CN103289648A - Environmentally-friendly energy-saving refrigerant capable of substituting R134a - Google Patents
Environmentally-friendly energy-saving refrigerant capable of substituting R134a Download PDFInfo
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- CN103289648A CN103289648A CN2013101690298A CN201310169029A CN103289648A CN 103289648 A CN103289648 A CN 103289648A CN 2013101690298 A CN2013101690298 A CN 2013101690298A CN 201310169029 A CN201310169029 A CN 201310169029A CN 103289648 A CN103289648 A CN 103289648A
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention relates to an environmentally-friendly energy-saving refrigerant capable of substituting R134a. The environmentally-friendly energy-saving refrigerant comprises dimethyl ether, 1,1-difluoroethane and pentafluoroethane, and the preparation method comprises the following step of: physically mixing the compositions under the liquid phase state according to the mass percent. The environmentally-friendly energy-saving refrigerant has the beneficial effects that the refrigerant can meet the environmentally-friendly requirement of the European Union, the ODP is zero, the GWP is far less than that of R134a and lower than 150; on the aspect of flammability, the A3 level of the dimethyl ether is improved to A2 level, and the hidden safety hazard is greatly reduced; and on the aspect of thermal parameter and performances, the thermal parameter is approximate to that of R134a, the refrigerant can be directly filled so as to replace the R134a, the heat transfer property is better, the volume refrigerating capacity is higher than that of the R134a, and the environmentally-friendly energy-saving refrigerant is a desirable substitute of the R134a.
Description
Technical field
The invention belongs to the refrigerant technology field, relate in particular to the environmental protection and energy saving refrigeration agent of a kind of alternative R134a.
Background technology
European Union regulation: from January 1st, 2017 all vehicles that newly dispatch from the factory will completely forbid and use the GWP value above the air-conditioning system of 150 fluorinated gas refrigeration agent.R134a belongs to the refrigeration agent of HFCs series, because its ODP value is 0, has nonflammablely, does not explode, and nontoxic, nonirritant does not have advantages such as corruption, is widely used at refrigerating fields such as refrigerator, refrigerator-freezer and air-conditionings.Though its ODP value is 0, because of its GWP value up to 1300, do not meet European Union regulation, will face and be substituted comprehensively, this means that R134a will soon step down from the stage of history fully.
Dme has and does not destroy ozonization as a kind of emerging environmental protection refrigerant, does not produce Greenhouse effect; Have inertia, non-carcinogenesis, characteristic such as almost non-toxic, flammable.Because its thermodynamic properties and R134a approach, when adopting dme to substitute R134a, need not to change system's major parts, become one of main research object of R134a substitute.But because dme combustibility is the A3 level, have potential safety hazard, it is difficult to cause it to promote the use of.In addition, because dme has corrosive nature to the caulking gum of refrigeration system, be unfavorable for that system normally moves.In numerous refrigeration agent patents about dme, only considered whether its thermal property is good, and seldom considered its corrodibility to the influence of refrigeration system, at present, open based on refrigeration agent research and the multinomial relevant patent of dme.
Carbon-hydrogen refrigerant R436a substitutes R134a.R436a is the natural refrigerant of hydrocarbon polymer, and its ODP value is that 0, GWP value is 3, does not damage ozonosphere, does not almost have Greenhouse effect.Its thermal property and R134 are close, need not change refrigeration system when changing refrigeration agent, and be compatible good with the lubricating oil of R134a, can directly be charged in the R134a refrigeration system.The vaporization heat of R436a is big, and molecular weight is little, and resistance to flow is little.But because its flammable rank is the A3 level, potential safety hazard is big, is unfavorable for promoting the use.
Disclose a kind of safe, nontoxic mix refrigerant that is used for heating/hot water supply system among the patent CN200680035307, this refrigeration agent prepares by mixing dme and carbonic acid gas under gas phase state.
Patent CN200710013386 has invented a kind of refrigerant composition that is applied to substitute in the automative air conditioning R134a.(DME or RE170,1, form by 1-C2H4F2 C2H4F2 (R152a) and Trimethylmethane (R600a) by dme for this refrigeration agent.Can be used as the alternative refrigerant of R134a in the automative air conditioning.
Having invented among the patent CN200710013387 provides a kind of refrigerant composition that is applied to substitute in the automative air conditioning R134a.This refrigeration agent is made up of dme, CF3I and Trimethylmethane.
Disclose a kind of ternary near-azeotrope refrigerant among the patent CN200810097393, this refrigeration agent is the tertiary mixture of being made up of 1,1,2,2-Tetrafluoroethane, dme and three kinds of materials of propane.This mix refrigerant is applicable to single stage compressive refrigerating system, alternative traditional R502 and R22.
Disclose a kind of environment friendly mixing refrigerant for air conditioner among the patent CN200810231909, contained by mass percentage: 10～40% dme, 55～85% propylene and 5～35% 1,1,1,2,3,3, the 3-heptafluoro-propane.Can be used as the desirable alternative refrigerant of R22 in the domestic air conditioning.
Disclose a kind of environment-protecting mixed refrigerating agent that contains dme, pentafluoride ethane and propane among the patent CN200810231911, this refrigeration agent is mainly used in substituting R22 in the domestic air conditioning.
Disclose a kind of efficient and environment-friendly type mix refrigerant among the patent CN200910023799, this refrigeration agent is made up of tertiary mixture dme, propylene and CF3I.This refrigeration agent can be used for substituting the refrigeration agent of R22, and need not to change existing equipment and production line, can directly fill jar.
Invented a kind of carbon-hydrogen mixed refrigerant for air-conditioner among the patent CN200910184064, formed by propylene, dme, pentafluoropropane.For domestic air conditioning, need not to change existing equipment, can realize that filling type substitutes R22.
Disclose a kind of carbon-hydrogen mixed refrigerant for automative air conditioning among the patent CN200910184065, mixed by propylene, dme and pentafluoropropane and form, in order to substitute the R134a refrigeration agent in the automative air conditioning.
Disclose a kind of refrigerant composition of low GWP value among the patent CN201010196224, (HFO-1234yf), 1, the 1-C2H4F2 C2H4F2 (form by HFC-152a) and dme (DME) by 2,3,3,3-tetrafluoeopropene for it.Can directly be used in existing R134a refrigeration system, not need the redesign of compressor.
In the above-mentioned disclosed refrigeration agent patent based on dme, the refrigeration agent that has is flammable big, belongs to the A3 level, has potential safety hazard; The unit volume refrigerating duty that has is less than normal, changes the back system and does not reach design effect; The refrigeration agent that has and air-conditioning system compatibility are relatively poor, are unfavorable for changing existing refrigeration agent; The refrigeration agent slip temperature that has is excessive, is unfavorable for that system normally moves; The refrigeration agent refrigerating efficiency that has is on the low side, is unfavorable for energy-saving run etc.
Summary of the invention
The present invention aims to provide the environmental protection and energy saving refrigeration agent of a kind of alternative R134a, environmental protection, energy-conservation, safe, reliable, and need not changing under the situation of refrigeration system major parts, directly filling to substitute R134a.
The environmental protection and energy saving refrigeration agent of a kind of alternative R134a, by dme, 1,1-C2H4F2 C2H4F2 and pentafluoride ethane are formed, and each constituent mass per-cent is as follows:
Dme: 50%-70%
1,1-C2H4F2 C2H4F2: 20%-30%
Pentafluoride ethane: 10%-20%
Refrigeration agent of the present invention, its preparation method are that above-mentioned each component is carried out physical mixed by mass percentage under liquid phase state.
Dme in the said components, its chemical molecular formula are CH3OCH3, and molar mass is 46.07, and normal boiling point is-24.81 ℃, and critical temperature is 127.15 ℃, and emergent pressure is 5.34MPa.
In the said components 1,1-C2H4F2 C2H4F2, its chemical molecular formula are CH3CHF2, and molar mass is 66.05, and normal boiling point is-24.02 ℃, and critical temperature is 113.26 ℃, emergent pressure is 4.52MPa.
Pentafluoride ethane in the said components, its chemical molecular formula are CHF2CF3, and molar mass is 120.02, and normal boiling point is-48.35 ℃, and critical temperature is 66.05 ℃, and emergent pressure is 3.59MPa.
The beneficial effect that the present invention has is: this refrigeration agent operating pressure and R134a are very approaching, and its ODP value is 0, do not destroy atmospheric ozone layer; The GWP value is 100～120, and less than the GWP value of R134a, the Greenhouse effect after the discharging are less; The flammable rank of this refrigeration agent reaches the A2 level; The mixed type refrigeration agent can be under the condition that does not change system's major parts direct filling to substitute R134a.
The remarkable advantage of its environmental protection and energy saving and good benefit concrete manifestation are as follows:.
A, environmental benefit
The present invention has tangible environmental benefit.Table one has provided the environmental protection index of refrigeration agent of the present invention and dme, R134a.Can find out from table one: ozone layer destroying index of the present invention (ODP) and dme, R134a are identical, are 0, can not destroy atmospheric ozone layer; For Greenhouse effect index (GWP), the GWP value of R134a refrigeration agent reaches 1300, and GWP value of the present invention is 100～120, and the GWP that satisfies European Union's proposition is not more than 150 requirement.This shows: the present invention and dme refrigeration agent all satisfy the requirement of relevant environment benefit.
Table one refrigeration agent environmental benefit relatively
| Refrigeration agent | Ozone layer destroying index (ODP) | Greenhouse effect index (GWP) |
| The present invention | 0 | 100—120 |
| R134a | 0 | 1300 |
| Dme | 0 | 0 |
| Related request | ODP=0 | GWP<150 |
B, safe effect
Refrigeration agent nontoxicity of the present invention, flammable rank are the A2 level.As shown in Table 2: for dme, refrigeration agent of the present invention is increased to the A2 level with the A3 level security of dme.
Table two refrigeration agent safe effect relatively
| Refrigeration agent | The present invention | R134a | Dme |
| Level of security | A2 | A1 | A3 |
C. thermal parameter
Table three has provided refrigeration agent of the present invention, R134a and dme in central air-conditioning handpiece Water Chilling Units operating mode (vaporization temperature: 3 ℃ commonly used; Condensing temperature: 40 ℃; 5 ℃ of condensate depression; 5 ℃ of superheating temperature) thermal parameter under.By table three as can be seen: refrigeration agent evaporating pressure of the present invention and condensing pressure and R134a are very approaching, and exhaust temperature is also comparatively approaching, can directly charge and replace R134a under the condition of not changing the refrigeration system major parts.Can obviously find out from table three: the dme exhaust temperature is higher, relatively announce among the patent CN00128145 based on dme, add the refrigeration agent of material such as part fire retardant, refrigeration agent of the present invention has embodied the low advantage of exhaust temperature.This patent slip temperature is little, belongs to near-azeotrope refrigerant, is conducive to system stable operation.
Table three refrigeration agent thermal parameter relatively
| Refrigeration agent | Evaporating pressure (MPa) | Condensing pressure (MPa) | Exhaust temperature (℃) | Slip temperature (℃) |
| The present invention | 0.309—0.337 | 0.912—1.153 | 60.52—70.28 | 0.3—0.8 |
| R134a | 0.326 | 1.0166 | 59.44 | —— |
| Dme | 0.2958 | 0.8891 | 70.63 | —— |
D, refrigeration performance
Table four refrigeration agent refrigeration performance relatively
As shown in Table 4: under above-mentioned operating mode, refrigerant volume refrigerating duty of the present invention is all big than R134a and dme, is 1.00-1.18 times of the R134a volume refrigerating capacity compressor, directly change R134a after, its refrigeration is better; Because quality refrigerating duty of the present invention is high 1.90-2.15 times than R134a, so its filling quantity will significantly reduce, is about about 50% of R134a; COP and the R134a of refrigeration agent of the present invention are suitable, and under preferable condition, refrigeration agent COP of the present invention is 1.05 times of R134a.
Comprehensive above-mentioned aspect, aspect environmental protection, refrigeration agent of the present invention satisfies European Union to the environmental requirement of refrigeration agent, its ODP be 0, GWP much smaller than R134a, and be lower than 150; Aspect flammable, the present invention is increased to the A2 level with the A3 level of dme, and potential safety hazard reduces greatly; At thermal parameter and aspect of performance, thermal parameter of the present invention and R134a approach, and can directly charge and replace R134a, and heat transfer property is better, and volume refrigerating capacity compressor is bigger than R134a.So refrigeration agent of the present invention is the ideal substitute of R134a.
Embodiment
In order further to understand advantage of the present invention, enumerate several specific embodiments below, the ratio of each component is mass percent among each embodiment.
Refrigeration agent of the present invention is 50%-70% dme by mass percent, 20%-30% 1, the 1-C2H4F2 C2H4F2,10%-20% pentafluoride ethane is mixing with physical condition under liquid phase state.
The chemical molecular formula of the dme among the embodiment is CH3OCH3, and molar mass is 46.07, and normal boiling point is-24.81 ℃, and critical temperature is 127.15 ℃, and emergent pressure is 5.34MPa; 1,1-C2H4F2 C2H4F2 chemical molecular formula is CH3CHF2, and molar mass is 66.05, and normal boiling point is-24.02 ℃, and critical temperature is 113.26 ℃, and emergent pressure is 4.52MPa; The pentafluoride ethane chemical molecular formula is CHF2CF3, and molar mass is 120.02, and normal boiling point is-48.35 ℃, and critical temperature is 66.05 ℃, and emergent pressure is 3.59MPa.
Embodiment one:
Dme with 60%, 30% 1,1-C2H4F2 C2H4F2,10% pentafluoride ethane carry out under liquid phase after the physical mixed as refrigeration agent.
Case study on implementation 2:
Dme with 60%, 25% 1,1-C2H4F2 C2H4F2,15% pentafluoride ethane carry out under liquid phase after the physical mixed as refrigeration agent.
Case study on implementation 3:
Dme with 60%, 20% 1,1-C2H4F2 C2H4F2,20% pentafluoride ethane carry out under liquid phase after the physical mixed as refrigeration agent.
Case study on implementation 4:
Dme with 65%, 25% 1,1-C2H4F2 C2H4F2,10% pentafluoride ethane carry out under liquid phase after the physical mixed as refrigeration agent.
Case study on implementation 5:
Dme with 65%, 20% 1,1-C2H4F2 C2H4F2,15% pentafluoride ethane carry out under liquid phase after the physical mixed as refrigeration agent.
Case study on implementation 6:
Dme with 70%, 20% 1,1-C2H4F2 C2H4F2,10% pentafluoride ethane carry out under liquid phase after the physical mixed as refrigeration agent.
3 ℃ of vaporization temperatures, 40 ℃ of condensing temperatures, 5 ℃ of supercooling temperatures, under the operating mode that temperature of superheat is 5 ℃, refrigeration parameter and the performance perameter of above-mentioned various cases see Table five.
The refrigeration performance of each case study on implementation of table five the present invention and other refrigeration agents relatively
Claims (6)
1. the environmental protection and energy saving refrigeration agent of an alternative R134a is characterized in that, by dme, 1,1-C2H4F2 C2H4F2 and pentafluoride ethane are formed, and each constituent mass per-cent is as follows:
Dme: 50%～70%
1,1-C2H4F2 C2H4F2: 20%～30%
Pentafluoride ethane: 10%～20%.
2. environmental protection and energy saving refrigeration agent according to claim 1 is characterized in that, each constituent mass per-cent is:
Dme: 60%～65%
1,1-C2H4F2 C2H4F2: 20%～25%
Pentafluoride ethane: 10%～15%.
3. environmental protection and energy saving refrigeration agent according to claim 1 is characterized in that, the dme in the described component, its chemical molecular formula is CH3OCH3, and molar mass is 46.07, and normal boiling point is-24.81 ℃, critical temperature is 127.15 ℃, and emergent pressure is 5.34MPa.
4. environmental protection and energy saving refrigeration agent according to claim 1 is characterized in that, 1 in the described component, 1-C2H4F2 C2H4F2, its chemical molecular formula are CH3CHF2, and molar mass is 66.05, normal boiling point is-24.02 ℃, and critical temperature is 113.26 ℃, and emergent pressure is 4.52MPa.
5. environmental protection and energy saving refrigeration agent according to claim 1 is characterized in that, the pentafluoride ethane in the described component, its chemical molecular formula is CHF2CF3, and molar mass is 120.02, and normal boiling point is-48.35 ℃, critical temperature is 66.05 ℃, and emergent pressure is 3.59MPa.
6. the preparation method of environmental protection and energy saving refrigeration agent according to claim 1 is characterized in that, described each component is carried out physical mixed by mass percentage under liquid phase state.
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Cited By (3)
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| CN104610918A (en) * | 2015-03-04 | 2015-05-13 | 天津大学 | Environment-friendly refrigerant suitable for refrigeration and cold storage system |
| CN107057647A (en) * | 2017-06-21 | 2017-08-18 | 合肥嘉仕诚能源科技有限公司 | It is a kind of for refrigerant of air-conditioning and preparation method thereof |
| CN114989783A (en) * | 2022-05-28 | 2022-09-02 | 哈尔滨工业大学 | Environment-friendly mixed refrigerant and preparation method thereof |
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| CN107057647A (en) * | 2017-06-21 | 2017-08-18 | 合肥嘉仕诚能源科技有限公司 | It is a kind of for refrigerant of air-conditioning and preparation method thereof |
| CN114989783A (en) * | 2022-05-28 | 2022-09-02 | 哈尔滨工业大学 | Environment-friendly mixed refrigerant and preparation method thereof |
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