CN104974718B - A kind of refrigerant and its application - Google Patents
A kind of refrigerant and its application Download PDFInfo
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- CN104974718B CN104974718B CN201510370935.3A CN201510370935A CN104974718B CN 104974718 B CN104974718 B CN 104974718B CN 201510370935 A CN201510370935 A CN 201510370935A CN 104974718 B CN104974718 B CN 104974718B
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- Prior art keywords
- refrigerant
- dimethyl ether
- fluoroethane
- performance
- environmental
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- 239000003507 refrigerant Substances 0.000 title claims abstract description 44
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims abstract description 37
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 claims abstract description 18
- UHCBBWUQDAVSMS-UHFFFAOYSA-N fluoroethane Chemical compound CCF UHCBBWUQDAVSMS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000470 constituent Substances 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 5
- 230000000694 effects Effects 0.000 abstract description 10
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 5
- 238000001704 evaporation Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000005057 refrigeration Methods 0.000 abstract description 4
- 230000008020 evaporation Effects 0.000 abstract description 2
- 238000004134 energy conservation Methods 0.000 abstract 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 28
- 239000000203 mixture Substances 0.000 description 19
- 239000007791 liquid phase Substances 0.000 description 10
- 238000009835 boiling Methods 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- SGDMQXAOPGGMAH-UHFFFAOYSA-N phenol;thiophene Chemical compound C=1C=CSC=1.OC1=CC=CC=C1 SGDMQXAOPGGMAH-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
- C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
- C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/122—Halogenated hydrocarbons
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of low GWP（Greenhouse effects potential）Value, high-effect refrigerator mix refrigerant, including 1,1,1,3,3- pentafluoropropane (C3H3F5, R245fa), fluoroethane（C2H5F, R161）With dimethyl ether (C2H6O, DME), shared mass percent is：1,1,1,3,3- pentafluoropropanes：2%~15%；Fluoroethane：0%~20%；Dimethyl ether：65%~98%.The ODP of the mix refrigerant（Ozone layer destroying potential）It is 0, GWP value is less than 120, and environmental-protecting performance is excellent, and unit mass, refrigerating effect per unit swept volume and R12 (dicholorodifluoromethane, freon) are quite, COP（Coefficient of performance of refrigerating）Slightly above R12, while having the evaporation being closer to R12 and condensing pressure can be filled directly in the former refrigeration system for using R12, have the advantages that alternative cost is low and energy conservation and environmental protection.
Description
Technical field
The present invention relates to a kind of refrigerants, and in particular in a kind of domestic refrigerator system, does not destroy atmospheric ozone layer（ODP
It is 0）, greenhouse effects are extremely low and thermodynamic property is excellent refrigerant mixture.
Background technology
Refrigerant is the carrier that refrigeration system is realized energy conversion and utilized, and the quality of thermodynamic property is to system capacity
Utilization ratio serves vital.In recent years, depletion of the ozone layer and two overall situation problem of greenhouse effects have caused global
Concern.Dicholorodifluoromethane（CCl2F2, R12）It is applied to refrigerator refrigeration system as a kind of once a very long time, has
The refrigerant of higher refrigerating efficiency due to containing chlorine atom and broken ring ozone layer, while having higher greenhouse effects potential again,
It has been prohibited to produce and has used.
Environment-friendly energy-saving working medium requires more excellent environmental performance.First, ozone layer destroying potential（ODP）It is 0,
Greenhouse effects potential（GWP）It is smaller；Secondly, it has a safety feature, you can combustion property is relatively low or non-combustible；Third, small toxicity meet state
Family's relevant regulations；4th, thermodynamic property is excellent, has higher cycle efficieny.Usually, existing pure refrigerants are difficult
Meet being required for alternative refrigerant, mix refrigerant may concentrate each constituent element advantage, formed and meet environmental protection, safety and property
The novel refrigerant of many requirements such as energy.Mix refrigerant use cost is cheap simultaneously, and the reply of alleviation China is contributed to eliminate
The pressure that CFCs and HCFCs classes refrigerant and industrial upgrading face.
But the pivot of mix refrigerant is HFCs substances at present, ODP values are 0, but have higher GWP value,
It cannot function as long-term alternative refrigerant.The patent of invention of Publication No. CN101671544A, it is proposed that constituent element R22, R142b and
The mix refrigerant of R21 is for substituting R12.All constituent elements of the mix refrigerant contain chlorine atom, and ODP values are not zero, because
This cannot be known as environment friendly refrigerating fluid.The patent of invention of Publication No. CN1740262A, it is proposed that constituent element R290, R600a and
THT（Tetrahydrochysene thiophene phenol）Mix refrigerant, be for quality proportioning when substituting R12：61%, 38.5% and 0.5%.Wherein constituent element
R290 and R600a be flammable and explosive substance and occupy 99.5% mass ratio, limit the filling quantity of mix refrigerant.It is public
The patent of invention that the number of opening is CN101307223A proposes that constituent element is the mix refrigerant of R134, R152a and R600a, optimizes matter
Amount proportioning is 1% ~ 25%, 40% ~ 81% and 18% ~ 35%.The refrigerant has smaller condensation, evaporation slip temperature, heat
Mechanical property is slightly below R12, but due to R134a and R152a containing larger quality proportioning, and both refrigerants GWP compared with
Height, therefore environmental-protecting performance is poor.The patent of invention of Publication No. CN101003723A disclose a kind of constituent element be R152a,
The mix refrigerant of R227ea and R125, three kinds of constituent elements all have higher GWP value, therefore do not have preferable environmental-protecting performance.
It is higher or with flammable or volume system often to there is GWP value in the refrigerant mixture proposed in existing patent
The shortcomings of cold is smaller or temperature glide is larger, thus develop with higher refrigeration performance, preferably with existing system compatibility
And the refrigerator refrigerant with more preferably environmental-protecting performance seems particularly urgent.
Invention content
The present invention is intended to provide a kind of mix refrigerant, the environmental-protecting performance and thermodynamic property of this kind of mix refrigerant are close
Or it is better than R12, it can not change any part in the system using R12 and directly substitute use, be a kind of system of low alternative cost
Cryogen.
A kind of refrigerant provided by the invention, includes the raw material of following masses percentage：
1,1,1,3,3- pentafluoropropanes：2% ~ 15%；
Fluoroethane：0% ~20%；
Dimethyl ether：65% ~ 98%；
Wherein each constituent element mass percent and be 100%.
As a preferred embodiment, above-mentioned refrigerant includes the raw material of following masses percentage：
1,1,1,3,3- pentafluoropropanes：2% ~ 14%；
Dimethyl ether：86% ~ 98%；
Wherein each constituent element mass percent and be 100%.
Further, above-mentioned refrigerant includes the raw material of following masses percentage：
1,1,1,3,3- pentafluoropropanes： 7% ~ 12%；
Dimethyl ether： 88% ~ 93%；
Wherein each constituent element mass percent and be 100%.
As another preferred embodiment, above-mentioned refrigerant includes the raw material of following masses percentage：
1,1,1,3,3- pentafluoropropanes：8% ~ 10 %；
Fluoroethane：10% ~20%；
Dimethyl ether：70% ~ 82%；
Wherein each constituent element mass percent and be 100%.
The present invention provides the refrigerants to substitute the application of R12 in domestic refrigerator.
Mix refrigerant provided by the invention is particluarly suitable in domestic refrigerator suitable for R12 is substituted for substituting
R12.When being used to substitute R12 in domestic refrigerator, the domestic refrigerator system can not change any part of appliance, directly
The mix refrigerant is charged to substitute R12.
Beneficial effects of the present invention：
(1) environmental performance is excellent, and ODP values are 0, and GWP value is less than 120；
(2) 1,1,1,3,3- pentafluoropropane of flame-retardant composition is added, the combustibility of mix refrigerant can be weakened, improves safety
Property, increase the filling quantity of refrigerant；
(3) evaporating pressure, condensing pressure, pressure ratio and refrigerating effect per unit swept volume etc. are suitable with R12, and temperature glide is smaller,
COP values are close or are better than R12；
(4) it under the premise of equipment any part can not being changed, directly charges in the former domestic refrigerator system for using R12.
Specific implementation mode
It is further illustrated the present invention below by embodiment, but is not limited to following embodiment.
Refrigerant provided by the invention, preparation method are by 1,1,1,3,3- pentafluoropropane, and fluoroethane and dimethyl ether are pressed
Physical mixed is carried out under liquid phase state according to its corresponding quality proportioning.
1 in said components, 1,1,3,3- pentafluoropropane (fire retardant), molecular weight is 134.05 gmol-1, standard boiling
Point is -15.14 DEG C, and critical-temperature is 154.01 DEG C, and critical pressure is 3.651 MPa, GWP value 858.
Fluoroethane in said components, molecular weight are 46.06 gmol-1, normal boiling point is -34.55 DEG C, critical-temperature
It it is 102.15 DEG C, critical pressure is 5.091 MPa, GWP value 4.
Dimethyl ether in said components, molecular weight 46.07gmol-1, normal boiling point is -24.78 DEG C, critical-temperature
It it is 127.15 DEG C, critical pressure is 5.337 MPa, GWP value 0.
Several embodiments are listed below illustrate the present invention specific implementation process, but the present invention be not limited only to it is following several
Kind embodiment, all includes constituent element of the present invention and proportioning, and screens thinking and embodiment with the mix refrigerant in the present invention
Belong to the scope of the present invention.
Embodiment 1：By 1,1,1,3,3- pentafluoropropanes and dimethyl ether according to 5: 95 mass percent under liquid phase state
Carry out physical mixed.
Embodiment 2：By 1,1,1,3,3- pentafluoropropanes and dimethyl ether according to 7: 93 mass percent under liquid phase state
Carry out physical mixed.
Embodiment 3：By 1,1,1,3,3- pentafluoropropanes and dimethyl ether according to 9: 91 mass percent under liquid phase state
Carry out physical mixed.
Embodiment 4：By 1,1,1,3,3- pentafluoropropanes and dimethyl ether according to 11: 89 mass percent under liquid phase state
Carry out physical mixed.
Embodiment 5：By 1,1,1,3,3- pentafluoropropanes and dimethyl ether according to 13: 87 mass percent under liquid phase state
Carry out physical mixed.
Embodiment 6：By 1,1,1,3,3- pentafluoropropane, fluoroethane and dimethyl ether exist according to 8: 10: 82 mass percent
Physical mixed is carried out under liquid phase state.
Embodiment 7：By 1,1,1,3,3- pentafluoropropane, fluoroethane and dimethyl ether exist according to 8: 20: 72 mass percent
Physical mixed is carried out under liquid phase state.
Embodiment 8：By 1,1,1,3,3- pentafluoropropane, fluoroethane and dimethyl ether exist according to 10: 10: 80 mass percent
Physical mixed is carried out under liquid phase state.
Embodiment 9：By 1,1,1,3,3- pentafluoropropane, fluoroethane and dimethyl ether exist according to 10: 20: 70 mass percent
Physical mixed is carried out under liquid phase state.
It is compared by analyzing above-described embodiment, and with the performance of R12, it can be found that the features of the present invention and effect.Under
The environmental-protecting performance and thermal performance of above-described embodiment and R12 are analyzed by specific data in face.
1, environmental-protecting performance
Table 1 compares above-described embodiment and the environmental-protecting performance of R12.Wherein ODP values as a reference value and take 1.0 using R12；
GWP value is with CO2As a reference value, and take 1.0.
1 environmental-protecting performance of table compares
The ODP values that can be seen that the present invention from the data in table are 0, and GWP value is respectively less than 120, are had compared with R12
There is more significant environmental-protecting performance.
2, temperature glide and thermal performance
2 temperature glide table of table
As seen from the table, the temperature glide of each embodiment is smaller, is conducive to the thermodynamics for improving domestic refrigerator system
Performance.
The present invention calculate the domestic refrigerator standard condition that uses for：- 23.3 DEG C of evaporating temperature, 54.4 DEG C of condensation temperature, mistake
11.1 DEG C of temperature, 5 DEG C of degree of supercooling.Under this operating mode, calculation of thermodynamics is carried out to above-described embodiment and obtains thermal performance（Vapor pres- sure
Powerp e, condensing pressurep con, pressure ratioπ=p con/p e）With opposite thermal performance (opposite COPR, relative unit quality refrigerating capacityq m, phase
To refrigerating effect per unit swept volumeq v), and compared with the thermal performance of R12, it is shown in Table 3.Opposite thermal performance refers to each embodiment heating power
The ratio of performance and thermal performances of the R12 under above-mentioned operating mode.
The comparison of 3 thermal parameter of table and thermal performance
As can be seen that the evaporating pressure of above-described embodiment, condensing pressure and pressure ratio are closer to R12；It is single simultaneously
Position quality refrigerating capacity is about 2.8 times of R12, and COP values are all higher than R12.Embodiment 1-5 is the pure matter of binary, unit volume system
Cold is slightly lower compared with R12；Embodiment 6-9 is the pure matter of ternary, and refrigerating effect per unit swept volume is suitable with R12.
In general, in the embodiment of the present invention gained mix refrigerant, have excellent environmental-protecting performance, higher safety
Property and economy, can be as the long-term alternative refrigerant of R12.
Claims (3)
1. a kind of refrigerant, it is characterised in that：Include the raw material of following masses percentage：
1,1,1,3,3- pentafluoropropanes：8%~10%；
Fluoroethane：10% ~20%；
Dimethyl ether：70% ~ 72%；
Wherein each constituent element mass percent and be 100%.
2. a kind of refrigerant described in claim 1 substitutes the application of R12 in domestic refrigerator.
3. application according to claim 2, it is characterised in that：The domestic refrigerator system does not change any part of appliance,
The refrigerant can directly be charged to substitute R12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510370935.3A CN104974718B (en) | 2015-06-30 | 2015-06-30 | A kind of refrigerant and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510370935.3A CN104974718B (en) | 2015-06-30 | 2015-06-30 | A kind of refrigerant and its application |
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| Publication Number | Publication Date |
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| CN104974718A CN104974718A (en) | 2015-10-14 |
| CN104974718B true CN104974718B (en) | 2018-10-23 |
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| CN201510370935.3A Expired - Fee Related CN104974718B (en) | 2015-06-30 | 2015-06-30 | A kind of refrigerant and its application |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106479443A (en) * | 2016-09-29 | 2017-03-08 | 太原理工大学 | A kind of environment protection energy-saving type heat pump mixed working fluid and its application |
| CN110373157B (en) * | 2019-07-22 | 2020-11-10 | 珠海格力电器股份有限公司 | Refrigerant composition and method for preparing same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6641752B2 (en) * | 1996-11-04 | 2003-11-04 | E. I. Du Pont De Nemours And Company | Azeotrope-like compositions containing fluoroethane |
| CN101624513A (en) * | 2009-08-03 | 2010-01-13 | 江苏天腾化工有限公司 | Carbon-hydrogen mixed refrigerant for vehicle air-conditioner and preparation method thereof |
| CN101624512A (en) * | 2009-08-03 | 2010-01-13 | 江苏天腾化工有限公司 | Carbon-hydrogen mixed refrigerant for air-conditioner and preparation method thereof |
| CN103965836A (en) * | 2014-04-02 | 2014-08-06 | 浙江大学 | Environment-friendly refrigerant for automobile air conditioner and preparation method of refrigerant |
-
2015
- 2015-06-30 CN CN201510370935.3A patent/CN104974718B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6641752B2 (en) * | 1996-11-04 | 2003-11-04 | E. I. Du Pont De Nemours And Company | Azeotrope-like compositions containing fluoroethane |
| CN101624513A (en) * | 2009-08-03 | 2010-01-13 | 江苏天腾化工有限公司 | Carbon-hydrogen mixed refrigerant for vehicle air-conditioner and preparation method thereof |
| CN101624512A (en) * | 2009-08-03 | 2010-01-13 | 江苏天腾化工有限公司 | Carbon-hydrogen mixed refrigerant for air-conditioner and preparation method thereof |
| CN103965836A (en) * | 2014-04-02 | 2014-08-06 | 浙江大学 | Environment-friendly refrigerant for automobile air conditioner and preparation method of refrigerant |
Non-Patent Citations (2)
| Title |
|---|
| Theoretical and experimental investigation on the flame-retarding characteristic of R245fa;Zhao Yang;《Experimental Thermal and Fluid Science》;20120909(第44期);第613–619页 * |
| 一种新型天然混合工质在汽车空调系统中替代R134a的试验研究;王辉等;《流体机械》;20110913;第39卷(第5期);第66-69页 * |
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