CN104592942B - A kind of flame retardant type refrigerant and preparation method thereof - Google Patents
A kind of flame retardant type refrigerant and preparation method thereof Download PDFInfo
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- CN104592942B CN104592942B CN201410820325.4A CN201410820325A CN104592942B CN 104592942 B CN104592942 B CN 104592942B CN 201410820325 A CN201410820325 A CN 201410820325A CN 104592942 B CN104592942 B CN 104592942B
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- ionic liquid
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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
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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
- C09K2205/11—Ethers
- C09K2205/112—Halogenated ethers
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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
- C09K2205/126—Unsaturated fluorinated 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
Abstract
The invention discloses a kind of flame retardant type refrigerant, in parts by weight, consisting of：14.85~28.5 parts of 3 bromine, 3,3 difluoropropenes, 0.15~1.8 part of ionic liquid, 2,3,3,3 60~80 parts of tetrafluoropropenes, 1,1,2,2 four fluoro ethyls 2,2,2 1~10 part of trifluoroethyl ethers, the invention also discloses the preparation method of the refrigerant, present invention process is simple, cost is low, and the refrigerant product of preparation has good anti-flammability and low GWP.
Description
Technical field
The present invention relates to refrigerant art, particularly a kind of flame retardant type refrigerant and preparation method thereof.
Background technology
HFO-1234yf has an excellent ambient parameter as single working medium refrigerant, its global warming potential GWP=4,
Ozone depletion potential ODP=0, lifetime climate performance (LCCP) are less than HFC-134a, and air analyte is identical with HFC-134a.
And its systematic function is better than HFC-134a.If substituting HFC-134a refrigerants from HFO-1234yf, car manufactures are just
It can continue to continue to use former on-board air conditioner (Mobile Air-Conditioning, MAC) system.So HFO-1234yf is considered as
It is the young mobile refrigerant replacement for relatively having potentiality, has been received by car manufactures in West Europe at present, opened in 2011
Beginning progressively promotes.HFO-1234yf GWP compares with atmospheric lifetime, and other substitute HFC-134a refrigerants with obvious
Environmental advantage, but it has low combustibility, there is the hidden danger for causing fire.Therefore researcher, which develops, a variety of contains HFO-
1234yf composition, it is flammable to reduce it by adding fire retardant.As China Patent Publication No. CN102971394A is disclosed
A kind of heat transfer system using heat-transfer fluid, method and composition, the heat-transfer fluid include：(a) about 30 weight % are extremely
About 65 weight % HFC-134a；(b) about 0 weight % to about 70 weight % HFO1234ze；About 0 weight (c)
% to about 70 weight % HFO-1234yf is measured, condition is that the total amount of HFO-1234ze and HFO-1234yf in said composition is
At least about 35 weight %, the percentage by weight are based on the total amount of component (a)-(c) in said composition.The invention refer to fire-retardant
The addition of agent can reduce combustibility.
And for example China Patent Publication No. CN101636466A provides azeotrope-like comprising tetrafluoropropene and CF3I
Composition and application thereof, including for refrigerant composition earl august eugene lund ian robert, refrigeration system, foaming agent and sprayable composition, bag
Include aerosol propellants.CF in said composition3I components can be used as fire retardant, for suppressing HFO1234yf combustibility.
Existing method, which is employed to add fire retardant or nonflammable component, improves anti-flammability because fire retardant with
The poor compatibility of HFO1234yf tetrafluoropropenes, disperses uneven, causes flame retardant effect poor, while its refrigeration for being prepared
Agent product has higher GWP compared with HFO1234yf either simplex matter, still has considerable influence to environment.
The content of the invention
The technical problem to be solved in the present invention is the defects of overcoming prior art, there is provided a kind of technique is simple, cost is low, green
Flame retardant type refrigerant that colour circle is protected and preparation method thereof.
In order to solve the above-mentioned technical problem, the present invention is achieved by the following technical solutions：A kind of flame retardant type refrigerant,
In parts by weight, its composition is as follows：
Described ionic liquid is preferably chlorination 1- pi-allyl -3- methylimidazoles, chlorination 1- butyl -3- methylimidazoles, chlorination
One kind in 1- ethyl-3-methylimidazoles, acetic acid 1- ethyl-3-methylimidazoles.
The present invention also provides the preparation method of described flame retardant type refrigerant, comprises the following steps：
(1) by proportioning, by bromo- 3, the 3- difluoropropenes of 14.85~28.5 parts of 3- and 0.15~1.8 part of ionic liquid in liquid phase shape
10~20h is mixed under state, obtains ionic liquid fire retardant；
(2) by proportioning, the ionic liquid fire retardant that step (1) is obtained and 60~80 part 2,3,3,3- tetrafluoropropenes, 1~10
1,1,2,2- tetra- fluoro ethyls -2,2 of part, 2- trifluoroethyl ether mixtures obtain flame retardant type refrigerant product.
Mixture described in step (2) preferably refers to the turbulent flow circulation mixing 20-40h under liquid phase state.
The method comprises the steps of firstly, preparing ionic liquid fire retardant, and bromo- 3, the 3- difluoropropenes (BFO) of 3- are fully dissolved with ionic liquid,
Generate ionic liquid fire retardant；Ionic liquid fire retardant and 2,3,3,3- tetrafluoropropenes (HFO1234yf), 1,1,2,2- tetra- fluoro ethyl-
2,2,2- trifluoroethyl ethers are added in turbulent recirculating still with certain proportioning, and product is obtained by sufficient turbulent mixture.
HFO1234yf, 1,1,2,2- tetra- fluoro ethyl -2,2,2- trifluoroethyls ether have good solubility and diffusion with ionic liquid fire retardant
Rate, it can effectively reduce HFO1234yf flammable performance.
The commercially available acquirement of the raw material used in the present invention, as ionic liquid can use Shanghai flute cypress chemicals technology limited
The ionic liquid product of company；Bromo- 3, the 3- difluoropropenes (BFO) of 3- can useLark waffle Technology Co., Ltd.Product；
2,3,3,3- tetrafluoropropenes (HFO1234yf, molecular formula C3H2F4) can be using the product of Juhua Group Co.；1,1,2,2- tetrafluoro
Ethyl -2,2,2- trifluoroethyls ether (HFE-347, molecular formula CF3CH2OCF2CF2H the product of Juhua Group Co. can) be used.
Turbulent recirculating still in the present invention is commercially available prod, the turbulent recirculating still product developed such as Wuhan Engineering Univ.
Compared with prior art, the invention has the advantages that：
1st, technique is simple, cost is low, the method comprises the steps of firstly, preparing ionic liquid fire retardant, by bromo- 3, the 3- difluoropropenes (BFO) of 3-
Fully dissolved with ionic liquid, generate ionic liquid fire retardant；Ionic liquid fire retardant and 2,3,3,3- tetrafluoropropenes (HFO1234yf),
1,1,2,2- tetra- fluoro ethyl -2,2,2- trifluoroethyls ether (HFE-347) are added in turbulent recirculating still with certain proportioning, make material
In turbulent condition, the mixing of storeroom or scattered more quick, uniform, preparation technology is enormously simplify, reduces cost, is had
Mass produced beneficial to industrialization；
2nd, the product being prepared has a good flame-retardance, and the ionic liquid fire retardant in product has fluid temperature section
Greatly, the feature such as soluble end wide, steam forces down, good, good flame retardation effect of heat endurance；2,3,3,3- tetrafluoropropenes, 1,1,2,2-
Four fluoro ethyls -2,2,2- trifluoroethyls ether have good solubility and diffusivity with ionic liquid fire retardant, can further reduced
HFO1234yf flammable performance, the anti-flammability of refrigerant is improved, refrigerant product LFL values (volume %) of the invention are 13.2
More than；
3rd, green, refrigerant global warming potential (GWP) of the invention is below 25, ozone depletion potential (ODP)
For 0.
Embodiment
The present invention is further detailed below in conjunction with specific embodiment, but the invention is not limited in described reality
Apply example.
The commercially available acquirement of raw material and equipment in the present invention, which part material and facility are described as follows：
Bromo- 3, the 3- difluoropropenes (BFO) of 3-：It is purchased fromLark waffle Technology Co., Ltd.。
2,3,3,3- tetrafluoropropenes (HFO1234yf)：Juhua Group Co. produces.
1,1,2,2- tetra- fluoro ethyl -2,2,2- trifluoroethyls ether (HFE-347)：Juhua Group Co. produces.
Ionic liquid (AMIMCI, BMIMCI, EMIMCI, EMIMAc)：Purchased from Shanghai Di Bai chemicals Technology Co., Ltd..
Turbulent recirculating still：The turbulent recirculating still product that Wuhan Engineering Univ develops.
Embodiment 1
A kind of flame retardant type refrigerant, based on every part of 1Kg, the formula that feeds intake is as follows：
Its preparation method is as follows：
The preparation of step (1) ionic liquid fire retardant
By proportioning, bromo- 3, the 3- difluoropropenes (BFO) of 27.16 parts of 3-, 0.84 part of chlorination 1- alkene are added in 200L reactors
Propyl group -3- methylimidazoles ionic liquid (AMIMCI), 15h is mixed under liquid phase state, obtains ionic liquid fire retardant.
Step (2) mixture
By proportioning, the ionic liquid fire retardant that step (1) is prepared and 70 part 2,3,3,3- tetrafluoropropenes
(HFO1234yf), 2 part 1,1,2,2- tetra- fluoro ethyl -2,2,2- trifluoroethyls ether (HFE-347, molecular formula CF3CH2OCF2CF2H)
Add in 200L turbulent flow recirculating stills, turbulent flow circulation mixing 30h, obtains product under liquid phase state.Numbering is WN-1.
Embodiment 2
A kind of flame retardant type refrigerant, based on every part of 1Kg, the formula that feeds intake is as follows：
Its preparation method is as follows：
The preparation of step (1) ionic liquid fire retardant
By proportioning, bromo- 3, the 3- difluoropropenes (BFO) of 28.5 parts of 3-, 1.5 parts of chlorination 1- fourths are added in 200L reactors
Base -3- methylimidazoles ionic liquid (BMIMCI), 20h is mixed under liquid phase state, obtains ionic liquid fire retardant.
Step (2) mixture
By proportioning, the ionic liquid fire retardant that step (1) is prepared and 60 part 2,3,3,3- tetrafluoropropenes
(HFO1234yf), 10 part 1,1,2,2- tetra- fluoro ethyl -2,2,2- trifluoroethyls ether (HFE-347, molecular formula
CF3CH2OCF2CF2H) add in 200L turbulent flow recirculating stills, turbulent flow circulation mixing 40h, obtains product under liquid phase state.Numbering
For WN-2.
Embodiment 3
A kind of flame retardant type refrigerant, based on every part of 1Kg, the formula that feeds intake is as follows：
Its preparation method is as follows：
The preparation of step (1) ionic liquid fire retardant
By proportioning, bromo- 3, the 3- difluoropropenes (BFO) of 14.85 parts of 3-, 0.15 part of chlorination 1- second are added in 200L reactors
Base -3- methylimidazoles (EMIMCI), 10h is mixed under liquid phase state, obtains ionic liquid fire retardant.
Mixture of the step (2) in turbulent recirculation reactor
By proportioning, the ionic liquid fire retardant that step (1) is prepared and 80 part 2,3,3,3- tetrafluoropropenes
(HFO1234yf), 1 part 1,1,2,2- tetra- fluoro ethyl -2,2,2- trifluoroethyls ether (HFE-347, molecular formula CF3CH2OCF2CF2H)
Add in 200L turbulent flow recirculating stills, turbulent flow circulation mixing 20h, obtains product under liquid phase state.Numbering is WN-3.
Embodiment 4
A kind of flame retardant type refrigerant, based on every part of 1Kg, the formula that feeds intake is as follows：
Its preparation method is as follows：
The preparation of step (1) ionic liquid fire retardant
By proportioning, bromo- 3, the 3- difluoropropenes (BFO) of 18.2 parts of 3-, 1.8 parts of acetic acid 1- second are added in 200L reactors
Base -3- methylimidazoles ionic liquid (EMIMAc), 18h is mixed under liquid phase state, obtains ionic liquid fire retardant.
Step (2) mixture
By proportioning, the ionic liquid fire retardant that step (1) is prepared and 75 part 2,3,3,3- tetrafluoropropenes
(HFO1234yf), 5 part 1,1,2,2- tetra- fluoro ethyl -2,2,2- trifluoroethyls ether (HFE-347, molecular formula CF3CH2OCF2CF2H)
Add in 200L turbulent flow recirculating stills, turbulent flow circulation mixing 25h, obtains product under liquid phase state.Numbering is WN-4.
Performance test：
Embodiment 1-4 products obtained therefroms are done into burning test according to U.S.'s ASTM-E681-01 standards, wherein LFL is burning
The lower limit value of the limit, LFL values are bigger, and flammability is lower.LFL value experimental results are shown in Table 1.
Table 1：Embodiment 1-4 products obtained therefroms and HFO1234yf performance comparisions
| Numbering | LFL values (volume %) | GWP |
| WN-1 | 16.8 | 23 |
| WN-2 | 19.1 | 25 |
| WN-3 | 14.7 | 15 |
| WN-4 | 13.2 | 21 |
| HFO1234yf | 6.9 | 4 |
Claims (3)
1. a kind of flame retardant type refrigerant, in parts by weight, its composition are as follows：
It is characterized in that described ionic liquid is chlorination 1- pi-allyl -3- methylimidazoles, chlorination 1- butyl -3- methylimidazoles, chlorine
Change one kind in 1- ethyl-3-methylimidazoles, acetic acid 1- ethyl-3-methylimidazoles.
2. the preparation method of the flame retardant type refrigerant described in claim 1, it is characterised in that comprise the following steps：
(1) by proportioning, by bromo- 3, the 3- difluoropropenes of 14.85~28.5 parts of 3- and 0.15~1.8 part of ionic liquid under liquid phase state
10~20h is mixed, obtains ionic liquid fire retardant；
(2) by proportioning, the ionic liquid fire retardant that step (1) is obtained and 60~80 part 2,3,3,3- tetrafluoropropenes, 1~10 part 1,
1,2,2- tetra- fluoro ethyl -2,2,2- trifluoroethyl ether mixtures obtain flame retardant type refrigerant product.
3. the preparation method of flame retardant type refrigerant according to claim 2, it is characterised in that the mixture described in step (2) is
Refer to the turbulent flow circulation mixing 20-40h under liquid phase state.
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| CN105885080A (en) * | 2016-05-05 | 2016-08-24 | 巨化集团技术中心 | Foamer composition and preparation method thereof |
| EP3592822A4 (en) * | 2017-03-06 | 2020-12-30 | Arkema, Inc. | Refrigerants with reduced flammability profile |
| CN107134592A (en) * | 2017-06-27 | 2017-09-05 | 山东大学 | A kind of fluoro ether electrolyte for lithium cells and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101400756A (en) * | 2006-03-14 | 2009-04-01 | 旭硝子株式会社 | Working medium for heat cycle, rankine cycle system, heat pump cycle system, and refrigeration cycle system |
| CN102089400A (en) * | 2008-07-08 | 2011-06-08 | 纳幕尔杜邦公司 | Compositions comprising ionic liquids and fluoroolefins and use thereof in absorption cycle systems |
| CN103189466A (en) * | 2010-11-08 | 2013-07-03 | 赢创德固赛有限公司 | Working medium for absorption heat pumps |
| WO2014151344A1 (en) * | 2013-03-15 | 2014-09-25 | Honeywell International Inc. | Low gwp heat transfer compositions containing difluoromethane, a fluorinated ethane and 1,3,3,3-tetrafluoropropene |
| CN104072691A (en) * | 2014-06-26 | 2014-10-01 | 衢州市中通化工有限公司 | Preparation method for flame retardant expanded polystyrene with core-shell structure |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101400756A (en) * | 2006-03-14 | 2009-04-01 | 旭硝子株式会社 | Working medium for heat cycle, rankine cycle system, heat pump cycle system, and refrigeration cycle system |
| CN102089400A (en) * | 2008-07-08 | 2011-06-08 | 纳幕尔杜邦公司 | Compositions comprising ionic liquids and fluoroolefins and use thereof in absorption cycle systems |
| CN103189466A (en) * | 2010-11-08 | 2013-07-03 | 赢创德固赛有限公司 | Working medium for absorption heat pumps |
| WO2014151344A1 (en) * | 2013-03-15 | 2014-09-25 | Honeywell International Inc. | Low gwp heat transfer compositions containing difluoromethane, a fluorinated ethane and 1,3,3,3-tetrafluoropropene |
| CN104072691A (en) * | 2014-06-26 | 2014-10-01 | 衢州市中通化工有限公司 | Preparation method for flame retardant expanded polystyrene with core-shell structure |
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