CN101864276A

CN101864276A - Environment-friendly refrigerant

Info

Publication number: CN101864276A
Application number: CN201010196200A
Authority: CN
Inventors: 陈武; 刘世杰
Original assignee: Jimei University
Current assignee: Jimei University
Priority date: 2010-06-03
Filing date: 2010-06-03
Publication date: 2010-10-20

Abstract

The invention discloses an environment-friendly refrigerant used for refrigerators, air-conditioners and heat pumps. The refrigerant is composed of trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), 1,1-difluoroethane (HFC-152a) and difluoromethane (HFC-32). The preparation method is characterized by physically mixing the components under normal temperature according to corresponding proportion. The ozone depletion potential (ODP) is zero and the global warming potential (GWP) is low, therefore, the refrigerant conforms to the requirement of environmental protection, and the refrigerant has physical property equivalent to that of HFC-134a and can be used in the existing HFC-134a system and serve as the substitute refrigerant of HFC-134a.

Description

Environment friendly refrigerating fluid

Technical field

The present invention relates to a kind of refrigerant composition, relate in particular to a kind of environment friendly refrigerating fluid that substitutes HFC-134a in refrigeration, air-conditioning or the heat-pump apparatus that uses HFC-134a that is applied to have now.

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 class refrigeration agent.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 a kind of refrigeration, air-conditioning or heat pump environment friendly refrigerating fluid, 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 a kind of environment friendly refrigerating fluid, and it is by trans-1,3,3, and 3-tetrafluoeopropene (HFO-1234ze (E)), 1,1-C2H4F2 C2H4F2 (HFC-152a) and methylene fluoride (HFC-32) are formed; The mass percent of each component is:

Trans-1,3,3,3-tetrafluoeopropene (HFO-1234ze (E)): 40%～75%;

1,1-C2H4F2 C2H4F2 (HFC-152a): 20%～50%;

Methylene fluoride (HFC-32): 5%～15%.

The preparation method of refrigerant composition provided by the invention, be with trans-1,3,3,3-tetrafluoeopropene (HFO-1234ze (E)), 1,1-C2H4F2 C2H4F2 (HFC-152a) and methylene fluoride (HFC-32) carry 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 6WP is very low, 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
Component	Title	Molecular weight	Normal boiling point ℃	Critical temperature ℃	Emergent pressure MPa	??ODP	??GWP	??HFO-1234??ze(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	??HFO-1234??ze(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	??HFC-32	Methylene fluoride	??52.02	??-51.65	??78.11	??5.782	??0	??550

The present invention is further illustrated below in conjunction with specific embodiment.

Embodiment

Embodiment 1: get 40% HFO-1234ze (E), 50% HFC-152a, 10% HFC-32, carry out at normal temperatures after the physical mixed as refrigeration agent.

Embodiment 2: get 45% HFO-1234ze (E), 40% HFC-152a, 15% HFC-32, carry out at normal temperatures after the physical mixed as refrigeration agent.

Embodiment 3: get 55% HFO-1234ze (E), 35% HFC-152a, 10% HFC-32, carry out at normal temperatures after the physical mixed as refrigeration agent.

Embodiment 4: get 60% HFO-1234ze (E), 32% HFC-152a, 8% HFC-32, carry out at normal temperatures after the physical mixed as refrigeration agent.

Embodiment 5: get 65% HFO-1234ze (E), 30% HFC-152a, 5% HFC-32, carry out at normal temperatures after the physical mixed as refrigeration agent.

Embodiment 6: get 75% HFO-1234ze (E), 20% HFC-152a, 5% HFC-32, 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
Parameter and performance	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Embodiment 6	??HFC-13??4a	Evaporating pressure MPa	??0.316	??0.335	??0.313	??0.303	??0.289	??0.281	??0.315
Condensing pressure MPa	??1.665	??1.765	??1.658	??1.608	??1.544	??1.510	??1.682	Evaporating pressure MPa	??0.316	??0.335	??0.313	??0.303	??0.289	??0.281	??0.315
Condensing pressure MPa	??1.665	??1.765	??1.658	??1.608	??1.544	??1.510	??1.682	Pressure ratio	??5.27	??5.27	??5.30	??5.31	??5.33	??5.37	??5.35
System amount refrigerating duty KJ/kg	??169.33	??158.74	??153.17	??148.3	??143.12	??133.41	??125.23	Pressure ratio	??5.27	??5.27	??5.30	??5.31	??5.33	??5.37	??5.35
System amount refrigerating duty KJ/kg	??169.33	??158.74	??153.17	??148.3	??143.12	??133.41	??125.23	Volume refrigerating capacity compressor KJ/m3	??1927	??1936	??1863	??1800	??1727	??1652	??1884
??COP	??3.50	??3.32	??3.43	??3.44	??3.46	??3.41	??3.49	Volume refrigerating capacity compressor KJ/m3	??1927	??1936	??1863	??1800	??1727	??1652	??1884
??COP	??3.50	??3.32	??3.43	??3.44	??3.46	??3.41	??3.49	??ODP	??0	??0	??0	??0	??0	??0	??0
??GWP	??116.6	??132.3	??99.2	??84.8	??66.1	??54.5	??1300	??ODP	??0	??0	??0	??0	??0	??0	??0

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:

Claims

1. environment friendly refrigerating fluid is characterized in that: it is by trans-1, and 3,3,3-tetrafluoeopropene (HFO-1234ze (E)), 1,1-C2H4F2 C2H4F2 (HFC-152a) and methylene fluoride (HFC-32) are formed; The mass percent of each component is:

Trans-1,3,3,3-tetrafluoeopropene (HFO-1234ze (E)): 40%～75%;

1,1-C2H4F2 C2H4F2 (HFC-152a): 20%～50%;

Methylene fluoride (HFC-32): 5%～15%.