CN104974718A - Refrigerant and applications thereof - Google Patents

Refrigerant and applications thereof Download PDF

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Publication number
CN104974718A
CN104974718A CN201510370935.3A CN201510370935A CN104974718A CN 104974718 A CN104974718 A CN 104974718A CN 201510370935 A CN201510370935 A CN 201510370935A CN 104974718 A CN104974718 A CN 104974718A
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CN
China
Prior art keywords
refrigerant
pentafluoropropane
dme
refrigeration agent
performance
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Granted
Application number
CN201510370935.3A
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Chinese (zh)
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CN104974718B (en
Inventor
赵贯甲
尹建国
何建龙
马素霞
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Taiyuan University of Technology
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Taiyuan University of Technology
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    • 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

Abstract

The invention discloses a high efficient refrigerator mixed refrigerant with a low global warming potential (GWP) value. The refrigerant comprises the following components in percentage by weight: 2 to 15% of 1,1,1,3,3-pentafluoropropane (C3H3F5, R245fa), 0 to 20% of fluoroethane (C2H5F, R161), and 65 to 98% of dimethyl ether (C2H6O, DME). The ozone depression potential (ODP) of the refrigerant is 0, the GWP value is less than 120, the environmental performance is excellent, moreover, the refrigerating capacity of the refrigerant in unit quality or unit volume is equivalent to R12 (dichlorodifluoromethane, namely freon), the COP (coefficient of performance) of the refrigerant is slightly higher than that of R12; and at the same time, the evaporation and condensing pressures of the refrigerant is approximate to those of R12, so the refrigerant can be directly injected into the refrigerating system that uses R12 originally, and has the advantages of low replacement cost, energy saving, and environment-friendliness.

Description

A kind of refrigeration agent and application thereof
Technical field
The present invention relates to a kind of refrigeration agent, be specifically related in a kind of home freezer system, do not destroy the extremely low and refrigerant mixture that thermomechanical property is excellent of atmospheric ozone layer (ODP is 0), Greenhouse effect.
Background technology
Refrigeration agent is the carrier that refrigeration system realizes Conversion of energy and utilization, and the quality of its thermomechanical property plays vital effect to system capacity utilising efficiency.In recent years, depletion of the ozone layer and Greenhouse effect two overall situation problem have caused global concern.Refrigerant 12 (CCl 2f 2, R12) be applied to refrigerator refrigeration system as a kind of once a very long time, there is the refrigeration agent of higher refrigerating efficiency, due to ring ozonosphere broken containing chlorine atom, there is again higher Greenhouse effect potential simultaneously, be prohibited to produce and use.
Environment-friendly energy-saving working medium requires to have more excellent environmental performance.First, ozone layer destroying potential (ODP) is 0, and Greenhouse effect potential (GWP) is less; Secondly, safety performance is good, and namely combustibility is lower or non-combustible; 3rd, toxicity is little, meets national relevant regulations; 4th, thermomechanical property is excellent, has higher cycle efficiency.Usually, existing pure refrigerants is difficult to all requirements meeting alternative refrigerant, and mix refrigerant may concentrate each constituent element advantage, forms the novel refrigerant meeting many requirements such as environmental protection, safety and performance.Simultaneously mix refrigerant use cost is cheap, contributes to alleviating China's reply and eliminates the pressure that CFCs and HCFCs class refrigeration agent and industrial upgrading face.
But the pivot of current mix refrigerant is HFCs class material, and ODP value is 0, but has higher GWP value, can not as long-term alternative refrigerant.Publication number is the patent of invention of CN101671544A, and proposing constituent element is that the mix refrigerant of R22, R142b and R21 is for alternative R12.The all constituent elements of this mix refrigerant are all containing chlorine atom, and its ODP value is non-vanishing, therefore can not be called environment friendly refrigerating fluid.Publication number is the patent of invention of CN1740262A, and proposing constituent element is R290, R600a and THT(tetrahydrochysene thiophene phenol) mix refrigerant, for quality proportioning during alternative R12 be: 61%, 38.5% and 0.5%.Wherein constituent element R290 and R600a is flammable and explosive substance and occupies the mass ratio of 99.5%, limits the filling quantity of mix refrigerant.Publication number is the patent of invention proposition constituent element of CN101307223A is the mix refrigerant of R134, R152a and R600a, and it optimizes quality proportioning is 1% ~ 25%, 40% ~ 81% and 18% ~ 35%.This refrigeration agent has less condensation, evaporation slip temperature, and thermomechanical property is a little less than R12, but due to containing R134a and R152a of larger quality proportioning, and these two kinds of refrigeration agent GWP are all higher, and therefore environmental-protecting performance is poor.Publication number is the mix refrigerant that the patent of invention of CN101003723A discloses that a kind of constituent element is R152a, R227ea and R125, and three kinds of constituent elements all have higher GWP value, therefore do not possess good environmental-protecting performance.
It is higher or have combustibility or the shortcoming such as volume refrigerating capacity compressor is less or temperature glide is larger often to there is GWP value in the refrigerant mixture proposed in existing patent, and therefore exploitation has higher refrigeration performance, better seems particularly urgent with existing system compatibility and the refrigerator refrigerant with better environmental-protecting performance.
Summary of the invention
The present invention aims to provide a kind of mix refrigerant, the environmental-protecting performance of this kind of mix refrigerant and thermomechanical property close to or be better than R12, in the system using R12, can not changing any parts directly substitute and use, is a kind of refrigeration agent of low alternative cost.
A kind of refrigeration agent provided by the invention, comprises the raw material of following masses per-cent:
1,1,1,3,3-pentafluoropropane: 2% ~ 15%;
Fluoroethane: 0% ~ 20%;
Dme: 65% ~ 98%;
Wherein each constituent element mass percent and be 100%.
As a kind of preferred version, above-mentioned refrigeration agent, comprises the raw material of following masses per-cent:
1,1,1,3,3-pentafluoropropane: 2% ~ 14%;
Dme: 86% ~ 98%;
Wherein each constituent element mass percent and be 100%.
Further, above-mentioned refrigeration agent, comprises the raw material of following masses per-cent:
1,1,1,3,3-pentafluoropropane: 7% ~ 12%;
Dme: 88% ~ 93%;
Wherein each constituent element mass percent and be 100%.
As another kind of preferred version, above-mentioned refrigeration agent, comprises the raw material of following masses per-cent:
1,1,1,3,3-pentafluoropropane: 8% ~ 10 %;
Fluoroethane: 10% ~ 20%;
Dme: 70% ~ 82%;
Wherein each constituent element mass percent and be 100%.
The invention provides the application that described refrigeration agent substitutes R12 in home freezer.
Mix refrigerant provided by the invention is suitable for alternative R12, is particluarly suitable in home freezer for alternative R12.When in home freezer for alternative R12 time, described home freezer system can not change any equipment unit, directly charges described mix refrigerant with alternative R12.
Of the present invention beneficial effect:
(1) environmental performance is excellent, and ODP value is 0, and GWP value is less than 120;
(2) add flame-retardant composition 1,1,1,3,3-pentafluoropropane, the combustibility of mix refrigerant can be weakened, improve security, increase the filling quantity of refrigeration agent;
(3) evaporating pressure, condensing pressure, pressure ratio and refrigerating effect per unit swept volume etc. are all suitable with R12, and temperature glide is less, and COP value is close or be better than R12;
(4), under the prerequisite of any parts of equipment can not be changed, the home freezer system in former use R12 is directly charged.
Embodiment
Further illustrate the present invention below by embodiment, but be not limited to following examples.
Refrigeration agent provided by the invention, its preparation method is by 1,1,1,3,3-pentafluoropropane, and fluoroethane and dme carry out physical mixed according to its corresponding quality proportioning under liquid phase state.
1,1,1,3,3-pentafluoropropane (fire retardant) in said components, molecular weight is 134.05 gmol -1, normal boiling point is-15.14 DEG C, and critical temperature is 154.01 DEG C, and emergent pressure is 3.651 MPa, and GWP value is 858.
Fluoroethane in said components, molecular weight is 46.06 gmol -1, normal boiling point is-34.55 DEG C, and critical temperature is 102.15 DEG C, and emergent pressure is 5.091 MPa, and GWP value is 4.
Dme in said components, its molecular weight is 46.07gmol -1, normal boiling point is-24.78 DEG C, and critical temperature is 127.15 DEG C, and emergent pressure is 5.337 MPa, and GWP value is 0.
List several embodiment below so that specific embodiment of the invention process to be described; but the present invention is not limited only to following several embodiment; allly comprise constituent element of the present invention and proportioning, and screen thinking with the mix refrigerant in the present invention and embodiment all belongs to scope.
Embodiment 1: by 1,1,1,3,3-pentafluoropropane and dme according to 5: 95 mass percent under liquid phase state, carry out physical mixed.
Embodiment 2: by 1,1,1,3,3-pentafluoropropane and dme according to 7: 93 mass percent under liquid phase state, carry out physical mixed.
Embodiment 3: by 1,1,1,3,3-pentafluoropropane and dme according to 9: 91 mass percent under liquid phase state, carry out physical mixed.
Embodiment 4: by 1,1,1,3,3-pentafluoropropane and dme according to 11: 89 mass percent under liquid phase state, carry out physical mixed.
Embodiment 5: by 1,1,1,3,3-pentafluoropropane and dme 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 dme carry out physical mixed according to the mass percent of 8: 10: 82 under liquid phase state.
Embodiment 7: by 1,1,1,3,3-pentafluoropropane, fluoroethane and dme carry out physical mixed according to the mass percent of 8: 20: 72 under liquid phase state.
Embodiment 8: by 1,1,1,3,3-pentafluoropropane, fluoroethane and dme carry out physical mixed according to the mass percent of 10: 10: 80 under liquid phase state.
Embodiment 9: by 1,1,1,3,3-pentafluoropropane, fluoroethane and dme carry out physical mixed according to the mass percent of 10: 20: 70 under liquid phase state.
By analyzing above-described embodiment, and comparing with the performance of R12, feature of the present invention and effect can be found.Environmental-protecting performance and the thermal performance of above-described embodiment and R12 is analyzed below by concrete data.
1, environmental-protecting performance
Table 1 compares the environmental-protecting performance of above-described embodiment and R12.Wherein ODP value gets 1.0 using R12 as benchmark value; GWP value is with CO 2as benchmark value, and get 1.0.
Table 1 environmental-protecting performance compares
Data as can be seen from table, ODP value of the present invention is 0, and GWP value is all less than 120, has comparatively significant environmental-protecting performance compared with R12.
2, temperature glide and thermal performance
Table 2 temperature glide table
As seen from the table, the temperature glide of each embodiment is all smaller, is conducive to the thermomechanical property improving home freezer system.
The home freezer standard condition that the present invention calculates employing is: vaporization temperature-23.3 DEG C, condensing temperature 54.4 DEG C, superheating temperature 11.1 DEG C, condensate depression 5 DEG C.Under this operating mode, calculation of thermodynamics is carried out to above-described embodiment and obtains thermal performance (evaporating pressure p e, condensing pressure p con, pressure ratio π= p con/ p e) with relative thermal performance (relative COP r, relative unit quality refrigerating duty q m, relative unit volume refrigerating capacity compressor q v), and compare with the thermal performance of R12, in table 3.Relative thermal performance refers to the ratio of each embodiment thermal performance and the thermal performance of R12 under above-mentioned operating mode.
The comparison of table 3 thermal parameter and thermal performance
Can find out, the evaporating pressure of above-described embodiment, condensing pressure and pressure ratio are all comparatively close with R12; Unit mass refrigerating duty is about 2.8 times of R12 simultaneously, and COP value is all greater than R12.Embodiment 1-5 is the pure matter of binary, and its refrigerating effect per unit swept volume is lower slightly compared with R12; Embodiment 6-9 is the pure matter of ternary, and its refrigerating effect per unit swept volume is suitable with R12.
In general, the mix refrigerant of gained in the embodiment of the present invention, have excellent environmental-protecting performance, higher security and economy, can as the long-term alternative refrigerant of R12.

Claims (6)

1. a refrigeration agent, is characterized in that: the raw material comprising following masses per-cent:
1,1,1,3,3-pentafluoropropane: 2% ~ 15%;
Fluoroethane: 0% ~ 20%;
Dme: 65% ~ 98%;
Wherein each constituent element mass percent and be 100%.
2. refrigeration agent according to claim 1, is characterized in that: the raw material comprising following masses per-cent:
1,1,1,3,3-pentafluoropropane: 2% ~ 14%;
Dme: 86% ~ 98%;
Wherein each constituent element mass percent and be 100%.
3. refrigeration agent according to claim 2, is characterized in that: the raw material comprising following masses per-cent:
1,1,1,3,3-pentafluoropropane: 7% ~ 12%;
Dme: 88% ~ 93%;
Wherein each constituent element mass percent and be 100%.
4. refrigeration agent according to claim 1, is characterized in that: the raw material comprising following masses per-cent:
1,1,1,3,3-pentafluoropropane: 8% ~ 10 %;
Fluoroethane: 10% ~ 20%;
Dme: 70% ~ 82%;
Wherein each constituent element mass percent and be 100%.
5. the refrigeration agent described in an any one of claim 1 ~ 4 substitutes the application of R12 in home freezer.
6. application according to claim 5, is characterized in that: described home freezer system does not change any equipment unit, directly can charge described refrigeration agent with alternative R12.
CN201510370935.3A 2015-06-30 2015-06-30 A kind of refrigerant and its application Active CN104974718B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
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
CN110373157A (en) * 2019-07-22 2019-10-25 珠海格力电器股份有限公司 Refrigerant composition and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
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
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
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
CN103965836A (en) * 2014-04-02 2014-08-06 浙江大学 Environment-friendly refrigerant for automobile air conditioner and preparation method of refrigerant

Patent Citations (4)

* Cited by examiner, † Cited by third party
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
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
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
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)

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Title
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Cited By (2)

* Cited by examiner, † Cited by third party
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
CN110373157A (en) * 2019-07-22 2019-10-25 珠海格力电器股份有限公司 Refrigerant composition and preparation method thereof

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