CN102676122B - Environment-friendly refrigerant and preparation method thereof - Google Patents
Environment-friendly refrigerant and preparation method thereof Download PDFInfo
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- CN102676122B CN102676122B CN201210169724.XA CN201210169724A CN102676122B CN 102676122 B CN102676122 B CN 102676122B CN 201210169724 A CN201210169724 A CN 201210169724A CN 102676122 B CN102676122 B CN 102676122B
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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
Due to HCFC-22(difluorochloromethane) there is certain ODP(ODP) and higher GWP(global warming potential), belong to the material that is required that time limit is superseded, and existing main surrogate R-407C(1,1,1, the mixture of R-410A(methylene fluoride and pentafluoride ethane) etc. the mixture of 2-Tetrafluoroethane, pentafluoride ethane and methylene fluoride), itself just there is certain defect, aspect refrigeration performance, can not meet the demands, and environmental performance is also undesirable, GWP is relatively high, even higher than HCFC-22.
HFC-32(methylene fluoride) have good thermal performance, ODP is that 0, GWP is 716, and environmental performance is excellent, although have certain combustibility, combustibility is not strong, belongs to A2L class refrigeration agent; The saturated liquid specific volume of HFC-32 is larger, can reduce the filling quantity of refrigerant of system; Simultaneously the refrigerating effect per unit swept volume of HFC-32 is larger, and volume that can compresses machine reduces the cost of refrigeration system; But the exhaust temperature of HFC-32 is higher, operating pressure is also higher.
HFC-152a(1,1-C2H4F2 C2H4F2) there is good thermal performance, ODP is that 0, GWP is only 133, environmental performance is excellent, but has certain combustibility.Under identical air conditioning condition, the coefficient of refrigerating performance of HFC-152a is better than HFC-134a, can reduce energy consumption; Meanwhile, HFC-152a has larger saturated liquid specific volume, can reduce the filling quantity of refrigerant of system.
HFC-134(1,1,2,2-Tetrafluoroethane) be the isomers of HFC-134a, thermodynamic properties is similar with HFC-134a, and ODP is that 0, GWP is 1110, lower than HFC-134a, non-combustible; Under identical air conditioning condition, the coefficient of refrigerating performance of HFC-134 is better than HCFC-22 and R-410A.
Although HFC-32, tri-kinds of refrigeration agents of HFC-152a and HFC-134 all have deficiency separately while using separately, if but by HFC-32, HFC-152a and HFC-134 mix use, form a kind of refrigeration agent of novel environment-friendly type, can, in conjunction with three's advantage separately, at utmost reduce unfavorable factor.
In prior art, Chinese patent document CN1412266A(02124112.0) announced the mixture that a kind of methylene fluoride (HFC-32), HFA 134a (HFC-134a) and 1,1,1-Halothane (HFC-143a) form; Chinese patent document CN 1200067C(03148532.4) a kind of methylene fluoride (HFC-32), pentafluoride ethane (HFC-125), 1,1,1 have been announced, 2-Tetrafluoroethane (HFC-134a) and/or 1, the mixture that 1,2,2-Tetrafluoroethane (HFC-134), propylene (R1270) form; Chinese patent CN1244663C(200310118983.0) announced the mixture that a kind of methylene fluoride (HFC-32), pentafluoride ethane (HFC-125) and 1,1-C2H4F2 C2H4F2 (HFC-152a) form; Chinese patent document CN 100400615C(200410077955.3) disclose a kind of 1, the mixture that 1-C2H4F2 C2H4F2 (HFC-152a) and 1,1,1,3,3,3-HFC-236fa (HFC-236fa) form; Chinese patent document CN101006154A(200580028315.6) announce a kind of binary or tertiary mixture and (be selected from 1,1,1,2-Tetrafluoroethane (HFC-134a), pentafluoride ethane (HFC-125), 1,1,1-Halothane (HFC-143a), 1,1-C2H4F2 C2H4F2 (HFC-152a), dme (DME), Trimethylmethane (HC-600a)); Chinese patent document CN 100489051C(200710114770.9) announced the mixture that a kind of methylene fluoride (HFC-32), pentafluoride ethane (HFC-125) and Trimethylmethane (HC-600a) form; Chinese patent document CN100500793C(200810014733.5) announced the mixture that a kind of pentafluoride ethane (HFC-125), HFA 134a (HFC-134a) and dme (DME) form; Chinese patent document CN100485010C(200610016352.1) announced the mixture that a kind of methylene fluoride (HFC-32), dme (DME) and HFA 134a (HFC-134a) form; Chinese patent CN101381595B(200810231909.2) announced the mixture that a kind of dme (DME), propylene (R1270) and HFC-227ea (HFC-227ea) form; Chinese patent document CN101649188A(200910023799.5) announced the mixture that a kind of dme (DME), propylene (R1270) and CF3I (R13I1) form; Chinese patent document CN 102079964A(200910225801.7) announced the mixture that a kind of methylene fluoride (HFC-32) and HFA 134a (HFC-134a) form; Chinese patent document CN102079966A(200910225803.6) announced a kind of methylene fluoride (HFC-32), 1, the mixture that 1-C2H4F2 C2H4F2 (HFC-152a) and HFA 134a (HFC-134a) form; Chinese patent document CN 102079967A(200910225804.0) announced the mixture that a kind of methylene fluoride (HFC-32), pentafluoride ethane (HFC-125) and HFA 134a (HFC-134a) form.
In above-mentioned patent, disclosed refrigerant composition exists or GWP value is higher or not directly charge and be applied to HFC-134a system or the shortcoming such as combustibility is larger, therefore, need exploitation there is better refrigeration performance, with the better compatible and new refrigerant with better environmental-protecting performance of existing system.
Summary of the invention
The invention provides a kind of low GWP(global warming potential) the refrigeration agent of environment-friendly type, this refrigeration agent does not only destroy atmospheric ozone layer, and the Greenhouse effect that produce are less, have the thermal parameter suitable with HCFC-22 and thermal property simultaneously.
A refrigeration agent for environment-friendly type, by methylene fluoride, 1,1-C2H4F2 C2H4F2 and 1,1,2,2-Tetrafluoroethane form, 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 that 0, GWP is 716, and environmental performance is excellent, although have certain combustibility, combustibility is not strong, belongs to A2L class refrigeration agent.
The saturated liquid specific volume of HFC-32 is larger, can reduce to a great extent the filling quantity of refrigerant of system, thereby reaches the object of indirect reduction novel refrigerant GWP.
The refrigerating effect per unit swept volume of HFC-32 is larger, and volume that can compresses machine reduces the cost of refrigeration system; But the exhaust temperature of HFC-32 is higher, operating pressure is also higher, therefore, needs as required, adds in right amount.
Described 1,1-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 better than HFC-134a, can reduce energy consumption.
The ODP of HFC-152a is that 0, GWP is only 133, have excellent environment friendly, and the saturated liquid specific volume of HFC-152a is larger, can reduce the filling quantity of refrigerant of system, thereby reaches the object 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 using under safe prerequisite, at utmost bring into play that HFC-152a coefficient of refrigerating performance is high, saturated liquid specific volume large and advantages of environment protection.
Described 1,1,2,2-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 that 0, GWP is 1110, lower than HFC-134a, non-combustible; Under identical air conditioning condition, the coefficient of refrigerating performance of HFC-134 is better than HCFC-22 and R-410A, adds in right amount, 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, between each component of refrigeration agent, there is synergy, especially, aspect security, the feature of environmental protection and economy, the property indices of refrigeration agent all increases.
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, when 1-C2H4F2 C2H4F2 10% and 1,1,2,2-Tetrafluoroethane 40%, refrigeration agent is flammable, and volume lower limit is the highest, 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, when 1-C2H4F2 C2H4F2 30% and 1,1,2,2-Tetrafluoroethane 20%, GWP is minimum, to environmental impact minimization.
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, when 1-C2H4F2 C2H4F2 10% and 1,1,2,2-Tetrafluoroethane 20%, saturated liquid specific volume is larger, and 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, when 1-C2H4F2 C2H4F2 20% and 1,1,2,2-Tetrafluoroethane 10%, saturated liquid 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, during 2,2-Tetrafluoroethane 10%, refrigerating effect per unit swept volume is maximum, reduce the volume of compressor, the cost that reduces refrigeration system has larger saturated liquid specific volume simultaneously, can effectively reduce the filling quantity of system refrigerant.
The present invention also provides a kind of method of preparing the refrigeration agent of environment-friendly type of the present invention, is about to described component and by its mass percent, under liquid phase state, carries out physical mixed, obtains the refrigeration agent of described environment-friendly type.
Refrigeration agent provided by the invention compared with prior art, has the following advantages:
(1) saturated liquid specific volume is larger, can greatly reduce the filling quantity of refrigeration agent in refrigeration system, is equivalent to reduce the GWP of refrigeration agent, reduces the possibility of combustiblematerials burning after refrigrant leakage simultaneously;
(2) unit volume refrigerating duty is larger, can reduce the volume of compressor, reduces the cost of refrigeration system;
(3) environmental performance is good, and ODP is that 0, GWP reduces greatly with respect to HCFC-22 and R-410A.
Accompanying drawing explanation
Accompanying drawing 1 is the comparison of the embodiment of the present invention 1, embodiment 4 and HCFC-22 and R-410A vapour pressure.
Embodiment
Embodiment 1
HFC-32, HFC-152a and HFC-134 mass percent by 50: 10: 40 under liquid phase are carried out to physical mixed, obtain the refrigeration agent of environment-friendly type.
Embodiment 2
HFC-32, HFC-152a and HFC-134 mass percent by 50: 20: 30 under liquid phase are carried out to physical mixed, obtain the refrigeration agent of environment-friendly type.
Embodiment 3
HFC-32, HFC-152a and HFC-134 mass percent by 50: 30: 20 under liquid phase are carried out to physical mixed, obtain the refrigeration agent of environment-friendly type.
Embodiment 4
HFC-32, HFC-152a and HFC-134 mass percent by 70: 10: 20 under liquid phase are carried out to physical mixed, obtain the refrigeration agent of environment-friendly type.
Embodiment 5
HFC-32, HFC-152a and HFC-134 mass percent by 70: 20: 10 under liquid phase are carried out to physical mixed, obtain the refrigeration agent of environment-friendly type.
Embodiment 6
HFC-32, HFC-152a and HFC-134 mass percent by 80: 10: 10 under liquid phase are carried out to physical mixed, obtain the refrigeration agent of environment-friendly type.
Now the performance of the performance of prepared refrigeration agent in embodiment 1 ~ 6 and HCFC-22 and main surrogate R-410A thereof is compared, feature 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 in embodiment 1 ~ 6.Wherein ODP value is usingd CFC-11 as benchmark value 1.0, and GWP value is with CO
2as benchmark value 1.0(100).
Table 1 refrigeration agent comparison of environmental performance
| 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-152a | 0 | 133 |
| HFC-134 | 0 | 1110 |
| HCFC-22 | 0.050 | 1810 |
| R-410A | 0 | 2100 |
As can be seen from Table 1, the ODP of the refrigeration agent that embodiment 1 ~ 6 is prepared is 0, and atmospheric ozone layer is not had to destruction, is all better than HCFC-22.Moreover, the GWP of the refrigeration agent that embodiment 1 ~ 6 is prepared is less than HCFC-22, only has 34.2% ~ 45.0% of HCFC-22, and 29.5% ~ 38.8% of R-410A meets current Ozonosphere protection, 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 in embodiment 1 ~ 6.
Performance comparison that table 2 is flammable
| 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 | / |
As can be seen from Table 2, although prepared refrigeration agent all has certain combustibility in embodiment 1 ~ 6, in all embodiment, the flammable volume lower limit of prepared refrigeration agent is all higher, flammable performance a little less than, under certain condition, all can well be applied in refrigeration system.
Wherein, embodiment 1 is flammable, and volume lower limit is the highest, the safest during use.
C. thermal parameter and thermal performance
Table 3 has compared (7.2 ℃ of vaporization temperatures under 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 above-described embodiment 1 ~ 6 (is evaporating pressure P
e, condensing pressure P
c, pressure ratio P
e/ P
c, exhaust temperature t
dis) and relatively thermal performance (thermal performance refers to the ratio of refrigeration agent thermal performance and HCFC-22 thermal performance relatively, that is: relative coefficient of performance, relative saturation flowing fluid ratio volume V
l, relative unit volume refrigerating capacity compressor q
v).
Thermal parameter and thermal performance comparison relatively under table 3 standard air conditioning condition
As seen from Table 3, under standard air conditioning condition, the saturated liquid specific volume of the refrigeration agent that embodiment 2 ~ 6 is prepared is all greater than HCFC-22 and R-410A, can greatly reduce the filling quantity of refrigeration agent in refrigeration system, be equivalent to reduce the GWP of novel refrigerant, also reduced the possibility of combustiblematerials burning after system is revealed simultaneously; Simultaneously unit volume refrigerating duty and the HCFC-22 of the prepared refrigeration agent of embodiment 1 ~ 3 are substantially equal, can be for directly alternative, and need not redesign compressor; The unit volume refrigerating duty of the refrigeration agent that embodiment 4 ~ 6 is prepared is compared and is improved a lot with HCFC-22, 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 is all 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 substantially equal with R-410A.
Claims (8)
1. a refrigeration agent for environment-friendly type, is characterized in that, by methylene fluoride, 1, and 1-C2H4F2 C2H4F2 and 1,1,2,2-Tetrafluoroethane forms, 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 of preparing the refrigeration agent of the arbitrary described environment-friendly type of claim 1～7, is characterized in that, described component is carried out under liquid phase state to physical mixed by its mass percent.
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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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