CN116814219A - Mixed refrigerant and preparation method thereof - Google Patents
Mixed refrigerant and preparation method thereof Download PDFInfo
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- CN116814219A CN116814219A CN202310684616.4A CN202310684616A CN116814219A CN 116814219 A CN116814219 A CN 116814219A CN 202310684616 A CN202310684616 A CN 202310684616A CN 116814219 A CN116814219 A CN 116814219A
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- 239000003507 refrigerant Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title abstract description 8
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 claims abstract description 42
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 10
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000007791 liquid phase Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005057 refrigeration Methods 0.000 abstract description 17
- 230000000704 physical effect Effects 0.000 abstract description 8
- 239000010687 lubricating oil Substances 0.000 abstract description 5
- 231100000053 low toxicity Toxicity 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 9
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- PGJHURKAWUJHLJ-UHFFFAOYSA-N 1,1,2,3-tetrafluoroprop-1-ene Chemical compound FCC(F)=C(F)F PGJHURKAWUJHLJ-UHFFFAOYSA-N 0.000 description 1
- KLHDWYHSMVRQHG-UHFFFAOYSA-N 1,1-difluoroethane difluoromethane Chemical compound FC(C)F.FCF KLHDWYHSMVRQHG-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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Abstract
The invention discloses a mixed refrigerant and a preparation method thereof, wherein the mixed refrigerant comprises the following components in percentage by mass: 40-60%; difluoromethane: 10-35%; difluoroethane: 5-25%; 5-20% of 2, 3-tetrafluoropropene. Compared with the existing refrigerant, the mixed refrigerant provided by the invention has similar physical properties (for example, the physical properties are relatively similar to those of the refrigerant R404A), so that in the replacement process, lubricating oil is not required to be replaced, a refrigeration system is not required to be changed greatly, and in addition, the mixed refrigerant provided by the invention has the advantages of low toxicity, easily obtained raw materials, low cost and the like.
Description
Technical Field
The invention belongs to the technical field of refrigeration, and particularly relates to a mixed refrigerant and a preparation method thereof.
Background
The current focus of attention in the application market of refrigerants is changed from eliminating Ozone Depletion Substances (ODS) to pushing substitution of high-temperature-effect potential (GWP) products, and the demands of low-GWP substitution refrigerants in different application fields such as air conditioners, commercial refrigeration, heat pumps and the like are becoming more vigorous and urgent.
Taking the refrigerant R404A as an example, the refrigerant R404A is a medium-low temperature refrigerant widely used at present, and has no damage to an ozone layer, so that the refrigerant R404A has long been used as a long-term substitute for the refrigerant R502 and is often applied to refrigeration equipment such as refrigerators, food freezing equipment, marine refrigeration equipment, industrial low-temperature refrigeration, commercial low-temperature refrigeration, transportation refrigeration equipment (refrigerated vehicles and the like), refrigeration condensing units, supermarket showcases and the like.
However, the GWP value of the refrigerant R404A is as high as 3922, and with further enhancement of the refrigerant management and control with high GWP value at home and abroad, HFCs refrigerant such as R404A faces reduction and elimination, so it is necessary to find a refrigerant with good environmental protection performance (low GWP value), and the refrigeration performance is equivalent to or even better than that of R404A, so as to maximally meet the requirements of environmental protection and high efficiency of the refrigerant.
The related literature discloses a composition containing a polyfluoroolefin and HFC-32 as a substitute for R404A, which, while effectively reducing GWP values and possessing good performance, contains about 40 mass percent of Hydrofluoroolefins (HFOs) and a flame retardant component R125 < 20%, which results in relatively expensive overall costs and lower safety levels. Still other related documents disclose a composition comprising from about 17% to about 40% by weight HFC-32; about 51 to about 83 weight percent tetrafluoropropene; about 0 wt% to about 9wt% CO 2 As a substitute for R404A, with CO 2 The duty ratio is increased, the refrigerating capacity is improved, but the discharge pressure is increased and higher than R404A, and a certain modification is needed to the refrigerating system.
Disclosure of Invention
Therefore, the invention provides a mixed refrigerant and a preparation method thereof, and aims to solve the technical problems of low GWP, low cost and environment friendliness and high efficiency of the mixed refrigerant provided under the condition of not changing the existing refrigeration system.
In order to achieve the above object, the present invention also provides a mixed refrigerant comprising, in mass percent:
pentafluoroethane: 40-60%;
difluoromethane: 10-35%;
difluoroethane: 5-25%;
5-20% of 2, 3-tetrafluoropropene.
Preferably, in the mixed refrigerant, the pentafluoroethane accounts for 40-50% by mass.
Preferably, in the mixed refrigerant, the pentafluoroethane accounts for 50% by mass.
Preferably, in the mixed refrigerant, the difluoromethane accounts for 20-30% by mass.
Preferably, in the mixed refrigerant, the difluoromethane accounts for 25% by mass.
Preferably, in the mixed refrigerant, the difluoroethane accounts for 10-20% by mass.
Preferably, in the mixed refrigerant, the difluoroethane accounts for 10-15% by mass.
Preferably, in the mixed refrigerant, the 2, 3-tetrafluoropropene accounts for 5-15% by mass.
Preferably, in the mixed refrigerant, the 2, 3-tetrafluoropropene accounts for 10-15% by mass.
In order to achieve the above object, the present invention also provides a method for preparing a mixed refrigerant, the method comprising the steps of:
taking pentafluoroethane, difluoromethane, difluoroethane and 2, 3-tetrafluoropropene for physical mixing in a liquid phase state, wherein the mass percentages of the pentafluoroethane, the difluoromethane, the difluoroethane and the 2, 3-tetrafluoropropene are as follows: 40-60%, 10-35%, 5-25% and 5-20%.
The invention has the following beneficial effects:
compared with the existing refrigerant, the mixed refrigerant provided by the invention has similar physical properties (for example, the physical properties are relatively similar to those of the refrigerant R404A), so that in the replacement process, lubricating oil does not need to be replaced, a refrigeration system does not need to be greatly changed, and in addition, the mixed refrigerant provided by the invention has the advantages of low toxicity, easily obtained raw materials, low cost and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph of vapor pressure versus temperature for an example of the mixed refrigerant of the present invention and comparative example 1.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
In the embodiment of the invention, the term "and/or" describes the association relation of the association objects, which means that three relations can exist, for example, a and/or B can be expressed as follows: a exists alone, A and B exist together, and B exists alone. The character "/" generally indicates that the context-dependent object is an "or" relationship.
It should be noted that the terms "first," "second," and the like in the description and the claims of the present invention and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order.
The term "plurality" in embodiments of the present invention means two or more, and other adjectives are similar.
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the embodiments of the present invention will be described in detail below with reference to the accompanying drawings. However, it will be understood by those of ordinary skill in the art that in various embodiments of the present invention, numerous specific details are set forth in order to provide a thorough understanding of the present invention. However, the claimed technical solution of the present invention can be realized without these technical details and various changes and modifications based on the following embodiments. The following embodiments are divided for convenience of description, and should not be construed as limiting the specific implementation of the present invention, and the embodiments can be mutually combined and referred to without contradiction.
The invention provides a mixed refrigerant, which comprises the following components in percentage by mass: 40-60%; difluoromethane: 10-35%; difluoroethane: 5-25%; 5-20% of 2, 3-tetrafluoropropene.
Wherein the pentafluoroethane accounts for 40-50% by mass. In other embodiments, the pentafluoroethane may also be 45%, 50%, or 55% by mass.
Wherein the mass percentage of difluoromethane is 20-30%. In other embodiments, difluoromethane may also be 15%, 20%, 25%, or 30% by mass.
Wherein the difluoroethane accounts for 10-20% by mass. In other embodiments, the difluoroethane may also comprise 8%, 10%, 12%, 15%, or 22% by mass.
Wherein the 2, 3-tetrafluoropropene accounts for 5-15% by mass. In other embodiments, the 2, 3-tetrafluoropropene may also comprise 7%, 9%, 10%, 11%, 13%, 15%, or 17% by mass.
Compared with the existing refrigerant, the mixed refrigerant provided by the invention has similar physical properties (for example, the physical properties are relatively similar to those of the refrigerant R404A), so that in the replacement process, lubricating oil does not need to be replaced, a refrigeration system does not need to be greatly changed, and in addition, the mixed refrigerant provided by the invention has the advantages of low toxicity, easily obtained raw materials, low cost and the like.
The mixed refrigerant provided by the present invention is analyzed in detail below, and table 1 illustrates basic parameters of each component of the mixed refrigerant provided by the present invention.
Table 1 basic parameters of the components of the Mixed refrigerant provided by the present invention
| Pentafluoroethane (PEA) | Difluoromethane | Difluoroethane | 2, 3-tetrafluoropropene | |
| Molecular weight | 120 | 52 | 66 | 114 |
| Boiling point/. Degree.C | -48.45 | -51.6 | -25.0 | -29.5℃ |
| Critical pressure/MPa | 3.62 | 5.78 | 4.52 | 3.82 |
| Critical temperature/°c | 66.02 | 78.10 | 113.26 | 97.4 |
| Latent heat of vaporization/kj/kg | 110.39 | 270.91 | 279.36 | 145.37 |
| Security level | A1 | A2L | A2 | A2L |
| ODP | 0 | 0 | 0 | 0 |
| GWP | 3170 | 677 | 138 | 1 |
The basic parameters of the mixed refrigerant provided by the invention are described below by combining examples and comparative examples, wherein pentafluoroethane is represented by R125, difluoromethane is represented by R32, and difluoroethane is represented by R152a;2, 3-tetrafluoropropene is represented by R1234 yf.
Example 1
R125, R32, R152a and R1234yf which are commonly used in the field of refrigerants and have the purity of more than 99.99 weight percent are taken, and in a liquid phase state, 60 percent of R125, 20 percent of R32, 10 percent of R152a and 10 percent of R1234yf are sequentially added into a pressure-resistant container according to the boiling point from high to low, and are fully and physically mixed.
Example 2
R125, R32, R152a and R1234yf which are commonly used in the field of refrigerants and have the purity of more than 99.99 weight percent are taken, and the R125, the R32, the R152a and the R1234yf which are 60 percent by mass percent and 20 percent by mass percent are fully and physically mixed in a liquid phase state.
Example 3
R125, R32, R152a and R1234yf which are commonly used in the field of refrigerants and have the purity of more than 99.99 weight percent are taken, and the R125, the R32, the R152a and the R1234yf which are 50 percent, 20 percent and 10 percent of the weight percentages are fully and physically mixed in a liquid phase state.
Example 4
R125, R32, R152a and R1234yf which are commonly used in the field of refrigerants and have the purity of more than 99.99 weight percent are taken, and the R125, the R32, the R152a and the R1234yf which are 50 percent, 30 percent and 10 percent of the weight percentages are fully and physically mixed in a liquid phase state.
Example 5
R125, R32, R152a and R1234yf which are commonly used in the field of refrigerants and have the purity of more than 99.99 weight percent are taken, and the R125, the R32, the R152a and the R1234yf which are 40 percent, 30 percent and 15 percent of the weight percentages are fully and physically mixed in a liquid phase state.
Example 6
R125, R32, R152a and R1234yf which are commonly used in the field of refrigerants and have the purity of more than 99.99 weight percent are taken, and the R125, the R32, the R152a and the R1234yf which are 40 percent, 35 percent and 15 percent of the mass percent are fully and physically mixed in a liquid phase state.
Example 7
R125, R32, R152a and R1234yf which are commonly used in the field of refrigerants and have the purity of more than 99.99 weight percent are taken, and the R125, the R32, the R152a and the R1234yf which are 50 percent by mass percent are fully and physically mixed in a liquid phase state.
Example 8
R125, R32, R152a and R1234yf which are commonly used in the field of refrigerants and have the purity of more than 99.99 weight percent are taken, and the R125, the R32, the R152a and the R1234yf which are 60 percent by mass percent and 10 percent by mass percent are fully and physically mixed in a liquid phase state.
Comparative example 1
Refrigerant R404A.
Table 2 basic parameters of examples and comparative example 1
| Molecular weight | Boiling point/. Degree.C | Critical pressure/MPa | Critical temperature/°c | GWP | |
| Comparative example 1 | 97.60 | -46.22 | 3.73 | 72.10 | 3922 |
| Example 1 | 89.01 | -47.30 | 4.35 | 80.50 | 2051 |
| Example 2 | 91.61 | -47.69 | 4.33 | 76.17 | 2045 |
| Example 3 | 83.92 | -45.47 | 4.54 | 83.65 | 1748 |
| Example 4 | 86.90 | -48.10 | 4.66 | 78.70 | 1802 |
| Example 5 | 78.83 | -46.64 | 4.71 | 82.92 | 1482 |
| Example 6 | 77.58 | -47.85 | 4.77 | 80.53 | 1519 |
| Example 7 | 90.32 | -44.57 | 4.33 | 83.27 | 1707 |
| Example 8 | 89.73 | -43.90 | 4.34 | 83.61 | 2004 |
Table 3 theoretical cycle calculation parameters for examples and comparative examples
Table 4 comparison of experimental data for example 2 and comparative example 1
Table 5 comparison of experimental data for example 3 and comparative example 1
As can be seen from table 3, at the set operating conditions: the mixed refrigerant provided in examples 1 to 8 of the present invention has excellent refrigerating performance at the evaporation temperature of-40 c, the condensation temperature of 40 c and the superheat degree of the evaporator of 5 c, and has a lower sliding temperature than the refrigerant R404A provided in comparative example 1, so that the heat exchanger in the refrigerating system is not required to be changed in the process of replacing the refrigerant (e.g., the refrigerant R404A) in the prior art.
Further, it is seen from the data in Table 3 that the refrigerating capacity of the present invention is larger than R404A, and the refrigerating capacity per unit volume is 85% -101% of R404A. COP (coefficient of performance) data results are very similar to R404A, the safety level is A1 or A2L, and the above results are combined to show that the invention meets the basic condition of replacing R404A.
Table 4 is experimental data tested under the same conditions using a cryocooler with an R404A refrigeration system, the experimental conditions being: ambient temperature: 11 ℃; compressor model: danfoss SC10CL with a discharge capacity of 7.27cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Refrigerant charge: 192 g; spatial volume: 270L. As can be seen from the results in Table 4 and Table 5, the invention can normally operate in the R404A refrigeration system, and can achieve the refrigeration effect close to R404A, the power consumption of the 24-hour experimental equipment of the refrigerator of the embodiment 3 is 3.42/KW.h, which is lower than that of R404A. Namely, under the condition that the refrigerating system is not changed and lubricating oil is not replaced, the volume refrigerating capacity of the refrigerating system is 0.88 relative to R404A, and the relative COP is 0.94, which is relatively close to theoretical calculation data. As can be seen in conjunction with fig. 1, the vapor pressures of the mixed refrigerants provided by the present invention (especially examples 2 and 5) and R404A are quite similar, thus facilitating direct replacement without requiring modification of existing refrigeration systems.
In order to achieve the above object, the present invention also provides a method for preparing a mixed refrigerant, comprising the steps of:
taking pentafluoroethane, difluoromethane, difluoroethane and 2, 3-tetrafluoropropene for physical mixing in a liquid phase state, wherein the mass percentages of the pentafluoroethane, the difluoromethane, the difluoroethane and the 2, 3-tetrafluoropropene are as follows: 40-60%, 10-35%, 5-25% and 5-20%.
The embodiment of the preparation method of the mixed refrigerant comprises the embodiment of the mixed refrigerant, and the beneficial effects of the mixed refrigerant can be equally applicable to the preparation method of the mixed refrigerant.
Wherein the pentafluoroethane accounts for 40-50% by mass. In other embodiments, the pentafluoroethane may also be 45%, 50%, or 55% by mass.
Wherein the mass percentage of difluoromethane is 20-30%. In other embodiments, difluoromethane may also be 15%, 20%, 25%, or 30% by mass.
Wherein the difluoroethane accounts for 10-20% by mass. In other embodiments, the difluoroethane may also comprise 8%, 10%, 12%, 15%, or 22% by mass.
Wherein the 2, 3-tetrafluoropropene accounts for 5-15% by mass. In other embodiments, the 2, 3-tetrafluoropropene may also comprise 7%, 9%, 10%, 11%, 13%, 15%, or 17% by mass.
The mixed refrigerant prepared by the preparation method provided by the invention has a lower GWP value (lower than 2051), 40-60% lower than that of the refrigerant R404A, and has similar physical properties (for example, the physical properties are similar to those of the refrigerant R404A) compared with the existing refrigerant, so that lubricating oil does not need to be replaced in the replacement process, a refrigerating system does not need to be greatly changed, and in addition, the mixed refrigerant provided by the invention has the advantages of low toxicity, easily obtained raw materials, low cost and the like.
It will be apparent that the embodiments described above are merely some, but not all, embodiments of the invention. Based on the embodiments of the present invention, those skilled in the art may make other different changes or modifications without making any creative effort, which shall fall within the protection scope of the present invention.
Claims (10)
1. A mixed refrigerant, characterized in that the components of the mixed refrigerant in mass percent comprise:
pentafluoroethane: 40-60%;
difluoromethane: 10-35%;
difluoroethane: 5-25%;
5-20% of 2, 3-tetrafluoropropene.
2. The mixed refrigerant according to claim 1, wherein the pentafluoroethane accounts for 40 to 50% by mass.
3. The mixed refrigerant according to claim 2, wherein the pentafluoroethane is present in an amount of 50% by mass.
4. The mixed refrigerant according to claim 1, wherein the difluoromethane is 20 to 30% by mass.
5. The mixed refrigerant as set forth in claim 4, wherein said difluoromethane is present in an amount of 25% by mass.
6. The mixed refrigerant according to claim 1, wherein the difluoroethane is present in an amount of 10 to 20% by mass.
7. The mixed refrigerant according to claim 6, wherein the difluoroethane is present in an amount of 10 to 15% by mass.
8. The mixed refrigerant as set forth in claim 1, wherein said 2, 3-tetrafluoropropene is present in an amount of 5 to 15% by mass.
9. The mixed refrigerant according to claim 8, wherein the 2, 3-tetrafluoropropene is present in an amount of 10 to 15% by mass.
10. A method for preparing a mixed refrigerant, comprising the steps of:
taking pentafluoroethane, difluoromethane, difluoroethane and 2, 3-tetrafluoropropene for physical mixing in a liquid phase state, wherein the mass percentages of the pentafluoroethane, the difluoromethane, the difluoroethane and the 2, 3-tetrafluoropropene are as follows: 40-60%, 10-35%, 5-25% and 5-20%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310684616.4A CN116814219A (en) | 2023-06-12 | 2023-06-12 | Mixed refrigerant and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310684616.4A CN116814219A (en) | 2023-06-12 | 2023-06-12 | Mixed refrigerant and preparation method thereof |
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| Publication Number | Publication Date |
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| CN116814219A true CN116814219A (en) | 2023-09-29 |
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| CN202310684616.4A Pending CN116814219A (en) | 2023-06-12 | 2023-06-12 | Mixed refrigerant and preparation method thereof |
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