CN102676122A - Environment-friendly refrigerant and preparation method thereof - Google Patents
Environment-friendly refrigerant and preparation method thereof Download PDFInfo
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- CN102676122A CN102676122A CN201210169724XA CN201210169724A CN102676122A CN 102676122 A CN102676122 A CN 102676122A CN 201210169724X A CN201210169724X A CN 201210169724XA CN 201210169724 A CN201210169724 A CN 201210169724A CN 102676122 A CN102676122 A CN 102676122A
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Abstract
The invention discloses an environment-friendly refrigerant and a preparation method thereof, wherein the refrigerant is prepared from the following components in percentage by weight: 40%-90% of difluoromethane, 5%-40% of 1, 1-difluoroethane and 5%-50% of 1, 1, 2, 2- tetrafluoroethane. The specific volume of saturated liquid of the environment-friendly refrigerant prepared by the method of the invention is larger, and the charge of the refrigerant in a refrigerating system can be greatly reduced, i.e. the GWP (global warming potential) of the refrigerant is reduced, and at the same time, the burning possibility of combustibles after the refrigerant leaks is reduced; the refrigerating capacity per unit volume is larger, the size of a compressor can be reduced, and the cost of a refrigerating system is reduced; and the refrigerant has a good environmental performance, ODP (ozone depression potential) is 0, GWP is greatly reduced relative to HCFC-22 and R-410A.
Description
Technical field
The present invention relates to refrigeration agent, relate in particular to refrigeration agent of a kind of environment-friendly type and preparation method thereof.
Background technology
Because HCFC-22 (difluorochloromethane) has certain ODP (ODP) and higher GWP (global warming potential); Belong to and be asked to the material that time limit is eliminated, and existing main surrogate R-407C (1,1; 1; The mixture of 2-Tetrafluoroethane, pentafluoride ethane and methylene fluoride), R-410A (mixture of methylene fluoride and pentafluoride ethane) waits itself just has certain defective, aspect refrigeration performance, can not meet the demands, and environmental performance is also undesirable; GWP is higher relatively, even is higher than HCFC-22.
HFC-32 (methylene fluoride) has good thermal performance, and ODP is 0, and GWP is 716, and environmental performance is excellent, though have certain combustibility, combustibility is not strong, belongs to A2L class refrigeration agent; The saturated aq specific volume of HFC-32 is bigger, can reduce the filling quantity of refrigerant of system; Simultaneously the refrigerating effect per unit swept volume of HFC-32 is bigger, and volume that can the compresses machine reduces the cost of refrigeration system; But the exhaust temperature of HFC-32 is higher, and WP is also higher.
HFC-152a (1, the 1-C2H4F2 C2H4F2) has good thermal performance, and ODP is 0, and GWP is merely 133, and environmental performance is excellent, but has certain combustibility.Under identical air conditioning condition, the coefficient of refrigerating performance of HFC-152a is superior to HFC-134a, can reduce energy consumption; Simultaneously, HFC-152a has bigger saturated aq specific volume, can reduce the filling quantity of refrigerant of system.
HFC-134 (1,1,2, the 2-Tetrafluoroethane) is the isomers of HFC-134a, and thermodynamic properties is similar with HFC-134a, and ODP is 0, and GWP is 1110, is lower than HFC-134a, and is not flammable; Under identical air conditioning condition, the coefficient of refrigerating performance of HFC-134 is superior to HCFC-22 and R-410A.
Though HFC-32; Three kinds of refrigeration agents of HFC-152a and HFC-134 all have deficiency separately when using separately; If but with HFC-32, HFC-152a and HFC-134 mix and use, form a kind of refrigeration agent of novel environment-friendly type; Can combine three's advantage separately, at utmost reduce unfavorable factor.
In the prior art, Chinese patent file CN1412266A (02124112.0) has announced a kind of methylene fluoride (HFC-32), 1,1,1,2-Tetrafluoroethane (HFC-134a) and 1,1, the mixture that 1-HFC-143a (HFC-143a) is formed; Chinese patent file CN 1200067C (03148532.4) has announced a kind of methylene fluoride (HFC-32), pentafluoride ethane (HFC-125), 1,1,1; 2-Tetrafluoroethane (HFC-134a) and/or 1; 1,2, the mixture that 2-Tetrafluoroethane (HFC-134), propylene (R1270) are formed; Chinese patent CN1244663C (200310118983.0) has announced a kind of methylene fluoride (HFC-32), pentafluoride ethane (HFC-125) and 1, the mixture that 1-C2H4F2 C2H4F2 (HFC-152a) is formed; It is a kind of 1 that Chinese patent file CN 100400615C (200410077955.3) discloses, 1-C2H4F2 C2H4F2 (HFC-152a) and 1,1,1,3,3, the mixture that 3-HFC-236fa (HFC-236fa) is formed; Chinese patent file CN101006154A (200580028315.6) has announced that a kind of binary or tertiary mixture (are selected from 1; 1; 1,2-Tetrafluoroethane (HFC-134a), pentafluoride ethane (HFC-125), 1,1; 1-HFC-143a (HFC-143a), 1,1-C2H4F2 C2H4F2 (HFC-152a), dme (DME), Trimethylmethane (HC-600a)); Chinese patent file CN 100489051C (200710114770.9) has announced the mixture that a kind of methylene fluoride (HFC-32), pentafluoride ethane (HFC-125) and Trimethylmethane (HC-600a) are formed; Chinese patent file CN100500793C (200810014733.5) has announced a kind of pentafluoride ethane (HFC-125), 1,1,1, the mixture that 2-Tetrafluoroethane (HFC-134a) and dme (DME) are formed; Chinese patent file CN100485010C (200610016352.1) has announced a kind of methylene fluoride (HFC-32), dme (DME) and 1,1,1, the mixture that 2-Tetrafluoroethane (HFC-134a) is formed; Chinese patent CN101381595B (200810231909.2) has announced a kind of dme (DME), propylene (R1270) and 1,1,1,2,3,3, the mixture that 3-HFC-227 (HFC-227ea) is formed; Chinese patent file CN101649188A (200910023799.5) has announced the mixture that a kind of dme (DME), propylene (R1270) and CF3I (R13I1) are formed; Chinese patent file CN 102079964A (200910225801.7) has announced a kind of methylene fluoride (HFC-32) and 1,1,1, the mixture that 2-Tetrafluoroethane (HFC-134a) is formed; Chinese patent file CN102079966A (200910225803.6) has announced a kind of methylene fluoride (HFC-32), 1,1-C2H4F2 C2H4F2 (HFC-152a) and 1,1,1, the mixture that 2-Tetrafluoroethane (HFC-134a) is formed; Chinese patent file CN 102079967A (200910225804.0) has announced a kind of methylene fluoride (HFC-32), pentafluoride ethane (HFC-125) and 1,1,1, the mixture that 2-Tetrafluoroethane (HFC-134a) is formed.
Disclosed refrigerant composition earl august eugene lund ian robert exists or the GWP value is higher or not directly charge and be applied to shortcomings such as HFC-134a system or combustibility are bigger in the above-mentioned patent; Therefore; Need exploitation have better refrigeration performance, with better compatible and the new refrigerant of existing system with better environmental-protecting performance.
Summary of the invention
The invention provides the refrigeration agent of the environment-friendly type of a kind of low GWP (global warming potential), this refrigeration agent does not only destroy atmospheric ozone layer, and the Greenhouse effect that produce are littler, have thermal parameter and the thermal property suitable with HCFC-22 simultaneously.
A kind of refrigeration agent of environment-friendly type, by methylene fluoride, 1,1-C2H4F2 C2H4F2 and 1,1,2, the 2-Tetrafluoroethane is formed, and each constituent mass per-cent is: methylene fluoride 40 ~ 90%, 1,1-C2H4F2 C2H4F2 5 ~ 40% and 1,1,2,2-Tetrafluoroethane 5 ~ 50%.
Described methylene fluoride, i.e. HFC-32, molecular formula is CH
2F
2, relative molecular weight is 52.02, and normal boiling point is-51.7 ℃, and critical temperature is 78.1 ℃, and emergent pressure is 5.78MPa.
HFC-32 has good thermal performance, and ODP is 0, and GWP is 716, and environmental performance is excellent, though have certain combustibility, combustibility is not strong, belongs to A2L class refrigeration agent.
The saturated aq specific volume of HFC-32 is bigger, can reduce the filling quantity of refrigerant of system to a great extent, thereby reaches the purpose of indirect reduction novel refrigerant GWP.
The refrigerating effect per unit swept volume of HFC-32 is bigger, and volume that can the compresses machine reduces the cost of refrigeration system; But the exhaust temperature of HFC-32 is higher, and WP is also higher, therefore, needs as required an amount of the interpolation.
Described 1, the 1-C2H4F2 C2H4F2, i.e. HFC-152a, molecular formula is CH
3CHF
2, relative molecular weight is 66.05, and normal boiling point is-24.0 ℃, and critical temperature is 113.3 ℃, and emergent pressure is 4.52MPa.
HFC-152a has good thermal performance, and under identical air conditioning condition, the coefficient of refrigerating performance of HFC-152a is superior to HFC-134a, can reduce energy consumption.
The ODP of HFC-152a is 0, and GWP is merely 133, have excellent environment friendly, and the saturated aq specific volume of HFC-152a is bigger, can reduce the filling quantity of refrigerant of system, thereby reaches the purpose that reduces refrigeration agent GWP.
Because HFC-152a has certain combustibility; Component as refrigeration agent; Consider its security; Therefore the consumption of HFC-152a can not be too much, can guarantee under prerequisite safe in utilization, brings into play at utmost that the HFC-152a coefficient of refrigerating performance is high, the saturated aq specific volume is big and advantages of environment protection.
Described 1,1,2, the 2-Tetrafluoroethane, i.e. HFC-134, molecular formula is CHF
2CHF
2, relative molecular weight is 102.03, and normal boiling point is-17.6 ℃, and critical temperature is 119.0 ℃, and emergent pressure is 4.64MPa.
HFC-134 is the isomers of HFC-134a, and thermodynamic properties is similar with existing refrigeration agent HFC-134a, has good thermal parameter and thermal property, and ODP is 0, and GWP is 1110, is lower than HFC-134a, and is not flammable; Under identical air conditioning condition, the coefficient of refrigerating performance of HFC-134 is superior to HCFC-22 and R-410A, and an amount of the interpolation can reduce the combustibility of refrigeration agent, improves its safety performance.
As preferably, each constituent mass per-cent of refrigeration agent is: methylene fluoride 50 ~ 80%, 1,1-C2H4F2 C2H4F2 10 ~ 30% and 1,1,2,2-Tetrafluoroethane 10 ~ 40%.
In this proportional range, have synergy between each component of refrigeration agent, especially aspect security, the feature of environmental protection and economy, each item performance index of refrigeration agent all increase.
As preferably, each constituent mass per-cent of refrigeration agent is methylene fluoride 48 ~ 52%, 1,1-C2H4F2 C2H4F2 8 ~ 12% and 1,1,2,2-Tetrafluoroethane 38 ~ 42%.When each constituent mass per-cent of refrigeration agent is methylene fluoride 50%, 1,1-C2H4F2 C2H4F2 10% and 1,1,2, during 2-Tetrafluoroethane 40%, refrigeration agent is flammable, and the volume lower limit is the highest, and is the safest during use.
As preferably, each constituent mass per-cent of refrigeration agent is methylene fluoride 48 ~ 52%, 1,1-C2H4F2 C2H4F2 28 ~ 32% and 1,1,2,2-Tetrafluoroethane 18 ~ 22%.When each constituent mass per-cent of refrigeration agent is methylene fluoride 50%, 1,1-C2H4F2 C2H4F2 30% and 1,1,2, during 2-Tetrafluoroethane 20%, GWP is minimum, and is minimum to environmental influence.
As preferably, each constituent mass per-cent of refrigeration agent is methylene fluoride 68 ~ 72%, 1,1-C2H4F2 C2H4F2 8 ~ 12% and 1,1,2,2-Tetrafluoroethane 18 ~ 22%.When each constituent mass per-cent of refrigeration agent is methylene fluoride 70%, 1,1-C2H4F2 C2H4F2 10% and 1,1,2, during 2-Tetrafluoroethane 20%, the saturated aq specific volume is bigger, and the relative unit volume refrigerating capacity compressor is higher, can reduce the filling quantity of system refrigerant.
As preferably, each constituent mass per-cent of refrigeration agent is methylene fluoride 68 ~ 72%, 1,1-C2H4F2 C2H4F2 18 ~ 22% and 1,1,2,2-Tetrafluoroethane 8 ~ 12%.When each constituent mass per-cent of refrigeration agent is methylene fluoride 70%, 1,1-C2H4F2 C2H4F2 20% and 1,1,2, during 2-Tetrafluoroethane 10%, the saturated aq specific volume is maximum, can effectively reduce the filling quantity of system refrigerant.
As preferably, each constituent mass per-cent of refrigeration agent is methylene fluoride 78 ~ 82%, 1,1-C2H4F2 C2H4F2 8 ~ 12% and 1,1,2,2-Tetrafluoroethane 8 ~ 12%.When each constituent mass per-cent of refrigeration agent is methylene fluoride 80%, 1,1-C2H4F2 C2H4F2 10% and 1,1; 2, during 2-Tetrafluoroethane 10%, refrigerating effect per unit swept volume is maximum; Reduce the volume of compressor; Reduce the cost of refrigeration system, have bigger saturated aq specific volume simultaneously, can effectively reduce the filling quantity of system refrigerant.
The present invention also provides a kind of method for preparing the refrigeration agent of environment-friendly type of the present invention, is about to said component and under liquid phase state, carries out physical mixed by its mass percent, obtains the refrigeration agent of described environment-friendly type.
Refrigeration agent provided by the invention compared with prior art has the following advantages:
(1) the saturated aq specific volume is bigger, can significantly reduce the filling quantity of refrigeration agent in the refrigeration system, is equivalent to reduce the GWP of refrigeration agent, reduces refrigeration agent simultaneously and leaks back combustiblematerials incendiary possibility;
(2) the unit volume refrigerating duty is bigger, can reduce the volume of compressor, reduces the cost of refrigeration system;
(3) environmental performance is good, and ODP is 0, and GWP reduces with respect to HCFC-22 and R-410A greatly.
Description of drawings
Accompanying drawing 1 is the comparison of the embodiment of the invention 1, embodiment 4 and HCFC-22 and R-410A vp.
Embodiment
Embodiment 1
HFC-32, HFC-152a and the HFC-134 mass percent by 50: 10: 40 under liquid phase is carried out physical mixed, obtain the refrigeration agent of environment-friendly type.
Embodiment 2
HFC-32, HFC-152a and the HFC-134 mass percent by 50: 20: 30 under liquid phase is carried out physical mixed, obtain the refrigeration agent of environment-friendly type.
Embodiment 3
HFC-32, HFC-152a and the HFC-134 mass percent by 50: 30: 20 under liquid phase is carried out physical mixed, obtain the refrigeration agent of environment-friendly type.
Embodiment 4
HFC-32, HFC-152a and the HFC-134 mass percent by 70: 10: 20 under liquid phase is carried out physical mixed, obtain the refrigeration agent of environment-friendly type.
Embodiment 5
HFC-32, HFC-152a and the HFC-134 mass percent by 70: 20: 10 under liquid phase is carried out physical mixed, obtain the refrigeration agent of environment-friendly type.
Embodiment 6
HFC-32, HFC-152a and the HFC-134 mass percent by 80: 10: 10 under liquid phase is carried out physical mixed, obtain the refrigeration agent of environment-friendly type.
The performance of prepared refrigeration agent among the embodiment 1 ~ 6 and the performance of HCFC-22 and main surrogate R-410A thereof are compared at present, characteristics of the present invention and effect are described.
A. environmental performance
Table 1 has compared the environmental performance of prepared refrigeration agent and HCFC-22 and R-410A among the embodiment 1 ~ 6.Wherein as benchmark value 1.0, the GWP value is with CO with CFC-11 for the ODP value
2As benchmark value 1.0 (100 years).
Table 1 refrigeration agent environmental performance relatively
| Working medium | ODP | GWP |
| Embodiment 1 | 0 | 815 |
| Embodiment 2 | 0 | 718 |
| Embodiment 3 | 0 | 610 |
| Embodiment 4 | 0 | 737 |
| Embodiment 5 | 0 | 639 |
| Embodiment 6 | 0 | 697 |
| HFC-32 | 0 | 716 |
| HFC- |
0 | 133 |
| HFC-134 | 0 | 1110 |
| HCFC-22 | 0.050 | 1810 |
| R- |
0 | 2100 |
Can find out that from table 1 ODP of the refrigeration agent that embodiment 1 ~ 6 is prepared is 0, and atmospheric ozone layer is not had destruction, all is superior to HCFC-22.Moreover, the GWP of the refrigeration agent that embodiment 1 ~ 6 is prepared has only 34.2% ~ 45.0% of HCFC-22 less than HCFC-22, and 29.5% ~ 38.8% of R-410A meets current protection ozonosphere, reduces the environmental requirement of Greenhouse effect.
B. flammable performance
Table 2 has compared the flammable performance of prepared refrigeration agent and HCFC-22 and R-410A among the embodiment 1 ~ 6.
Performance that table 2 is flammable relatively
| Working medium | Flammable volume lower limit % |
| Embodiment 1 | 14.5 |
| Embodiment 2 | 11.6 |
| Embodiment 3 | 9.8 |
| Embodiment 4 | 13.2 |
| Embodiment 5 | 11.1 |
| Embodiment 6 | 12.8 |
| HFC-32 | 14.4 |
| HFC-152a | 4.8 |
| HFC-134 | / |
| HCFC-22 | / |
| R-410A | / |
From table 2, can find out; Though prepared refrigeration agent all has certain combustibility among the embodiment 1 ~ 6, the flammable volume lower limit of prepared refrigeration agent is all higher among all embodiment, flammable performance a little less than; Under certain condition, all can well be applied in the refrigeration system.
Wherein, embodiment 1 flammable volume lower limit is the highest, and is the safest during use.
C. thermal parameter and thermal performance
Table 3 has compared (7.2 ℃ of vaporization temperatures under the standard air conditioning condition; 54.4 ℃ of condensing temperatures; 11.1 ℃ of 8.3 ℃ of condensate depression of superheating temperature), the thermal parameter of prepared refrigeration agent and HCFC-22, HFC-32, HFC-152a, HFC-134a and R-410A in the foregoing description 1 ~ 6 (is evaporating pressure P
e, condensing pressure P
c, pressure ratio P
e/ P
c, exhaust temperature t
Dis) and relative thermal performance (relatively thermal performance is meant the ratio of refrigeration agent thermal performance and HCFC-22 thermal performance, that is: relative coefficient of refrigerating performance COP, relative saturation flowing fluid ratio volume V
L, relative unit volume refrigerating capacity compressor q
v).
Thermal parameter and relative thermal performance are relatively under the table 3 standard air conditioning condition
Visible from table 3; Under the standard air conditioning condition; The saturated aq specific volume of the refrigeration agent that embodiment 2 ~ 6 is prepared is all greater than HCFC-22 and R-410A; Can significantly reduce the filling quantity of refrigeration agent in the refrigeration system, be equivalent to reduce the GWP of novel refrigerant, also reduce system simultaneously and revealed back combustiblematerials incendiary possibility; Simultaneously unit volume refrigerating duty and the HCFC-22 of the prepared refrigeration agent of embodiment 1 ~ 3 are equal basically, can be used for directly alternatively, and need not design compressor again; The unit volume refrigerating duty of the refrigeration agent that embodiment 4 ~ 6 is prepared is compared with HCFC-22 and is improved a lot, and can reduce the volume of compressor, reduces the cost of refrigeration system; The exhaust temperature of the refrigeration agent that embodiment 1 ~ 6 is prepared all is higher than HCFC-22, but all low than HFC-32; The relative coefficient of refrigerating performance of the refrigeration agent that embodiment 1 ~ 6 is prepared is all equal basically with R-410A.
Claims (8)
1. the refrigeration agent of an environment-friendly type is characterized in that, by methylene fluoride, 1, and 1-C2H4F2 C2H4F2 and 1,1,2, the 2-Tetrafluoroethane is formed, and each constituent mass per-cent is: methylene fluoride 40 ~ 90%, 1,1-C2H4F2 C2H4F2 5 ~ 40% and 1,1,2,2-Tetrafluoroethane 5 ~ 50%.
2. the refrigeration agent of environment-friendly type as claimed in claim 1 is characterized in that, each constituent mass per-cent is: methylene fluoride 50 ~ 80%, 1,1-C2H4F2 C2H4F2 10 ~ 30% and 1,1,2,2-Tetrafluoroethane 10 ~ 40%.
3. the refrigeration agent of environment-friendly type as claimed in claim 1 is characterized in that, each constituent mass per-cent is: methylene fluoride 48 ~ 52%, 1,1-C2H4F2 C2H4F2 8 ~ 12% and 1,1,2,2-Tetrafluoroethane 38 ~ 42%.
4. the refrigeration agent of environment-friendly type as claimed in claim 1 is characterized in that, each constituent mass per-cent is: methylene fluoride 48 ~ 52%, 1,1-C2H4F2 C2H4F2 28 ~ 32% and 1,1,2,2-Tetrafluoroethane 18 ~ 22%.
5. the refrigeration agent of environment-friendly type as claimed in claim 1 is characterized in that, each constituent mass per-cent is: methylene fluoride 68 ~ 72%, 1,1-C2H4F2 C2H4F2 8 ~ 12% and 1,1,2,2-Tetrafluoroethane 18 ~ 22%.
6. the refrigeration agent of environment-friendly type as claimed in claim 1 is characterized in that, each constituent mass per-cent is: methylene fluoride 68 ~ 72%, 1,1-C2H4F2 C2H4F2 18 ~ 22% and 1,1,2,2-Tetrafluoroethane 8 ~ 12%.
7. the refrigeration agent of environment-friendly type as claimed in claim 1 is characterized in that, each constituent mass per-cent is: methylene fluoride 78 ~ 82%, 1,1-C2H4F2 C2H4F2 8 ~ 12% and 1,1,2,2-Tetrafluoroethane 8 ~ 12%.
8. a method for preparing the refrigeration agent of the described environment-friendly type of claim 1 ~ 7 is characterized in that, said component is carried out physical mixed by its mass percent under liquid phase state, obtains the refrigeration agent of described environment-friendly type.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1076957A (en) * | 1992-02-03 | 1993-10-06 | 联合信号股份有限公司 | New refrigerant composition |
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2012
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1076957A (en) * | 1992-02-03 | 1993-10-06 | 联合信号股份有限公司 | New refrigerant composition |
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