CN104877637A - Mixed refrigerant - Google Patents
Mixed refrigerant Download PDFInfo
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- CN104877637A CN104877637A CN201510274735.8A CN201510274735A CN104877637A CN 104877637 A CN104877637 A CN 104877637A CN 201510274735 A CN201510274735 A CN 201510274735A CN 104877637 A CN104877637 A CN 104877637A
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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
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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
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
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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
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/122—Halogenated hydrocarbons
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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
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/128—Perfluorinated hydrocarbons
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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
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/132—Components containing nitrogen
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- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
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- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Lubricants (AREA)
Abstract
The invention provides a mixed refrigerant which is a mixture comprising the following components in mole percent: 10-20% of HFC-227, 15-25% of 1, 1, 1-trifluoroethane, 25-35% of hexafluoroethane, 25-35% of ethylene and 2-10% of nitrogen. The mixed refrigerant is safe, efficient, excellent in stability, nonflammable and high in temperature reduction speed and greatly shortens the temperature reduction process.
Description
Technical field
The invention belongs to refrigerant art, be specifically related to mix refrigerant, particularly one efficiently, be applicable to the non-flammable mix refrigerant that can be used for alternative conventional refrigeration working medium of middle cold zone (-120 DEG C----70 DEG C).
Background technology
Along with expanding economy and scientific and technical progress, low temperature environment particularly-120 DEG C---the warm area of-70 DEG C has become requisite measure in numerous industry.Such as, aerospace simulation is tested, the fields such as the biological activity of the test of electric and electronic sample Low-Temperature Reliability, medical field stores, the fresh-keeping and transport of sea going fisheries.
Minimum effective refrigeration temperature of traditional single-stage compression compression refrigeration recycle system is minimum can only reach about-40 DEG C, and in order to solve the refrigeration problem of less than-40 DEG C warm areas, cycle refrigerating method conventional at present has: two stage compression refrigeration circulates; Cascade refrigeration cycle; Polybasic mixture throttling freezes.Wherein, Cascade refrigeration cycle is now in the general cold field temperature range of-153 DEG C (envrionment temperature to) widespread use the most, but its system complex, efficiency is not high and reliability is very low, constrains it and further develops.
At present, employing multicomponent mixture work medium (multicomponent mixture work medium that several existing or novel single working medium is formed) throttling refrigeration technology is the preferred solution of International refrigeration educational circles.In China patent CN1189532C, CN101307223B, CN101270275B and CN101275067B, multicomponent mixture work medium refrigeration agent is reported to some extent.Wherein, the multicomponent mixed work medium throttling refrigerant of a kind of useful effect warm area at 150-200K (about-73 DEG C to-123 DEG C) is proposed in patent CN1189532C, but it comprises 5 groups of materials (comprising nearly 30 kinds of materials altogether), composition is too complicated, constrains its further application development; Mostly what patent CN101307223B, CN101270275B and CN101275067B related to is about-40 DEG C warm areas---show according to correlative study, its effective temperature range of operation of the multicomponent mixture work medium of a frozen composition is narrower, general at about 5-15K, surpass and go beyond the scope, efficiency sharply declines.Therefore, corresponding mix refrigerant can not run on lower warm area efficiently.
In addition, because chlorine atom in the fluorochlorohydrocarbon working medium (CFC) that refrigerating field tradition adopts is for the destruction of ozonosphere, existing mixing Substitute Working Medium many considerations zero odp value and the requirement of security, select the material of HFCs class mostly.The common feature of this type of material is: hydrogen atom quantity is more---therefore more unstable, inflammable and explosive.This application for Mix refrigerant cycle adds great restriction, especially in some fields very high to security requirement, as medical treatment and pharmacy etc.Therefore, in actual applications, need to add non-flammable working medium to suppress combustibility.In fact, if do not consider combustibility, the material that can be used as mixture group member is a lot, and comparatively speaking, fire-retardant refrigeration agent is just fewer.The heptafluoro-propane that the present invention adopts has outstanding flame retardant resistance, and environmental performance is superior, and ODP is zero, therefore can as a kind of outstanding fire retardant in Diversity refrigerant art.
Summary of the invention
One is the object of the present invention is to provide to be applicable to the multicomponent mixture work medium refrigeration agent of middle cold zone (-120 DEG C----70 DEG C) efficiently.Compared with prior art, the mixing medium composition that the present invention proposes is simple, and applicable warm area is lower, and cooling rate is fast, simultaneously nonflammable non-explosive, safety and stability.The present invention also aims to provide a kind of method preparing described mix refrigerant.
For foregoing invention object, the invention provides following technical scheme:
On the one hand, the invention provides a kind of mix refrigerant, described refrigeration agent is the mixture be made up of heptafluoro-propane, 1,1,1-Halothane, hexafluoroethane, ethene, nitrogen; In described mix refrigerant, the Mole percent specific concentration sum of each composition is 100%, wherein, the Mole percent specific concentration of described heptafluoro-propane is 10%-20%, 1, the Mole percent specific concentration of 1,1-Halothane is 15%-25%, and the Mole percent specific concentration of hexafluoroethane is 25%-35%, the percentage concentration of ethene is 25%-35%, and the Mole percent specific concentration of nitrogen is 2%-10%.
Preferably, the Mole percent specific concentration of described heptafluoro-propane is 13%-17%, 1,1, the Mole percent specific concentration of 1-Halothane is 17%-23%, the Mole percent specific concentration of hexafluoroethane is 27%-33%, and the percentage concentration of ethene is 27%-34%, and the Mole percent specific concentration of nitrogen is 3%-7%.
Preferably, the Mole percent specific concentration of described heptafluoro-propane is 14%-15%, 1,1, the Mole percent specific concentration of 1-Halothane is 18%-21%, the Mole percent specific concentration of hexafluoroethane is 29%-31%, and the percentage concentration of ethene is 29%-32%, and the Mole percent specific concentration of nitrogen is 4%-6%.
Preferably, the Mole percent specific concentration of described heptafluoro-propane is 15%, 1, the Mole percent specific concentration of 1,1-Halothane is 20%, and the Mole percent specific concentration of hexafluoroethane is 30%, the percentage concentration of ethene is 30%, and the Mole percent specific concentration of nitrogen is 5%.
Preferably, in described ground mix refrigerant, each component is made through physical mixed.
As mentioned above, describedly comprise heptafluoro-propane, 1,1, the mix refrigerant of 1-Halothane, hexafluoroethane, ethene, nitrogen exists optimizes concentration proportioning: in mix refrigerant, the Mole percent specific concentration sum of each composition is 100%, the Mole percent specific concentration of described heptafluoro-propane is 13%-17%, described 1,1, the Mole percent specific concentration of 1-Halothane is 17%-23%, the Mole percent specific concentration of described hexafluoroethane is 27%-33%, the percentage concentration of described ethene is 27%-34%, and the Mole percent specific concentration of described nitrogen is 3%-7%.
Above-mentionedly comprise heptafluoro-propane, 1,1, also there is optimum concentration range in the mix refrigerant of 1-Halothane, hexafluoroethane, ethene, nitrogen: in mix refrigerant, the Mole percent specific concentration sum of each composition is 100%, the Mole percent specific concentration of described heptafluoro-propane is 14%-15%, described 1,1, the Mole percent specific concentration of 1-Halothane is 18%-21%, the Mole percent specific concentration of described hexafluoroethane is 29%-31%, the percentage concentration of described ethene is 29%-32%, and the Mole percent specific concentration of described nitrogen is 4%-6%.
On the other hand, the invention provides a kind of method preparing described mix refrigerant, described method comprises: by the physical mixed preparation at normal temperatures of heptafluoro-propane, 1,1,1-Halothane, hexafluoroethane, ethene, nitrogen.
The technique effect that the present invention obtains is:
Mix refrigerant of the present invention is applicable to-120 DEG C----70 DEG C of warm areas, and composition is simple.Contrast with existing refrigeration agent, adopt this mix refrigerant to accelerate cooling rate, shorten temperature-fall period, reduce temperature fall time, this mix refrigerant has excellent flame retardant properties simultaneously, safety and stability more.
Embodiment
Describe further the technical scheme in the present invention below in conjunction with embodiment, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.These embodiments are only for illustrating the present invention, and where face not in office forms limitation of the scope of the invention.Based on the embodiment in the present invention, those of ordinary skill in the art, not making other embodiments all obtained under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1: get the heptafluoro-propane that Mole percent specific concentration is 17%, Mole percent specific concentration is 16% 1,1,1-Halothane, Mole percent specific concentration is the hexafluoroethane of 34%, Mole percent specific concentration be 30% ethene and Mole percent specific concentration be 3% nitrogen physical mixed at normal temperatures, obtain a kind of mix refrigerant.
Embodiment 2: get the heptafluoro-propane that Mole percent specific concentration is 16%, Mole percent specific concentration is 17% 1,1,1-Halothane, Mole percent specific concentration is the hexafluoroethane of 31%, Mole percent specific concentration be 29% ethene and Mole percent specific concentration be 7% nitrogen physical mixed at normal temperatures, obtain a kind of mix refrigerant.
Embodiment 3: get the heptafluoro-propane that Mole percent specific concentration is 20%, Mole percent specific concentration is 15% 1,1,1-Halothane, Mole percent specific concentration is the hexafluoroethane of 26%, Mole percent specific concentration be 27% ethene and Mole percent specific concentration be 8% nitrogen physical mixed at normal temperatures, obtain a kind of mix refrigerant.
Embodiment 4: get the heptafluoro-propane that Mole percent specific concentration is 15%, Mole percent specific concentration is 18% 1,1,1-Halothane, Mole percent specific concentration is the hexafluoroethane of 30%, Mole percent specific concentration be 32% ethene and Mole percent specific concentration be 5% nitrogen physical mixed at normal temperatures, obtain a kind of mix refrigerant.
Embodiment 5: get the heptafluoro-propane that Mole percent specific concentration is 15%, Mole percent specific concentration is 20% 1,1,1-Halothane, Mole percent specific concentration is the hexafluoroethane of 30%, Mole percent specific concentration be 30% ethene and Mole percent specific concentration be 5% nitrogen physical mixed at normal temperatures, obtain a kind of mix refrigerant.
Embodiment 6: combustibility test is carried out respectively to the mix refrigerant in embodiment 1-5, and chooses following several existing mix refrigerant and carry out flammable contrast test:
1. 1,1,2,2-Tetrafluoroethane/1 in CN101307223B, the quality proportioning of 1-C2H4F2 C2H4F2/Trimethylmethane is the mixture (hereinafter referred to as comparative example 1) of 8/66/26.
The mol ratio of 2. 1,1,2,2-Tetrafluoroethane in CN101275067B/dme/propane is the mixture (hereinafter referred to as comparative example 2) of 5/20/75.
3. 1,1,2,2-Tetrafluoroethane/1 in CN101270275B, the quality proportioning of 1-C2H4F2 C2H4F2/propane is the mixture (hereinafter referred to as comparative example 3) of 5/25/70.
The processing condition of test are with reference to USS ANSI-ASHRAE Standard34-2010 (Designation and Safety Classification of Refrigerants, hereinafter referred to as ANSI/ASHRAE 34), flammable testing method is with reference to USS ASTM E681 (Standard TestMethod for Concentration Limits of Flammability of Chemicals (Vapas and Gases)).
Table 1 below specifically show mix refrigerant of the present invention and contrasts with the performance quality of existing refrigerant applications in identical refrigeration cycle.Wherein CN1189532C represents 5 groups of material molar concentration rates in Chinese patent CN1189532C is the mixture of 20/40/3/16/21, setting in the corresponding embodiment 6 of comparative example 1,2,3 difference, design effort situation is envrionment temperature is 32 DEG C, target temperature-90 DEG C.
In table 1 embodiment, mix refrigerant performance gathers and compares with existing refrigerant performance
| Embodiment | Temperature fall time/h | Cooling rate/(DEG C/min) |
| 1 | 3.85 | 0.528 |
| 2 | 3.76 | 0.541 |
| 3 | 3.93 | 0.517 |
| 4 | 3.68 | 0.553 |
| 5 | 3.51 | 0.579 |
| CN1189532C | 4.53 | 0.449 |
| Comparative example 1 | 5.32 | 0.382 |
| Comparative example 2 | 5.17 | 0.393 |
| Comparative example 3 | 5.64 | 0.361 |
Above result shows, compared to existing technology, the embodiment of refrigeration agent provided by the invention is under the identical condition of Working environment, be down to target temperature-90 DEG C of required times from envrionment temperature 32 DEG C and be only 60% to 80% of relevant precedent, process of refrigeration obviously shortens, and substantially increases the working efficiency of refrigeration system.
Table 2 shows after the mensuration of embodiment 6 below, the Combined Combustion Index of the refrigeration agent in embodiments of the invention and related art.Wherein LFL
wrepresentation quality lower flammability limit (i.e. in the air of unit volume, the minimum mass that burning needs occurs combustiblematerials, can not burn lower than this quality), HOC represents the combustion heat (heat output of unit mass refrigeration agent).
The Combined Combustion Index of mix refrigerant in table 2 embodiment 6
| LFL w/(kg/m 3) | HOC/(kJ/kg) | |
| 1 | —— | —— |
| 2 | —— | —— |
| 3 | —— | —— |
| 4 | —— | —— |
| 5 | —— | —— |
| Comparative example 1 | 0.097 | 24600 |
| Comparative example 2 | 0.049 | 43800 |
| Comparative example 3 | 0.068 | 39800 |
According to the classification foundation (criteria for classification is incendivity hazard level) in ANSI/ASHRAE 34, the combustibility of refrigeration agent can be divided into 3 classes, comprising:
1st class (A1, non-combustible): when testing in 101kPa, the air of 60 DEG C, without the refrigeration agent of propagation of flame, namely non-combustible;
2nd class (A2 has incendivity): when testing in 101kPa, the air of 60 DEG C, have propagation of flame; When testing in 101kPa, the air of 23 DEG C, LFL
w>0.10kg/m3, and HOC<19000kJ/kg;
3rd class (A3, inflammable and explosive property): when testing in 101kPa, the air of 60 DEG C, have propagation of flame; When testing in 101kPa, the air of 23 DEG C, LFL
w≤ 0.10kg/m3, and HOC>=19000kJ/kg.
Table 3 shows the flammability class result to the mix refrigerant in embodiment 6 below.
The flammability class of mix refrigerant in table 3 embodiment 6
| Embodiment is numbered | |
| A3 | Comparative example 1, comparative example 2, comparative example 3 |
| A2 | —— |
| A1 | Embodiment 1-5 |
Visible, the mix refrigerant in embodiment 1-5 is non-flammable, and the mix refrigerant in comparative example 1-3 is then inflammable and explosive.Obviously, the mix refrigerant in the present invention is more suitable for for the high refrigerating field of security requirement: as medical treatment and pharmacy, biological sample storage, organ storage etc.
What the present invention proposed is applicable to-120 DEG C---and the mix refrigerant of-70 DEG C of warm areas also has good environmental protection characteristic, because component each in mix refrigerant of the present invention does not all comprise Cl atom, therefore the latent value ODP of its ozone depletion is 0, can not form destruction to ozonosphere.Can find out that the mixed refrigerant that the present invention proposes can as a kind of mix refrigerant of alternative traditional C FC class refrigeration agent well.
Claims (4)
1. a mix refrigerant, is characterized in that, described refrigeration agent is the mixture be made up of heptafluoro-propane, 1,1,1-Halothane, hexafluoroethane, ethene, nitrogen; In described mix refrigerant, the Mole percent specific concentration sum of each composition is 100%, wherein, the Mole percent specific concentration of described heptafluoro-propane is 10%-20%, 1, the Mole percent specific concentration of 1,1-Halothane is 15%-25%, and the Mole percent specific concentration of hexafluoroethane is 25%-35%, the percentage concentration of ethene is 25%-35%, and the Mole percent specific concentration of nitrogen is 2%-10%.
2. mix refrigerant according to claim 1, it is characterized in that: in described mix refrigerant, the Mole percent specific concentration of described heptafluoro-propane is 13%-17%, 1, the Mole percent specific concentration of 1,1-Halothane is 17%-23%, and the Mole percent specific concentration of hexafluoroethane is 27%-33%, the percentage concentration of ethene is 27%-34%, and the Mole percent specific concentration of nitrogen is 3%-7%.
3. mix refrigerant according to claim 1 and 2, it is characterized in that: the Mole percent specific concentration of described heptafluoro-propane is 14%-15%, 1,1, the Mole percent specific concentration of 1-Halothane is 18%-21%, the Mole percent specific concentration of hexafluoroethane is 29%-31%, and the percentage concentration of ethene is 29%-32%, and the Mole percent specific concentration of nitrogen is 4%-6%.
4. the mix refrigerant according to claim 1 or 2 or 3, it is characterized in that: the Mole percent specific concentration of described heptafluoro-propane is 15%, 1,1, the Mole percent specific concentration of 1-Halothane is 20%, the Mole percent specific concentration of hexafluoroethane is 30%, and the percentage concentration of ethene is 30%, and the Mole percent specific concentration of nitrogen is 5%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510274735.8A CN104877637A (en) | 2015-05-26 | 2015-05-26 | Mixed refrigerant |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510274735.8A CN104877637A (en) | 2015-05-26 | 2015-05-26 | Mixed refrigerant |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1460704A (en) * | 2002-05-17 | 2003-12-10 | 中国科学院理化技术研究所 | Multicomponent mixed work medium throttling refrigerant applicable to medium-low temperature zone |
| US20060197053A1 (en) * | 2005-02-04 | 2006-09-07 | Shiflett Mark B | Absorption cycle utilizing ionic liquid as working fluid |
| US20110115223A1 (en) * | 2009-06-29 | 2011-05-19 | Lightsail Energy Inc. | Compressed air energy storage system utilizing two-phase flow to facilitate heat exchange |
| CN102257334A (en) * | 2008-12-19 | 2011-11-23 | 纳幕尔杜邦公司 | Absorption power cycle system |
| CN102292608A (en) * | 2008-11-26 | 2011-12-21 | 纳幕尔杜邦公司 | Absorption cycle system having dual absorption circuits |
| CN102660229A (en) * | 2012-04-26 | 2012-09-12 | 中科赛凌（北京）科技有限公司 | Incombustible mixed refrigerant suitable for copious cooling temperature of 90-140DEG C below zero |
-
2015
- 2015-05-26 CN CN201510274735.8A patent/CN104877637A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1460704A (en) * | 2002-05-17 | 2003-12-10 | 中国科学院理化技术研究所 | Multicomponent mixed work medium throttling refrigerant applicable to medium-low temperature zone |
| US20060197053A1 (en) * | 2005-02-04 | 2006-09-07 | Shiflett Mark B | Absorption cycle utilizing ionic liquid as working fluid |
| CN102292608A (en) * | 2008-11-26 | 2011-12-21 | 纳幕尔杜邦公司 | Absorption cycle system having dual absorption circuits |
| CN102257334A (en) * | 2008-12-19 | 2011-11-23 | 纳幕尔杜邦公司 | Absorption power cycle system |
| US20110115223A1 (en) * | 2009-06-29 | 2011-05-19 | Lightsail Energy Inc. | Compressed air energy storage system utilizing two-phase flow to facilitate heat exchange |
| CN102660229A (en) * | 2012-04-26 | 2012-09-12 | 中科赛凌（北京）科技有限公司 | Incombustible mixed refrigerant suitable for copious cooling temperature of 90-140DEG C below zero |
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