temperature and normal pressure in a liquid phase, and the mixture is uniformly mixed to obtain a refrigerant.
Table 2 compares the above examples and comparative examples with the basic parameters of molecular weight, normal boiling point and environmental properties of R134 a.
TABLE 2 basic parameters of the Coolant
Figure BDA0002235940530000121
Figure BDA0002235940530000131
As can be seen from table 2, the GWP of the refrigerant provided in this example is not more than 150, and is much less than the GWP of R134 a.
This example provides an automotive air conditioning system comprising a compressor 1, a condenser and an evaporator in fluid communication, an expansion device 3, and a heat transfer composition in fluid communication with the refrigerant contained in this example or comparative example. Preferably, the compressor 1 is any one of a scroll compressor, a rotary compressor and a reciprocating compressor. Further preferably, the compressor 1 is a scroll compressor, and is high in efficiency, energy-saving and environment-friendly. Preferably, the condenser is an indoor side heat exchanger 2 in an automotive air conditioning system and the evaporator is an outdoor side heat exchanger 4 in the automotive air conditioning system. Further preferably, the indoor side heat exchanger 2 and the outdoor side heat exchanger 4 are microchannel heat exchangers. The micro-channel heat exchanger has compact structure and can reduce the filling amount. Further preferably, the expansion device 3 is an electronic expansion valve, which can more accurately adjust the supercooling and superheat degree of the refrigerant, and improve the cycle performance of the system.
The present invention also provides a method of replacing an existing heat exchange fluid contained in a heat exchange system, comprising: at least a part of the existing heat exchange fluid is removed from the heat exchange system, the existing heat exchange fluid is R134a, and at least a part of the existing heat exchange fluid is replaced by introducing any one of the refrigerants containing trifluoroiodomethane, so that the refrigerating capacity of the refrigerant is 81-107% of that of the R134 a. Preferably, the refrigerant containing trifluoroiodomethane in the present invention is used to replace the existing heat exchange fluid of all heat exchange systems, specifically as follows:
the refrigerants of the above embodiments and comparative examples are applied to the air conditioning system for a vehicle proposed in the present invention instead of the R134a refrigerant. As shown in fig. 1, a refrigerant is compressed into a high-temperature and high-pressure gas in a compressor 1, condensed into a medium-temperature and medium-pressure liquid by an indoor heat exchanger 2, throttled into a medium-temperature and low-pressure gas-liquid two-phase by an expansion device 3, i.e., an electronic expansion valve, evaporated into a low-temperature and low-pressure gas by an outdoor heat exchanger 4, and finally circulated in the compressor 1.
Table 3 compares the refrigerant in the above examples and comparative examples, which is calculated by simulation, i.e., the evaporation temperature of the working condition in the automobile air conditioning system is 6 ℃, the condensation temperature is 36 ℃, the superheat degree is 5 ℃, the supercooling degree is 5 ℃, and the isentropic efficiency is 0.7, with the thermodynamic parameters (i.e., the compression ratio and the exhaust gas temperature) and the relative thermodynamic properties (i.e., the relative specific volume refrigerating capacity and the relative efficiency COP) of R134 a.
TABLE 3 Performance comparison of refrigerant with R134a
Figure BDA0002235940530000141
Figure BDA0002235940530000151
(slip temperature is the difference between dew point temperature and bubble point temperature under working pressure, maximum value is taken)
Because the vehicle air conditioning system leaks easily, the temperature of refrigerant slides and should be as little as possible, reduces to leak the influence to the refrigerant ratio, to embodiment analysis can know: it can be seen from the preferred embodiments 1-26 that the temperature slip of the refrigerant is less than 0.7 deg.C, especially the temperature slip of the embodiments 2, 5, 8, 10 is almost equal to 0 deg.C, so that the adverse effect caused by the temperature slip is eliminated, and the problem of refilling after the refrigerant leaks is not considered. And the thermal performance of the refrigerant in each embodiment is similar to that of R134a, and direct replacement can be basically realized. Preferably, the refrigerant containing dimethylether (RE170) has a relatively higher COP than the refrigerant containing cyclopropane (RC 270). Preferably, the second component consists of two substances, namely a first substance and a second substance, wherein the mass ratio of the first substance is 4-56% and the mass ratio of the second substance is 4-44%, wherein the mass ratio is based on the total mass of the substances of the second component. In example 22, by combining four factors of volumetric cooling capacity, temperature glide, energy efficiency COP and flammability class, the refrigerant obtained according to the mass ratio of 52/4/36/8 in the combination of R13I1, R1234yf, R152a and RC270 has a GWP of only 50.32, a compression ratio lower than that of R134a, a unit volumetric cooling capacity of 1.086 slightly higher than that of R134a, and a COP of 0.991 slightly lower than that of R134a, which is the best one of the overall performances in the examples.
Meanwhile, the data of the embodiment and the comparative example are combined, so that when the mass ratio of the substances in each part of the formula is changed, the prepared refrigerant 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 an automobile air conditioning system are influenced when the refrigerant is used, for example, the mass ratio of the first component R13I1 in the comparative example 1 and the comparative example 2 is not in the range provided by the invention, and when the mass ratio is lower than the minimum value 36% of the mass ratio provided by the invention, the temperature slip of the obtained refrigerant is too high, and the volume refrigerating capacity is smaller; when the mass percentage is higher than the highest value of 80% given by the invention, the temperature slippage of the obtained refrigerant is large, and similarly, the analysis of comparative proportions 3 and 4 shows that when the mass percentage of other substances of a certain component in the refrigerant is not in the range provided by the invention, the temperature slippage of the obtained refrigerant is increased, and the relative volume refrigerating capacity of the refrigerant is probably smaller. It is comprehensively known that only when the mass ratio and the material composition of the substances are adopted in the refrigerant, the synergistic effect among the substances is well exerted, the refrigerant capable of replacing R134a is ensured under the conditions of ensuring the indexes of the prepared refrigerant such as the sliding temperature and/or the flammability, GWP, relative volume refrigerating capacity, energy efficiency, temperature sliding and the like, good environmental characteristics are kept, and the problem of low refrigerating capacity of a system using the refrigerant of the embodiment is solved.
The lubricating oil is preferably at least one selected from the group consisting of mineral oil, silicone oil, Polyalkylbenzene (PAB), polyol ester (POE), polyalkylene glycol (PAG), polyalkylene glycol ester (PAG ester), polyvinyl ether (PVE), poly (α -olefin), or a combination of at least two thereof, and preferably the mixture further comprises a stabilizer selected from the group consisting of diene-based compounds, phosphates, phenol compounds, and epoxides, and mixtures thereof, wherein the stabilizer is not more than 1% by mass based on the total mass of the mixture, thereby increasing the stability of the refrigerant therein and improving the heat exchange efficiency.
In summary, the invention provides a refrigerant containing trifluoroiodomethane, which comprises three components, wherein the three components comprise 36-80% of a first component, 8-56% of a second component and 4-24% of a third component in percentage by mass; the mass ratio is based on the total mass of the refrigerant substances; wherein the first component is trifluoroiodomethane (R13I 1); the second component is any two of trifluoromethyl methyl ether (RE143a), 1-difluoroethane (R152a), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)), 3,3, 3-trifluoropropene (R1243zf), 2,3,3, 3-tetrafluoropropene (R1234yf), isobutane (R600a), dimethylether (RE170) and fluoroethane (R161); the third component is one of dimethyl ether (RE170) and cyclopropane (RC 270); the refrigerant has a GWP of 150 or less. The automobile system using the refrigerant or the refrigerant mixture has obvious environmental protection advantage and good thermal performance, and has the performance equivalent to that of an R134a automobile air-conditioning system, thereby replacing the R134a automobile air-conditioning system.
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 (13)

1. The refrigerant containing the trifluoroiodomethane is characterized by comprising three components, wherein the three components comprise 36-80% of a first component, 8-60% of a second component and 4-24% of a third component in percentage by mass; the mass ratio is based on the total mass of the refrigerant substances; wherein the first component is trifluoroiodomethane (R13I 1); the second component is any two of trifluoromethyl methyl ether (RE143a), 1-difluoroethane (R152a), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)), 3,3, 3-trifluoropropene (R1243zf), 2,3,3, 3-tetrafluoropropene (R1234yf), isobutane (R600a), dimethylether (RE170) and fluoroethane (R161); the third component is one of dimethylether (RE170) and cyclopropane (RC 270); the refrigerant has a GWP of not more than 150.
2. The refrigerant containing trifluoroiodomethane according to claim 1, wherein the mass ratio of the first component is 48% to 64%, the second component is 36% to 60%, and the third component is 4% to 12%, wherein the mass ratio is based on the total mass of the refrigerant material.
3. The refrigerant containing trifluoroiodomethane according to claim 1, wherein the mass ratio of the first component is 48% to 80%, the second component is 36% to 44%, and the third component is 4% to 12%, wherein the mass ratio is based on the total mass of the refrigerant material.
4. The refrigerant containing trifluoroiodomethane according to claim 1, wherein the second component is composed of a first substance and a second substance, wherein the mass ratio of the first substance is 4% to 56% and the mass ratio of the second substance is 4% to 44% in terms of mass ratio, wherein the mass ratio is based on the total mass of the refrigerant substances.
5. The refrigerant containing trifluoroiodomethane according to any one of claims 1 to 4, wherein the third component is dimethylether (RE 170).
6. A mixture comprising a lubricating oil and a trifluoroiodomethane-containing refrigerant according to any one of the preceding claims 1 to 5.
7. A composition according to claim 6, wherein the lubricating oil is at least one member selected from the group consisting of mineral oil, silicone oil, polyalkyl benzenes (PABs), polyol esters (POEs), polyalkylene glycols (PAGs), polyalkylene glycol esters (PAG esters), polyvinyl ethers (PVEs), poly (α -olefins), and combinations of at least two thereof.
8. The mixture of claim 7, further comprising a stabilizer selected from the group consisting of: one of a diene-based compound, a phosphate, a phenol compound and an epoxide, and mixtures thereof.
9. A heat exchange system comprising a compressor (1), a condenser and an evaporator in fluid communication, an expansion device (3) and a heat transfer composition to effect said fluid communication, said heat transfer composition being a trifluoroiodomethane-containing refrigerant or mixture as claimed in any one of claims 1 to 8.
10. The heat exchange system of claim 9, wherein the heat exchange system is an automotive air conditioning system.
11. The heat exchange system according to claim 10, wherein the compressor (1) is any one of a scroll compressor, a rotary compressor and a reciprocating compressor.
12. The heat exchange system of claim 11, wherein: the indoor side heat exchanger (2) and the outdoor side heat exchanger (4) are micro-channel heat exchangers.
13. 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 the heat exchange system, said existing heat exchange fluid being R134a, characterized by: the refrigeration capacity of 81-107% of that of R134a refrigerant is ensured by introducing trifluoroiodomethane-containing refrigerant of any one of claims 1-5 to replace at least a portion of the existing heat exchange fluid.
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