CN102153992A

CN102153992A - Refrigerant capable of being directly filled for replacing R22

Info

Publication number: CN102153992A
Application number: CN2008102380724A
Authority: CN
Inventors: 于淑芳
Original assignee: Individual
Current assignee: Individual
Priority date: 2008-12-08
Filing date: 2008-12-08
Publication date: 2011-08-17

Abstract

The invention provides a refrigerant composition capable of being directly filled for replacing R22 in systems such as a household air conditioner/ heat pump and the like. The refrigerant comprises pentafluoroethane (R125), 1,1,1,2- tetrafluoroethane (R134a) and dimethyl ether (DME or RE170); and the preparation method of the refrigerant comprises the following step of physically mixing all the components under a liquid phase in the corresponding proportions. The refrigerant completely meets the requirement of environment protection and has the ODP (Ozone Destruction Potential) value of zero and low GWP (Global Warming Potential) value; the thermodynamic engineering performance and the parameters of the refrigerant are very close to R22; the pressure and the exhausting temperature of a compressor are lower than those of R22; any parts and the lubricating oil of the traditional R22 system do not need to be changed or replaced when R22 is replaced with the refrigerant; the refrigerant can be filled directly and has good cycle performance same as or slightly higher than R22.

Description

A kind of directly refrigeration agent of filling to substitute R 22

Technical field

The invention belongs to refrigerant art, relate to a kind of refrigerant composition, relate in particular to a kind of refrigerant composition that is applied to substitute in the refrigerated air-conditioning system such as domestic air conditioning/heat pump R22.

Background technology

According to the script regulation of Montreal protocol, developed country will stop the R22 production and consumption of non-feedstock property fully in the year two thousand thirty, and developing country's (comprising China) will stop the R22 production and consumption of non-feedstock property in the year two thousand forty.But in the up-to-date resolution that the Montreal protocol conference of contracting party that Montreal, CAN is held is reached, stipulate in September, 2007, developed country will stop the R22 production and consumption of non-feedstock property fully in the year two thousand twenty, the developing country that comprises China, be frozen on the mean level (ML) of 2009 and 2010 the production and consumption amounts with non-feedstock property HCFCs (wherein about 70% is R22) in 2013, the year two thousand thirty finishes comprehensively and eliminates.Compare original superseded timetable, whole superseded process shifts to an earlier date greatly, and about 80% systems such as domestic air conditioning/heat pump of domestic production at present and application adopt R22 to make refrigeration agent, this shows, the alternative situation of the R22 very research and development of sternness and substitute is extremely urgent.

Current, the main substitute of R22 comprises R407C (R32/125/134a) and R410A (R32/125) etc. on the domestic and international market, but these substitutes are still undesirable, and for example, the efficiency of R407C is lower, and its slip temperature is bigger, has restricted its market and has used; R410A and R22 system are incompatible, compressor that the alternative R22 of use R410A must more renew and two devices etc., and these two kinds of substitutes are direct filling to substitute R 22 all, needs system component or lubricated wet goods are done to change or change in alternative Process, has increased alternative cost greatly.In addition, existing directly R417A of filling to substitute R 22 (R125/134a/600) or R422A (R125/134a/600a) etc. when direct filling to substitute R 22, show that efficient reduces, cold reduces or shortcoming such as pressure increase, and substitution effect is unsatisfactory.

In the prior art, disclose among the patent application EP 1184438 by 55～94% pentafluoride ethane, 2.5～35% 1,1,1, the mixture that 2-Tetrafluoroethane and 3.5～25% dme are formed, but the mixture of forming with this ratio is when direct filling to substitute R 22, shows efficient reduction, hypertonia even defective such as inflammable, and effect is unsatisfactory.In patent application US20060011884, disclose contain at least 75% pentafluoride ethane, 5～24% 1,1,1, the mixture of 2-Tetrafluoroethane and 1～4% dme, when direct filling to substitute R 22, the mixture of forming with this ratio is the same with aforementioned invention, show defectives such as efficient reduction, hypertonia, effect is also undesirable.

In addition, the mixture of forming with materials such as pentafluoride ethane, Tetrafluoroethane and hydrocarbon polymers is disclosed among the U.S. Patent application US 2008029733; The mixture of forming with pentafluoride ethane and Tetrafluoroethane is disclosed among the patent application WO 2007102815; Chinese patent file CN 91112767.4, US 649356 and WO 9211339 disclose the mixture of forming with pentafluoride ethane, methylene fluoride and Tetrafluoroethane; Chinese patent file CN 91112768.2, U.S. US 412974 and WO 9105027 disclose the binary mixture of forming with pentafluoride ethane and methylene fluoride; Chinese patent file CN 92110844.3 discloses with methylene fluoride, 1,1, the mixture that 1-Halothane and pentafluoride ethane are formed; Chinese patent file CN 92112759.6 discloses the mixture of forming with methylene fluoride and Tetrafluoroethane; Chinese patent file CN 93102698.9 discloses with methylene fluoride, 1,1,1,2-Tetrafluoroethane and be selected from 1,1-C2H4F2 C2H4F2,1,1, the mixture that 1-Halothane, propane etc. are formed; Chinese patent file CN 96101957.3 discloses the mixture of forming with methylene fluoride, pentafluoride ethane and other fluorochemical; Chinese patent file CN 00121159.5 discloses with methylene fluoride, 1,1,1,2-Tetrafluoroethane and 1,1,1,2,3,3, the tertiary mixture that the 3-heptafluoro-propane is formed; Chinese patent file CN 00121158.7 discloses the tertiary mixture of forming with propane, pentafluoride ethane and methylene fluoride; Chinese patent file CN 03116856.6 discloses the tertiary mixture of forming with fluoroethane, pentafluoride ethane and methylene fluoride; Chinese patent file CN 200710068823.8 discloses the tertiary mixture of forming with methylene fluoride, pentafluoride ethane and trifluoromethane; U.S. US 7276176 and US 7258813 disclose with pentafluoride ethane, 1,1,1, the mixture that 2-Tetrafluoroethane and Trimethylmethane are formed; U.S. US 6846792 discloses with pentafluoride ethane, 1,1, the mixture of 1-Halothane and third rare composition; U.S. US 6783691 discloses with methylene fluoride, pentafluoride ethane, 1,1,1, the mixture that 2-Tetrafluoroethane and hydrocarbon polymer are formed; U.S. US 5624596 discloses the mixture of forming with methylene fluoride, pentafluoride ethane and hydrocarbon polymer.Mixture in these applications substantially all is to research and develop in order to substitute R22, but these mixtures exist or have high GWP value, or stronger combustibility is arranged, or has a bigger slip temperature, or incompatible with the R22 system, or efficient is lower, or costs an arm and a leg and substituted expenses height or the like problem.

Summary of the invention

At the deficiencies in the prior art, the invention provides a kind of directly refrigeration agent of filling to substitute R 22.Refrigeration agent of the present invention is used for systems such as domestic air conditioning/heat pump, has both met environmental protection requirement, again safety, reliable, refrigerating efficiency is high, but also need not to change or change existing systems parts and production line, can directly charge.

Refrigerant composition of the present invention, by pentafluoride ethane (R125), 1,1,1,2-Tetrafluoroethane (R134a) and dme (DME or RE170) are formed, and each constituent mass per-cent is as follows:

Pentafluoride ethane: 45～52%

1,1,1,2-Tetrafluoroethane: 45～52%

Dme: 3～6%

Preferably, refrigerant composition of the present invention, component is as follows, is mass percent:

Pentafluoride ethane 46～50%, 1,1,1,2-Tetrafluoroethane 46～50%, dme 3～5%.

Pentafluoride ethane in the said components (R125), its molecular formula are CHF ₂CF ₃, molar mass is 120.02, and normal boiling point is-48.1 ℃, and critical temperature is 66.02 ℃, and emergent pressure is 3.62MPa.

In the said components 1,1,1,2-Tetrafluoroethane (R134a), its molecular formula is CF ₃CH ₂F, molar mass is 102.03, and normal boiling point is-26.07 ℃, and critical temperature is 101.06 ℃, and emergent pressure is 4.059MPa.

Dme in the said components (DME or RE170), its molecular formula is CH ₃OCH ₃, molar mass is 46.07, and normal boiling point is-24.8 ℃, and critical temperature is 127.2 ℃, and emergent pressure is 5.34MPa.

The invention provides the preparation method of above-mentioned refrigeration agent, with pentafluoride ethane, 1,1,1,2-Tetrafluoroethane and dme carry out physical mixed by its corresponding mixture ratio and get final product under liquid phase state.

Refrigerant composition of the present invention; be to be used for the directly refrigeration agent of filling to substitute R 22 of system such as domestic air conditioning/heat pump; this refrigerant composition meets requirement on environmental protection fully; the ODP value is zero, and the GWP value is lower, and thermal property and parameter and R22 ten minutes are approaching; pressure and compressor exhaust temperature are low than R22; need not to change or change any parts and the lubricating oil of existing R22 system when alternative, can realize directly charging, and cycle performance and R22 height quite or slightly.

Beneficial effect of the present invention is as follows:

A. environmental performance

The environmental performance that table 1 has been listed the present invention and R22 compares, and as can be seen, ozone layer destroying potential value of the present invention (ODP) is zero, can not destroy atmospheric ozone layer, satisfies current domestic and international environment-friend substitution requirement to R22 fully, and the GWP value is lower.

Table 1 environmental performance relatively

B. thermal parameter:

The thermal parameter that table 2 has provided the present invention and R22 compares, under the air conditioning condition of ARI Standard 520 international standards, the force value of vaporizer, condenser inner refrigerant and exhaust temperature are all low than R22, can realize directly charging, and useful to the compressor long-time running.

Table 2 thermal parameter relatively

C. thermal property

The thermal property that table 3 has provided the present invention and R22 relatively, COP value of the present invention and R22 are quite or the summary height; Refrigerating effect per unit swept volume and R22 are suitable, can satisfy the workload demand that substitutes refrigeration air-conditioner behind the R22 fully.

Table 3 thermal property relatively

D. directly charge performance

Basic thermal parameter of the present invention and R22 are very approaching, and through meeting the material compatibility experimental verification of international standard regulation, metallic substance, plastic material and resilient material etc. in the present invention and the former R22 system all are compatible, needn't transform or change the parts and the pipeline of former R22 system during replacement; Through the checking of lubricating oil compatibility test, the mineral oil (MO) that the present invention and R22 system use mixes, thereby the present invention can directly charge in the R22 system, need not to change any pipeline component and lubricating oil.

In sum, ODP value of the present invention is zero, and the GWP value is lower, meets the environmental requirement of the alternative R22 of refrigeration air-conditioner such as domestic air conditioning/heat pump fully; Thermal parameter and performance and R22 are very approaching, need not to change the equipment and the parts of existing R22 refrigerated air-conditioning system, and mix with mineral oil, can realize directly charging, and be a kind of ideal substitute of R22.

Embodiment

The present invention is described further below in conjunction with embodiment, but be not limited thereto.

The ratio of each component is mass percent among the embodiment, pentafluoride ethane wherein (R125), and its molecular formula is CHF ₂CF ₃, molar mass is 120.02, and normal boiling point is-48.1 ℃, and critical temperature is 66.02 ℃, and emergent pressure is 3.62MPa; 1,1,1,2-Tetrafluoroethane (R134a), its molecular formula is CF ₃CH ₂F, molar mass is 102.03, and normal boiling point is-26.07 ℃, and critical temperature is 101.06 ℃, and emergent pressure is 4.059MPa; Dme (DME or RE170), its molecular formula is CH ₃OCH ₃, molar mass is 46.07, and normal boiling point is-24.8 ℃, and critical temperature is 127.2 ℃, and emergent pressure is 5.34MPa.

Embodiment 1: refrigerant composition, and component is as follows:

Pentafluoride ethane 45%, 1,1,1,2-Tetrafluoroethane 52%, dme 3%.

Preparation method: above three kinds of components are promptly got refrigeration agent after carrying out physical mixed under the liquid phase.

Embodiment 2: refrigerant composition, and component is as follows:

Pentafluoride ethane 46%, 1,1,1,2-Tetrafluoroethane 50%, dme 4%.The preparation method is with embodiment 1.

Embodiment 3: refrigerant composition, and component is as follows:

Pentafluoride ethane 46%, 1,1,1,2-Tetrafluoroethane 48%, dme 6%.The preparation method is with embodiment 1.

Embodiment 4: refrigerant composition, and component is as follows:

Pentafluoride ethane 48%, 1,1,1,2-Tetrafluoroethane 47%, dme 5%.The preparation method is with embodiment 1.

Embodiment 5: refrigerant composition, and component is as follows:

Pentafluoride ethane 50%, 1,1,1,2-Tetrafluoroethane 46%, dme 4%.The preparation method is with embodiment 1.

Embodiment 6: refrigerant composition, and component is as follows:

Pentafluoride ethane 52%, 1,1,1,2-Tetrafluoroethane 45%, dme 3%.The preparation method is with embodiment 1.

Under the air conditioning condition of ARI Standard 520 international standards, be that vaporization temperature is that 7.2 ℃, condensing temperature are that 54.4 ℃, temperature of superheat are that 11.1 ℃, supercooling temperature are that 8.3 ℃ and compressor efficiency are that the environmental parameter of the foregoing description refrigeration agent, physical parameter and thermal property are listed in the table 4 under 80% the operating mode.

The environmental parameter of table 4 refrigeration agent, physical parameter and thermal property

Remarks: ^*The corresponding ratio of expression and R22, wherein COP is the coefficient of performance.

Claims

1. a refrigerant composition is characterized in that, by pentafluoride ethane, 1,1,1,2-Tetrafluoroethane and dme are formed, and the mass percent of each component is as follows:

Pentafluoride ethane 45～52%

1,1,1,2-Tetrafluoroethane 45～52%

Dme 3～6%.

2. refrigerant composition as claimed in claim 1 is characterized in that component is as follows, is mass percent:

Pentafluoride ethane 46～50%, 1,1,1,2-Tetrafluoroethane 46～50%, dme 3～5%.

3. the preparation method of the described refrigerant composition of claim 1 is with pentafluoride ethane, 1,1,1, and 2-Tetrafluoroethane and dme carry out physical mixed by its corresponding mixture ratio under liquid phase state.