CN106621834A - Water-absorbing metal organic framework material-chitosan mixed matrix membrane, preparation and application - Google Patents
Water-absorbing metal organic framework material-chitosan mixed matrix membrane, preparation and application Download PDFInfo
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- CN106621834A CN106621834A CN201611191564.3A CN201611191564A CN106621834A CN 106621834 A CN106621834 A CN 106621834A CN 201611191564 A CN201611191564 A CN 201611191564A CN 106621834 A CN106621834 A CN 106621834A
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- shitosan
- framework materials
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 41
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000004941 mixed matrix membrane Substances 0.000 title abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 40
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 20
- 238000005266 casting Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000004744 fabric Substances 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000004528 spin coating Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000012528 membrane Substances 0.000 claims description 27
- 238000005213 imbibition Methods 0.000 claims description 22
- 238000001704 evaporation Methods 0.000 claims description 16
- 239000002808 molecular sieve Substances 0.000 claims description 16
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 8
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- NZSLBYVEIXCMBT-UHFFFAOYSA-N chloro hypochlorite;zirconium Chemical class [Zr].ClOCl NZSLBYVEIXCMBT-UHFFFAOYSA-N 0.000 claims description 4
- 239000001530 fumaric acid Substances 0.000 claims description 4
- 230000036571 hydration Effects 0.000 claims description 4
- 238000006703 hydration reaction Methods 0.000 claims description 4
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 3
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 2
- -1 NDA Chemical compound 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 210000000988 bone and bone Anatomy 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical class C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 2
- 230000003204 osmotic effect Effects 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical group O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 8
- 239000011159 matrix material Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000005373 pervaporation Methods 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 abstract 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 230000008595 infiltration Effects 0.000 description 17
- 238000001764 infiltration Methods 0.000 description 17
- 230000008020 evaporation Effects 0.000 description 14
- 239000002245 particle Substances 0.000 description 9
- 230000004907 flux Effects 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000873 masking effect Effects 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000006196 deacetylation Effects 0.000 description 4
- 238000003381 deacetylation reaction Methods 0.000 description 4
- 239000013384 organic framework Substances 0.000 description 4
- 239000013110 organic ligand Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/08—Polysaccharides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/78—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by condensation or crystallisation
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a water-absorbing metal organic framework material-chitosan mixed matrix membrane, and preparation and application thereof. The mixed matrix membrane is composed of chitosan and a water-absorbing metal organic framework material, wherein the mass ratio of the chitosan to the metal organic framework material is 100: (1-20); the film thickness is 1-2 microns. Dissolving a water-absorbing metal organic framework material into a dilute acetic acid solution, and uniformly stirring and dispersing; weighing chitosan to prepare a metal organic framework material-chitosan mixed solution; adding glutaraldehyde for crosslinking reaction; filtering with filter cloth, standing for defoaming to obtain casting solution, coating with spin coating method, and drying to obtain mixed matrix membrane. The method has simple process and rich and controllable raw materials. The prepared mixed matrix film has the thickness of 1-2 microns, is used for a pervaporation ethanol-water system, and has better separation performance.
Description
Technical field
The present invention relates to a kind of water imbibition metal-organic framework materials/shitosan mixed substrate membrane containing nano-grade molecular sieve and preparation and application, category
In technical field of membrane.
Background technology
Organic solvent is widely used in the fields such as petrochemical industry, fine chemistry industry, biological medicine and new forms of energy, especially anhydrous
Level organic solvent has important using value in some fields.Conventional dehydration of organic solvent main method has drier to take off
Water, special extract rectification and infiltration evaporation UF membrane etc..Infiltration evaporation for separate azeotrope, closely boil organic mixture, isomers and
Heat-sensitive materials have low energy consumption, green cleaning, do not introduce the advantages such as third component.Pervaporation Technology it is critical only that exploration
The excellent membrane material of energy.At present conventional organic permeable membrane material is mainly according to dissolving-diffusion theory, there is infiltration rate
The relation mutually restricted between selectivity.
Mixed substrate membrane containing nano-grade molecular sieve is a kind of new membrane structure being added to inorganic particulate in polymer, combines polymer and nothing
The advantage of machine particle bi-material.At present conventional particle filled composite mainly includes that silicon materials, material with carbon element, molecular sieve and metal are organic
The porous materials such as framework material.Metal-organic framework materials (metal organic framework) be with metal ion or from
Submanifold is node, and by organic ligand connector is used as, and the class formed by Coordinate self-assembly has having for regular pore structure
Machine inorganic hybridization coordination polymer crystal.This material has that specific surface area is big, aperture is adjustable, various structures, excellent performance etc.
Feature, has extensive research and application in fields such as absorption.The development of this hybrid new material, also to mixing
Matrix membrane brings new opportunity.Metal-organic framework materials have the characteristic of organic and inorganic materials concurrently, and its organic segment can promote
Interface compatibility between particle and organic polymer matrix, while the porous of its structure can improve adsorbance and diffusion speed
Degree, to improve permeability simultaneously and selectively providing possibility.But there is at present good hydrothermal stability and with water absorption
Metal-organic framework materials it is less, as it is inorganic particle filled prepare in polymer mixed substrate membrane containing nano-grade molecular sieve be applied to infiltration
Vaporization not yet has document report at present.
The content of the invention
The invention aims to improve the deficiencies in the prior art and provide a kind of water imbibition metal-organic framework materials-
Shitosan mixed substrate membrane containing nano-grade molecular sieve, it is a further object of the present invention to provide above-mentioned water imbibition metal-organic framework materials-shitosan mixing
The preparation method of matrix membrane, further object of the present invention is to provide above-mentioned water imbibition metal-organic framework materials-shitosan mixing
The purposes of matrix membrane.
The technical scheme is that：Water imbibition metal-organic framework materials-shitosan mixed substrate membrane containing nano-grade molecular sieve, it is characterised in that
It is made up of shitosan and water imbibition metal-organic framework materials, the mass ratio of wherein shitosan and metal-organic framework materials is
100：(1-20)；Thickness is 1-2 microns.
Present invention also offers the preparation method of above-mentioned water imbibition metal-organic framework materials-shitosan mixed substrate membrane containing nano-grade molecular sieve,
It is comprised the following steps that：
1) water imbibition metal-organic framework materials powder is added in aqueous acetic acid, and stirring makes it be uniformly dispersed；
2) in dissolving the chitosan in above-mentioned metal-organic framework materials dispersion liquid, and stir, being configured to metal has
Machine framework material-shitosan mixed solution；
3) glutaraldehyde is added in above-mentioned mixed solution, 1-2 hours are reacted, Jing filter-cloth filterings, standing and defoaming obtains casting film
Liquid；
4) casting solution is spun on supporter, drying and forming-film.
Preferred steps 1) acetic acid volume fraction is 1-3% in the aqueous acetic acid, powder is fully dispersed.
It is preferred that above-mentioned water imbibition metal-organic framework materials powder is prepared from by source metal and part, wherein source metal
For zirconium chloride, zirconium oxychloride or eight hydration zirconium oxychlorides, part be terephthalic acid (TPA), 2- amino terephthalic acid (TPA)s, fumaric acid, 2,
6- naphthalenedicarboxylic acids, maleic acid, 2,5-Dihydroxyterephthalic acid, 1,5- dihydroxy naphthlene -2,6- dicarboxylic acids or 3,3'- hydroxyl-[1,
1'- biphenyl] -4,4'- dicarboxylic acids.
It is preferred that chitosan mass fraction is 1.5-2.5% in above-mentioned metal-organic framework materials-shitosan mixed solution；
The mass ratio of shitosan and water imbibition metal-organic framework materials is 100：(1-20).
It is preferred that above-mentioned speed of agitator is 400-600r/min, mixing time is 20-24 hours.It is preferred that above-mentioned shitosan list
Body chain link is 50-60 with the mol ratio of glutaraldehyde：1.
It is preferred that above-mentioned steps 4) casting solution spin coating number of repetition 3-5 time.It is preferred that described supporter is zirconium oxide, polypropylene
Nitrile or aluminum oxide.
Membrane material prepared by the present invention can fully combine the characteristic of filler particles and polymer itself, to infiltration evaporation second
Alcohol-water system dehydration has good separation factor and permeation flux.Present invention also offers the organic bone of above-mentioned water imbibition metal
Frame material-application of the shitosan mixed substrate membrane containing nano-grade molecular sieve in the osmotic, evaporating and dewatering of alcohol-water mixed system.Its permeation flux is higher than
1000g/m2H, separation factor is more than 1500.
Beneficial effect：
The present invention is first the metal-organic framework materials with water absorption to be prepared for into mixed base as filler particles
Plasma membrane；Filler particles are distributed in advance in acetum simultaneously, particle surface can be made to increase the hydrophily bases such as hydroxyl, carboxyl
Group, improves dispersiveness.Mixed-matrix membrane process environmental protection prepared by the present invention, it is gentle it is controllable, simple to operate, do not introduce the
Tripartite modifies, and thickness is 1-2 microns, and the mixed substrate membrane containing nano-grade molecular sieve of preparation is applied to ethanol dehydration and has good infiltration evaporation performance.
Description of the drawings
Fig. 1 is infiltration evaporation experimentation schematic diagram；
Fig. 2 is the infiltration evaporation performance map of film in embodiment and comparative example, and its orbicular spot represents the permeation flux of film, square frame
Represent the separation factor of film；
Fig. 3 for institute's masking in embodiment 1 surface electron microscope；
Fig. 4 for institute's masking in embodiment 1 section electron microscope；
Fig. 5 for institute's masking in embodiment 2 surface electron microscope；
Fig. 6 for institute's masking in embodiment 3 surface electron microscope；
Fig. 7 for institute's masking in comparative example surface electron microscope.
Specific embodiment
Embodiment 1
Eight are selected to be hydrated zirconium oxychloride as source metal, fumaric acid prepares water imbibition metallic organic framework as organic ligand
Material MOF-801, is added in the acetum of 2vt% after being vacuum dried, and stirs 2 hours, and rotating speed 400r/min matches somebody with somebody
Into dispersion liquid.By deacetylation>90% shitosan is added in above-mentioned mixed liquor, is stirred at room temperature 24 hours, rotating speed 500r/
Min is configured to metal-organic framework materials/shitosan mixed solution, and wherein chitosan mass concentration is 2.5wt%, shitosan with
The mass ratio 100 of metal-organic framework materials MOF-801：5.A certain amount of glutaraldehyde is proportionally added into in above-mentioned solution, its
The monomer segments of middle shitosan are 60 with the mol ratio of glutaraldehyde：1, reaction 1 hour after, Jing filter-cloth filterings and stand 10 minutes take off
Bubble obtains casting solution.Casting solution is spun on pretreated polyacrylonitrile flat milipore filter, repeats film three times, room temperature is done
It is dry to obtain film 1.Fig. 1 is infiltration evaporation performance test process schematic.Fig. 2 is the infiltration vapour of different films in embodiment and comparative example
Change ethanol dehydration performance.It can be seen that film 1 is used for into infiltration evaporation ethanol dehydration, (operation temperature is 50 degrees Celsius, former
Feed liquid consists of the aqueous solution of 90% ethanol 10%), separation factor is 1888, and flux is 1074g/m2h.Fig. 3 is the surface of film 1
SEM schemes, and as can be seen from Figure metal-organic framework materials are dispersed in film surface.Fig. 4 schemes for the section SEM of film 1, Cong Zhongke
The thickness for finding out UF membrane layer is 1 micron.
Embodiment 2
Using after vacuum drying water imbibition metal-organic framework materials MOF-801 (eight hydration zirconium oxychlorides as source metal,
Fumaric acid is used as organic ligand) acetum of 2.5vt% is dissolved into, and stir 2 hours, rotating speed 500r/min is made into dispersion
Liquid.By deacetylation>90% shitosan is added in above-mentioned mixed liquor, is stirred at room temperature 24 hours, and rotating speed 400r/min is prepared
Into the shitosan that mass concentration is 1.5wt%/metallic organic framework mixed solution, wherein shitosan and metal-organic framework materials
Mass ratio be 100：2.5.Be proportionally added into a certain amount of glutaraldehyde in above-mentioned solution, wherein the monomer segments of shitosan with
The mol ratio of glutaraldehyde is 50：1, react 1.5 hours, stand a few minutes filter-cloth filtering deaeration and obtain casting solution.Then by casting film
Liquid is spun on pretreated polyacrylonitrile ultrafiltration film, repeats film three times, and drying at room temperature obtains film 2.The thickness of UF membrane layer
Spend for 1.5 microns, Fig. 5 is the film surface electron microscope for preparing, as can be seen from the figure some are a small amount of for film surface portion Regional Dispersion
Particle.The infiltration evaporation performance data figure of different films can be obtained from Fig. 2, and the infiltration evaporation ethanol of the mixed substrate membrane containing nano-grade molecular sieve takes off
Water performance test (operation temperature is 50 degrees Celsius, and material liquid consists of the aqueous solution of 90% ethanol 10%), separation factor is 1472,
Flux is 1006g/m2h。
Embodiment 3
Using after vacuum drying water imbibition metal-organic framework materials MOF-804 (eight hydration zirconium oxychlorides as source metal,
2,5-Dihydroxyterephthalic acid is used as organic ligand) acetum of 3vt% is dissolved into, and stir 1 hour, rotating speed
600r/min is made into dispersion liquid.By deacetylation>90% shitosan is added in above-mentioned mixed liquor, is stirred at room temperature 20 hours,
Rotating speed 500r/min is configured to shitosan/metallic organic framework mixed solution that mass concentration is 2wt%, wherein shitosan and gold
The mass ratio of category organic framework material MOF-801 is 100：12.A certain amount of glutaraldehyde is proportionally added into in above-mentioned solution, its
The monomer segments of middle shitosan are 60 with the mol ratio of glutaraldehyde：1, react 1 hour, stand a few minutes filter-cloth filtering deaeration and obtain
Casting solution.Then casting solution is spun on pretreated polyacrylonitrile ultrafiltration film, repeats film five times, be dried to obtain film 3.
The thickness of UF membrane layer is 1.5 microns, Fig. 6 for film 3 surface electron microscope, it can be seen that it is more to there is particle in surface, there is reunion
Phenomenon, the infiltration evaporation performance data figure of different films can be obtained from Fig. 2, and the infiltration evaporation ethanol of the mixed substrate membrane containing nano-grade molecular sieve takes off
Water performance test (operation temperature is 60 degrees Celsius, and material liquid consists of the aqueous solution of 90% ethanol 10%), separation factor is 1740,
Flux is 1436g/m2h。
Comparative example 1
By deacetylation>90% shitosan is dissolved in the acetum of 2vt%, is stirred at room temperature 20 hours, rotating speed
600r/min, is configured to the chitosan solution that mass concentration is 2.5wt%.A certain amount of penta is proportionally added into in above-mentioned solution
The monomer segments of dialdehyde, wherein shitosan are 60 with the mol ratio of glutaraldehyde：1, react 2 hours, a few minutes are stood, filter-cloth filtering
Deaeration obtains casting solution.Then casting solution is spun on pretreated polyacrylonitrile ultrafiltration film, repeats film three times, be dried
Obtain comparative film.Fig. 7 is the film surface electron microscope for preparing, and as can be seen from the figure film surface is smooth complete.The different films from Fig. 2
Infiltration evaporation performance data figure can obtain, the infiltration evaporation ethanol dehydration performance test (operation temperature of the mixed substrate membrane containing nano-grade molecular sieve
For 50 degrees Celsius, material liquid consists of the aqueous solution of 90% ethanol 10%), separation factor is 798, and flux is 977g/m2h。
Claims (10)
1. water imbibition metal-organic framework materials-shitosan mixed substrate membrane containing nano-grade molecular sieve, it is characterised in that by shitosan and water imbibition metal
Organic framework material is constituted, and wherein the mass ratio of shitosan and metal-organic framework materials is 100：(1-20)；Thickness is that 1-2 is micro-
Rice.
2. a kind of method for preparing water imbibition metal-organic framework materials-shitosan mixed substrate membrane containing nano-grade molecular sieve as claimed in claim 1,
It is comprised the following steps that：
1) water imbibition metal-organic framework materials powder is added in aqueous acetic acid, and stirring makes it be uniformly dispersed；
2) in dissolving the chitosan in above-mentioned metal-organic framework materials dispersion liquid, and stir, be configured to the organic bone of metal
Frame material-shitosan mixed solution；
3) glutaraldehyde is added in above-mentioned mixed solution, 1-2 hours are reacted, Jing filter-cloth filterings, standing and defoaming obtains casting solution；
4) casting solution is spun on supporter, drying and forming-film.
3. method according to claim 2, it is characterised in that step 1) acetic acid volume fraction is in the aqueous acetic acid
1-3%.
4. method according to claim 2, it is characterised in that described water imbibition metal-organic framework materials powder is by gold
Category source and part are prepared from, and wherein source metal is zirconium chloride, zirconium oxychloride or eight hydration zirconium oxychlorides, and part is terephthaldehyde
Acid, 2- amino terephthalic acid (TPA)s, fumaric acid, NDA, maleic acid, 2,5-Dihydroxyterephthalic acid, 1,5- dihydroxies
Base naphthalene -2,6- dicarboxylic acids or 3,3'- hydroxyl-[1,1'- biphenyl] -4,4'- dicarboxylic acids.
5. method according to claim 2, it is characterised in that step 2) described in metal-organic framework materials-shitosan mix
It is 1.5-2.5% to close chitosan mass fraction in solution；The mass ratio of shitosan and water imbibition metal-organic framework materials is
100：(1-20).
6. method according to claim 2, it is characterised in that step 2) described in speed of agitator be 400-600r/min,
Mixing time is 20-24 hours.
7. method according to claim 2, it is characterised in that step 3) the shitosan monomer segments rub with glutaraldehyde
You are than being 50-60：1.
8. method according to claim 2, it is characterised in that step 4) casting solution spin coating number of repetition 3-5 time.
9. method according to claim 2, it is characterised in that step 4) described in supporter be zirconium oxide, polyacrylonitrile or
Aluminum oxide.
10. a kind of water imbibition metal-organic framework materials-shitosan mixed substrate membrane containing nano-grade molecular sieve as claimed in claim 1 is in alcohol-water
Application in the osmotic, evaporating and dewatering of mixed system.
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