CN105771677A - Sodium alga acid/ covalent organic framework composite membrane, preparation and application - Google Patents
Sodium alga acid/ covalent organic framework composite membrane, preparation and application Download PDFInfo
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- CN105771677A CN105771677A CN201610103809.6A CN201610103809A CN105771677A CN 105771677 A CN105771677 A CN 105771677A CN 201610103809 A CN201610103809 A CN 201610103809A CN 105771677 A CN105771677 A CN 105771677A
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- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- 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
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- 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
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- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
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- 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
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Abstract
The invention discloses a sodium alga acid/ covalent organic framework composite membrane.The membrane is composed of sodium alga acid and a covalent organic framework according to the mass ratio of 100: (5-30), wherein the covalent organic framework is composed of terephthalaldehyde and melamine according to the mass ratio of (1-1.5): 1 in a polycondensation mode.The preparing method comprises the steps that terephthalaldehyde and melamine serve as monomers, polycondensation is conducted in dimethyl sulfoxide solvent, the product is extracted through methyl alcohol, tetrahydrofuran and methyl alcohol in sequence, and then the covalent organic framework is obtained; the covalent organic framework is dispersed into deionized water and mixed with sodium alga acid to form membrane casting liquid, and after a polyacrylonitrile ultrafiltration membrane is coated with the membrane casting liquid in a spinning mode, the composite membrane is obtained through crosslinking and drying.The sodium alga acid/ covalent organic framework composite membrane has the advantages that the preparation process is easy and convenient, controllability is strong, the raw materials are easy to get, and the method is universal.The prepared composite membrane is used for a pervaporation ethyl alcohol-aqueous solution system, has high permeation flux and high selectivity for water molecules and has good operation stability at the high temperature.
Description
Technical field
The present invention relates to a kind of sodium alginate/covalent organic framework composite membrane and preparation and application, belong to macromolecule-organic hybrid films
Technical field.
Background technology
The energy and environment are 21 century two significant challenge facing of the whole world, and AND ENERGY RESOURCES CONSUMPTION IN CHINA increases day by day, consumes energy every year
Amount adds up to about 400,000,000 tons of standard coals.Therefore, country has put into effect multinomial policies and regulations, carries forward vigorously regenerative resource, especially
The development of biomass energy, and carry out the application of alcohol fuel gasoline in China.With biomass for raw material production fuel second
In the flow process of alcohol, the water smoking, energy consumption was high (accounting for the 20% of total energy consumption), and separating difficulty is big for the azeotropic mixture of second alcohol and water.
Conventional dewatering is special extract rectification method and absorption method, and special extract rectification method process is complicated, and energy consumption is higher；Though absorption method technique
Relatively easy, but belong to intermittently operated.Compared with the above two, Pervaporation can greatly simplification of flowsheet, reduction production
Energy consumption, has the biggest development potentiality.
Process of pervaporation follows dissolving-diffusion mechanism, utilizes the physical difference of second alcohol and water, can strengthen respectively course of dissolution and
Diffusion process.But the shifting permeability of membrane material and selectivity tradeoff effect, always high performance membrane material
The bottleneck of preparation.Numerous studies show, inorganic filler can improve the network structure of polymer matrix, between regulation macromolecular chain
Away from and chain rigidity, regulation film hydrophobe balance, introduce additional transmission channels and screening function etc., thus overcome Trade-off to imitate
Should.But interface interaction is poor between macromolecule and inorganic particle, it is easily formed defect, thus affects the stability of film.
For improving permeability of the membrane, selectivity and stability simultaneously, this research design prepares the multi-functional material of covalent organic framework
Material, and prepare composite membrane in filling it into sodium alginate, it is intended to utilize the hydrophilic of covalent organic framework to promote hydrone
Preferential adsorption, the selectivity utilizing the specific pore size of covalent organic framework to realize hydrone spread.In addition the organic bone of covalency
Frame is the stabilizing material formed by strong covalent bond, and has more preferable interface between organic framework structured and polymeric hydantoin sodium alginate
The compatibility, thus mechanical stability and the heat stability of membrane material can be improved.Up to the present, the organic bone of sodium alginate/covalency
For pervaporation ethanol dehydration, frame composite membrane has no that document is reported.
Summary of the invention
The present invention provides a kind of sodium alginate/covalent organic framework composite membrane and preparation method and application, and this preparation method simplicity can
Control, prepared composite membrane may be used for the dehydration of pervaporation ethanol-water system, has higher separating property and stability.
The present invention is realized by the following technical programs, a kind of sodium alginate/covalent organic framework composite membrane, this Sargassum
Acid sodium/covalent organic framework composite membrane is to be made up of with covalent organic framework 100:5 in mass ratio～30 sodium alginate；Wherein,
Covalent organic framework is to be formed by terephthalaldehyde and tripolycyanamide in mass ratio 1～1.5:1 polycondensation, the grain of covalent organic framework
Footpath is 60～100nm, and aperture is 0.4～0.6nm.
The preparation method of above-mentioned sodium alginate/covalent organic framework composite membrane, step is as follows:
Step one, the preparation of covalent organic framework: be dissolved in dimethyl sulfoxide solvent by tripolycyanamide, form quality volume
Concentration is the solution of 0.02～0.04g/mL, then by adding terephthaldehyde in solution with tripolycyanamide mass ratio 1～1.5:1
Aldehyde；At 180 DEG C, it is stirred vigorously and is passed through argon gas-sealed, react 48～96h, obtain tan precipitate thing；By this precipitate
It is dried 24h with DMF and oxolane centrifuge washing final vacuum successively, obtains yellow powdery solid；
This yellow powdery solid is placed in apparatus,Soxhlet's, uses methanol, oxolane, methanol respectively to extract at 80 DEG C successively
24～48h, the product after extraction is vacuum dried at 120 DEG C, finally gives covalent organic framework；
The film forming of step 2, sodium alginate/covalent organic framework composite membrane: the covalent organic framework that step one prepares is dissolved in
In ionized water, ultrasonic disperse 15min, obtain dispersion liquid；Then dispersion liquid is mixed to get molten with a certain amount of sodium alginate
Liquid A, wherein, covalent organic framework and the mass ratio 0.05～0.3:1 of sodium alginate, sodium alginate quality in solution A
Mark is 1.5%；Solution A stirs 4～6h with the rotating speed of 300r/min at 30 DEG C, filters, stands, after deaeration, obtains
Homogenizing casting solution；Uniformly being spun on polyacrylonitrile ultrafiltration film by casting solution, drying at room temperature obtains composite membrane；By answering of obtaining
Close film and immerse the CaCl of 0.5M2Solution cross-links, takes out after 5～15min, residual with a large amount of deionized water rinsing film surfaces
The calcium ion stayed；Composite membrane after crosslinking is dried the most at room temperature, finally gives sodium alginate/covalent organic framework composite membrane.
Above-mentioned sodium alginate/covalent organic framework composite membrane is used for pervaporation ethanol-water system dehydration, 76 DEG C, raw material dense
Under conditions of the degree ethanol water for mass fraction 90%, permeation flux is 1452～2397g/m2H, separation factor is
329～1293.
It is an advantage of the current invention that: sodium alginate/covalent organic framework composite membrane preparation process is easy, controllability is strong, raw material is easy
, method general.The composite membrane prepared for pervaporation ethanol-water solution system, hydrone is had high permeating flux,
High selectivity, this composite membrane at high temperature has good operational stability simultaneously.
Accompanying drawing explanation
Fig. 1 is the section Electronic Speculum figure of the film 1 that embodiment 1 obtains.
Fig. 2 is the section Electronic Speculum figure of the film 2 that embodiment 2 obtains.
Fig. 3 is the section Electronic Speculum figure of the film 3 that embodiment 3 obtains.
Fig. 4 is the section Electronic Speculum figure of the comparative film that comparative example obtains.
The permeation flux of the film that Fig. 5 is embodiment 1-3 and comparative example obtains and the comparison diagram of separation factor.
Detailed description of the invention
Being described in further detail technical solution of the present invention below in conjunction with specific embodiments and the drawings, described is embodied as
The present invention is only explained by example, not in order to limit the present invention.
Embodiment 1, preparing sodium alginate/covalent organic framework composite membrane, step is as follows:
6g tripolycyanamide is dissolved in 300mL dimethyl sulfoxide solvent, is subsequently adding 6g terephthalaldehyde.At 180 DEG C
Under be stirred vigorously and be passed through argon gas-sealed, after reaction 48h, obtain tan precipitate thing.By this precipitate successively with N, N-
Dimethylformamide and oxolane centrifuge washing final vacuum are dried 24h, obtain yellow powdery solid.By this yellow powder
Shape solid is placed in apparatus,Soxhlet's, uses methanol, oxolane, methanol respectively to extract 24h, after extraction at 80 DEG C successively
Product be vacuum dried at 120 DEG C, obtain covalent organic framework；
The covalent organic framework weighing 0.019g step one prepared is dissolved in 25mL deionized water, ultrasonic disperse 15min,
To dispersion liquid.Then in dispersion liquid add 0.38g sodium alginate, the solution obtained at 30 DEG C with the rotating speed of 300r/min
Stirring 4h, filters, stands, after deaeration, obtains homogenizing casting solution.Casting solution is uniformly spun on polyacrylonitrile ultrafiltration film,
Drying at room temperature obtains composite membrane.The composite membrane obtained is immersed the CaCl of 0.5M2Solution cross-links, takes out after 5min,
And with the calcium ion of a large amount of deionized water rinsing film remained on surface.Composite membrane after crosslinking is dried the most at room temperature, final
To sodium alginate/covalent organic framework composite membrane (film 1), the section Electronic Speculum figure of film 1 is as shown in Figure 1.
Film 1 is used for the dehydration of pervaporation ethanol-water system, 76 DEG C, material concentration be that the ethanol of mass fraction 90% is water-soluble
Under conditions of liquid, permeation flux is 1452g/m2H, separation factor is 702, as shown in Figure 5.
Embodiment 2, preparing sodium alginate/covalent organic framework composite membrane, step is as follows:
9g tripolycyanamide is dissolved in 300mL dimethyl sulfoxide solvent, is subsequently adding 13.5g terephthalaldehyde.180
It is stirred vigorously and is passed through argon gas-sealed at DEG C, after reaction 72h, obtain tan precipitate thing.This precipitate is used successively N,
Dinethylformamide and oxolane centrifuge washing final vacuum are dried 24h, obtain yellow powdery solid.By this yellow powder
Powder solid is placed in apparatus,Soxhlet's, uses methanol, oxolane, methanol respectively to extract 36h at 80 DEG C successively, extraction
After product be vacuum dried at 120 DEG C, obtain covalent organic framework；
Weigh covalent organic framework 0.057g to be dissolved in 25mL deionized water, ultrasonic disperse 15min, obtain dispersion liquid.So
Adding 0.38g sodium alginate in backward dispersion liquid, the solution obtained stirs 5h, mistake with the rotating speed of 300r/min at 30 DEG C
After filter, standing, deaeration, obtain homogenizing casting solution.Casting solution is uniformly spun on polyacrylonitrile ultrafiltration film, drying at room temperature
Obtain composite membrane.The composite membrane obtained is immersed the CaCl of 0.5M2Solution cross-links, takes out after 10min, and with big
The calcium ion of amount deionized water rinsing film remained on surface.Composite membrane after crosslinking is dried the most at room temperature, finally gives Sargassum
Acid sodium/covalent organic framework composite membrane (film 2), the section Electronic Speculum figure of film 2 is as shown in Figure 2.
Film 2 is used for the dehydration of pervaporation ethanol-water system, 76 DEG C, material concentration be that the ethanol of mass fraction 90% is water-soluble
Under conditions of liquid, permeation flux is 1738g/m2H, separation factor is 789, as shown in Figure 5.
Embodiment 3, preparing sodium alginate/covalent organic framework composite membrane, step is as follows:
12g tripolycyanamide is dissolved in 300mL dimethyl sulfoxide solvent, is subsequently adding 18g terephthalaldehyde.180
It is stirred vigorously and is passed through argon gas-sealed at DEG C, after reaction 96h, obtain tan precipitate thing.This precipitate is used successively N,
Dinethylformamide and oxolane centrifuge washing final vacuum are dried 24h, obtain yellow powdery solid.By this yellow powder
Powder solid is placed in apparatus,Soxhlet's, uses methanol, oxolane, methanol respectively to extract 48h at 80 DEG C successively, extraction
After product be vacuum dried at 120 DEG C, obtain covalent organic framework.
Weigh covalent organic framework 0.097g to be dissolved in 25mL deionized water, ultrasonic disperse 15min, obtain dispersion liquid.So
Adding 0.38g sodium alginate in backward dispersion liquid, the solution obtained stirs 6h, mistake with the rotating speed of 300r/min at 30 DEG C
After filter, standing, deaeration, obtain homogenizing casting solution.Casting solution is uniformly spun on polyacrylonitrile ultrafiltration film, drying at room temperature
Obtain composite membrane.The composite membrane obtained is immersed the CaCl of 0.5M2Solution cross-links, takes out after 15min, and with big
The calcium ion of amount deionized water rinsing film remained on surface.Composite membrane after crosslinking is dried the most at room temperature, finally gives Sargassum
Acid sodium/covalent organic framework composite membrane (film 3), the section Electronic Speculum figure of film 3 is as shown in Figure 3.
Film 3 is used for the dehydration of pervaporation ethanol-water system, 76 DEG C, material concentration be that the ethanol of mass fraction 90% is water-soluble
Under conditions of liquid, permeation flux is 2397g/m2H, separation factor is 1293, as shown in Figure 5.
Comparative example, preparing pure sodium alginate film, step is as follows:
Being dissolved in 25mL deionized water by 0.38g sodium alginate, the solution obtained rotating speed with 300r/min at 30 DEG C stirs
Mix 5h, filter, stand, after deaeration, obtain homogenizing casting solution.Casting solution is uniformly spun on polyacrylonitrile ultrafiltration film,
Drying at room temperature obtains composite membrane.The composite membrane obtained is immersed the CaCl of 0.5M2Solution cross-links, takes out after 12min,
And with the calcium ion of a large amount of deionized water rinsing film remained on surface.Composite membrane after crosslinking is dried the most at room temperature, final
To pure sodium alginate film (comparative film), the section Electronic Speculum figure of this comparative film is as shown in Figure 4.
This comparative film is used for the dehydration of pervaporation ethanol-water system, 76 DEG C, material concentration be the ethanol of mass fraction 90%
Under conditions of aqueous solution, permeation flux is 1521g/m2H, separation factor is 329, as shown in Figure 5.
Although above in conjunction with accompanying drawing, invention has been described, but the invention is not limited in above-mentioned detailed description of the invention,
Above-mentioned detailed description of the invention is only schematic rather than restrictive, and those of ordinary skill in the art is in the present invention
Enlightenment under, without deviating from the spirit of the invention, it is also possible to make many variations, these belong to the guarantor of the present invention
Within protecting.
Claims (3)
1. sodium alginate/covalent organic framework composite membrane, it is characterised in that this sodium alginate/covalent organic framework composite membrane
It is to be made up of with covalent organic framework 100:5 in mass ratio～30 sodium alginate；Wherein, covalent organic framework is by benzene two
Formaldehyde and tripolycyanamide in mass ratio 1～1.5:1 polycondensation form, and the particle diameter of covalent organic framework is 60～100nm, and aperture is
0.4～0.6nm.
2. the preparation method of sodium alginate as claimed in claim 1/covalent organic framework composite membrane, it is characterised in that
Comprise the following steps:
Step one, the preparation of covalent organic framework:
Tripolycyanamide is dissolved in dimethyl sulfoxide solvent, forms the solution that mass body volume concentrations is 0.02～0.04g/mL,
Then by adding terephthalaldehyde in solution with tripolycyanamide mass ratio 1～1.5:1；It is stirred vigorously at 180 DEG C and is passed through
Argon gas-sealed, reacts 48～96h, obtains tan precipitate thing；By this precipitate successively with DMF and four
Hydrogen furan centrifuge washing final vacuum is dried 24h, obtains yellow powdery solid；This yellow powdery solid is placed in Soxhlet carry
Taking in device, use methanol, oxolane, methanol respectively to extract 24～48h at 80 DEG C successively, the product after extraction is in 120 DEG C
Lower vacuum drying, finally gives covalent organic framework；
The film forming of step 2, sodium alginate/covalent organic framework composite membrane:
The covalent organic framework that step one prepares is dissolved in deionized water, ultrasonic disperse 15min, obtains dispersion liquid；Then
Dispersion liquid and a certain amount of sodium alginate are mixed to get solution A, wherein, covalent organic framework and the mass ratio of sodium alginate
0.05～0.3:1, sodium alginate mass fraction in solution A is 1.5%；Solution A is turning with 300r/min at 30 DEG C
Speed stirring 4～6h, filters, stands, after deaeration, obtains homogenizing casting solution；
Uniformly being spun on polyacrylonitrile ultrafiltration film by casting solution, drying at room temperature obtains composite membrane；The composite membrane obtained is immersed
The CaCl of 0.5M2Solution cross-links, after 5～15min take out, with the calcium of a large amount of deionized water rinsing film remained on surface from
Son；Composite membrane after crosslinking is dried the most at room temperature, finally gives sodium alginate/covalent organic framework composite membrane.
3. sodium alginate as described in claim 1/covalent organic framework composite membrane or as the preparation side described in claim 2
The application of sodium alginate/covalent organic framework composite membrane that method prepares, it is characterised in that take off for pervaporation ethanol-water system
Water, 76 DEG C, material concentration be mass fraction 90% ethanol water under conditions of, permeation flux is 1452～2397g/m2H,
Separation factor is 329～1293.
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| CN107129583A (en) * | 2017-05-25 | 2017-09-05 | 西北师范大学 | The synthetic method of porous organic covalent frame material with triazine structure |
| CN107970790A (en) * | 2017-11-30 | 2018-05-01 | 天津大学 | Functionally gradient covalent organic framework film and preparation and application |
| CN108355613A (en) * | 2018-03-02 | 2018-08-03 | 南京师范大学常州创新发展研究院 | Magnetic covalent organic framework material and its preparation method and application |
| CN108380055A (en) * | 2018-02-28 | 2018-08-10 | 天津大学 | The sodium alginate hybridized film of hollow ZIF-8 nano particles filling and preparation and application |
| CN110465210A (en) * | 2019-08-02 | 2019-11-19 | 北京化工大学常州先进材料研究院 | The preparation and application of SNW-1/ polyacrylonitrile nanofiber flexible membrane |
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| CN107129583A (en) * | 2017-05-25 | 2017-09-05 | 西北师范大学 | The synthetic method of porous organic covalent frame material with triazine structure |
| CN107970790B (en) * | 2017-11-30 | 2020-08-18 | 天津大学 | Functionally gradient covalent organic framework membrane, preparation and application |
| CN107970790A (en) * | 2017-11-30 | 2018-05-01 | 天津大学 | Functionally gradient covalent organic framework film and preparation and application |
| CN108380055A (en) * | 2018-02-28 | 2018-08-10 | 天津大学 | The sodium alginate hybridized film of hollow ZIF-8 nano particles filling and preparation and application |
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| CN110465210A (en) * | 2019-08-02 | 2019-11-19 | 北京化工大学常州先进材料研究院 | The preparation and application of SNW-1/ polyacrylonitrile nanofiber flexible membrane |
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| CN110698710A (en) * | 2019-09-23 | 2020-01-17 | 北京师范大学 | Method for preparing covalent organic framework material film by quantitative layer-by-layer self-assembly |
| CN110665378A (en) * | 2019-10-31 | 2020-01-10 | 北京工业大学 | Transition metal ion modified covalent organic framework/polymer hybrid membrane, preparation and application |
| CN113122008A (en) * | 2020-01-14 | 2021-07-16 | 欧菲影像技术（广州）有限公司 | Protective film and preparation method and application thereof |
| CN111760474A (en) * | 2020-07-17 | 2020-10-13 | 天津工业大学 | Preparation method of COFs @ HPAN nanofiltration composite membrane |
| CN111760474B (en) * | 2020-07-17 | 2022-05-03 | 天津工业大学 | Preparation method of COFs @ HPAN nanofiltration composite membrane |
| CN112337319A (en) * | 2020-10-21 | 2021-02-09 | 天津大学 | Mixed-dimension assembled covalent organic framework composite membrane, preparation and application |
| CN112295422A (en) * | 2020-10-26 | 2021-02-02 | 天津大学 | Calcium alginate-covalent organic framework material nanosheet-hydrolyzed polyacrylonitrile three-layer membrane and preparation and application thereof |
| CN113185726A (en) * | 2021-04-15 | 2021-07-30 | 华中科技大学 | Method for promoting metal coordination covalent organic framework material to disperse in liquid phase |
| CN113185726B (en) * | 2021-04-15 | 2022-05-20 | 华中科技大学 | Method for promoting metal coordination covalent organic framework material to disperse in liquid phase |
| CN114570067A (en) * | 2022-02-24 | 2022-06-03 | 福州大学 | COF-F constructed super-hydrophobic fabric membrane and preparation method and application thereof |
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