CN109722226A - A kind of environment-protecting mixed refrigerating agent and preparation method thereof for substituting R134a - Google Patents
A kind of environment-protecting mixed refrigerating agent and preparation method thereof for substituting R134a Download PDFInfo
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Abstract
The invention discloses a kind of environment-protecting mixed refrigerating agents and preparation method thereof for substituting R134a.It is a kind of for substituting the environment-protecting mixed refrigerating agent of R134a, by 3,3,3- trifluoro propenes, difluoromethane and 1,1; 1,2- tetrafluoroethane composition, each component molar percentage are as follows: the 3,3 of 29~92%; 3- trifluoro propene, 3~20% difluoromethane and 5~61% HFA 134a.Due to joined the substances such as 3,3,3- trifluoro propenes, 1,1,2,2- tetrafluoroethane in HFA 134a, so as to improve the environmental-protecting performance of mix refrigerant, GWP value is greatly reduced relative to R134a.Furthermore; environment-protecting mixed refrigerating agent prepared by the present invention; with excellent thermal parameter and thermal property, in refrigeration systems, cycle efficieny, coefficient of refrigerating performance, refrigerating effect per unit swept volume be better than R134a or suitable with R134a, saturated vapor pressure is close with R134a can directly to substitute R134a.The invention also discloses a kind of environment-protecting mixed refrigerating agents, and Fe is added in said mixture2O3、MnO2, ZnO or Al2O3Nano particle, so as to improve the intermiscibility between refrigerant and mineral type refrigerator oil.
Description
Technical field
The present invention relates to a kind of mix refrigerant more particularly to a kind of environment-protecting mixed refrigerating agents and its system for substituting R134a
Preparation Method.
Background technique
R134a is a kind of current China and the international widely used car air conditioner refrigerant, due to it to ozone layer without
Destruction is used as always the substitute of R12 refrigerant.However, R134a still has stronger greenhouse gases effect
(GWP value 1550).Currently, Chinese auto industry is in the rapid growth stage, it is contemplated that incited somebody to action in the year two thousand thirty China's car ownership
Increased by 1.9 hundred million compared with 2015.Meanwhile as the air-conditioning installation rate of light-duty passenger-car is close to 100%, car air conditioner refrigerant
Discharge will be with economic growth and continue to increase.
In recent years, global warming grows in intensity, and in order to cope with climate change, countries in the world are stepping up to promote hydrofluorocarbon
(HFCs) the substitution process of refrigerant.Studies have shown that limiting the discharge of HFCs refrigerant in the world, global gas can be made
Temperature rise high-amplitude slows down 0.5 DEG C in the end of this century, can make very big contribution to inhibition global warming.Current EU countries and
The U.S. has put into effect specific car air conditioner refrigerant management policy, respectively at 2017 and 2021 in the light-duty of new production
R134a is disabled in passenger vehicle air conditioner.Currently, China is that (sales volume accounts for about global total amount to the maximum air conditioning for automobiles country of consumption in the whole world
24%) and the maximum country that also R134a is not managed in the whole world.Cut down and substitute car air conditioner refrigerant
R134a not only conforms with the policy tendency and background of energy-saving and emission-reduction, at the same China will also be fulfiled Montreal Protocol make it is important
Contribution.Therefore, urgent that environmental protection, efficient alternative refrigerant and the relevant technologies have become China's air conditioning for automobiles industry is found
Business.
The world such as Montreal protocol and Kyoto Protocol contractual requirement signatories to a treaty gradually cut down and finally disable
Refrigerant R134a, while higher environmental requirement is proposed to its substitute, in addition to the refrigerant to be looked for novelty does not have ozone layer
Destruction, the refrigerant also to be looked for novelty have alap GWP value.
In the prior art, Chinese patent document CN200810231909.2 discloses a kind of by 80~89% propane and 11
The alkanes refrigerant of~20% iso-butane composition；Patent US2008029733 disclose with pentafluoroethane, tetrafluoropropane and
The refrigerant mixture of the material compositions such as hydrocarbon；Patent KR200500494148 disclose it is a kind of by 71~90% third
Alkane and 10~29% 1,1- Difluoroethane composition mix refrigerant；Chinese patent document CN200810238072.4 is disclosed
The mixture being made of 45~52% pentafluoroethane, 45~52% HFA 134a and 3~6% dimethyl ether；
It is disclosed in patent CN200810097 a kind of by 1,1,1,2- tetrafluoroethane, the ternary of three kinds of material compositions of dimethyl ether and propane
Azeotropic mixture；Chinese patent CN201010198685.7 disclose in 2,3,3,3- tetrafluoropropene, trans- 1,3,3,3- tetra-
Fluoropropene and 1, the mixture of 1- Difluoroethane composition；Chinese patent CN201010196200.0 disclose it is a kind of with trans- 1,3,
The mixture of 3,3- tetrafluoropropenes, difluoromethane and difluoromethane composition；Chinese patent document CN2010196224.6 is disclosed
A kind of mixture being made of 2,3,3,3- tetrafluoropropene, difluoromethane and dimethyl ether.
Refrigerant disclosed in above-mentioned patent exist or GWP value it is higher or not directly fill tank applied to R134a system,
Or the disadvantages of flammable larger, it is more preferably compatible and with more with existing system therefore, it is necessary to develop with more preferable refrigeration performance
The novel refrigerant of good environmental-protecting performance.
Summary of the invention
The present invention provides a kind of environment-protecting mixed refrigerating agent for substituting R134a, which does not destroy atmospheric ozone not only
Layer, while there is the thermal parameter and thermal property quite even more excellent with R134a, and have lower GWP value.
It is a kind of for substituting the environment-protecting mixed refrigerating agent of R134a, by 3,3,3- trifluoro propenes, difluoromethane, 1,1,1,2-
Tetrafluoroethane and oxidized metal nano particle composition, each component molar percentage are as follows: the 3 of 29~92%, 3,3- trifluoro propenes, 3
~20% difluoromethane, 5~61% 1,1,1,2- tetrafluoroethane and 0~0.05% oxidized metal nano particle.
It is preferably used in the environment-protecting mixed refrigerating agent of substitution R134a, each component molar percentage are as follows: the 3 of 63~90%, 3,
3- trifluoro propene, 5~15% difluoromethane and 5~32% 1,1,1,2- tetrafluoroethane.
It is preferably used in the environment-protecting mixed refrigerating agent of substitution R134a, each component molar percentage are as follows: the 3 of 29~58%, 3,
3- trifluoro propene, 5~15% difluoromethane and 32~61% 1,1,1,2- tetrafluoroethane.
It is preferably used in the environment-protecting mixed refrigerating agent of substitution R134a, which is characterized in that each component molar percentage are as follows: 64
~85% 3,3,3- trifluoro propene, 5~10% difluoromethane and 10~26% 1,1,1,2- tetrafluoroethane.
The oxidized metal nano particle is Fe2O3、MnO2, ZnO or Al2O3。
The preparation method of the environment-protecting mixed refrigerating agent for substituting R134a, by 29~92% trifluoro propene, 3
~20% difluoromethane, 5~61% 1,1,1,2- tetrafluoroethane and 0~0.05% oxidized metal nano particle successively add
Entering in the autoclave body with stirring, control autoclave body temperature is -0 DEG C~-20 DEG C, so that trifluoro propene, difluoromethane, 1,1,1,2- tetra-
Fluoroethane and oxidized metal nano particle obtain the environment-protecting mixed refrigerating agent of the substitution R134a in liquid phase state physical mixed.
By adopting the above technical scheme, the beneficial effects of the present invention are:
(1) good environmental protection, ODP value are 0, and GWP value is greatly reduced relative to R134a；
(2) there is excellent thermal parameter and thermal property, cycle efficieny, coefficient of refrigerating performance, unit in refrigeration systems
Volume refrigerating capacity compressor is better than R134a or suitable with R134a.
(3) simultaneously have with saturated vapor pressure similar in R134a, can directly substitute R134a, without redesign refrigeration system.
(4) intermiscibility of mix refrigerant and mineral type lubricating oil is higher than HF hydrocarbon and hydrogen fluorohydrocarbon class mix refrigerant.
Detailed description of the invention
The saturated vapor curve graph of Fig. 1 mix refrigerant and R134a.
Specific embodiment
In order to keep the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Embodiment 1
The preparation of mix refrigerant is carried out in the 2L stainless steel stirred tank with refrigerating function.Stirred tank temperature is set
It is -10 DEG C, 278.4g3,3,3- trifluoro propenes, 54g difluoromethane and 6222.2g1,1,1,2- tetrafluoro second is sequentially added into kettle
Alkane, after the completion of sample filling, turn on agitator is cooled to -20 DEG C, is kept stirring 2h, control equilibrium still pressure 0.2MPa with
It is interior, so that 3,3,3- trifluoro propenes, difluoromethane and HFA 134a mix under liquid phase state.Treatment process terminates
Afterwards, mix refrigerant is obtained, wherein the molar percentage of 3,3,3- trifluoro propenes is the molar percentage of 29%, difluoromethane
It is 10%, the molar percentage of HFA 134a is 61%.
Embodiment 2~10
The preparation method of 2~10 environment-protecting mixed refrigerating agent of embodiment is similar to Example 1, except that 3 are changed, 3,
The molar percentage of 3- trifluoro propene, difluoromethane and HFA 134a, specific usage amount are as shown in table 1.
Table 1
Embodiment 11
The preparation of mix refrigerant is carried out in the 2L stainless steel stirred tank with refrigerating function.1.60g is received first
Rice grain Fe2O3It is added in equilibrium still, setting stirred tank temperature is -10 DEG C.625.8g3,3,3- trifluoropropyl is sequentially added into kettle
Alkene, 54g difluoromethane and 224.4g HFA 134a, after the completion of sample filling, turn on agitator is cooled to -20
DEG C, it is kept stirring 2h, controls equilibrium still pressure within 0.2MPa, so that 3,3,3- trifluoro propenes, difluoromethane and 1,1,1,
2- tetrafluoroethane mixes under liquid phase state.After treatment process, mix refrigerant is obtained, wherein 3,3,3- trifluoro propenes
Molar percentage be 67.99%, the molar percentage of difluoromethane is 10%, the molar percentage of 1,1,1,2- tetrafluoroethane
For 22%, Fe2O3Nano particle molar percentage is 0.01%.
Embodiment 12~14
The preparation method of 12~14 environment-protecting mixed refrigerating agent of embodiment is similar to embodiment 11, the difference is that by Fe2O3
Nano particle changes into MnO2, ZnO or Al2O3Nano particle, specific usage amount are as shown in table 2.
Table 2
| Embodiment | Component | Additional amount/g |
| 12 | MnO2Nano particle | 0.88 |
| 13 | ZnO nano particle | 0.81 |
| 14 | Al2O3Nano particle | 1.12 |
The performance of environment-protecting mixed refrigerating agent for substituting R134a of the invention:
The performance of above-described embodiment is compared with R134a now, illustrates the features of the present invention and effect.
1. environmental performance
Table 3 compares above-described embodiment and the environmental performance of R134a.Wherein ODP value is using CFC-11 as a reference value 1.0,
GWP value is with CO2As a reference value 1.0 (100 years).
3 comparison of environmental performance table of table
From table 3 it is observed that Ozone depletion potential (ODP) value of above-described embodiment is zero, do not have to atmospheric ozone layer
There is destruction, this point is better than R134a.
Moreover, greenhouse potential quality (GWP) value of above-described embodiment more meets current protection also much smaller than R134a
Ozone layer, the environmental protection requirement for reducing global warming effect.
2. thermal parameter and thermal performance
Table 4 compare under air conditioning for automobiles standard condition (evaporating temperature=2 DEG C, condensation temperature=60 DEG C, 5 DEG C of degree of supercooling, mistake
Temperature=5 DEG C) thermal parameter (evaporating pressure, condensing pressure, pressure ratio, delivery temperature) of above-described embodiment and R134a and opposite
Thermal performance (Relative volumes refrigerating capacity, opposite COP).Described opposite thermal performance refers to practical thermal performance and R134a heat
The ratio of power performance.
Mix refrigerant performance comparison sheet in 4 embodiment of table
As seen from Table 4, under the operating condition of air conditioning for automobiles, the condensing pressure of refrigerant obtained by Examples 1 to 10, evaporation
Pressure, pressure ratio and R134a are close, and are in allowed band, can directly substitute R134a, do not need to redesign refrigeration system
System.In addition, the refrigerating effect per unit swept volume and unit volume wasted work amount of refrigerant obtained by Examples 1 to 10 are close with R134a, phase
R134a is all larger than to coefficient of refrigerating performance, shows that the cycle efficieny of refrigeration system is improved.
3. saturated vapor pressure curve
Attached drawing 1 compares refrigerant obtained by embodiment 1~14 and the saturated vapor curve of R134a.(saturated vapor is buckled
Line is measured by static method experimental provision, and measurement temperature range is -30~80 DEG C, and temperature uncertainty of measurement is 0.02 DEG C, pressure
Uncertainty of measurement is 2kPa.)
From figure 1, it may be seen that the saturated vapor pressure curve very phase with R134a of refrigerant obtained by embodiment 1~14
Closely, without change compressor under the premise of, can directly tank fill in the refrigeration system of R134a.
Claims (6)
1. a kind of for substituting the environment-protecting mixed refrigerating agent of R134a, which is characterized in that by 3,3,3- trifluoro propenes, difluoromethane,
HFA 134a and oxidized metal nano particle composition, each component molar percentage are as follows: the 3 of 29~92%, 3,3- tri-
Fluoropropene, 3~20% difluoromethane, 5~61% 1,1,1,2- tetrafluoroethane and 0~0.05% oxidized metal nanometer
Grain.
2. as described in claim 1 a kind of for substituting the environment-protecting mixed refrigerating agent of R134a, which is characterized in that each group centimorgan
Your percentage are as follows: 63~90% 3,3,3- trifluoro propene, 5~15% difluoromethane and 5~32% 1,1,1,2- tetrafluoro
Ethane.
3. as described in claim 1 a kind of for substituting the environment-protecting mixed refrigerating agent of R134a, which is characterized in that each group centimorgan
Your percentage are as follows: 29~58% 3,3,3- trifluoro propene, 5~15% difluoromethane and 32~61% 1,1,1,2- tetrafluoro
Ethane.
4. as described in claim 1 a kind of for substituting the environment-protecting mixed refrigerating agent of R134a, which is characterized in that each group centimorgan
Your percentage are as follows: 64~85% 3,3,3- trifluoro propene, 5~10% difluoromethane and 10~26% 1,1,1,2- tetrafluoro
Ethane.
5. according to claim 1 a kind of for substituting the environment-protecting mixed refrigerating agent of R134a, which is characterized in that described
Oxidized metal nano particle is Fe2O3、MnO2, ZnO or Al2O3。
6. as described in claim 1 for substituting the preparation method of the environment-protecting mixed refrigerating agent of R134a, which is characterized in that will
29~92% trifluoro propene, 3~20% difluoromethane, 5~61% 1,1,1,2- tetrafluoroethane and 0~0.05% oxygen
Change metal nanoparticle to sequentially add in the autoclave body with stirring, control autoclave body temperature is -0 DEG C~-20 DEG C, so that trifluoropropyl
Alkene, difluoromethane, HFA 134a and oxidized metal nano particle obtain described replace in liquid phase state physical mixed
For the environment-protecting mixed refrigerating agent of R134a.
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| CN201811540743.2A CN109722226B (en) | 2018-12-17 | 2018-12-17 | Environment-friendly mixed refrigerant for replacing R134a and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090158771A1 (en) * | 2007-10-12 | 2009-06-25 | Ineos Fluor Holdings Limited | Heat Transfer compositions |
| CN107987797A (en) * | 2017-12-08 | 2018-05-04 | 西安近代化学研究所 | A kind of environment-protecting mixed refrigerating agent of replacement HCFC-22 |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090158771A1 (en) * | 2007-10-12 | 2009-06-25 | Ineos Fluor Holdings Limited | Heat Transfer compositions |
| CN107987797A (en) * | 2017-12-08 | 2018-05-04 | 西安近代化学研究所 | A kind of environment-protecting mixed refrigerating agent of replacement HCFC-22 |
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