CN111154456A - Environment-friendly mixed refrigerant containing trifluoroiodomethane and preparation method thereof - Google Patents
Environment-friendly mixed refrigerant containing trifluoroiodomethane and preparation method thereof Download PDFInfo
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- CN111154456A CN111154456A CN202010109876.5A CN202010109876A CN111154456A CN 111154456 A CN111154456 A CN 111154456A CN 202010109876 A CN202010109876 A CN 202010109876A CN 111154456 A CN111154456 A CN 111154456A
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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
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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
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- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/11—Ethers
- C09K2205/112—Halogenated ethers
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- C—CHEMISTRY; METALLURGY
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- 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
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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
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/22—All components of a mixture being fluoro compounds
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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
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/40—Replacement mixtures
- C09K2205/43—Type R22
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Abstract
The invention discloses an environment-friendly mixed refrigerant containing trifluoroiodomethane and a preparation method thereof, wherein the mixed refrigerant comprises the following substances in parts by weight: 0.1-37 parts of trifluoroiodomethane, 0.1-87 parts of difluoromethane, 1-26 parts of fluoroethane and 0.1-12 parts of fluoromethyl ether. The refrigerant of the invention has the characteristics of low GWP value, high safety and low toxicity.
Description
Technical Field
The invention relates to a refrigerant, in particular to an environment-friendly mixed refrigerant containing trifluoroiodomethane and a preparation method thereof.
Background
The refrigerant is also called as a refrigeration working medium and is a working medium of a refrigeration cycle, and the heat is transferred by utilizing the phase change of the refrigerant, namely the refrigerant absorbs heat when vaporizing in the evaporator and releases heat when condensing in the condenser. There are over 80 substances currently available as refrigerants, the most common being ammonia, freons, water and a few hydrocarbons. The R22 refrigerant has excellent thermal and transmission performance and may be used widely in air conditioner and other fields. However, R22 is a typical class of CFCs that depletes the ozone layer and has a greenhouse effect, which is limited by the Montreal protocol and the Kyoto protocol, respectively. In developed countries, R22 is used as a refrigerant for up to 2020. For developing countries, R22 is allowed to be used as refrigerant for 2040 years at most. Under such circumstances, research on the replacement work of R22 refrigerant has been conducted in various countries.
Currently, there are two main international technical solutions for replacing R22 refrigerant: one is represented by northern Europe, which claims to adopt natural working medium as a substitute; the other is a mixed working medium which takes HFCs as a substitute and is represented by the United states and Japan. Because the mixed working medium has the characteristic of balancing the physical properties of the refrigerant, the mixed working medium plays an important role in a refrigerant substitution scheme and becomes a research hotspot of domestic and foreign scholars and enterprises.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to solve the technical problem that the GWP of the current refrigerant is too high.
In order to achieve the aim, the invention provides an environment-friendly mixed refrigerant containing trifluoroiodomethane and a preparation method thereof, wherein the mixed refrigerant comprises the following substances in parts by weight: 0.1-37 parts of trifluoroiodomethane, 0.1-85 parts of difluoromethane, 1-25 parts of fluoroethane and 0.1-13 parts of fluoromethyl ether.
As a preferable technical scheme, the environment-friendly mixed refrigerant containing trifluoroiodomethane and the preparation method thereof are characterized in that fluoroethane is selected from one or two of 1, 2-difluoroethane and 1,1,1, 2-tetrafluoroethane.
As a preferable technical scheme, the fluoromethyl ether is 1,1, 1-trifluoromethyl ether.
As a preferred technical scheme, the 27 parts of trifluoroiodomethane, 47 parts of difluoromethane, 10.5 parts of 1,1,1, 2-tetrafluoroethane, 8.5 parts of 1, 2-difluoroethane and 0.5 part of 1,1, 1-trifluoromethyl ether.
The preparation method of the refrigerant is as a preferable technical proposal: the preparation method comprises the following steps of physically mixing 0.1-37 parts of trifluoroiodomethane, 0.1-85 parts of difluoromethane, 1-25 parts of fluoroethane and 0.1-13 parts of fluoromethyl ether at the temperature of 20-35 ℃.
The preparation method of the refrigerant is as a preferable technical proposal: 27 parts of trifluoroiodomethane, 47 parts of difluoromethane, 10.5 parts of 1,1,1, 2-tetrafluoroethane, 8.5 parts of 1, 2-difluoroethane and 7 parts of 1,1, 1-trifluoromethylether are physically mixed at 20-35 ℃.
The invention has the advantages that: according to the invention, trifluoroiodomethane, fluoroethane and fluoromethyl ether are physically mixed according to the mixture ratio of 0.1-37 parts of trifluoroiodomethane, 0.1-85 parts of difluoromethane, 1-25 parts of fluoroethane and 0.1-13 parts of fluoromethyl ether, so that the GWP value of the obtained refrigerant is less than 150, and the refrigerant has the characteristics of high safety and low toxicity. The invention combines trifluoroiodomethane with a small amount of 1,1, 1-trifluoromethyl ether to obtain the refrigerant with GWP value less than 100.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
Global Warming Potential (GWP) is an index for assessing the relative global warming contribution from air emissions of one kilogram of a particular greenhouse gas as compared to one kilogram of carbon dioxide. GWPs for different time ranges can be calculated to show the atmospheric lifetime effect for a given gas. GWP for the 100 year time frame is the value generally referenced. For mixtures, the weighted average may be calculated from the individual GWPs of each component.
Refrigeration capacity (sometimes referred to as cooling capacity) is a term that defines the change in enthalpy of a refrigerant in an evaporator per pound of refrigerant circulated, i.e., the amount of heat removed by the refrigerant in the evaporator over a given period of time. Refrigeration capacity is a measure of the refrigeration capacity of a refrigerant or heat transfer composition. Therefore, the higher the cooling capacity, the greater the cooling effect.
Coefficient of performance (COP) is the ratio of the amount of heat removed to the energy input required to operate the cycle. The higher the COP, the higher the energy efficiency.
COP is directly related to the Energy Efficiency Ratio (EER), which is the efficiency rating of a refrigeration or air conditioning apparatus at a specific set of internal and external temperatures.
The normal temperature in the present invention is in the range of 25-35 ℃.
Example 1:
27 parts of trifluoroiodomethane, 47 parts of difluoromethane, 8.5 parts of 1, 2-difluoroethane, 10.5 parts of 1,1,1, 2-tetrafluoroethane and 0.5 part of 1,1, 1-trifluoromethylether are taken according to parts by weight, and 5 components are physically mixed at normal temperature to obtain the refrigerant.
Example 2:
taking 0.1 part of trifluoroiodomethane, 47 parts of difluoromethane, 8.5 parts of 1, 2-difluoroethane, 10.5 parts of 1,1,1, 2-tetrafluoroethane and 0.5 part of 1,1, 1-trifluoromethyl ether by weight, and physically mixing the 5 components at normal temperature to obtain the refrigerant.
Example 3:
taking 65 parts by weight of trifluoroiodomethane, 47 parts by weight of difluoromethane, 8.5 parts by weight of 1, 2-difluoroethane, 10.5 parts by weight of 1,1,1, 2-tetrafluoroethane and 0.5 part by weight of 1,1, 1-trifluoromethy ether, and physically mixing the 5 components at normal temperature to obtain the refrigerant.
Example 4:
45 parts of trifluoroiodomethane, 47 parts of difluoromethane, 8.5 parts of 1, 2-difluoroethane, 10.5 parts of 1,1,1, 2-tetrafluoroethane and 0.5 part of 1,1, 1-trifluoromethylether are taken according to parts by weight, and 5 components are physically mixed at normal temperature to obtain the refrigerant.
Example 5:
27 parts of trifluoroiodomethane, 1 part of difluoromethane, 8.5 parts of 1, 2-difluoroethane, 10.5 parts of 1,1,1, 2-tetrafluoroethane and 0.5 part of 1,1, 1-trifluoromethyl ether are taken according to parts by weight, and 5 components are physically mixed at normal temperature to obtain the refrigerant.
Example 6:
27 parts of trifluoroiodomethane, 85 parts of difluoromethane, 8.5 parts of 1, 2-difluoroethane, 10.5 parts of 1,1,1, 2-tetrafluoroethane and 0.5 part of 1,1, 1-trifluoromethyl ether are taken according to parts by weight, and 5 components are physically mixed at normal temperature to obtain the refrigerant.
Example 7:
27 parts of trifluoroiodomethane, 47 parts of difluoromethane, 8.5 parts of 1, 2-difluoroethane, 10.5 parts of 1,1,1, 2-tetrafluoroethane and 0.1 part of 1,1, 1-trifluoromethylether are taken according to parts by weight, and 5 components are physically mixed at normal temperature to obtain the refrigerant.
Example 8:
27 parts of trifluoroiodomethane, 47 parts of difluoromethane, 8.5 parts of 1, 2-difluoroethane, 10.5 parts of 1,1,1, 2-tetrafluoroethane and 13 parts of 1,1, 1-trifluoromethylether are taken according to parts by weight, and 5 components are physically mixed at normal temperature to obtain the refrigerant.
Example 9:
27 parts of trifluoroiodomethane, 47 parts of difluoromethane, 8.5 parts of 1, 2-difluoroethane, 10.5 parts of 1,1,1, 2-tetrafluoroethane and 2 parts of 1,1, 1-trifluoromethylether are taken according to parts by weight, and 5 components are physically mixed at normal temperature to obtain the refrigerant.
Example 10:
27 parts of trifluoroiodomethane, 47 parts of difluoromethane, 10 parts of 1, 2-difluoroethane, 10.5 parts of 1,1,1, 2-tetrafluoroethane and 0.5 part of 1,1, 1-trifluoromethyl ether are taken according to parts by weight, and 5 components are physically mixed at normal temperature to obtain the refrigerant.
Example 11:
27 parts of trifluoroiodomethane, 47 parts of difluoromethane, 8.5 parts of 1, 2-difluoroethane, 6.5 parts of 1,1,1, 2-tetrafluoroethane and 0.5 part of 1,1, 1-trifluoromethylether are taken according to parts by weight, and 5 components are physically mixed at normal temperature to obtain the refrigerant.
Example 12:
27 parts of trifluoroiodomethane, 47 parts of difluoromethane, 10 parts of 1, 2-difluoroethane, 10.5 parts of 1,1,1, 2-tetrafluoroethane and 0.5 part of 1,1, 1-trifluoromethyl ether are taken according to parts by weight, and 5 components are physically mixed at normal temperature to obtain the refrigerant.
Example 13:
27 parts of trifluoroiodomethane, 47 parts of difluoromethane, 19 parts of 1,1,1, 2-tetrafluoroethane and 0.5 part of 1,1, 1-trifluoromethylether are taken according to parts by weight, and 4 components are physically mixed at normal temperature to obtain the refrigerant.
Example 14:
27 parts of trifluoroiodomethane, 47 parts of difluoromethane, 1 part of 1, 2-difluoroethane and 7 parts of 1,1, 1-trifluoromethylether are taken according to parts by weight, and 4 components are physically mixed at normal temperature to obtain the refrigerant.
Example 15:
27 parts of trifluoroiodomethane, 47 parts of difluoromethane, 25 parts of 1, 2-difluoroethane and 7 parts of 1,1, 1-trifluoromethylether are taken according to parts by weight, and 4 components are physically mixed at normal temperature to obtain the refrigerant.
Example 16:
27 parts of trifluoroiodomethane, 47 parts of difluoromethane, 8.5 parts of 1, 2-difluoroethane, 10.5 parts of 1,1,1, 2-tetrafluoroethane and 0.5 part of 1-fluoromethyl ether are taken according to parts by weight, and 5 components are physically mixed at normal temperature to obtain the refrigerant.
Example 17:
27 parts of trifluoroiodomethane, 47 parts of difluoromethane, 8.5 parts of 1, 2-difluoroethane, 10.5 parts of 1,1,1, 2-tetrafluoroethane, 0.5 part of 1,1, 1-trifluoromethyl ether and 0.5 part of 1-fluoromethyl ether are taken according to parts by weight, and 6 components are physically mixed at normal temperature to obtain the refrigerant.
Example 18:
27 parts of trifluoroiodomethane, 47 parts of difluoromethane, 8.5 parts of 1, 2-difluoroethane, 10.5 parts of 1,1,1, 2-tetrafluoroethane and 7 parts of 1-fluoromethyl ether are taken according to parts by weight, and 5 components are physically mixed at normal temperature to obtain the refrigerant.
Comparative example 1
47 parts by weight of difluoromethane, 8.5 parts by weight of 1, 2-difluoroethane, 10.5 parts by weight of 1,1,1, 2-tetrafluoroethane and 0.5 part by weight of 1,1, 1-trifluoromethylether are taken, and 4 components are physically mixed at normal temperature to obtain the refrigerant.
Comparative example 2
27 parts of trifluoroiodomethane, 47 parts of difluoromethane, 8.5 parts of 1, 2-difluoroethane and 10.5 parts of 1,1,1, 2-tetrafluoroethane are taken according to parts by weight, and 4 components are physically mixed at normal temperature to obtain the refrigerant.
Comparative example 3
27 parts of trifluoromethane, 47 parts of difluoromethane, 8.5 parts of 1, 2-difluoroethane, 10.5 parts of 1,1,1, 2-tetrafluoroethane and 0.5 part of 1,1, 1-trifluoromethyl ether are taken according to parts by weight, and 5 components are physically mixed at normal temperature to obtain the refrigerant.
Comparative example 4
27 parts of trifluoroiodomethane, 47 parts of difluoromethane, 8.5 parts of 1, 2-difluoroethane, 10.5 parts of 1,1,1, 2-tetrafluoroethane and 0.5 part of methyl ether are taken according to parts by weight, and 5 components are physically mixed at normal temperature to obtain the refrigerant.
The trifluoroiodomethane used in the above examples has the formula CF3I, the molar mass is 195.91g/mol, the boiling point is-21.85 ℃, the critical temperature is 123.29 ℃, and the critical pressure is 3.953 MPa;
the design working conditions of the refrigerating machine are that the evaporation temperature is 7.2 ℃, the condensation temperature is 54.4 ℃, the supercooling degree is 8.3 ℃, the superheat degree is 11.1 ℃ and the isentropic efficiency of the compressor is 0.75, and according to the cycle performance, the performance comparison of the embodiment and the existing refrigerant is shown in the following table, wherein the relative refrigerating capacity and the relative COP are the comparison quantity based on R22. From the GWP and relative burn value of the mixed refrigerant produced in example 1, comparative example 4 in the following table, it can be seen that both the GWP and the relative burn value are low when trifluoroiodomethane and trifluoromethylether are added simultaneously to the mixed refrigerant. Meanwhile, as can be seen from the following examples, the mixed refrigerant prepared by the present invention has the characteristic of lower toxicity compared to the R22 refrigerant.
Example Performance calculations and comparison with existing refrigerant Performance
The mixed refrigerant containing trifluoroiodomethane provided by the invention has good environmental protection characteristics, and the following table shows 4 examples and 1 comparative example, wherein the ozone depletion value ODP, the OEL value and the global warming potential GWP of the examples 1 to 4 are compared with the existing refrigerant, and it can be seen that the mixed refrigerant provided by the invention not only has ODP of 0, but also has OEL value of more than 1500 and GWP value of less than 150.
R407C*And R410A*The data of (2) is referred to "handbook of refrigerant usage, Caodesheng, Stanline, Beijing, publication of metallurgy industry, 2003. "
The data of the existing refrigerant refers to' the refrigerant operating manual, compiled by Cao De Sheng and Schlin, Beijing, the publisher of the metallurgical industry, 2003. "
Calculated according to the pure component ODP value and weighted according to the mass concentration.
The flammability radical ASHRAE standard 34-2013 of the present invention requires, at the same time, the present invention sets the flammability level of R22 to 1 and the flammability level of other substances to be relative to R22, more than 1 being more flammable and less than 1 being less flammable.
The present invention occupational contact limit OEL data were determined as required by the ASHRAE34-2013 standard, while the listed control data refer to the RCL data and safety groups of the ASHRAE34-2013 standard non-blended and co-blended mixed refrigerants.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It should be understood by those skilled in the art that the above embodiments do not limit the present invention in any way, and all technical solutions obtained by using equivalent alternatives or equivalent variations fall within the scope of the present invention.
Claims (4)
1. The environment-friendly mixed refrigerant containing trifluoroiodomethane and the preparation method thereof are characterized in that the mixed refrigerant consists of the following substances in parts by weight: 0.1-37 parts of trifluoroiodomethane, 0.1-85 parts of difluoromethane, 1-25 parts of fluoroethane and 0.1-13 parts of fluoromethyl ether.
2. The environmentally friendly mixed refrigerant containing trifluoroiodomethane and the preparation method thereof according to claim 1, wherein the fluoroethane is one or two selected from 1, 2-difluoroethane and 1,1,1, 2-tetrafluoroethane.
3. The environment-friendly mixed refrigerant containing trifluoroiodomethane and the preparation method thereof according to claim 1, wherein the fluoromethyl ether is 1,1, 1-trifluoromethyl ether.
4. The environment-friendly mixed refrigerant containing trifluoroiodomethane and the preparation method thereof according to claim 1, wherein the preparation method of the refrigerant comprises the following steps: the preparation method comprises the following steps of physically mixing 0.1-37 parts of trifluoroiodomethane, 0.1-85 parts of difluoromethane, 1-25 parts of fluoroethane and 0.1-13 parts of fluoromethyl ether at the temperature of 20-35 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113563847A (en) * | 2021-07-27 | 2021-10-29 | 珠海格力电器股份有限公司 | Quaternary environment-friendly mixed refrigerant, preparation method thereof and refrigeration system |
| CN114702938A (en) * | 2022-04-19 | 2022-07-05 | 珠海格力电器股份有限公司 | Mixed refrigerant and air conditioning system |
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| CN110257014A (en) * | 2019-07-19 | 2019-09-20 | 珠海格力电器股份有限公司 | Mixed refrigeration working medium |
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| CN1076957A (en) * | 1992-02-03 | 1993-10-06 | 联合信号股份有限公司 | New refrigerant composition |
| CN1122606A (en) * | 1993-03-05 | 1996-05-15 | 宜康有限公司 | Fluoroiodocarbon blends as CFC and halon replacements |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113563847A (en) * | 2021-07-27 | 2021-10-29 | 珠海格力电器股份有限公司 | Quaternary environment-friendly mixed refrigerant, preparation method thereof and refrigeration system |
| CN114702938A (en) * | 2022-04-19 | 2022-07-05 | 珠海格力电器股份有限公司 | Mixed refrigerant and air conditioning system |
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