CN110591650B - Heat transfer composition suitable for centrifugal refrigerating unit - Google Patents

Heat transfer composition suitable for centrifugal refrigerating unit Download PDF

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CN110591650B
CN110591650B CN201910863768.4A CN201910863768A CN110591650B CN 110591650 B CN110591650 B CN 110591650B CN 201910863768 A CN201910863768 A CN 201910863768A CN 110591650 B CN110591650 B CN 110591650B
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CN110591650A (en
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于艳翠
赵桓
雷佩玉
梁尤轩
黄宇杰
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Gree Electric Appliances Inc of Zhuhai
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09K5/045—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 containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/11—Ethers
    • C09K2205/112—Halogenated ethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/122—Halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/126—Unsaturated fluorinated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09K2205/22—All components of a mixture being fluoro compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/40—Replacement mixtures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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    • Y02P20/10—Process efficiency

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Abstract

The present invention provides a heat transfer composition suitable for use in a centrifugal chiller unit comprising three components, wherein the first component is one of 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) or 1,1,1, 2-tetrafluoroethane (R134a), the second component is trifluoromethyl methyl ether (RE143a), and the third component is one of 2,3,3, 3-tetrafluoropropene (R1234yf), 3,3, 3-trifluoropropene (R1243zf), and trans 1,3,3, 3-tetrafluoropropene (R1234ze (E)), 1, 1-difluoroethane (R152 a). The GWP of the heat transfer composition is less than or equal to 600, the ODP is 0, and the heat transfer composition has obvious environmental protection advantages. In addition, the heat transfer composition has good thermal performance, is applied to a centrifugal refrigerating unit system unit, has the capacity and the energy efficiency equivalent to those of a centrifugal refrigerating unit system using R134a working medium, can replace R134a working medium, and does not change the centrifugal refrigerating unit system at all.

Description

Heat transfer composition suitable for centrifugal refrigerating unit
Technical Field
The invention relates to a refrigerant technology, in particular to a heat transfer composition suitable for a centrifugal refrigerating unit.
Background
With the trend of environmental protection becoming more serious, and with respect to the "greenhouse effect" of HFCs, the montreal protocol amendment requires a refrigerant which is not ozone-depleting and has a low GWP value to replace the current high GWP refrigerant, and is effectively applied to air conditioning systems. For example, R134a is commonly used for large-scale air-conditioning water chilling units, the GWP is 1300, the ODP is 0, and at present, the technical means usually starts from the aspects of single working medium and mixed working medium, and searches for the working medium which meets the requirements of safety and environmental protection and the energy efficiency of the air-conditioning system, but a perfect working medium for replacing R134a is not found.
Disclosure of Invention
In view of this, the invention provides a heat transfer composition suitable for a centrifugal refrigerating unit, wherein the GWP of the heat transfer composition is less than or equal to 600, the ODP is 0, the heat transfer composition has obvious environmental protection advantages and good thermal performance, and the problem that the conventional refrigerant replacing R134a is low in system capacity or energy efficiency when applied to the centrifugal refrigerating unit is solved.
In order to achieve the purpose, the invention adopts the technical scheme that: a heat transfer composition suitable for use in a centrifugal chiller unit comprising three components, wherein a first component is one of 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) or 1,1,1, 2-tetrafluoroethane (R134a), a second component is trifluoromethyl methyl ether (RE143a), and a third component is one of 2,3,3, 3-tetrafluoropropene (R1234yf), 3,3, 3-trifluoropropene (R1243zf), and trans 1,3,3, 3-tetrafluoropropene (R1234ze (E)), 1, 1-difluoroethane (R152a), wherein the heat transfer composition has a Global Warming Potential (GWP) of no greater than 600.
Further optionally, it consists essentially of 12-16% by mass of 1,1,1,2,3,3, 3-heptafluoropropane (R227ea), 4-36% by mass of said second component and 52-84% by mass of said third component. The heat transfer composition comprising the three components has the mass ratio of the components within the above range, respectively, has better refrigeration capacity and energy efficiency performance, and has low GWP.
Further optionally, the third component is one of 2,3,3, 3-tetrafluoropropene (R1234yf), 3,3, 3-trifluoropropene (R1243zf), and trans 1,3,3, 3-tetrafluoropropene (R1234ze (E)). The third component is preferably selected from the group consisting of temperature glide, refrigeration capacity and energy efficiency.
Further optionally, it consists essentially of 28-44% by mass of 1,1,1, 2-tetrafluoroethane (R134a), 4-44% by mass of the second component and 28-68% by mass of the third component. The heat transfer composition containing the three components has the mass ratio of the components within the range, and has better refrigeration capacity and energy efficiency performance and small temperature slippage.
Further optionally, it may also contain a lubricant, which acts to lubricate and cool the various moving parts of the compressor in the refrigeration system in which the heat transfer composition is used, ensuring proper operation of the compressor, and playing an extremely important role in the useful life of the compressor.
Further optionally, wherein the lubricant is selected from the group consisting of ester oils, which have good compatibility with the heat transfer composition of the present invention, ensuring proper operation of a refrigeration system in which the composition is used, while having a positive impact on the life of the refrigeration system.
Further optionally, the heat transfer composition is used to replace R134a, solving the problem of low capacity or low energy efficiency of centrifugal chiller system.
The present invention also provides a centrifugal refrigeration unit comprising a compressor, a condenser and an evaporator in fluid communication, an expansion device, and a heat transfer composition to effect said fluid communication, said heat transfer composition being any of the heat transfer compositions described above.
Further optionally, the compressor is an oil-free centrifugal compressor, and the evaporator is a shell-and-tube heat exchanger, so that the energy efficiency of the refrigeration system in the operation process is ensured.
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 system, the existing heat exchange fluid being R134a, and replacing at least a portion of the existing heat exchange fluid by introducing into the system a heat transfer composition to form the heat transfer composition of any of the above, and to provide a refrigeration capacity of 70% to 110% of the refrigeration capacity of R134a refrigerant.
The components of the present invention are commercially available or can be prepared by methods known in the art. The content ratio of each component in the invention is obtained by screening a large amount, and is a condition for ensuring the excellent performance of the heat transfer composition.
The invention has the beneficial effects that:
(1) the introduced 1,1,1,2,3,3, 3-heptafluoropropane and 1,1,1, 2-tetrafluoroethane (R134a) are incombustible components, and the combustibility of the components such as trifluoromethyl ether (RE143a), 2,3,3, 3-tetrafluoropropene (R1234yf), 3,3, 3-trifluoropropene (R1243zf), trans 1,3,3, 3-tetrafluoropropene (R1234ze (E)) and 1, 1-difluoroethane (R152a) can be weakened by changing the content of the incombustible components, so that a weakly combustible or incombustible heat transfer composition with good safety performance, wherein the GWP is 600 or less and the ODP is 0, is obtained.
(2) Compared with the R134a working medium, the heat transfer composition has obvious environmental protection advantages, has good thermal performance, is applied to a centrifugal refrigerating unit system, has the capacity and the energy efficiency equivalent to those of the centrifugal refrigerating unit system using the R134a working medium, can replace the R134a working medium, and does not change the centrifugal refrigerating unit system.
(3) In addition to volumetric refrigeration capacity and energy efficiency, the selection of the components of the heat transfer composition of the present invention also takes into account temperature glide, the combination of greater boiling point differences between the members of the group having the potential to form a zeotropic mixture with a greater temperature difference of phase transition (glide temperature), and the glide temperature of the heat transfer composition of the present invention being less than 0.5 ℃.
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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 a single-pole compression cycle system of a centrifugal chiller system according to an embodiment of the present invention;
in the figure:
1-a compressor; 2-a condenser; 3-an evaporator; 40-a throttle valve;
Detailed Description
The present invention is directed to a heat transfer composition prepared by combining a first component which is 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) or 1,1,1, 2-tetrafluoroethane (R134a), a second component which is trifluoromethyl methyl ether (RE143a), a third component which is one or more of 2,3,3, 3-tetrafluoropropene (R1234yf), 3,3, 3-trifluoropropene (R1243zf) and trans 1,3,3, 3-tetrafluoropropene (R1234ze (E)), 1, 1-difluoroethane (R152a) and the like:
combination mode A first component A second component Third component Combination mode A first component A second component Third component
Combination of one R227ea RE143a R1234yf Five combination R134a RE143a R1243zf
Combination two R227ea RE143a R1243zf Six combinations R134a RE143a R1234ze(E)
Combination III R227ea RE143a R1234ze(E) Combined seven R134a RE143a R152a
Four combination R134a RE143a R1234yf Combined eight R227ea RE143a R152a
Preferably, the following combinations are performed:
combination mode A first component A second component Third component Combination mode A first component A second component Third component
Combination of one R227ea RE143a R1234yf Four combination R134a RE143a R1234yf
Combination two R227ea RE143a R1243zf Five combination R134a RE143a R1243zf
Combination III R227ea RE143a R1234ze(E) Six combinations R134a RE143a R1234ze(E)
Combined seven R134a RE143a R152a
When the combination mode is determined, the components are physically mixed in different mass proportions under the normal temperature and normal pressure liquid phase state, and the components are uniformly mixed to form the heat transfer composition suitable for the centrifugal refrigerating unit. Wherein, the 1,1,1,2,3,3, 3-heptafluoropropane and the 1,1,1, 2-tetrafluoroethane (R134a) are non-flammable refrigerants, and the flammability of the rest refrigerants can be weakened by adding the non-flammable refrigerants, so that the safety requirement is met. The basic parameters of the component materials are shown in Table 1.
TABLE 1 basic parameters of the component materials in the Heat transfer compositions
Figure BDA0002200633700000051
Specific examples are given below in which the proportions of the components are mass percentages, with the sum of the mass percentages of the component materials for each heat transfer composition being 100%. In each of the examples and comparative examples, the components were physically mixed in a liquid phase state at normal temperature and pressure in a fixed mass ratio, and uniformly mixed to obtain a heat transfer composition. Comparative examples of the examples are shown in table 2.
TABLE 2 examples and comparative examples
Figure BDA0002200633700000052
Figure BDA0002200633700000061
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 thermophysical basic parameters of the heat transfer compositions
Figure BDA0002200633700000062
Figure BDA0002200633700000071
As shown in Table 3, the GWP of the heat transfer composition provided by the invention is less than or equal to 600, the ODP is 0, and the heat transfer composition has obvious environmental protection advantage and the GWP is far lower than that of R134 a. In addition, the molecular weight, the standard boiling point and the critical temperature of the mixed working medium are equivalent to those of R134 a.
Preferably, the above examples and comparative examples are applied to R134a replacing a centrifugal refrigerator unit system, the condenser 2 may be a finned tube type or a shell and tube type, a finned condenser is used in the present embodiment, and the centrifugal refrigerator unit system is preferably not modified by any device components. Further preferably, the centrifugal refrigerating unit system comprises a centrifugal compressor 1, a condenser 2, a ternary mixed refrigerant and water as a heat exchange medium, wherein the expansion device is a throttle valve 40, and a gas-liquid separation filter screen is arranged on the inner side of the evaporator 3 structure, so as to prevent the compressor from sucking gas and carrying liquid. The heat transfer compositions of the above examples and comparative examples were heat exchanged, compressed, throttled, and replaced R134a refrigerant in the centrifugal chiller unit system.
Table 4 compares the thermodynamic parameters (i.e., compression ratio and discharge temperature) and relative thermodynamic properties (i.e., relative specific capacity and relative efficiency COP) of the heat transfer compositions of the foregoing examples and comparative examples at refrigeration conditions (i.e., 6 ℃ vapor temperature, 36 ℃ condensation temperature, 5 ℃ superheat degree, 5 ℃ subcooling degree) with R134 a.
TABLE 4 Performance comparison of Heat transfer compositions with R134a
Figure BDA0002200633700000081
(slip temperature is the difference between dew point temperature and bubble point temperature under working pressure, maximum value is taken)
As can be seen from table 4, the heat transfer composition of the present invention, some of the refrigerant examples, have a volumetric refrigeration capacity greater than the volumetric refrigeration capacity of R134a, and a temperature glide of 0.1 ℃ or less, and are azeotropic refrigerants. The volumetric refrigerating capacity of other refrigerant embodiments is less than R134a volumetric refrigerating capacity, the relative volumetric refrigerating capacity of most embodiments is not less than 0.82, the relative volumetric refrigerating capacity of a small amount of embodiments is about 0.7, the temperature slippage is less than 0.5 ℃, and the refrigerant belongs to a near azeotropic refrigerant. The energy efficiency COPs of all examples were less than the energy efficiency COPs of R134a, but greater than 0.9.
It can be known from the data in table 3 and the data representing the examples and comparative examples that when the contents of the components of the formula of the present invention are changed or the components of the prepared mixed working medium are changed, the components cannot play a good role in synergy, the GWP and/or the slip temperature and/or the flammability of the mixed working medium can be increased, and the heat exchange effect and the environmental protection performance of the unit can be affected when the mixed working medium is used.
Specifically, for the formulation of the heat transfer composition of the present invention: comprises 12 to 16 mass percent of 1,1,1,2,3,3, 3-heptafluoropropane (R227ea), 4 to 36 mass percent of the second component in the invention document and 52 to 84 mass percent of the third component in the invention document. It is evident from comparative example 1 that when the mass percent of first component R227ea is less than 12%, the ternary heat transfer composition obtained has a GWP, relative volumetric refrigeration capacity, energy efficiency, and temperature glide index comparable to the data of the examples of the present invention, but increased flammability due to the reduced level of non-flammable component R227 ea. In comparative example 2, the mass percent ratio of the first component R227ea was greater than 16%, which resulted in a ternary heat transfer composition having a higher GWP and a greater temperature glide. In comparative example 4, it can be clearly analyzed that the synergistic effect of the mass percentages of the components of the present invention, when the mass percentage of the third component is less than 52%, the mass percentage of the second component and the first component cannot simultaneously satisfy the mass percentage range of the formulation of the present invention, and the GWP of the resulting ternary heat transfer composition is slightly larger. Analysis in conjunction with comparative example 3 and comparative example 5 shows that the heat transfer composition resulting from the removal of the second component from the formulation of the present invention has a relatively low volumetric cooling capacity, and the heat transfer composition resulting from the removal of the first component from the formulation of the present invention has a GWP, relative volumetric cooling capacity, energy efficiency, and temperature glide index comparable to those of the examples of the present invention, but which is flammable and presents a safety issue.
Specifically, for the formulation of the heat transfer composition of the present invention: comprises 28-44% of 1,1,1, 2-tetrafluoroethane (R134a) by mass, 4-44% of the second component in the invention document by mass and 28-68% of the third component in the invention document by mass. Comparative example 6 demonstrates that when the mass percent of the first component R134a is less than 28%, the ternary heat transfer composition obtained has a GWP, relative volumetric refrigeration capacity, energy efficiency, and temperature glide index comparable to the data of the examples of the present invention, but increased flammability due to the reduced level of the non-flammable component R134 a. In comparative example 7, the mass percent of the first component R134a was greater than 44%, which resulted in a ternary heat transfer composition having a higher GWP. In comparative example 8, it can be clearly analyzed that the synergistic effect of the mass percentages of the components of the present invention is observed, and when the mass percentage of the third component is less than 24%, the mass percentage of the second component and the first component cannot simultaneously satisfy the mass percentage range of the formulation of the present invention, and the GWP of the resulting ternary heat transfer composition is high. Analysis in conjunction with comparative example 9 and comparative example 10 shows that the heat transfer composition obtained by removing the third component from the formulation of the present invention has a higher GWP, and the heat transfer composition obtained by removing the first component from the formulation of the present invention has a GWP, relative volumetric cooling capacity, energy efficiency, and temperature glide index comparable to those of the examples of the present invention, but is flammable and presents a safety issue.
In conclusion, the heat transfer composition has the environment-friendly characteristics of low GWP and zero ODP, has excellent thermal performance under the same refrigeration working condition, is applied to a centrifugal refrigerating unit system, has the capacity refrigeration capacity and the energy efficiency COP equivalent to those of the centrifugal refrigerating unit system using R134a working medium, has small temperature slippage, and can be used as an environment-friendly refrigerant for replacing R134 a. Meanwhile, the heat transfer composition provided by the invention can be added with additives such as lubricant according to the requirements of the refrigeration system to enhance the performance of the heat transfer composition and the stability of the refrigeration 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 (5)

1. A heat transfer composition suitable for use in a centrifugal chiller unit characterized in that it is composed of three components, a first component being 12% to 16% by mass of 1,1,1,2,3,3, 3-heptafluoropropane (R227ea), a second component being 4% to 36% by mass of trifluoromethyl methyl ether (RE143a), and a third component being 52% to 84% by mass of one of 2,3,3, 3-tetrafluoropropene (R1234yf), 3,3, 3-trifluoropropene (R1243zf), and trans 1,3,3, 3-tetrafluoropropene (R1234ze (E)), wherein said heat transfer composition has a Global Warming Potential (GWP) of no greater than 600.
2. A heat transfer composition suitable for use in a centrifugal chiller as set forth in claim 1 wherein said heat transfer composition is used in place of R134 a.
3. A centrifugal refrigeration unit comprising a compressor (1), a condenser (2) and an evaporator (3) in fluid communication, an expansion device and a heat transfer composition to effect said fluid communication, said heat transfer composition being as claimed in any one of claims 1-2.
4. A centrifugal chiller unit as set forth in claim 3 wherein: the compressor (1) is an oil-free centrifugal compressor, and the evaporator (3) is a shell-and-tube heat exchanger.
5. A method of replacing an existing heat exchange fluid contained in a heat exchange system, comprising: it includes: removing at least a portion of the existing heat exchange fluid from the system, the existing heat exchange fluid being R134a, and replacing at least a portion of the existing heat exchange fluid by introducing into the system a heat transfer composition to form the heat transfer composition of any of claims 1-2, and ensuring a refrigeration capacity of 70% to 110% of the refrigeration capacity of R134a refrigerant.
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