CN108927002A - A method of preparing large pore size ultrafiltration membrane - Google Patents

A method of preparing large pore size ultrafiltration membrane Download PDF

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Publication number
CN108927002A
CN108927002A CN201810835362.0A CN201810835362A CN108927002A CN 108927002 A CN108927002 A CN 108927002A CN 201810835362 A CN201810835362 A CN 201810835362A CN 108927002 A CN108927002 A CN 108927002A
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CN
China
Prior art keywords
ultrafiltration membrane
additive
film
pore size
casting solution
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CN201810835362.0A
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Chinese (zh)
Inventor
周勇
许浩
高从堦
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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Priority to CN201810835362.0A priority Critical patent/CN108927002A/en
Publication of CN108927002A publication Critical patent/CN108927002A/en
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    • 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
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/02—Foam dispersion or prevention
    • 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
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0011—Casting solutions therefor
    • 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
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0013—Casting processes
    • 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
    • B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
    • B01D67/003—Organic membrane manufacture by inducing porosity into non porous precursor membranes by selective elimination of components, e.g. by leaching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/12—Specific ratios of components used

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Water Supply & Treatment (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention discloses the methods for preparing large pore size ultrafiltration membrane, and polysulfones and additive are dissolved into solvent and obtain casting solution；The casting solution is subjected to vacuum defoamation in vacuum desiccator；Obtained casting solution is cast on smooth glass plate, is then immersed in progress inversion of phases film forming in coagulation bath；The film of preparation is immersed in pure water and washes off solvent, obtains the ultrafiltration membrane；The additive is sorbic acid or one of trimesic acid or Pyromellitic Acid.The present invention in casting solution by adding additive appropriate, change the membrance casting condition in film forming procedure, film surface cortex aperture and supporting layer micropore can be adjusted, after additive was added, film surface contact angle decreased significantly compared with former film, and as there is apparent increased trend in the aperture that the increase film of additive level shows.

Description

A method of preparing large pore size ultrafiltration membrane
Technical field
The invention belongs to ultrafiltration membrane preparation technical field, a kind of specifically method for preparing large pore size ultrafiltration membrane.
Background technique
Research of the ultrafiltration membrane in China is about the time for having had 40 or five ten years away from the present in eighties of last century the seventies, As the continuous development and progress society in epoch have higher requirement to membrane material and performance.Polyether sulfone (PES) is a kind of Material with superperformance, glass transition temperature are up to 225 DEG C, have excellent heat-resisting, alkaline-resisting, compression resistance, it is corrosion-resistant with And the performances such as superior blood compatibility, the material are highly suitable for film field, especially ultrafiltration membrane.
The preparation of casting solution plays a key role the quality for often affecting final film properties in filming technology, gathers Concentration, the selection of solvent and the type of additive for closing object are the basic composition of casting solution, the additive in these types of component It playing a crucial role, the type of additive and the difference of content are huge to the structure of film and the influence difference of performance, Therefore domestic and foreign scholars have done a large amount of work to the exploration of additive, have studied various different types of additives.It is organic to add Adding agent is mainly to change the performance of film by changing film surface aperture structure and film inner hole continuity.Invention one The method that kind prepares large pore size ultrafiltration membrane.
Summary of the invention
The object of the present invention is to provide a kind of methods for preparing large pore size ultrafiltration membrane.
The technical solution adopted by the present invention is that such:
A method of large pore size ultrafiltration membrane is prepared, is included the following steps:
1) polysulfones and additive are dissolved into solvent and obtain casting solution；
2) casting solution is subjected to vacuum defoamation in vacuum desiccator；
3) obtained casting solution is cast on smooth glass plate, is then immersed in progress inversion of phases film forming in coagulation bath；
4) film of preparation is immersed in pure water and washes off solvent, obtain the ultrafiltration membrane；
It is characterized by: the additive is one in sorbic acid or trimesic acid or Pyromellitic Acid in step 1) Kind.
In above-mentioned preparation method, polysulfones is polyether sulfone, polymer content 15wt% in the casting solution.
Step 1) the solvent is DMAC N,N' dimethyl acetamide (DMAC).
Step 1) the additive be sorbic acid, trimesic acid and Pyromellitic Acid any one, Determination of sorbic is 1wt%~10wt%, trimesic acid content are 1wt%~4wt%, and Pyromellitic Acid content is 0.5wt%~3wt%.
Step 2) the vacuum defoamation time is 3~5 hours.
The step 3) carries out knifing using 250 μm of scraper, and coagulation bath temperature is 25 DEG C, and immersing the coagulation bath time is 5 ~20 seconds.
Ultrafiltration membrane obtained impregnates 12 hours in pure water in the step 4), and ultrafiltration membrane thickness obtained is 250 μm.
The beneficial effects of the present invention are: preparation method of the present invention is simple, raw material sources are cheap extensively；Pass through in polyether sulfone points A small amount of sorbic acid, trimesic acid and Pyromellitic Acid are not added, change original membrance casting condition, it can be to ultrafiltration membrane surface hole Diameter size and film inner hole penetrability are adjusted, and are suitable for UF membrane field.According to can be with to membrane plane and section SEM figure Observation, sorbic acid have the tendency that significantly increasing in concentration 1%wt~10%wt lower film surface apertures and pure water flux, film section Hole has better penetrability；Trimesic acid concentration 1%wt~4%wt and Pyromellitic Acid concentration (0.5%wt~3% Wt) there is identical trend, since the thermodynamical equilibrium that the introducing of additive changes solution causes film surface aperture to become larger, by It is non-solubility acid in additive, the diffusion of solvent and non-solvent is slightly hindered in inversion of phases film forming procedure, to press down The generation for having made the big cavity of film makes film have better penetrability.
Detailed description of the invention
Fig. 1 is the surface Scanning Electron microscope photo of ultrafiltration membrane in embodiment 1；
Fig. 2 is the surface Scanning Electron microscope photo of embodiment 3；
Fig. 3 is the surface Scanning Electron microscope photo of embodiment 4；
Fig. 4 is the surface Scanning Electron microscope photo of embodiment 5；
Fig. 5 is the electron scanning micrograph of embodiment 6；
Fig. 6 is the electron scanning micrograph of embodiment 8；
Fig. 7 is the electron scanning micrograph of embodiment 9；
Fig. 8 is the electron scanning micrograph of embodiment 10；
Fig. 9 is the electron scanning micrograph of embodiment 11；
Figure 10 is the electron scanning micrograph of embodiment 12.
Specific embodiment
The present invention is done below with reference to embodiment and is further explained.The following example is merely to illustrate the present invention, but It is not used to limit practical range of the invention.
Embodiment 1: additive-free poly (ether-sulfone) ultrafiltration membrane is prepared
(1) preparation of casting solution: weighing 7.5g polyether sulfone and be added in 42.5gDMAC, and heating stirring 3 hours, temperature control At 70+5 DEG C, clear and transparent solution is obtained.Solution is placed in vacuum desiccator and carries out vacuum defoamation, 5 hours of deaeration obtain Spare to casting solution, wherein polyether sulfone content is 15wt%.
(2) preparation of poly (ether-sulfone) ultrafiltration membrane: casting solution being cast on smooth glass plate, is carried out with scraper to casting solution Uniformly blade coating, immerses coagulation bath later, and wherein coagulation bath is pure water, and temperature is 25 DEG C, to complete gel later to get polyethers Then sulfone ultrafiltration membrane impregnates film with pure water, spare.The contact angle of its blank film is 75.05 ± 3, and pure water flux is 116.02L/m3.h±40.Film surface aperture about 11.2nm.
Embodiment 2: it is prepared with the polysulfone ultrafiltration membrane of additive
7.5g polyether sulfone and 0.5g sorbic acid are weighed, is added in 42gDMAC, heating stirring 3 hours, temperature is controlled in 70+5 DEG C, obtain clear and transparent solution.Solution is placed in vacuum desiccator and carries out vacuum defoamation, 5 hours of deaeration obtain casting film Liquid, spare, wherein polyether sulfone content is 15wt%, Determination of sorbic 1wt%.Operation later such as (2) step in embodiment.Contact Angle is 57.45 ± 2, pure water flux 335.13L/m3.h ± 40, film surface aperture 11.6nm.
Embodiment 3
Determination of sorbic in embodiment 2 is become into 2wt%, other steps are constant.Contact angle 52.8 ± 2, pure water flux 281.07L/m3.h ± 50, film surface aperture 12.0nm.
Embodiment 4
Determination of sorbic in embodiment 2 is become into 5wt%, other steps are constant.Contact angle is 59.68 ± 1, pure water flux 328.94L/m3.h ± 40, film surface aperture 17.4nm.
Embodiment 5
Determination of sorbic in embodiment 2 is become into 10wt%, other steps are constant.Contact angle is 55.0 ± 1, pure water flux 511.92L/m3.h ± 50, film surface aperture 22.5nm.
Embodiment 6
Change sorbic acid in embodiment 2 into TMA, content 1wt%, other steps are constant.Contact angle is 55.36 ± 1, Pure water flux 149.53L/m3.h ± 30, film surface aperture 14.9nm.
Embodiment 7
TMA content in embodiment 6 is become into 2wt%, other steps are constant.Contact angle is 53.85 ± 3, pure water flux 412.63L/m3.h ± 50, film surface aperture 13.5nm.
Embodiment 8
TMA content in embodiment 6 is become into 3wt%, other steps are constant.Contact angle is 64.45 ± 1, pure water flux 624.91L/m3.h ± 50, film surface aperture 15.2nm.
Embodiment 9
TMA content in embodiment 6 is become into 4wt%, other steps are constant.Contact angle is 60.38 ± 1, pure water flux 726.83L/m3.h ± 70, film surface aperture 18.4nm.
Embodiment 10
Change sorbic acid in embodiment 2 into Pyromellitic Acid, content 0.5wt%, other steps are constant.Contact angle is 61.46 ± 2, pure water flux 200.26L/m3.h ± 30, film surface aperture 14.6nm.
Embodiment 11
Pyromellitic Acid content in embodiment 10 is become into 1wt%, other steps are constant.Contact angle is 68.38 ± 2, pure Water flux 485.60L/m3.h ± 20, film surface aperture 18.5nm.
Embodiment 12
Pyromellitic Acid content in embodiment 10 is become into 2wt%, other steps are constant.Contact angle is 65.77 ± 2, pure Water flux 715.73L/m3.h ± 50, film surface aperture 20.8nm.
Embodiment 13
Pyromellitic Acid content in embodiment 10 is become into 3wt%, other steps are constant.Contact angle is 61.19 ± 2, pure Water flux 1050.36L/m3.h ± 100, film surface aperture 17.8nm.

Claims (7)

1. a kind of method for preparing large pore size ultrafiltration membrane, includes the following steps:
1) polysulfones and additive are dissolved into solvent and obtain casting solution；
2) casting solution is subjected to vacuum defoamation in vacuum desiccator；
3) obtained casting solution is cast on smooth glass plate, is then immersed in progress inversion of phases film forming in coagulation bath；
4) film of preparation is immersed in pure water and washes off solvent, obtain the ultrafiltration membrane；
It is characterized by: the additive is sorbic acid or one of trimesic acid or Pyromellitic Acid in step 1).
2. the method for preparing large pore size ultrafiltration membrane as described in claim 1, it is characterised in that: the polysulfones is polyether sulfone.
3. the method for preparing large pore size ultrafiltration membrane as claimed in claim 2, it is characterised in that: in the casting solution, polyether sulfone Mass percentage be 15%.
4. the method for preparing large pore size ultrafiltration membrane as described in claim 1, it is characterised in that: in step 1),
The solvent is DMAC N,N' dimethyl acetamide.
5. the method for preparing large pore size ultrafiltration membrane as described in claim 1, it is characterised in that: in step 1),
The additive Determination of sorbic is 1wt%~10wt%.
6. the method for preparing large pore size ultrafiltration membrane as described in claim 1, it is characterised in that: in step 1),
The additive trimesic acid content is 1wt%~4wt%.
7. the method for preparing large pore size ultrafiltration membrane as described in claim 1, it is characterised in that: in step 1),
The additive Pyromellitic Acid content is 0.5wt%~3wt%.
CN201810835362.0A 2018-07-26 2018-07-26 A method of preparing large pore size ultrafiltration membrane Pending CN108927002A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101073750A (en) * 2007-03-30 2007-11-21 浙江大学 Method for producing density and gradient sectional porous ultrafiltration membrane
CN103212302A (en) * 2013-04-03 2013-07-24 北京工业大学 Method for preparing macromolecule hollow porous fiber membrane by using chemical reaction inductive phase conversion method
CN107855007A (en) * 2017-07-13 2018-03-30 枫科(北京)膜技术有限公司 A kind of asymmetric forward osmosis membrane and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101073750A (en) * 2007-03-30 2007-11-21 浙江大学 Method for producing density and gradient sectional porous ultrafiltration membrane
CN103212302A (en) * 2013-04-03 2013-07-24 北京工业大学 Method for preparing macromolecule hollow porous fiber membrane by using chemical reaction inductive phase conversion method
CN107855007A (en) * 2017-07-13 2018-03-30 枫科(北京)膜技术有限公司 A kind of asymmetric forward osmosis membrane and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
YONG SOO KANG ET.AL: ""Asymmetric membrane formation via immersion precipitation method. I. Kinetic effect"", 《JOURNAL OF MEMBRANE SCIENCE》 *
周海平: ""密度梯度结构的聚砜超滤膜的制备研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *

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