CN109876682A - Carbon nano-tube hybridization mixed-matrix infiltrating and vaporizing membrane and the preparation method and application thereof - Google Patents
Carbon nano-tube hybridization mixed-matrix infiltrating and vaporizing membrane and the preparation method and application thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000011159 matrix material Substances 0.000 title claims abstract description 38
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 37
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 36
- 230000008016 vaporization Effects 0.000 title claims abstract description 36
- 238000009396 hybridization Methods 0.000 title claims abstract description 35
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 11
- 239000000796 flavoring agent Substances 0.000 claims abstract description 6
- 235000019634 flavors Nutrition 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 37
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 claims description 28
- PSQYTAPXSHCGMF-BQYQJAHWSA-N β-ionone Chemical compound CC(=O)\C=C\C1=C(C)CCCC1(C)C PSQYTAPXSHCGMF-BQYQJAHWSA-N 0.000 claims description 26
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 17
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 claims description 14
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 claims description 14
- 229930007744 linalool Natural products 0.000 claims description 14
- SFEOKXHPFMOVRM-UHFFFAOYSA-N (+)-(S)-gamma-ionone Natural products CC(=O)C=CC1C(=C)CCCC1(C)C SFEOKXHPFMOVRM-UHFFFAOYSA-N 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000004132 cross linking Methods 0.000 claims description 10
- 239000003431 cross linking reagent Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000007790 scraping Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- -1 dimethyl siloxane Chemical class 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000000284 extract Substances 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 241001122767 Theaceae Species 0.000 claims 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 abstract description 35
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 abstract description 35
- 238000000926 separation method Methods 0.000 abstract description 18
- 230000004907 flux Effects 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 4
- 239000002033 PVDF binder Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000000605 extraction Methods 0.000 abstract description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 abstract 2
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 abstract 2
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 29
- 239000002048 multi walled nanotube Substances 0.000 description 21
- 230000008595 infiltration Effects 0.000 description 18
- 238000001764 infiltration Methods 0.000 description 18
- 238000001704 evaporation Methods 0.000 description 17
- 230000008020 evaporation Effects 0.000 description 17
- 244000269722 Thea sinensis Species 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 235000006468 Thea sinensis Nutrition 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 235000020279 black tea Nutrition 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 235000013616 tea Nutrition 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 235000009569 green tea Nutrition 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- UFLHIIWVXFIJGU-ARJAWSKDSA-N (Z)-hex-3-en-1-ol Chemical compound CC\C=C/CCO UFLHIIWVXFIJGU-ARJAWSKDSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 108090000862 Ion Channels Proteins 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 244000062793 Sorghum vulgare Species 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000006286 aqueous extract Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Polymers C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 229960001047 methyl salicylate Drugs 0.000 description 1
- 235000019713 millet Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000329 molecular dynamics simulation Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229940100595 phenylacetaldehyde Drugs 0.000 description 1
- 238000013082 photovoltaic technology Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229960002415 trichloroethylene Drugs 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 235000020097 white wine Nutrition 0.000 description 1
- 235000014101 wine Nutrition 0.000 description 1
Abstract
The invention discloses a kind of carbon nano-tube hybridization mixed-matrix infiltrating and vaporizing membranes and the preparation method and application thereof, pass through the nano hybridization mixed-matrix infiltrating and vaporizing membrane of carbon nanotube particulate and the compound preparation of PDMS, carbon nanotube particulate is uniformly dispersed, film is fine and close, the nano hybridization mixed-matrix infiltrating and vaporizing membrane for adding carbon nanotube has better separating property compared to PDMS/PVDF film, flux and separation factor all increase, and are especially promoted in terms of flux larger.It, which is applied, has many advantages, such as that low energy consumption, process equipment is simple, the rate of recovery is high, easy to operate, highly-safe compared with other separate modes such as the methods of rectifying, extraction, absorption in the separation of volatile flavour.
Description
Technical field
The present invention relates to a kind of carbon nano-tube hybridization mixed-matrix infiltrating and vaporizing membranes and the preparation method and application thereof, belong to film
Separation field.
Background technique
The separating technology of film is emerging advanced isolation technics, is widely used in water, the energy, food, chemical industry and health care etc.
Direction.However wherein infiltration evaporation (PV) is widely used as liquid separation process, is such as dehydrated using hydrophilic film valuable
Organic solvent, or organic solvent is concentrated from aqueous solution using hydrophobic film.Organic-organic mixing is separated using organic film selection
Object is also feasible.Infiltration evaporation is a kind of energy saving, environmental-friendly isolation technics.Infiltrating and vaporizing membrane can be divided into preferentially by function
Water permeable membrane (Hydrophilic Membrane) and ethanol-permselective membrane (Organophilic Membrane).Ethanol-permselective membrane material
Material usually selects silicon-containing polymer, fluoropolymer and cellulose derivative etc. to be used as separating layer, and hydrophobicity is strong, can be from aqueous solution
The organic matter of middle selective removal a small amount of (or even micro).In numerous evaporation alcohol permselective membrane materials, poly dimethyl
Siloxanes (PDMS) has excellent separating property, PDMS composite membrane hydrophobicity with higher and good thermal stability, change
Stability and mechanical stability are learned, but still is not able to satisfy the separating property of industrial requirements.Therefore hydrophobic nanoporous is filled
Material becomes research hotspot.
Carbon nanotube is a kind of novel carbon structure being just found for 1991, it is by the sp in carbon atom2Based on hydridization,
Be mixed with sp3 hydridization it is constructed at ideal structure.Carbon nanotube be considered as the graphene roll by sheet at it is seamless, hollow
Tube body.Its structure is complete graphene grid, therefore its theoretical strength is close to the intensity of carbon-carbon bond, it is strong for theoretical prediction
About rigid 100 times are spent, density but only has rigid 1/6, and has high collapse resistance, anti-distortion ability, therefore referred to as super fibre
Dimension.Carbon nanotube also has high specific surface area, maximum up to 1315m2/ g, also because having excellent characterization of adsorption.Always
For, carbon nanotube (CNTs) is a kind of Novel Carbon Nanomaterials with excellent properties, such as high mechanical stiffness, specific surface area
It is big etc..Atom, molecular dynamics simulation with known inorganic material studies have shown that compare, and carbon nanotube is as gas separation membrane material
When material, there is high permeation flux and selectivity.The presence of carbon nanotube makes film permeability with higher, and faster
Mass transfer rate can remove volatile organic matter from water, such as methylene chloride, chloroform, benzene, trichloro ethylene and toluene.
Infiltration evaporation (PV) technology in the food industry application slowly composed and, the research of PV technology is mainly concentrated
In the concentration and recycling of fruit juice aromatic substance, good application feasibility is shown.It is also employed in white wine and grape wine in recent years
The recycling of fragrance also presents good application prospect.But it is empty that there are also huge excavations in terms of tea aroma object separation
Between, also only KANANI etc. have studied poly- caprylil methicone (polyoctylmethyloctylsiloxane, POMS) and
Dimethyl silicone polymer (polydimethylsiloxane, PDMS) film is to -2- hexenoic aldehyde trans- in green tea, linalool, suitable
The infiltration evaporation of the green tea aromatic substances such as formula -3- hexenol, isopentyl aldehyde, isobutylaldehyde, benzyl alcohol, phenylacetaldehyde and β-ionone separates effect
The separating effect of fruit, discovery PDMS film is substantially better than POMS film, this conclusion has this experimental work certain directive significance.
The PDMS/PVDF composite membrane prepared at present to the separation of linalool, leaf-alcohol, trans- -2- hexenoic aldehyde and benzyl alcohol because
Son is higher, is 28.87~64.49, but permeation flux is lower, only 0.8~1.2g/ (m2It h), need to be to membrane material and structure
Further is adjusted and optimized.
Summary of the invention
Goal of the invention: the technical problem to be solved by the present invention is in view of the deficiencies of the prior art, provide a kind of carbon nanometer
Pipe hybridized mixed matrix infiltrating and vaporizing membrane forms effective membrane channels using carbon nanotube as additive, promotes point of film
From performance, asked with solving present in separation and recovery tea aroma object that the rate of recovery is low, equipment requirement is high, solvent-oil ratio is big etc.
Topic.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows:
A kind of preparation method of carbon nano-tube hybridization mixed-matrix infiltrating and vaporizing membrane, includes the following steps:
Step 1: dimethyl silicone polymer (PDMS), crosslinking agent and catalyst are mixed, and are stirred 5~6h, are obtained solution A；
Separately carbon nanotube particulate (MWCNTs) is taken to be added to 5~30min of ultrasound in solvent, obtains solution B；By solution B with it is a part of molten
Liquid A mixing, obtains scraping film liquid after filtering, deaeration, standing after stirring 2~3h；
Step 2: pvdf membrane is fixed in horizontal glass plate, and film liquid of scraping prepared by step 1 is then poured over PVDF
Knifing is carried out on film, stands 2~3h at room temperature, and 50~70 DEG C of vacuum drying make crosslinking obtain hybridized film completely；
Step 3: remaining solution A is toppled in hybridized film obtained in step 2, is carried out secondary knifing, is finally obtained
Carbon nano-tube hybridization mixed-matrix infiltrating and vaporizing membrane (MWCNTs/PDMS).
Wherein, in step 1, the viscosity number at 25 DEG C of the dimethyl silicone polymer is 500~1000cP.
Preferably, the crosslinking agent is ethyl orthosilicate (TEOS)；The catalyst is dibutyl tin dilaurate
(DBTL)。
The mixing mass ratio of the dimethyl siloxane (PDMS), crosslinking agent and catalyst be 8~12:1:0.01~
0.08, preferably 10:1:0.05.
Preferably, the partial size of the carbon nanotube particulate is 30~100nm, is added to solvent with mass fraction 0.1~5%
In n-hexane.
The mixing mass ratio of solution B and a part of solution A is 4~8:1, preferably 5:1.
In step 3, the quality of remaining solution A at least accounts for the half of complete soln A mass, and secondary knifing prevents separation
Film film layer directly contacts organic liquid, destroys membrane structure, influences film properties.Film can be extended simultaneously uses the time, enhances film
Separating effect.Monofilm is about 90 hours using the time, and secondary knifing caudacoria extends 2 times using the time, separating property
Enhancing.
The carbon nano-tube hybridization mixed-matrix infiltrating and vaporizing membrane that above-mentioned preparation method is prepared is also in protection of the invention
In range.
Further requirement of the present invention protects the carbon nano-tube hybridization mixed-matrix infiltrating and vaporizing membrane in separating volatile fragrance
Volatile flavour gaultherolin, linalool and β-ionone in the application of object, especially separation tea extract.
Infiltration evaporation separation is 30~50 DEG C in temperature, and vacuum degree is 160~300Pa, and feed rate is 0.25~0.4L/
Under the process conditions of min, the volatile flavour that the concentration range in tea extract is 5~100ppm is separated with good
Effect.
The utility model has the advantages that
The application passes through the nano hybridization mixed-matrix infiltrating and vaporizing membrane of carbon nanotube particulate and the compound preparation of PDMS, and carbon is received
Mitron particle is uniformly dispersed, film is fine and close, adds the nano hybridization mixed-matrix infiltrating and vaporizing membrane of carbon nanotube compared to PDMS/
Pvdf membrane has better separating property, and flux and separation factor all increase, and is especially promoted in terms of flux larger.It is answered
Separation used in volatile flavour has compared with other separate modes such as the methods of rectifying, extraction, absorption that low energy consumption, technique is set
The advantages that standby simple, the rate of recovery is high, easy to operate, highly-safe.
Detailed description of the invention
The present invention is done with reference to the accompanying drawings and detailed description and is further illustrated, of the invention is above-mentioned
And/or otherwise advantage will become apparent.
Fig. 1 is that embodiment prepares MWCNTs/PDMS nano hybridization mixed-matrix infiltrating and vaporizing membrane and separating volatile virtue
The apparatus structure schematic diagram of perfumery；
Fig. 2 a is the surface Scanning Electron microscope photo of PDMS film；
Fig. 2 b is the surface Scanning Electron microscope photo of MWCNTs/PDMS film prepared by embodiment 4.
Specific embodiment
According to following embodiments, the present invention may be better understood.
Structure depicted in Figure of description, ratio, size etc., only to cooperate the revealed content of specification, with
Understand for those skilled in the art and read, be not intended to limit the invention enforceable qualifications, therefore does not have technically
Essential meaning, the modification of any structure, the change of proportionate relationship or the adjustment of size can be generated not influencing the present invention
Under effect and the purpose that can reach, should all still it fall in the range of disclosed technology contents can cover.Meanwhile
Cited such as "upper", "lower", "front", "rear", " centre " term in this specification are merely convenient to being illustrated for narration, and
It is non-that to limit the scope of the invention, relativeness is altered or modified, under the content of no substantial changes in technology, when
Also it is considered as the enforceable scope of the present invention.
Fig. 1 is following embodiment preparation MWCNTs/PDMS nano hybridization mixed-matrix infiltrating and vaporizing membrane and separation volatilization
The apparatus structure schematic diagram of property aromatic substance, which includes sequentially connected heat-collecting magnetic stirring device 1, circulating pump 2, membrane module
3, pressure gauge 4, cold-trap 5, surge valve 6 and vacuum pump 7.The MWCNTs/PDMS nano hybridization mixed-matrix of preparation is permeated into vapour
Change film (area 19.625cm2) be installed in membrane module, feed liquid is placed in magnetic stirring apparatus by device when running, with circulating pump
Drive the feed liquid circulation of feed side；Meanwhile vacuum pump operation, negative pressure is formed in membrane module per-meate side, the volatility virtue isolated
Perfumery condenses in cold-trap.
Embodiment 1
Scrape the preparation of film liquid: 10:1:0.5 in mass ratio weighs PDMS, crosslinking agent TEOS and catalyst DBTL mixing, stirring
5h obtains solution A；It separately takes carbon nanotube particulate to be added in solvent hexane with mass fraction for 0.5%, obtains solution B, ultrasound
The solution A of half and solution B are mixed with the ratio of 1:4 after 10min, filtering, deaeration, standing 2h obtain knifing after stirring 2h
Liquid；
Hydridization film preparation: pvdf membrane is fixed in horizontal glass plate, and the film liquid of scraping of above-mentioned preparation is then poured over it
Upper carry out knifing, stands 2h at room temperature, and placing into 60 DEG C of vacuum oven makes crosslinking obtain hybridized film completely；
Infiltration evaporation film preparation: the other half solution A is poured in hybridized film, is carried out secondary knifing, is stood at room temperature
2h, 60 DEG C of vacuum drying make crosslinking obtain MWCNTs/PDMS nano hybridization mixed-matrix infiltrating and vaporizing membrane completely.
The MWCNTs/PDMS nano hybridization mixed-matrix infiltrating and vaporizing membrane of preparation is in separating volatile aromatic substance using such as
Under:
The gaultherolin for being 100ppm using concentration, linalool and β-ionone concentration are 5ppm aqueous solution as per-meate side
Feed liquid, the operating condition of infiltration evaporation are 25 DEG C of temperature, vacuum degree 160-300Pa, charging rate 0.32L/min, the time
Be 2 hours, claim condensate liquid weight, measure the concentration of feed liquid with three kinds of compounds in the condensate liquid that is collected into, obtain this
Gaultherolin, linalool and β-ionone flux are respectively 1.61g/ (m under part2.h)、2.11g/(m2) and 0.063g/ .h
(m2.h)。
Embodiment 2
Scrape the preparation of film liquid: 12:1:0.08 in mass ratio weighs PDMS, crosslinking agent TEOS and catalyst DBTL mixing, stirs
6h is mixed, solution A is obtained；Carbon nanotube particulate is separately taken to be added in solvent hexane with mass fraction for 2%, it will after ultrasonic 15min
The solution A and solution B of half are mixed with the ratio of 1:8, obtain scraping film liquid after filtering, deaeration, standing 1.5h after stirring 3h；
Hydridization film preparation: pvdf membrane is fixed in horizontal glass plate, and then the film liquid of scraping of above-mentioned preparation is poured onto
Knifing is carried out, stands 2h at room temperature, placing into 50 DEG C of vacuum oven makes crosslinking obtain hybridized film completely；
Infiltration evaporation film preparation: the other half solution A is poured in hybridized film, is carried out secondary knifing, is stood at room temperature
2h, 50 DEG C of vacuum drying make crosslinking obtain MWCNTs/PDMS nano hybridization mixed-matrix infiltrating and vaporizing membrane completely.
The MWCNTs/PDMS nano hybridization mixed-matrix infiltrating and vaporizing membrane of preparation is in separating volatile aromatic substance using such as
Under:
The gaultherolin for being 100ppm using concentration, linalool and β-ionone concentration are 10ppm aqueous solution as infiltration
Side feed liquid, the operating condition of infiltration evaporation are 30 DEG C of temperature, vacuum degree 168-300Pa, charging rate 0.32L/min, when
Between be 5 hours, claim condensate liquid weight, measure feed liquid and the concentration of condensate liquid that is collected into, obtain salicylic acid under this condition
Methyl esters, linalool and β-ionone flux are respectively 1.69g/ (m2.h)、2.01g/(m2) and 0.064g/ (m .h2.h)；Separation
The factor is respectively 131.3,65.8 and 94.1.
Embodiment 3
Scrape the preparation of film liquid: 10:1:0.05 in mass ratio weighs PDMS, crosslinking agent TEOS and catalyst DBTL mixing, stirs
6h is mixed, solution A is obtained；MWCNTs particle is separately taken to be added in solvent hexane with mass fraction for 5%, by half after ultrasonic 0.5h
Solution A and solution B mixed with the ratio of 1:5, stir filtering after 2h, deaeration, standing 1h obtain scraping film liquid；
Hydridization film preparation: pvdf membrane is fixed in horizontal glass plate, and then the film liquid of scraping of above-mentioned preparation is poured onto
Knifing is carried out, stands 2h at room temperature, placing into 70 DEG C of vacuum oven makes crosslinking obtain hybridized film completely；
Infiltration evaporation film preparation: the other half solution A is poured in hybridized film, is carried out secondary knifing, is stood at room temperature
2h, 70 DEG C of vacuum drying make crosslinking obtain MWCNTs/PDMS nano hybridization mixed-matrix infiltrating and vaporizing membrane completely.
The MWCNTs/PDMS nano hybridization mixed-matrix infiltrating and vaporizing membrane of preparation is in separating volatile aromatic substance using such as
Under:
The gaultherolin for being 100ppm using concentration, linalool and β-ionone concentration are 5ppm mixed solution as infiltration
Side feed liquid, the operating condition of infiltration evaporation are 35 DEG C of temperature, vacuum degree 160-300Pa, charging rate 0.4L/min, the time
For 5h, claim condensate liquid weight, measure the concentration of feed liquid with the condensate liquid being collected into, obtain under this condition gaultherolin,
Linalool and β-ionone flux are respectively 1.61g/ (m2·h)、2.11g/(m2And 0.063g/ (m h)2H), separation because
Son is respectively 99.1,62.3 and 128.1.
Embodiment 4
Scrape the preparation of film liquid: 10:1:0.05 in mass ratio weighs PDMS, crosslinking agent TEOS and catalyst DBTL mixing, stirs
6h is mixed, solution A is obtained；It separately takes MWCNTs particle to be added in solvent hexane with mass fraction for 5%, obtains solution B, ultrasound
The solution A of half and solution B are mixed with the ratio of 1:5 after after 0.5h, filtering, deaeration, standing 2h obtain knifing after stirring 2h
Liquid；
Hydridization film preparation: pvdf membrane is fixed in horizontal glass plate, and the film liquid of scraping of above-mentioned preparation is then poured over it
Upper carry out knifing, stands 2h at room temperature, and placing into 60 DEG C of vacuum oven makes crosslinking obtain hybridized film completely；
Infiltration evaporation film preparation: the other half solution A is poured in hybridized film, is carried out secondary knifing, is stood at room temperature
2h, 60 DEG C of vacuum drying make crosslinking obtain MWCNTs/PDMS nano hybridization mixed-matrix infiltrating and vaporizing membrane completely.
The MWCNTs/PDMS nano hybridization mixed-matrix infiltrating and vaporizing membrane of preparation is in separation black tea volatile flavour
Using as follows:
The preparation of black tea extracting solution: 1:20 in mass ratio mixes black tea powder with hot water, extracts at 90-95 DEG C
30min, centrifuge separation；By MWCNTs/PDMS nano hybridization mixed-matrix infiltrating and vaporizing membrane (area 19.625cm2) be installed on
In the membrane module of Fig. 1, feed liquid by black tea Aqueous extracts (millet paste) as infiltration evaporation, the operating condition of infiltration evaporation is temperature 30
DEG C, vacuum degree 200Pa, charging rate 0.4L/min, time 6h.The quality of per-meate side condensate liquid is weighed, feed liquid is measured
With gaultherolin, linalool and the β-ionone concentration in collection liquid, obtain under this condition gaultherolin, linalool and
β-ionone flux is respectively 1.1353mg.m-2.h-1And 0.9016mg.m-2.h-1, 19.0368mg.m-2.h-1.Show the party
Method has good prospect and operability.
Fig. 2 a and 2b are the surface Scanning Electron microscope of the MWCNTs/PDMS film of PDMS film and the preparation of embodiment 4 respectively
Photo, it is seen that MWCNTs particle is well dispersed in MWCNTs/PDMS film, it can be seen that apparent carbon nanotube is distributed in PDMS painting
In layer.
Linalool (Linalool), gaultherolin (Methylsalicylate), β-ionone (Beta-ionone) warp
Concentration is decreased obviously after nano hybridization mixed-matrix infiltration evaporation film process, and the aromatic substance concentration collected is significantly larger than original solution
Concentration, the enriched concentration of three kinds of aromatic substances be respectively 1.14mg/L, 0.9mg/L and 18.55mg/L this show that MWCNTs/PDMS receives
Rice hybridized mixed matrix infiltration evaporation membrane separating effect is significant.
The present invention provides a kind of think ofs of carbon nano-tube hybridization mixed-matrix infiltrating and vaporizing membrane and the preparation method and application thereof
Road and method, there are many method and the approach for implementing the technical solution, the above is only a preferred embodiment of the present invention,
It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, can also do
Several improvements and modifications out, these modifications and embellishments should also be considered as the scope of protection of the present invention.What is be not known in the present embodiment is each
The available prior art of component part is realized.
Claims (10)
1. a kind of preparation method of carbon nano-tube hybridization mixed-matrix infiltrating and vaporizing membrane, which comprises the steps of:
Step 1: dimethyl silicone polymer, crosslinking agent and catalyst are mixed, and are stirred 5~6h, are obtained solution A；Separately take carbon nanometer
Tube particle is added to 5~30min of ultrasound in solvent, obtains solution B；Solution B is mixed with a part of solution A, after stirring 2~3h
It obtains scraping film liquid after filtering, deaeration, standing；
Step 2: pvdf membrane is fixed in horizontal glass plate, and then film liquid of scraping prepared by step 1 is poured on pvdf membrane
Knifing is carried out, stands 2~3h at room temperature, 50~70 DEG C of vacuum drying make crosslinking obtain hybridized film completely；
Step 3: remaining solution A is toppled in hybridized film obtained in step 2, carries out secondary knifing, is finally obtained carbon and is received
Mitron hybridized mixed matrix infiltrating and vaporizing membrane.
2. the preparation method of carbon nano-tube hybridization mixed-matrix infiltrating and vaporizing membrane according to claim 1, which is characterized in that
In step 1, the viscosity number at 25 DEG C of the dimethyl silicone polymer is 500~1000cP.
3. the preparation method of carbon nano-tube hybridization mixed-matrix infiltrating and vaporizing membrane according to claim 1, which is characterized in that
In step 1, the crosslinking agent is ethyl orthosilicate；The catalyst is dibutyl tin dilaurate.
4. the preparation method of carbon nano-tube hybridization mixed-matrix infiltrating and vaporizing membrane according to claim 1, which is characterized in that
In step 1, the mixing mass ratio of the dimethyl siloxane, crosslinking agent and catalyst is 8~12:1:0.01~0.08.
5. the preparation method of carbon nano-tube hybridization mixed-matrix infiltrating and vaporizing membrane according to claim 1, which is characterized in that
In step 1, the partial size of the carbon nanotube particulate is 30~100nm, is added to solvent hexane with mass fraction 0.1~5%
In.
6. the preparation method of carbon nano-tube hybridization mixed-matrix infiltrating and vaporizing membrane according to claim 1, which is characterized in that
In step 1, the mixing mass ratio of solution B and a part of solution A is 4~8:1.
7. the preparation method of carbon nano-tube hybridization mixed-matrix infiltrating and vaporizing membrane according to claim 1, which is characterized in that
In step 3, the quality of remaining solution A at least accounts for the half of complete soln A mass.
8. the carbon nano-tube hybridization mixed-matrix infiltrating and vaporizing membrane that any one preparation method is prepared in claim 1~7.
9. application of the carbon nano-tube hybridization mixed-matrix infiltrating and vaporizing membrane in separating volatile aromatic substance described in claim 8.
10. application according to claim 9, which is characterized in that the volatile flavour is present in tea extract,
Including gaultherolin, linalool and β-ionone.
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