A kind of environmental protection type refrigeration composition
Technical field
The present invention relates to a kind of refrigerant compositions, can substitute HFC-134a, HCFC-22 and R404A more particularly, to a kind of
Environmental protection type refrigeration composition.
Background technology
Substitute of the HFA 134a (HFC-134a) as CFC-12, has been obtained extensively with the performance which is excellent
Application, but as which has up to 1430 greenhouse effect value, the first batch of high GWP value eliminated is classified as by " Kyoto Protocol "
One of cold-producing medium.For the HFC-134a being applied in small-type refrigeration appliance, major part is substituted using HC-600a,
And for the replacement for being applied to industrial and commercial refrigeration and air conditioning for automobiles HFC-134a has become the focus of countries in the world research and is badly in need of solution
Problem certainly.
International community is mainly to the research direction that HFC-134a is substituted at present:Carbon dioxide (CO2), 1,1- Difluoroethanes
(HFC-152a), 2,3,3,3- tetrafluoropropenes (HFO-1234yf) etc..But these schemes respectively have pluses and minuses:Using CO2Ring
Guaranteed cost is good, non-combustible, but system pressure height, efficiency are low, and system needs redesign, alternative cost high;Using HFC-152a
Although efficiency is high, cold-producing medium price is low, combustibility is strong for which, need to increase secondary circuit etc. causes alternative cost high;Use
Although HFO-1234yf and combinations thereof low, system reforms of combustibility are few, relative efficiency is low, refrigerating capacity is little and refrigerant cost compared with
It is high.Therefore countries in the world, in the research for persistently carrying out HFC-134a substitutes, wherein mix refrigerant is a main research
Direction.
For substitute HFC-134a mix refrigerant, present technology substantially based on HFC-134a, be further added by one kind,
Two or more suitable components constitute mix refrigerant, specifically have following report:
Chinese patent CN101283071A disclose it is a kind of with Trans-1,3,3,3- tetrafluoropropenes (HFO-1234ze (E)) and
1,1,1,2- HFC-134as (HFC-134a) or 1,1,1,2,3,3,3- heptafluoro-propanes (HFC-227ea) or 1,1,1,2,2- five
The mixture that fluoroethane (HFC-125) is constituted;
CN102083935B discloses one kind with 2,3,3,3- tetrafluoropropenes (HFO-1234yf) and 1,1,1,2- HFC-134as
(HFC-134a) mixture for constituting;
CN102918132A discloses one kind with Trans-1,3,3,3- tetrafluoropropenes (HFO-1234ze (E)), difluoromethane
And the mixture that constitutes of 1,1,1,2- HFC-134as (HFC-134a) (HFC-32);
CN102066518A discloses one kind with 2,3,3,3- tetrafluoropropenes (HFO-1234yf), 1,1,1,2- HFC-134as
And the mixture that constitutes of 1,1- Difluoroethanes (HFC-152a) (HFC-134a);
CN102083935A discloses a kind of 1,1,1,2- HFC-134as (HFC-134a), 2,3,3,3- tetrafluoropropenes
(HFO-1234yf) mixture for constituting;
CN102083935A discloses a kind of 1,1,1,2- HFC-134as (HFC-134a), 2,3,3,3- tetrafluoropropenes
(HFO-1234yf) mixture for constituting;
CN102712837A discloses a kind of 1,1,1,2- HFC-134as (HFC-134a), 2,3,3,3- tetrafluoropropenes
And the mixture that constitutes of difluoromethane (HFC-32) (HFO-1234yf);
CN102703033A discloses one kind with 2,3,3,3- tetrafluoropropenes (HFO-1234yf), 1,1,1,2- HFC-134as
And the mixture that constitutes of dimethyl ether (DME) (HFC-134a).
The mix refrigerant of the replacement HFC-134a based on tetrafluoropropene (HFO-1234yf and HFO-1234ze), have with
Lower report:
CN102216411A discloses one kind with 2,3,3,3- tetrafluoropropenes (HFO-1234yf) and propylene (HC-1270) group
Into mixture;
CN1973016A disclose it is a kind of with carbon dioxide (CO2) and 2,3,3,3- tetrafluoropropenes (HFO-1234yf) or
The mixture that Trans-1,3,3,3- tetrafluoropropenes (HFO-1234ze (E)) are constituted;
CN101671542A discloses one kind with 2,3,3,3- tetrafluoropropenes (HFO-1234yf), 1,1- Difluoroethanes
(HFC-152a) and iso-butane composition mixture;
CN101864277A discloses one kind with 2,3,3,3- tetrafluoropropenes (HFO-1234yf), 1,1- Difluoroethanes
And the mixture that constitutes of dimethyl ether (DME) (HFC-152a);
The composition of replacement HFC-134a disclosed above exist or GWP value it is higher, or combustibility compared with it is strong, or efficiency it is relatively low,
Or volume refrigerating capacity compressor it is less, or not directly charge the shortcomings of being applied to HFC-134a systems.Therefore exploitation is needed with refrigeration property
Can it is more excellent, and existing system compatibility is more preferably and environmental-protecting performance more preferably substitutes the cold-producing medium of HFC-134a.
HCFC-22 due to higher GWP (global warming potential) values and ODP (ozone depletion potential) value, to environment not
Close friend, is the material for being required that time limit is superseded.Its substitute R410A and R407C, although ODP is 0, but GWP is still higher,
And compressor, heat exchanger, pipeline and system will be redesigned when in use, cannot be in the refrigeration system using HCFC-22
In directly substitute use.Therefore, substantial amounts of research has been carried out to the new substitute of HCFC-22 both at home and abroad, has mainly had following report:
The patent of invention of Publication No. CN1055300C and CN1244663C, using HFC-32, HFC-125 and HFC-152a
Substitute of the ternary mixture as HCFC-22;
The patent of invention of publication number CN1412266A, using the mixture replacing of HFC-32, HFC-134a and HFC-143a
HCFC-22;
The patent of invention of publication number CN1136065A, using the mixture replacing of HFC-32, HFC-125 and HFC-227ea
HCFC-22;
Mixture replacing HCFC-22s of the CN1189525A using HFC-32, HFC-134a and HFC-227ea;
The patent of invention of publication number CN1780892A, employs the mixture replacing of HFC-161, HFC-32 and HFC-125
HCFC-22;
The patent of invention of publication number CN1173525A, using the mixture replacing of HC-290, HC-600a and TS fire retardant
HCFC-22;
The patent of invention of publication number CN1255502C, using the mixture replacing HCFC-22 of HC-1270, FC-13I 1 and HC-170;
Publication number CN1269391A adopts HCFC-22 and HFC-152a mixtures;
Mixture of the patent of invention of publication number CN1236801A using HCFC-22, HFC-152a and HFC-125;
Mixture of the patent of invention of publication number CN1837323A using HCFC-22, HFC-152a and HCFC-124.
The disclosed above refrigerant composition earl august eugene lund ian robert that can substitute HCFC-22 exist or GWP value it is higher, or ODP be not 0, or can
Combustion property compared with it is strong, or efficiency it is relatively low, or volume refrigerating capacity compressor it is less the shortcomings of.Therefore need exploitation more excellent, environmentally friendly with refrigeration performance
Performance more preferably substitutes the cold-producing medium of HCFC-22.
Additionally, R404A is widely used as the substitute of R502, but domestic and international not yet replacement to which is carried out specially at present
Door research, only Chinese patent CN1544569A clearly propose to substitute with the composition of HFC-161, HFC-125 and HFC-143a
R502 and R404A, but there is the defects such as GWP is higher and refrigerating capacity declines in said composition.Therefore still carry out environmental performance by necessary
The research of the good substitute of more excellent, performance.
Therefore, still it is hopeful further to improve the substitute composition of HFC-134a, HCFC-22 or R404A, and has
Wish to can be while the composition for substituting HFC-134a, HCFC-22 and R404A is further improved.
The content of the invention
It is an object of the invention to provide a kind of environmental protection type refrigeration composition, can substitute HFC-134a, HCFC-22 and R404A,
With refrigeration performance it is good, combustibility is weak, alternative cost is low the characteristics of.
To reach goal of the invention the technical solution used in the present invention it is:
A kind of environmental protection type refrigeration composition, it is characterised in that the refrigerant compositions include HFO-1234ze (E), HFE-143a and
HFC-32, and the mass percent of each component is:
HFO-1234ze(E):30%~90%;
HFE-143a:1%~15%;
HFC-32:5%~60%.
In refrigerant compositions of the present invention, the physical data of the component for using is as follows:
Trans-1,3,3,3- tetrafluoropropenes (HFO-1234ze (E)), its molecular formula are CHFCHCF3, molecular weight is 114.04,
Normal boiling point is -19.0 DEG C, and critical-temperature is 109.4 DEG C, and critical pressure is 3.64MPa, and GWP value is 6;
F-methyl methyl ether (CF3OCH3, HFE-143a), its molecular formula be CF3OCH3, molecular weight is 100.04, and normal boiling point is
- 24.0 DEG C, critical-temperature is 104.8 DEG C, and critical pressure is 3.59MPa, and GWP value is 840;
Difluoromethane (HFC-32), its molecular formula are CH2F2, molecular weight is 52.02, and normal boiling point is -51.7 DEG C, stagnation temperature
Spend for 78.2 DEG C, critical pressure is 5.78MPa, and GWP value is 675;
Fluoroethane (HFC-161), its molecular formula are CH3CH2F, molecular weight are 48.06, and normal boiling point is -37.1 DEG C, stagnation temperature
Spend for 102.2 DEG C, critical pressure is 4.7Mpa, and GWP value is 12.
It is above-mentioned including HFO-1234ze (E), the refrigerant compositions of HFE-143a and HFC-32 that the present invention is provided, and can act as
Heat transfer medium.The refrigerant compositions can be used for substitute HFC-134a, HCFC-22 and R404A in one kind, two or three.
As a kind of preferred mode, it is described including HFO-1234ze (E), the refrigerant compositions of HFE-143a and HFC-32 in,
The mass percent of each component is:
HFO-1234ze(E):80%~90%;
HFE-143a:1%~10%;
HFC-32:5%~10%.
Now, including HFO-1234ze (E) (80%~90%), HFE-143a (1%~10%) and HFC-32 (5%~10%)
Refrigerant compositions, its GWP be less than 150, be particularly suitable for substitute HFC-134a as heat transfer medium.Further, it is special
Be not suitable for for air conditioning for automobiles, business air conditioner, refrigerating box or household freezer, HFC-134a is substituted as heat transfer medium.
It is as second preferred mode, described including HFO-1234ze (E), the refrigerant compositions of HFE-143a and HFC-32
In, the mass percent of each component is:
HFO-1234ze(E):50%~60%;
HFE-143a:1%~10%;
HFC-32:35%~40%.
Used as the third preferred mode, the refrigerant compositions including HFO-1234ze (E), HFE-143a and HFC-32 enter
One step contains HFC-161, and the mass percent of each component is:
HFO-1234ze(E):50%~60%;
HFE-143a:1%~10%;
HFC-32:35%~40%;
HFC-161:1%~10%.
Now, as the refrigerant compositions described in the third preferred mode, can act as heat transfer medium.The refrigerant compositions
Can be used for substitute HFC-134a, HCFC-22 and R404A in one kind, two or three.
Further, as second preferred mode and as the refrigerant compositions described in the third preferred mode, its GWP
Less than 300, it is particularly suitable for substituting HCFC-22 as heat transfer medium.Further, it is particularly suitable for domestic air conditioning,
Business air conditioner, refrigerating box, household freezer or freezer, are used to substitute HCFC-22 as heat transfer medium.
As the 4th kind of preferred mode, it is described including HFO-1234ze (E), the refrigerant compositions of HFE-143a and HFC-32 in,
The mass percent of each component is:
HFO-1234ze(E):30%~50%;
HFE-143a:1%~15%;
HFC-32:50%~60%.
Now, as the refrigerant compositions described in the 4th kind of preferred mode, its GWP is less than 500, is particularly suitable for substituting
R404A is used as heat transfer medium.Further, it is particularly suitable for refrigerating box, household freezer or freezer, it is used for as heat transfer medium
Substitute R404A.
The present invention provide refrigerant compositions compared with existing disclosed technology, with advantages below:
(1) environmental performance is better than substituted HFC-134a, HCFC-22 and R404A, and ozone layer depletion potential ODP values are zero,
Global warming potential GWP value is greatly lowered compared with HFC-134a, HCFC-22 and the R404A for being substituted;
(2) it is flammable weak, it is safe;
(3) under standard air conditioning condition, the evaporating pressure of HFC-134a substitutes, condensing pressure and pressure ratio etc. are and HFC-134a
Quite, refrigerating effect per unit swept volume is above HFO-1234yf and HFO-1234ze (E), suitable with HFC-134a;Energy Efficiency Ratio is equal
It is higher than HFO-1234yf, suitable with HFO-1234ze (E) and HFC-134a;Temperature glide is little;Combination property compared with HFO-1234yf,
HFO-1234ze (E) and HFC-134a are greatly improved;
(4) under standard air conditioning condition, the evaporating pressure of HCFC-22 substitutes, condensing pressure and pressure ratio etc. are and HCFC-22
Quite, refrigerating effect per unit swept volume is above HC-290 and HFC-161, suitable with HCFC-22;Energy Efficiency Ratio is suitable with HCFC-22;
Combination property is sufficiently close to HCFC-22;
(5) under freezing operating mode, the evaporating pressure of R404A substitutes, condensing pressure and pressure ratio etc. are suitable with R404A, singly
Position volume refrigerating capacity compressor is suitable with R404A with Energy Efficiency Ratio;Combination property is sufficiently close to R404A;
(6) on the premise of equipment critical piece is not changed, HFC-134a or R404A refrigerant compositions of the present invention directly can be used
It is in the former system using HFC-134a or R404A, simultaneous with the former refrigeration system pipeline part using HFC-134a or R404A
Hold, and filling quantity can be reduced, improve refrigerating capacity and Energy Efficiency Ratio, there is save resources, energy saving.
Specific embodiment
The present invention is further described with reference to specific embodiment, but does not limit the invention to these and be embodied as
Mode.One skilled in the art would recognize that present invention encompasses what is potentially included in Claims scope is all alternative
Scheme, improvement project and equivalents.
The present invention provide refrigerant compositions, its preparation method be by Trans-1,3,3,3- tetrafluoropropenes (HFO-1234ze (E)),
F-methyl methyl ether (CF3OCH3, HFE-143a) and difluoromethane (HFC-32), or Trans-1,3,3,3- tetrafluoropropenes
(HFO-1234ze (E)), f-methyl methyl ether (CF3OCH3, HFE-143a), difluoromethane (HFC-32) and fluoroethane (HFC-161),
Physical mixed is carried out under liquid phase state according to the corresponding proportioning of each component.
Embodiment 1:By HFO-1234ze (E), HFE-143a and HFC-32 under liquid phase press 90:5:5 mass percent is carried out
Physical mixed.
Embodiment 2:By HFO-1234ze (E), HFE-143a and HFC-32 under liquid phase press 89:1:10 mass percent is carried out
Physical mixed.
Embodiment 3:By HFO-1234ze (E), HFE-143a and HFC-32 under liquid phase press 80:10:10 mass percent is entered
Row physical mixed.
Embodiment 4:By HFO-1234ze (E), HFE-143a and HFC-32 under liquid phase press 60:5:35 mass percent is carried out
Physical mixed.
Embodiment 5:By HFO-1234ze (E), HFE-143a and HFC-32 under liquid phase press 59:1:40 mass percent is carried out
Physical mixed.
Embodiment 6:By HFO-1234ze (E), HFE-143a, HFC-32 and HFC-161 under liquid phase press 55:5:35:5 matter
Amount percentage carries out physical mixed.
Embodiment 7:By HFO-1234ze (E), HFE-143a, HFC-32 and HFC-161 under liquid phase press 50:5:35:10
Mass percent carries out physical mixed.
Embodiment 8:By HFO-1234ze (E), HFE-143a and HFC-32 under liquid phase press 30:10:60 mass percent is entered
Row physical mixed.
Embodiment 9:By HFO-1234ze (E), HFE-143a and HFC-32 under liquid phase press 50:1:49 mass percent is carried out
Physical mixed.
Embodiment 10:By HFO-1234ze (E), HFE-143a and HFC-32 under liquid phase press 35:15:50 mass percent is entered
Row physical mixed.
Embodiment 11:By HFO-1234ze (E), HFE-143a and HFC-32 under liquid phase press 35:10:55 mass percent is entered
Row physical mixed.
Now by the performance of refrigerant compositions described in above-described embodiment with to corresponding target substitution thing HFC-134a, HCFC-22 and R404A
It is compared, the characteristics of illustrate the present invention and effect.
1st, comparison of environmental performance
Table 1 compares the environmental performance of refrigerant compositions described in above-described embodiment and HFC-134a, HCFC-22 and R404A.Its
, using CFC-11 as a reference value 1.0, GWP value is with CO for middle ODP values2As a reference value 1.0 (100 years).
1 comparison of environmental performance of table
Working medium |
ODP |
GWP |
Embodiment 1 |
0 |
80 |
Embodiment 2 |
0 |
80 |
Embodiment 3 |
0 |
150 |
HFC-134a |
0 |
1430 |
Embodiment 4 |
0 |
280 |
Embodiment 5 |
0 |
280 |
Embodiment 6 |
0 |
280 |
Embodiment 7 |
0 |
280 |
HCFC-22 |
0.04 |
1790 |
Embodiment 8 |
0 |
490 |
Embodiment 9 |
0 |
350 |
Embodiment 10 |
0 |
460 |
Embodiment 11 |
|
460 |
R404A |
0 |
3700 |
From table 1 it follows that Ozone depletion potential (ODP) value of refrigerant compositions described in above-described embodiment is zero, in fact
A 1-3 is applied for HFC-134a substitutes, its global warming potential (GWP) value is 80~150, respectively less than HFC-134a and symbol
The requirement that European Union's MAC instruction is not more than 150 to car air conditioner refrigerant GWP value is closed, the impact to environment is much smaller than HFC-134a,
Environmental performance is very excellent, is the long-term substitute of HFC-134a;Embodiment 4-7 be HCFC-22 substitutes, its global warming
Potential (GWP) value is 280, and respectively less than HCFC-22, the impact to environment are much smaller than HCFC-22, and environmental performance is very excellent,
Can be used as the long-term substitute of HCFC-22;Embodiment 8-11 is R404A substitutes, and its global warming potential (GWP) value is
350~490, respectively less than R404A, the impact to environment are much smaller than R404A, and environmental performance is excellent, can be used as the long-term of R404A
Substitute.
2nd, HFC-134a substitutes thermal parameter and thermal performance under standard air conditioning condition compares
Under standard air conditioning condition, (i.e. evaporating temperature=7.2 DEG C, condensation temperature=54.4 DEG C, suction temperature=18.3 DEG C, are subcooled
Temperature=46.1 DEG C), the thermal parameter of refrigerant compositions described in embodiment 1-3 and HFC-134a is (i.e.:Evaporating pressure P0, it is cold
Solidifying pressure Pk, pressure ratio Pk/P0, delivery temperature t2) and relative thermal performance is (i.e.:COP, unit mass refrigerating capacity q0, it is single
Position volume refrigerating capacity compressor qv) be relatively shown in Table 2.
The comparison of thermal parameter and thermal performance under 2 HFC-134a substitute standard air conditioning conditions of table
As seen from Table 2, under standard air conditioning condition, the condensing pressure of refrigerant compositions described in the various embodiments described above is and HFC-134a
Quite;Pressure ratio is below HFO-1234ze (E) and HFC-134a;Delivery temperature is suitable with HFC-134a, directly can charge in original
Using in the system of HFC-134a;The density of refrigerant compositions described in the various embodiments described above be below HFO-1234yf,
HFO-1234ze (E) and HFC-134a, it is possible to reduce the filling quantity of systematic working medium;The volume of refrigerant compositions described in each embodiment
Refrigerating capacity is above HFO-1234yf and HFO-1234ze (E), and refrigerant compositions described in section Example are higher than HFC-134a, respectively
The COP values of refrigerant compositions described in embodiment are above HFO-1234yf, HFO-1234ze (E) and HFC-134a, in performance
It is obviously improved compared with HFO-1234yf, HFO-1234ze (E) and HFC-134a.
3rd, HCFC-22 substitutes thermal parameter and thermal performance under standard air conditioning condition
Under standard air conditioning condition, (i.e. evaporating temperature=7.2 DEG C, condensation temperature=54.4 DEG C, suction temperature=18.3 DEG C, are subcooled
Temperature=46.1 DEG C), the thermal parameter of refrigerant compositions described in embodiment 4-7 embodiment and HCFC-22 is (i.e.:Evaporating pressure
P0, condensing pressure Pk, pressure ratio Pk/P0, delivery temperature t2) and relative thermal performance is (i.e.:COP, unit mass refrigerating capacity
q0, refrigerating effect per unit swept volume qv) be relatively shown in Table 3.
The comparison of thermal parameter and thermal performance under 3 HCFC-22 substitute standard air conditioning conditions of table
As seen from Table 3, under standard air conditioning condition, the condensing pressure and evaporating pressure of refrigerant compositions described in the various embodiments described above
It is suitable with HCFC-22 and R407C;Delivery temperature is suitable with HCFC-22, less than R407C, directly can charge in former use
In the system of R407C;Also can be to charging use after the former system conversion lubricating oil using HCFC-22;Freeze described in each embodiment
The volume refrigerating capacity compressor of composition is suitable with HCFC-22 and R407C with Energy Efficiency Ratio COP value, in performance and HCFC-22 and R407C
It is sufficiently close to.
4th, R404A substitutes thermal parameter and thermal performance under freezing operating mode:
Under freezing operating mode, (i.e. evaporating temperature=- 23.3 DEG C, condensation temperature=54.4 DEG C, suction temperature=32.2 DEG C, are subcooled temperature
=32.2 DEG C of degree), the thermal parameter of refrigerant compositions described in embodiment 8-11 embodiment and R404A is (i.e.:Evaporating pressure P0、
Condensing pressure Pk, pressure ratio Pk/P0, delivery temperature t2) and relative thermal performance is (i.e.:COP, unit mass refrigerating capacity q0、
Refrigerating effect per unit swept volume qv) be relatively shown in Table 4.
The comparison of thermal parameter and thermal performance under 4 R404A substitutes of table freezing operating mode
As seen from Table 4, under freezing operating mode, the condensing pressure of refrigerant compositions described in the various embodiments described above and evaporating pressure are and R404A
Quite;Delivery temperature is suitable with R404A, directly can charge in the former system for using R404A;Refrigeration train described in each embodiment
The volume refrigerating capacity compressor of compound is suitable with R404A with Energy Efficiency Ratio COP value, is sufficiently close to R404A in performance.