CN104592943B - A kind of preparation method of fluorine-containing iodo compositions of hydrocarbons - Google Patents
A kind of preparation method of fluorine-containing iodo compositions of hydrocarbons Download PDFInfo
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- CN104592943B CN104592943B CN201410820694.3A CN201410820694A CN104592943B CN 104592943 B CN104592943 B CN 104592943B CN 201410820694 A CN201410820694 A CN 201410820694A CN 104592943 B CN104592943 B CN 104592943B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 239000011737 fluorine Substances 0.000 title claims abstract description 10
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 10
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 7
- 125000002346 iodo group Chemical group I* 0.000 title claims abstract description 7
- 150000002430 hydrocarbons Chemical group 0.000 title 1
- 239000004067 bulking agent Substances 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 6
- 239000011521 glass Substances 0.000 claims description 20
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 20
- 239000000314 lubricant Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 230000004907 flux Effects 0.000 claims description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 11
- 229910052796 boron Inorganic materials 0.000 claims description 11
- 239000007822 coupling agent Substances 0.000 claims description 11
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- AMXYRHBJZOVHOL-UHFFFAOYSA-N nona-2,6-dien-1-ol Chemical class CCC=CCCC=CCO AMXYRHBJZOVHOL-UHFFFAOYSA-N 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 3
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 2
- JBLINBYLQKLDKH-UHFFFAOYSA-N CI.[F] Chemical compound CI.[F] JBLINBYLQKLDKH-UHFFFAOYSA-N 0.000 claims 1
- 229910052787 antimony Inorganic materials 0.000 claims 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- VPAYJEUHKVESSD-UHFFFAOYSA-N trifluoroiodomethane Chemical compound FC(F)(F)I VPAYJEUHKVESSD-UHFFFAOYSA-N 0.000 abstract description 8
- DYEAVVXVJITWPH-UHFFFAOYSA-N [N+](=O)(O)[O-].C(CCC)C=1NC=CN1 Chemical compound [N+](=O)(O)[O-].C(CCC)C=1NC=CN1 DYEAVVXVJITWPH-UHFFFAOYSA-N 0.000 abstract 1
- 239000003507 refrigerant Substances 0.000 description 26
- 239000000047 product Substances 0.000 description 24
- 239000012071 phase Substances 0.000 description 12
- 238000012546 transfer Methods 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 8
- 239000011858 nanopowder Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 239000004530 micro-emulsion Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 238000005057 refrigeration Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 238000005461 lubrication Methods 0.000 description 3
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 description 3
- 229920001281 polyalkylene Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 241001269238 Data Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000003416 augmentation Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 235000019628 coolness Nutrition 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000011557 critical solution Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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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
- C09K2205/102—Alcohols
-
- 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
- C09K2205/126—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
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- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
The invention discloses a kind of fluorine-containing iodo compositions of hydrocarbons, in parts by weight, consisting of：0.5~10 part of bulking agent of nanometer, 2,3,3,3 80~900 parts of tetrafluoropropenes, 10~300 parts of CF3I, 1 pi-allyl 3,0.0008~0.01 part of butyl imidazole nitrate ion liquid.The invention also discloses the preparation method of the fluorine-containing iodo compositions of hydrocarbons.The present invention has the advantages of technique is simple, cost is low, green, good product performance.
Description
Technical field
The present invention relates to refrigerant art, and in particular to a kind of preparation method of fluorine-containing iodo compositions of hydrocarbons.
Background technology
Lubricant made of adding nano material in lubrication can significantly increase greasy property and load-carrying properties, improve
The quality of product, particularly suitable for the lubrication occasion of harsh conditions, improve refrigerant and freezing using nano particle additive
Macroscopic property, heat-transfer character, the flow behavior of oil, so as to reach Optimal Parameters, augmentation of heat transfer, improve oil-soluble, raising pressure
Contracting machine wearability, noise and other effects is reduced, will be the important innovations hand for the efficiency and reliability for improving refrigeration air conditioner heat pump equipment
One of section.
Such as Yong member of Imperial Academy (the Yong member of Imperial Academy, Bi Shengshan, Shi Lin .HFC134a/TiO2Nano-particle working medium system is applied to refrigerator
Experimental study [J] Journal of Chemical Industry and Engineering, 2006 (5):HFC134a/ ore deposits 141-145.) being added to nano particle in refrigeration oil
Thing refrigeration oil/nano-TiO2Working medium system is applied in domestic refrigerator, it is found that its performance parameter is slightly better than HFC134a/ Esters oils
System.
And for example China Patent Publication No. CN102295917A discloses a kind of nano particle reinforced type refrigerant hydrate phase
Become the preparation method of cold-storage working substance, it is using the solubilization of compound surfactant, refrigerant is soluble in water, thermodynamics is made
Nano-particle, is then scattered in refrigerant microemulsion by stable refrigerant microemulsion, and nano particle reinforced refrigeration is made
Agent hydrate phase change cold-storage working substance.By the way that nano-particle is stably dispersed in into refrigerant microemulsion system come heat and mass transfer enhancement,
Increase reaction interface, induce nonhomogen-ous nucleation, so as to significantly reduce the induction time and degree of supercooling of hydrate generation, effectively
The brilliant effect of rush is reached.The technique is disperseed using ultrasonic wave, and large-scale production should not be realized.
And for example China Patent Publication No. CN101434833 A disclose a kind of nano refrigerant hydrate phase change cold-storage working substance
And preparation method thereof, surfactant is soluble in water, the aqueous solution of surfactant is made, refrigerant is then added drop-wise to table
In the aqueous solution of face activating agent, stirring is until solution is changed into bright from muddiness.In water and made according to surfactant
Solubility in cryogen, can be soluble in water by surfactant, can also be dissolved in refrigerant.The system, which need not apply, to be stirred
Mix, disturb and with outfield aqueous phase can be made mutually to be sufficiently mixed with refrigerant uniformly, refrigerant mutually by micelle or (and) in the form of micro emulsion
Be scattered in aqueous phase, or aqueous phase by micelle or (and) be scattered in refrigerant phase in the form of micro emulsion, the droplet size of dispersed phase
It is for 100 nanometers and following.But this kind of method has influence on the mass-transfer performance of refrigerant to add based on surfactant.
For another example Chinese patent notification number CN1240805C discloses a kind of refrigerant gas hydrate static state side of quickly generating
Method, the inventive method are as follows：Using wire through aqueous solution of anionic surfactant and refrigerant two-phase interface and with appearance
Wall face is in contact, and wire moves close to the moment of wall, makes contact of the refrigerant gas hydrate in wire with wall
Locate rapid crystallization nucleation, hereafter refrigerant gas hydrate quickly generates in the presence of surfactant, whole hydration reaction
Carried out always in static water.
Existing method, which is employed to mechanical agitation and perturbation action, mixes refrigerant, or adds surfactant and formed
Microemulsion, nano-particle etc. are difficult to be uniformly distributed in two-phase system, also must be continuous in the case of additive is added
It is continuously applied to extraneous stirring or circulates to promote the presence or absence of two-phase mixtures, this external force and continuity all to make the mixability of two-phase
It is a greater impact, so as to have impact on the heat transfer property of refrigerant product.In addition, external mechanical shearing force, electromagnetic field and super
Sound wave etc. also greatly increases equipment investment and energy consumption and cumbersome.
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
The preparation method for the fluorine-containing iodo compositions of hydrocarbons that colour circle is protected, product heat transfer property is excellent.
In order to solve the above-mentioned technical problem, the present invention is achieved by the following technical solutions：A kind of fluorine-containing idohydrocarbon group
The preparation method of compound, comprises the following steps：
(a) based on every part of 1Kg, in stirring-type reaction kettle, the stibium doping stannic oxide that 5 parts of particle diameters are 1~10nm is received
Ground rice body is distributed in 1000 parts of ethanol, adds the organic boron coupling agents 0.05 of SBW- III of Qingdao Siwei Chemical Co., Ltd.
Part, 3h is reacted under 25 DEG C of normal temperature, then adds 100 parts of polyalkylene glycol lubricants, 5 parts of 2,6- nonadienols, 25 DEG C of normal temperature
Lower reaction 6h, a nanometer bulking agent is obtained, it is standby；
(b) based on every part of 1Kg, 10 parts of nanometer bulking agent, 2,3,3,3- tetrafluoropropenes 900 that step (a) is prepared
Part, 100 parts of CF3I, 0.01 part of 1- pi-allyl -3- butyl imidazole nitrate ions liquid are in stirring-type reaction kettle in liquid
30h is first pre-mixed under phase, is then added in the GEN-3 type high fluxs microchannel glass reactor of Corning Incorporated's production,
Fluorine-containing idohydrocarbon composition product is mixed to get with flow velocity 100Kg/h.
The present invention is by nanometer bulking agent and 2,3,3,3- tetrafluoropropenes (HFO1234yf), CF3I (CF3I), 1- alkene
Propyl group -3- butyl imidazole nitrate ion liquid is premixed with certain proportioning, is then added in the glass reactor of high flux microchannel, is passed through
After being sufficiently mixed to get product.HFO1234yf、、CF3I has good with 1- pi-allyl -3- butyl imidazole nitrate ion liquid
Solubility and diffusivity.Nanometer bulking agent is added in composition, micro nanosphere body improves sliding, improves each component
Compatibility in lubricating oil, make lubricating oil contact with other components more abundant.Stibium doping stannic oxide (ATO) nano-powder
With chemical resistance, acid and alkali-resistance, fast light, organic solvent-resistant, do not aoxidize, fire-retardant, high temperature resistant, corrosion-resistant, mechanical stability etc. are made
With can effectively reduce HFO1234yf flammable performance.
The lubricant includes naphthenic mineral oil, paraffinic mineral oil, ester oil, PAG, polyvinylether, alkyl
Benzene, polyester, one or more combinations of polyolefin.It is preferred that PAG (PAG) and polyalcohol esters (POE).
The commercially available acquirement of heretofore described raw material, such asStibium doping stannic oxide (ATO) nano-powderRiver can be selected
Nan Wangwu nanosecond science and technology Co., Ltd product.The limited public affairs of Qingdao four-dimension chemical industry can be selected in chelate coordinate organic boron coupling agent
The organic boron coupling agent products of SBW- III of department.1- pi-allyls -3- butyl imidazole nitrate ion liquid [ABIm] [NO3] can be selected in
[ABIm] [NO of Lanzhou Chemical Physics research institute of the academy of sciences of state production3] ion liquid product.2,3,3,3- tetrafluoropropenes
(HFO1234yf, molecular formula:C3H2F4) product that Juhua Group Co. develops can be selected.Ju Hua groups can be selected in CF3I
The product that company develops.
Micro passage reaction is the chemical reaction system for the miniaturization that a kind of unit process interface yardstick is micron dimension.By
There is small size, bigger serface and regular microchannel in it, it shows extraordinary in mass transfer, heat transfer etc.
Ability, hence it is evident that better than traditional reactor, microcosmic mixing is mixing on molecular scale, it is to burning, polymerizeing, organic synthesis,
The fast reaction processes such as precipitation, crystallization have important influence.Its reason is the fast reaction system needs short residence time
With the local mixing of high intensity with avoid on molecular scale from collection.Heretofore described high flux microchannel glass reactor
For commercially available prod, the GEN-1 that can such as use Corning Incorporated to produce, GEN-2, GEN-3 type glass reactors.
Normal temperature of the present invention refers to 25 DEG C.
Compared with prior art, the invention has the advantages that：
1st, technique is simple, cost is low, after the present invention is using refrigerant mixture is premixed by proportioning, is then added to high flux
In the glass reactor of microchannel, by being sufficiently mixed to get product, high flux microchannel glass reactor has small size, big
The features such as specific surface area and regular microchannel, there is the local mixing of short residence time and high intensity to avoid molecular scale
On from collection, various ingredients can be made to obtain high intensity mixing, enormously simplify preparation technology；
2nd, product has good lubrication agent compatibility and heat transfer property, and adding nanometer bulking agent in component improves composition
Compatibility in lubricating oil.Microballoon can be helped fully to be soaked in 2,3,3,3- tetrafluoropropenes.Increase refrigerant is being moistened
Dissolubility in lubrication prescription.Cause the reduction of lubricant viscosity, and in compression refrigerating system, make lubricant effectively from non-pressure
Contracting region is back to constricted zone.The reduction of lubricant quantity will also improve the heat transfer of refrigerant in condenser zone, and
Therefore the refrigerating capacity and efficiency of system are improved, separation temperature is below -1 DEG C；
3rd, product high cooling efficiency, due to introducing 1- pi-allyl -3- butyl imidazole nitrate ion liquid in component, increase
Refrigerating efficiency, improve the solubility and diffusivity of refrigerant.2,6- nonadienols can suppress the degraded of CF3I
Trend.
4th, green, the refrigerant composition earl august eugene lund ian robert global warming potential (GWP) of preparation of the invention is below 14, ozone damage
It is 0 to consume potentiality (ODP).
Embodiment
The commercially available acquirement of heretofore described raw material, which part raw material and description of equipment are as follows：
Stibium doping stannic oxide (ATO) nano-powder：He'nan Wangwu Nano Technology Co., Ltd.'s product, particle diameter 1
~10nm.
The organic boron coupling agents of SBW- III：The organic boron coupling agent products of SBW- III of Qingdao Siwei Chemical Co., Ltd..
1- pi-allyls -3- butyl imidazole nitrate ion liquid [ABIm] [NO3]：Chinese Academy of Sciences's Lanzhou Chemical Physics research
[the ABIm] [NO produced3] ion liquid product.
2,3,3,3- tetrafluoropropenes (HFO1234yf, molecular formula:C3H2F4)：The product that Juhua Group Co. develops.
CF3I：The product that Juhua Group Co. develops.
High flux microchannel glass reactor：GEN-1, GEN-2, GEN-3 type glass reaction of Corning Incorporated's production
Device.
The present invention is further detailed below in conjunction with specific embodiment, but the invention is not limited in described reality
Apply example.
Embodiment 1:
The preparation of step (1) nanometer bulking agent, based on every part of 1Kg, charge ratio is as follows：
Preparation method is：
By proportioning, in stirring-type reaction kettle, by 3 partsStibium doping stannic oxide (ATO) nano-powderIt is distributed to 1000 parts
In ethanol, 0.03 part of organic boron coupling agent of SBW- III is added, reacts 5h under normal temperature (25 DEG C), then add 50 parts of polyalkylenes
Glycol (PAG) lubricant, 2 parts of 2,6- nonadienols, 2h is reacted under normal temperature (25 DEG C), that is, obtains a nanometer bulking agent, it is standby.
Step (2) mixture, based on every part of 1Kg, charge ratio is as follows：
Preparation method is：By proportioning, the nanometer bulking agent that 0.5 part of step (1) is prepared and 80 part 2,3,3,3- tetra-
Fluoropropene (HFO1234yf), 50 parts of CF3Is, 0.0008 part of 1- pi-allyl -3- butyl imidazole nitrate ion liquid are stirring
Mix in formula reactor and be pre-mixed 10h under liquid phase, being then added to high flux microchannel glass reactor, (Corning Incorporated gives birth to
Production, GEN-1 types glass reactor) in, with flow velocity 10Kg/h flow velocitys by being sufficiently mixed to get product.Numbering is WN-1
Embodiment 2
The preparation of step (1) nanometer bulking agent, based on every part of 1Kg, charge ratio is as follows：
Preparation method is：By proportioning, in stirring-type reaction kettle, by 1 partStibium doping stannic oxide (ATO) nano-powderPoint
It is scattered to1000In part ethanol, addThe organic boron coupling agents 0.01 of SBW- IIIPart, 4h is reacted under normal temperature (25 DEG C), is then addedIt is more First alkoxide (POE) lubricant 10Part, 1 part of 2,6- nonadienols, react 4h under normal temperature (25 DEG C), that is, obtain a nanometer bulking agent.
Step (2) mixture, based on every part of 1Kg, charge ratio is as follows：
Preparation method is：By proportioning, the nanometer bulking agent that 1 part of step (1) is prepared and 700 part 2,3,3,3- tetrafluoros
Propylene (HFO1234yf), 300 parts of CF3Is, 0.005 part of 1- pi-allyl -3- butyl imidazole nitrate ion liquid are stirring
20h is pre-mixed under liquid phase in formula reactor, being then added to high flux microchannel glass reactor, (Corning Incorporated gives birth to
Production, GEN-2 types glass reactor) in, with flow velocity 50Kg/h flow velocitys by being sufficiently mixed to get product.Numbering is WN-2.
Embodiment 3
The preparation of step (1) nanometer bulking agent, based on every part of 1Kg, charge ratio is as follows：
Preparation method is：By proportioning, in stirring-type reaction kettle, by 5 partsStibium doping stannic oxide (ATO) nano-powderPoint
It is scattered in 1000 parts of ethanol, adds 0.05 part of III organic boron coupling agents of SBW-, react 3h under normal temperature (25 DEG C), then adds poly-
100 parts of aklylene glycol (PAG) lubricant, 5 parts of 2,6- nonadienols, 6h is reacted under normal temperature (25 DEG C), that is, obtains a nanometer increase-volume
Agent.
Step (2) mixture, based on every part of 1Kg, charge ratio is as follows：
Preparation method is：By proportioning, the nanometer bulking agent that 10 parts of steps (1) are prepared and 900 part 2,3,3,3- tetra-
Fluoropropene (HFO1234yf), 100 parts of CF3Is, 0.01 part of 1- pi-allyl -3- butyl imidazole nitrate ion liquid are stirring
30h is pre-mixed under liquid phase in formula reactor, being then added to high flux microchannel glass reactor, (Corning Incorporated gives birth to
Production, GEN-3 types glass reactor) in, with flow velocity 100Kg/h flow velocitys by being sufficiently mixed to get product.Numbering is WN-3.
Embodiment 4
The preparation of step (1) nanometer bulking agent, based on every part of 1Kg, charge ratio is as follows：
Preparation method is：
By proportioning, in stirring-type reaction kettle, by 2 partsStibium doping stannic oxide (ATO) nano-powderIt is distributed to 1000 parts
In ethanol, 0.04 part of organic boron coupling agent of SBW- III is added, reacts 1h under normal temperature (25 DEG C), then add 30 parts of polyalkylenes
Glycol (PAG) lubricant, 3 parts of 2,6- nonadienols, 8h is reacted under normal temperature (25 DEG C), that is, obtains a nanometer bulking agent, it is standby.
Step (2) mixture, based on every part of 1Kg, charge ratio is as follows：
Preparation method is：By proportioning, the nanometer bulking agent that 4.5 parts of steps (1) are prepared and 150 part 2,3,3,3- tetra-
Fluoropropene (HFO1234yf), 10 parts of CF3Is, 0.003 part of 1- pi-allyl -3- butyl imidazole nitrate ion liquid are stirring
15h is pre-mixed under liquid phase in formula reactor, being then added to high flux microchannel glass reactor, (Corning Incorporated gives birth to
Production, GEN-1 types glass reactor) in, with flow velocity 30Kg/h flow velocitys by being sufficiently mixed to get product.Numbering is WN-4.
Embodiment 5
The preparation of step (1) nanometer bulking agent, based on every part of 1Kg, charge ratio is as follows：
Preparation method is：
By proportioning, in stirring-type reaction kettle, by 4 partsStibium doping stannic oxide (ATO) nano-powderIt is distributed to 1000 parts
In ethanol, 0.02 part of organic boron coupling agent of SBW- III is added, reacts 2h under normal temperature (25 DEG C), then add 70 parts of polyalkylenes
Glycol (PAG) lubricant, 4 parts of 2,6- nonadienols, 10h is reacted under normal temperature (25 DEG C), that is, obtains a nanometer bulking agent, it is standby.
Step (2) mixture, based on every part of 1Kg, charge ratio is as follows：
Preparation method is：By proportioning, the nanometer bulking agent that 7.5 parts of steps (1) are prepared and 400 part 2,3,3,3- tetra-
Fluoropropene (HFO1234yf), 200 parts of CF3Is, 0.007 part of 1- pi-allyl -3- butyl imidazole nitrate ion liquid are stirring
Mix in formula reactor and be pre-mixed 25h under liquid phase, being then added to high flux microchannel glass reactor, (Corning Incorporated gives birth to
Production, GEN-2 types glass reactor) in, with flow velocity 80Kg/h flow velocitys by being sufficiently mixed to get product.Numbering is WN-5.
Performance test：
Embodiment 1-5 products obtained therefroms are according to ANSI/ASHRAE 86-1994 standards " the floc point test side of refrigeration-grade oil
Method " (Methods of Testing the Floe.Point of Refrigeration Grade Oils), determines PAG
The compatibility of lubricant base fluid and embodiment 1-5 products obtained therefroms, the wherein weight percent concentration of lubricant is 20 weight %.Will
Lubricant and refrigerant are added in heavy-walled glass tubes by weight.Then by the seal of tube.When solution temperature is from room temperature (20 DEG C)
To -60 DEG C (coolings circulation) and from room temperature to+95 DEG C (heat cycles) it is slowly varying when, pass through visual observations and detect phase point
From.Temperature when occurring to be separated (i.e. one is separated into two-phase) is all observed in cooling and heat cycles, by given weight
Minimum under amount % lubricant concentrations is recorded as separation temperature (critical solution temperature, CST), and data are shown in Table 1.
Table 1：Embodiment 1-5 products obtained therefrom performance datas
Claims (1)
1. a kind of preparation method of fluorine-containing iodo compositions of hydrocarbons, it is characterised in that comprise the following steps：
(a) based on every part of 1Kg, in stirring-type reaction kettle, by the antimony doped stannic oxide nanometer powder that 5 parts of particle diameters are 1~10nm
Body is distributed in 1000 parts of ethanol, adds 0.05 part of the III organic boron coupling agents of SBW- of Qingdao Siwei Chemical Co., Ltd., and 25
3h is reacted under DEG C normal temperature, 100 parts of polyalkylene glycol lubricants, 5 parts of 2,6- nonadienols is then added, is reacted under 25 DEG C of normal temperature
6h, a nanometer bulking agent is obtained, it is standby；
(b) based on every part of 1Kg, 10 parts of nanometer bulking agent that step (a) is prepared, 900 parts of 2,3,3,3- tetrafluoropropene, three
100 parts of fluorine iodomethane, 0.01 part of 1- pi-allyl -3- butyl imidazole nitrate ions liquid are first under liquid phase in stirring-type reaction kettle
30h is pre-mixed, is then added in the GEN-3 type high fluxs microchannel glass reactor of Corning Incorporated's production, with flow velocity
100Kg/h is mixed to get fluorine-containing idohydrocarbon composition product.
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