CN101851490A - Refrigerant composition capable of replacing HFC-134a - Google Patents

Refrigerant composition capable of replacing HFC-134a Download PDF

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Publication number
CN101851490A
CN101851490A CN 201010198685 CN201010198685A CN101851490A CN 101851490 A CN101851490 A CN 101851490A CN 201010198685 CN201010198685 CN 201010198685 CN 201010198685 A CN201010198685 A CN 201010198685A CN 101851490 A CN101851490 A CN 101851490A
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hfc
hfo
refrigerant composition
tetrafluoeopropene
gwp
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CN101851490B (en
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陈武
刘世杰
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Jimei University
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Jimei University
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Abstract

The invention discloses a refrigerant composition capable of replacing HFC-134a, consisting of 2,3,3,3-tetrafluoropropene (HFO-1234yf), trans-1,3,3,3-tetrafluoropropene (HFO-1234ze (E)) and 1,1-difluoroethane (HFC-152a). The ozone depleting potential (ODP) value of the refrigerant composition is zero and the value of global warm potential (GWP) is extraordinary low, thus conforming to the requirement of environmental protection, and the refrigerant composition of the invention has the physical property equivalent to the physical property of HFC-134a, can be directly used for the existing HFC-134a system without redesigning a compressor.

Description

The refrigerant composition of alternative HFC-134a
Technical field
The present invention relates to a kind of refrigerant composition, relate in particular to a kind of refrigerant composition that is applied to have now alternative HFC-134a in refrigeration, air-conditioning or the heat-pump apparatus that uses HFC-134a.
Background technology
With HCFC-22, CFC-12, CFC-11 is that the freonll-11 of representative has good thermodynamic cycle performance, is widely used in industries such as refrigeration, air-conditioning.But this type of material has higher ozone depletion potential (ODP), and atmospheric residence time is very long, and global warming potential (GWP) is also very high, is one of main chemical substance of destroying atmospheric ozone layer, generation Greenhouse effect.Deleterious ultraviolet radiation can directly arrive earth surface after ozonosphere went to pot, and the plant plankton in farm crop and the ocean is produced severe impairment, but also can influence the immunity system of human body, the sickness rate of increase skin carcinoma, cataract etc.Global warming is another severe environmental problem that the mankind face, and brings serious consequence to ecotope, and thousands of times of GWP values have also played the effect of adding fuel to the flames to a large amount of dischargings of the refrigeration agent of carbonic acid gas.Montreal protocol and amendment thereof are forbidden CFC class material substantially, and regulation is progressively cut down to finally banning use of HCFC-22.In recent years, the exploitation about the refrigeration agent substitute products is one of important topic of organic fluorine chemical industry and association area research always.
The refrigeration agent substitute products that use mainly are HFC-134a, R410A and R407C etc. at present.But these refrigeration agents respectively have relative merits, still are not very desirable.Wherein, the thermal conduction of R407C is relatively poor, and volume refrigerating capacity compressor under the identical operating mode and COP value in order to reach the refrigerating duty identical with HCFC-22, need the heat-transfer effect of enhanced heat exchange device all less than HCFC-22, and manufacturing cost will increase.The volume refrigerating capacity compressor of R410A is big more a lot of than HCFC-22, but its evaporating pressure, condensing pressure are also high a lot of than HCFC-22, can not directly be used for substituting HCFC-22, need to redesign compressor, interchanger, pipeline and system in use, and, these two kinds of mix refrigerants all have higher GWP value, and a large amount of dischargings can the aggravation global warming.HFC-134a has good thermomechanical property and good safety in utilization, has become the refrigeration agent of widespread use in the domestic and international refrigerating and air conditioning industry, and its ODP is zero, but GWP is still higher, and a large amount of uses can cause global warming equally.Fluorine-containing greenhouse gases (F-gas) the control laws and regulations requirement that European Union in 2004 passes through, from on January 1st, 2011, European Union will forbid that the automative air conditioning of new production uses the GWP value greater than 150 refrigeration agent, and from January 1st, 2017, forbid that all automative air conditionings use GWP greater than 150 refrigeration agent, therefore, study refrigeration agent that hangs down GWP and the trend that matching system becomes refrigeration, air-conditioning and heat pump industry development thereof and inevitable.
Summary of the invention
The objective of the invention is to research and develop the refrigerant composition of a kind of alternative HFC-134a, to make refrigeration agent ODP newly developed be zero and can suppress global warming, especially research and develop a kind of cycle performance and HFC-134a quite, can directly be used in the refrigeration agent that has the HFC-134a system now and can be used as the long-term surrogate of HFC-134a.
For achieving the above object, technical solution of the present invention is:
The present invention is the refrigerant composition of a kind of alternative HFC-134a, and it is by 2,3,3,3-tetrafluoeopropene (HFO-1234yf), trans-1,3,3,3-tetrafluoeopropene (HFO-1234ze (E)) and 1,1-C2H4F2 C2H4F2 (HFC-152a) is formed, and the mass percent of each component is:
2,3,3,3-tetrafluoeopropene (HFO-1234yf): 30%~70%;
Trans-1,3,3,3-tetrafluoeopropene (HFO-1234ze (E)): 5%~30%;
1,1-C2H4F2 C2H4F2 (HFC-152a): 25%~60%.
The preparation method of refrigerant composition provided by the invention is with 2,3,3,3-tetrafluoeopropene (HFO-1234yf), trans-1,3,3,3-tetrafluoeopropene (HFO-1234ze (E)) and 1,1-C2H4F2 C2H4F2 (HFC-152a) carries out physical mixed at normal temperatures by its specified quality proportioning.
The present invention has the following advantages and beneficial effect:
1, ODP value of the present invention is zero, and GWP very low (less than 150) meets environmental protection requirement.Table 1 has been listed the basic parameter of each component of the present invention.
2, thermal parameter and HFC-134a are very approaching, the present invention directly can be charged in refrigeration, air-conditioning or the heat pump set of the existing HFC-134a of use, need not to be specialized designs compressor of the present invention and system thereof.
3, cycle performance is good.COP value of the present invention is suitable with HFC-134a, and volume refrigerating capacity compressor is also very approaching with HFC-134a, need not the parts and the pipeline of the system that changes when substituting HFC-134a, meets HFC-134a alternate long term growth requirement.
In a word; refrigerant composition provided by the invention is to develop with substituting of refrigeration agent for satisfying refrigeration, air-conditioning or heat pump, especially can be used for existing HFC-134a system and substitute HFC-134a; thermal property is suitable in HFC-134a, meets requirement on environmental protection.
The basic parameter of the contained component of table 1 environment friendly refrigerating fluid
Component Title Molecular weight Normal boiling point ℃ Critical temperature ℃ Emergent pressure MPa ??ODP ??GWP
??HFO-1234yf 2,3,3, the 3-tetrafluoeopropene ??114.04 ??-29.45 ??94.7 ??3.382 ??0 ??4
??HFO-1234ze??(E) Trans-1,3,3, the 3-tetrafluoeopropene ??114.04 ??-18.95 ??109.37 ??3.636 ??0 ??4
??HFC-152a 1, the 1-C2H4F2 C2H4F2 ??66.05 ??-24.02 ??113.26 ??4.517 ??0 ??120
The present invention is further illustrated below in conjunction with specific embodiment.
Embodiment
The present invention is the refrigerant composition of a kind of alternative HFC-134a, and it is by 2,3,3,3-tetrafluoeopropene (HFO-1234yf), trans-1,3,3,3-tetrafluoeopropene (HFO-1234ze (E)) and 1,1-C2H4F2 C2H4F2 (HFC-152a) is formed, and the mass percent of each component is:
Embodiment 1: get 30% HFO-1234yf, 10% HFO-1234ze (E), 60% HFC-152a, carry out at normal temperatures after the physical mixed as refrigeration agent.
Embodiment 2: get 35% HFO-1234yf, 30% HFO-1234ze (E), 35% HFC-152a, carry out at normal temperatures after the physical mixed as refrigeration agent.
Embodiment 3: get 40% HFO-1234yf, 10% HFO-1234ze (E), 50% HFC-152a, carry out at normal temperatures after the physical mixed as refrigeration agent.
Embodiment 4: get 45% HFO-1234yf, 15% HFO-1234ze (E), 40% HFC-152a, carry out at normal temperatures after the physical mixed as refrigeration agent.
Embodiment 5: get 55% HFO-1234yf, 10% HFO-1234ze (E), 35% HFC-152a, carry out at normal temperatures after the physical mixed as refrigeration agent.
Embodiment 6: get 70% HFO-1234yf, 5% HFO-1234ze (E), 25% HFC-152a, carry out at normal temperatures after the physical mixed as refrigeration agent.
The design conditions of refrigeration system are taken as: average vaporization temperature is 2 ℃, and average condensing temperature is 60 ℃, and superheating temperature is 5 ℃, and condensate depression is 5 ℃, according to cycle calculations, the foregoing description have related parameter and cycle performance index as shown in table 2.Also listed the parameter of HFC-134a in the table 2, for comparing.
Table 2 embodiment of the invention performance
Parameter and performance Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 ??HFC-13??4a
Evaporating pressure MPa ??0.311 ??0.314 ??0.321 ??0.327 ??0.336 ??0.347 ??0.315
Condensing pressure MPa ??1.605 ??1.609 ??1.637 ??1.653 ??1.681 ??1.707 ??1.682
Pressure ratio ??5.15 ??5.12 ??5.10 ??5.06 ??5.0 ??4.92 ??5.35
Quality refrigerating duty KJ/kg ??161.63 ??133.96 ??148.25 ??137.26 ??129.42 ??116.95 ??125.23
Volume refrigerating capacity compressor KJ/m3 ??1877 ??1801 ??1878 ??1865 ??1873 ??1860 ??1884
??COP ??3.55 ??3.45 ??3.50 ??3.46 ??3.42 ??3.36 ??3.49
??ODP ??0 ??0 ??0 ??0 ??0 ??0 ??0
??GWP ??73.6 ??38.3 ??62 ??50.4 ??44.6 ??33 ??1300
As can be seen from Table 2, every performance and the parameter of the present invention and HFC-134a are more approaching, and ozone layer destroying potential of the present invention (ODP) is zero, can not destroy atmospheric ozone layer, and Greenhouse effect potential (GWP) is very low, meets requirement on environmental protection.
The preparation method:
The preparation method of refrigerant composition provided by the invention is with 2,3,3,3-tetrafluoeopropene (HFO-1234yf), trans-1,3,3,3-tetrafluoeopropene (HFO-1234ze (E)) and 1,1-C2H4F2 C2H4F2 (HFC-152a) carries out physical mixed at normal temperatures by its specified quality proportioning.

Claims (1)

1. the refrigerant composition of an alternative HFC-134a is characterized in that: it is by 2,3, and 3,3-tetrafluoeopropene (HFO-1234yf), trans-1,3,3,3-tetrafluoeopropene (HFO-1234ze (E)) and 1,1-C2H4F2 C2H4F2 (HFC-152a) is formed, and the mass percent of each component is:
2,3,3,3-tetrafluoeopropene (HFO-1234yf): 30%~70%;
Trans-1,3,3,3-tetrafluoeopropene (HFO-1234ze (E)): 5%~30%;
1,1-C2H4F2 C2H4F2 (HFC-152a): 25%~60%.
CN201010198685A 2010-06-04 2010-06-04 Refrigerant composition capable of replacing HFC-134a Expired - Fee Related CN101851490B (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102516945A (en) * 2011-12-20 2012-06-27 集美大学 Refrigerant composition capable of substituting HCFC-22
CN104531079A (en) * 2014-12-11 2015-04-22 中国科学院理化技术研究所 Tetrafluoropropylene-containing mixture refrigerant
CN105038711A (en) * 2015-07-30 2015-11-11 天津大学 Mixed refrigerant containing 1,1-difluoroethane
CN106833536A (en) * 2016-12-26 2017-06-13 浙江衢化氟化学有限公司 A kind of refrigerant composition earl august eugene lund ian robert containing HF hydrocarbon
CN110628387A (en) * 2019-09-12 2019-12-31 珠海格力电器股份有限公司 Low-flammability heat transfer composition and heat exchange system
WO2021062963A1 (en) 2019-09-30 2021-04-08 浙江衢化氟化学有限公司 Composition of fluoroolefin and fluoroalkane
WO2022017109A1 (en) 2020-07-21 2022-01-27 浙江衢化氟化学有限公司 Composition containing fluorohydrocarbon and preparation method therefor

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CN1977025A (en) * 2004-04-29 2007-06-06 霍尼韦尔国际公司 Azeotrope-like compositions of tetrafluoropropene and hydrofluorocarbons
WO2008027555A2 (en) * 2006-09-01 2008-03-06 E. I. Du Pont De Nemours And Company Method for circulating selected heat transfer fluids through a closed loop cycle
RU2007136789A (en) * 2005-03-04 2009-04-10 Е.И.Дюпон де Немур энд Компани (US) COMPOSITIONS CONTAINING FLUOROLEFIN
WO2010059677A2 (en) * 2008-11-19 2010-05-27 E. I. Du Pont De Nemours And Company Tetrafluoropropene compositions and uses thereof

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CN1969028A (en) * 2004-04-16 2007-05-23 霍尼韦尔国际公司 Azeotrope-like compositions of tetrafluoropropene and trifluoroiodomethane
CN1977025A (en) * 2004-04-29 2007-06-06 霍尼韦尔国际公司 Azeotrope-like compositions of tetrafluoropropene and hydrofluorocarbons
RU2007136789A (en) * 2005-03-04 2009-04-10 Е.И.Дюпон де Немур энд Компани (US) COMPOSITIONS CONTAINING FLUOROLEFIN
WO2008027555A2 (en) * 2006-09-01 2008-03-06 E. I. Du Pont De Nemours And Company Method for circulating selected heat transfer fluids through a closed loop cycle
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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102516945A (en) * 2011-12-20 2012-06-27 集美大学 Refrigerant composition capable of substituting HCFC-22
CN104531079B (en) * 2014-12-11 2018-04-17 中国科学院理化技术研究所 A kind of mix refrigerant containing tetrafluoropropene
CN104531079A (en) * 2014-12-11 2015-04-22 中国科学院理化技术研究所 Tetrafluoropropylene-containing mixture refrigerant
CN105038711A (en) * 2015-07-30 2015-11-11 天津大学 Mixed refrigerant containing 1,1-difluoroethane
KR20180090295A (en) * 2016-12-26 2018-08-10 저쟝 취화 플루오-케미스트리 컴퍼니 리미티드 Refrigerant compositions containing hydrofluoroolefins
WO2018120257A1 (en) 2016-12-26 2018-07-05 浙江衢化氟化学有限公司 Refrigerant composition containing hydrofluoroolefin
CN106833536A (en) * 2016-12-26 2017-06-13 浙江衢化氟化学有限公司 A kind of refrigerant composition earl august eugene lund ian robert containing HF hydrocarbon
CN106833536B (en) * 2016-12-26 2019-08-20 浙江衢化氟化学有限公司 A kind of refrigerant composition containing HF hydrocarbon
KR102115769B1 (en) 2016-12-26 2020-05-27 저쟝 취화 플루오-케미스트리 컴퍼니 리미티드 Refrigerant composition containing hydrofluoroolefin
US11104833B2 (en) 2016-12-26 2021-08-31 Zhejiang Quhua Fluor-Chemistry Co Ltd Hydrofluoroolefins-containing refrigerant composition
CN110628387A (en) * 2019-09-12 2019-12-31 珠海格力电器股份有限公司 Low-flammability heat transfer composition and heat exchange system
WO2021062963A1 (en) 2019-09-30 2021-04-08 浙江衢化氟化学有限公司 Composition of fluoroolefin and fluoroalkane
JP2022519506A (en) * 2019-09-30 2022-03-24 浙江衢化▲弗▼化学有限公司 Composition of Fluoroolefins and Fluoroalkanes
WO2022017109A1 (en) 2020-07-21 2022-01-27 浙江衢化氟化学有限公司 Composition containing fluorohydrocarbon and preparation method therefor

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