CN105749766B - A kind of Kynoar/TiO2The preparation method of Nano sol composite hyperfiltration membrane - Google Patents

A kind of Kynoar/TiO2The preparation method of Nano sol composite hyperfiltration membrane Download PDF

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CN105749766B
CN105749766B CN201610116417.3A CN201610116417A CN105749766B CN 105749766 B CN105749766 B CN 105749766B CN 201610116417 A CN201610116417 A CN 201610116417A CN 105749766 B CN105749766 B CN 105749766B
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tio
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CN105749766A (en
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王志伟
张�杰
王巧英
曾豪
陈妹
郑君健
潘辰
张星冉
王煊博
吴志超
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Tongji University
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    • 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
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • 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
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The present invention relates to a kind of Kynoar/TiO2Composite hyperfiltration membrane is made in the preparation method of Nano sol composite hyperfiltration membrane, including the preparation and mixing of Nano sol liquid precursors and reaction medium, the preparation of scattered, pre- casting solution and casting solution of Nano sol, film, the step such as subsequent treatment of extraction and film.The present invention is made by sol-gal process contains nano-TiO2The sol solutionses of nascent particle and with organic solvent be sufficiently mixed it is scattered after be blended into the pre- casting solution of polymer, the dispersed ultrafiltration composite membrane of nanometer is then made using immersion precipitation phase inversion process.Sol solutionses of the present invention process to be uniformly dispersed, stable replace powder state nano-TiO2Particle, effectively overcomes powder state nano particle and is added to and occur reuniting in casting solution and cause the unstable phenomenon of casting solution, the Compound Ultrafiltration film-strength height of gained, flux height, anti-pollution, easy cleaning, and production cost is low.

Description

A kind of Kynoar/TiO2The preparation method of Nano sol composite hyperfiltration membrane
Technical field
The present invention relates to a kind of Kynoar/TiO2The preparation method of Nano sol composite hyperfiltration membrane, it is molten to be related to nanometer Glue, casting solution, film forming prepare three phases, and prepared film is applied to embrane method sewage treatment process, especially membrane biological reaction Application in device.
Background technology
Embrane method sewage treatment process is the novel process for developing application of membrane separation technology in sewage treatment area, because of tool Have the advantages that energy consumption is low, stable effluent quality and enjoy favor.Wherein, membrane Bio-reactor Technology is by membrane separation technique and dirt New process for treating waste water caused by the combination of aquatic organism treatment technology, has good effluent quality, facility compact, floor space Less, the advantages that anti impulsion load, operational management facilitate, had broad application prospects in terms of sewage disposal and reuse.As The core of membrane bioreactor and embrane method sewage disposal technology, the performance of film are to influence its service life and system run all right Property an important factor for, fouling membrane be limit application of membrane expand key, therefore its antipollution be modified be technical field of membrane Study hotspot.
Membrane material species is various, wherein being no lack of the polymeric material of function admirable, wherein Kynoar is because with good Chemical stability and film forming, heat resistance and excellent mechanical strength the features such as receive much concern in recent years.But its molecule knot Structure determines the low and stronger hydrophobic essence of its surface energy, therefore when carrying out aqueous phase separation, the Kynoar of one-component Film is easily absorbing the lyophobic dusts such as protein in water, colloidal particle and causes Pore Blocking and pollution, causes membrane filterability It can reduce, it is necessary to frequently clean, so as to shorten service life, limit its application.And to polyvinylidene fluoride film Hydrophilic modifying can reduce the interaction especially between protein between film surface and retention pollutant, so as to reduce pollution The absorption of material, improve the antifouling property of film.The hydrophilic modifying of film mainly has two methods：Surface is modified and this is modifies. The surface of film, which is modified, includes surface grafting, coating and chemical surface treatment etc., but surface modification can not be lasting there is effect The problems such as influence its actual sewage processing in application；Body method of modifying includes blending and modifying and modification by copolymerization, wherein common Mixed modification method can closely be tied due to additive between film matrix by various chemical bonds and other physics chemical actions Close, modified effect is stable, and operates relatively simple and receive significant attention.The material of blending and modifying includes such as polyvinyl alcohol, gathered The hydrophilic high molecular material of ether sulfone etc. and such as Nano-meter SiO_22, nano-TiO2Deng inorganic nano material.In recent years, nano material Because the property such as its small-size effect, hydrophilic is widely used in membrane modifying, wherein nano-TiO2Because belonging to high water wetted material（Contact Angle<18°）, there is preferable chemical stability, antibiotic property, nontoxic and turn into study hotspot.But nano particle is higher Surface energy and specific surface area then add nano material Interaction Force and surface-active so that group easily occurs each other for particle Gather and gather, it is difficult to it is dispersed, it have impact on a nanometer blend film modified performance.
The A of CN 102091540 disclose sulfonated polyether sulfone/TiO2The preparation method of nano combined milipore filter, includes successively (1) preparation of hygrometric state sulfonated polyether sulfone milipore filter, (2) nano-TiO2The preparation of colloidal dispersion and (3) sulfonated polyether sulfone/ TiO2The self assembly of nano combined milipore filter prepares three steps.Step (1) and the preparation process class of pre- casting solution in this patent Seemingly.And step (2) is：By the nano-TiO that particle scale is 5-40 nm2Powder and dispersant in mass ratio 1: (0.1-0.2) Add in distilled water, be ultrasonically treated 0.5-1.0 H-shapeds at room temperature into nano-TiO2Colloidal dispersion.Step (3) is：By hygrometric state Sulfonated polyether sulfone milipore filter takes out from coagulating bath, is immersed in step (2) nano-TiO2Sonic oscillation 1-5 in colloidal dispersion Min, stand 1-3 h, nano-TiO2Hygrometric state sulfonated polyether sulfone/TiO is formed in sulfonated polyether sulfone film surface self-organization2It is nano combined Milipore filter, then by alcohol solution washing and 40-50 DEG C of drying of low temperature drying, obtain sulfonated polyether sulfone/TiO2It is nano combined super Filter membrane.First, nano-TiO in the patent2Prepared by colloidal dispersion is the addition by powder state particle, nano-powder The reunion of grain make it that it more difficult is uniformly dispersed.Secondly, sulfonated polyether sulfone/TiO in the patent2Nano combined milipore filter is by receiving Rice grain is self-assembly of poly (ether sulfone) film surface, due to nano-TiO2Particle belongs to highly polar material and sulfonated polyether sulfone The bad adhesion of base-material, and the nano-particle for being dispersed in film surface easily comes off, and the more difficult stabilization of film properties, limits it in actual membrane The application of method sewage treatment area.
The content of the invention
It is an object of the invention to overcome the shortcomings of that conventional nano is modified membrane preparation method, there is provided one kind can be to greatest extent Ground reduces the problem of nanometer skewness of blend film caused by nanometer reunion, ensures casting solution by using Nano sol liquid Stability, lift the strainability and antifouling property of nano composite membrane.
In order to achieve the above object, the technical solution adopted by the present invention is：
Kynoar/nano-TiO involved in the present invention2The preparation method of colloidal sol composite hyperfiltration membrane, including following step Suddenly：
(a) nano-TiO2The preparation of colloidal sol：By butyl titanate and absolute ethyl alcohol with 1:The volume ratio mixing of (9 ~ 18) is stirred 30min is mixed, obtains the precursors of clear homogeneous；By absolute ethyl alcohol and deionized water with 1:The volume ratio mixing group of (6 ~ 12) Into mixed solution, mechanical agitation 20min ~ 30min, and it is 1 ~ 3 with the pH value of dust technology or watery hydrochloric acid regulation mixed solution, obtains To homogeneous transparent solution be reaction medium；Precursors are added dropwise to reaction medium in 40 DEG C ~ 60 DEG C water-baths In, 1 ~ 2h of ultrasound is stirred, obtained faint yellow emulsion is nano-TiO2Sol solutionses；Control nano-TiO2Metatitanic acid in sol solutionses The volume ratio of four butyl esters and deionized water is 1: (0.5~1.5) ；
(b) Kynoar/nano-TiO2The preparation of colloidal sol composite hyperfiltration membrane casting solution：Organic solvent is divided into two parts, It is respectively used to the preparation of pre- casting solution and containing nano-TiO2Sol solutionses it is scattered, Kynoar is added to containing pore-foaming agent and In the mixed liquor of part organic solvent at 80 DEG C 3 ~ 5d of mechanical agitation, form the pre- casting solution of homogeneous；Then by ultrasonic disperse 20 ~ 30min's contains nano-TiO2The remainder organic solvent mixed liquor of sol solutionses is added to 1 ~ 2d of stirring in pre- casting solution, Formation prepares Kynoar/nano-TiO2The casting solution of colloidal sol composite hyperfiltration membrane；Wherein：For disperseing TiO2The amount of sol solutionses Volume ratio with total organic solvent amount is (0.15 ~ 0.35):1；
(c) Kynoar/nano-TiO2The preparation of colloidal sol composite hyperfiltration membrane：By step（B）Gained casting solution is cast in On glass plate or non-woven fabrics, spread to film, relative humidity be make under conditions of 45 ~ 70%, temperature is 15 DEG C ~ 40 DEG C it is organic molten 15 ~ 30s is evaporated in agent, and glass plate or non-woven fabrics then are immersed into 0.5 ~ 24h in the coagulating bath that temperature is 20 DEG C ~ 25 DEG C, make it Gel film forming, then filter membrane is taken out from coagulating bath, dry at room temperature, produce Kynoar/nano-TiO2Colloidal sol is compound super Filter membrane.
In the present invention, the organic solvent in described step (b) is dimethyl sulfoxide, DMA, N, N- bis- NMF, the combination of one or two kinds of arbitrary proportion in 1-METHYLPYRROLIDONE.
In the present invention, the total organic solvent mass concentration in described step (b) is 65 ~ 85%.
It is used to disperse TiO in the present invention, in the organic solvent being divided into two parts in described step (b)2The amount of sol solutionses Ratio with total organic solvent amount is (0.15 ~ 0.35):1.
In the present invention, one kind for polyethylene glycol or in polyvinylpyrrolidone of pore-foaming agent in described step (b) or The combination of two kinds of arbitrary proportions, mass concentration are 6 ~ 12%.
In the present invention, the Kynoar solution mass concentration in described step (b) is 8 ~ 16%.
In the present invention, TiO in the casting solution in described step (b)2Mass content is 0.01 ~ 5%.
In the present invention, the coagulating bath in described step (c) is arbitrarily compared for deionized water or deionized water with absolute ethyl alcohol The mixed liquor of example.
In the present invention, the knifing thickness control in described step (c) is 0.15 ~ 0.35 mm.
The present invention has the advantages that compared to prior art：
1）Instant invention overcomes sol-gal process to prepare nano-TiO2Length experimental period, the characteristics of process complexity, omit Nano-TiO2Two steps of gel and calcining in particulate production, enormously simplify operating process.
2）The present invention effectively overcomes powder state nano-TiO2The reunion precipitation that particle is added in polymeric casting film liquid is existing As so that casting solution is integrally uniform and stable, so as to which the dispersed polymer nanocomposite membrane of nanometer be made.
3）Using the method for organic solvent substep addition in the present invention, it is easy to the nascent particle of nanometer in Nano sol solution Dispersed and film casting solution stabilization.
Brief description of the drawings
Fig. 1 is nano-TiO in the colloidal sol of embodiment 32The TEM figures of nascent particle.
Fig. 2 is to determine casting solution stability result using Turbiscan multiple Scatterings technology in embodiment 1.
Fig. 3 prepares the photo after standing 4 months afterwards and at room temperature for casting solution in embodiment 1.(a) figure is just to prepare Casting solution photo afterwards, (b) figure are the casting solution photo after standing 4 months.
Fig. 4 is the film formation surface shape appearance figure of the nano composite membrane of embodiment 2.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but scope of the present invention is not It is confined to the scope involved by embodiment.
Embodiment 1
(a) by butyl titanate and absolute ethyl alcohol with 1:12 ratios mix 30 min and obtain the reaction of clear homogeneous Presoma.Absolute ethyl alcohol and deionized water are with 6:The min of mixed solution mechanical agitation 30 of 1 ratio composition, and with dust technology or Watery hydrochloric acid regulation pH value is 2, and obtained homogeneous transparent solution is reaction medium.By precursors in 50 DEG C of water-baths by It is added dropwise in reaction medium, it is TiO that stirring 60 min of ultrasound, which obtain faint yellow emulsion,2Sol solutionses, TiO2Titanium in sol solutionses The ratio of sour four butyl esters and deionized water is 1:1.
(b) by 8% Kynoar be added to containing in 10% perforating agent and 62% organic solvent mixed liquor in 80 DEG C of machineries 4 d are stirred, form the pre- casting solution of homogeneous.The min of ultrasonic disperse 30 is then contained into 0.15%TiO2Sol solutionses and 20% organic The mixed liquor of solvent, which is added in pre- casting solution to stir to be formed after 2 d, prepares PVDF/ nano-TiOs2The casting solution of sol-gel modified film.
(c) above-mentioned casting solution is cast on non-woven fabrics, spreads to film, relative humidity be 60%, temperature be 25 DEG C Under the conditions of solvent is evaporated 15 s, it is that gel time is in 25 DEG C of coagulating baths that glass plate or non-woven fabrics then are immersed into temperature 0.5 h, make its gel film forming, then filter membrane is taken out from coagulating bath, dry at room temperature, that is, obtain PVDF/ nano-TiOs2Colloidal sol Composite hyperfiltration membrane.
Embodiment 2
(a) by butyl titanate and absolute ethyl alcohol with 1:12 ratios mix 30 min and obtain the reaction of clear homogeneous Presoma.Absolute ethyl alcohol and deionized water are with 6:The min of mixed solution mechanical agitation 30 of 1 ratio composition, and with dust technology or Watery hydrochloric acid regulation pH value is 2, and obtained homogeneous transparent solution is reaction medium.By precursors in 45 DEG C of water-baths by It is added dropwise in reaction medium, it is TiO that stirring 60 min of ultrasound, which obtain faint yellow emulsion,2Sol solutionses, TiO2Titanium in sol solutionses The ratio of sour four butyl esters and deionized water is 1:0.9.
(b) by 7% Kynoar be added to containing in 11% perforating agent and 64% organic solvent mixed liquor in 80 DEG C of machineries 5 d are stirred, form the pre- casting solution of homogeneous.The min of ultrasonic disperse 30 is then contained into 1% TiO2Sol solutionses and 17% organic molten The mixed liquor of agent, which is added in pre- casting solution to stir to be formed after 2 d, prepares PVDF/ nano-TiOs2The casting solution of sol-gel modified film.
(c) above-mentioned casting solution is cast on non-woven fabrics, spreads to film, relative humidity be 50%, temperature be 25 DEG C Under the conditions of solvent is evaporated 25 s, it is that gel time is in 25 DEG C of coagulating baths that glass plate or non-woven fabrics then are immersed into temperature 0.5 h, make its gel film forming, then filter membrane is taken out from coagulating bath, dry at room temperature, that is, obtain PVDF/ nano-TiOs2Colloidal sol Composite hyperfiltration membrane.
Embodiment 3
(a) by butyl titanate and absolute ethyl alcohol with 1：15 ratios mix 30 min and obtain the reaction of clear homogeneous Precursor.Absolute ethyl alcohol and deionized water are with 9:The min of mixed solution mechanical agitation 30 of 1 ratio composition, and with dust technology or Watery hydrochloric acid regulation pH value is 1.5, and obtained homogeneous transparent solution is reaction medium.By precursors in 60 DEG C of water-baths by It is added dropwise in reaction medium, it is TiO that stirring 20 min of ultrasound, which obtain faint yellow emulsion,2Sol solutionses, TiO2Titanium in sol solutionses The ratio of sour four butyl esters and deionized water is 1:0.8.
(b) by 10% Kynoar be added to containing in 8% perforating agent and 60% organic solvent mixed liquor in 80 DEG C of machineries 4 d are stirred, form the pre- casting solution of homogeneous.The min of ultrasonic disperse 30 is then contained into 0.5% TiO2Sol solutionses and 22% organic The mixed liquor of solvent, which is added in pre- casting solution to stir to be formed after 1 d, prepares PVDF/ nano-TiOs2The casting solution of sol-gel modified film.
(c) above-mentioned casting solution is cast on non-woven fabrics, spreads to film, relative humidity be 50%, temperature be 20 DEG C Under the conditions of solvent is evaporated 20 s, it is that gel time is in 25 DEG C of coagulating baths that glass plate or non-woven fabrics then are immersed into temperature 1 h, make its gel film forming, then filter membrane is taken out from coagulating bath, dry at room temperature, that is, obtain PVDF/ nano-TiOs2Colloidal sol is answered Close milipore filter.
In summary embodiment, analytic explanation accompanying drawing are as follows：
Fig. 1 is nano-TiO in the colloidal sol of embodiment 32The TEM figures of nascent particle, as can be seen from Figure nanometer come into being particle Particle diameter is between 5 ~ 10 nm.
Fig. 2 is to determine casting solution stability result using Turbiscan multiple Scatterings technology in embodiment 1, can by figure Find out in the min of minute 30, relatively steady always with height change transmitted light in sample cell, no crest or trough occur, and say Bright sample is stable.
Fig. 3 prepares the photo after standing 4 months afterwards and at room temperature for casting solution in embodiment 1.(a) figure is just to prepare Casting solution photo afterwards, (b) figure are the casting solution photo after standing 4 months.It is seen that sample it is highly stable and without precipitation and Flocculate agglomeration.
Fig. 4 is the film formation surface shape appearance figure of the nano composite membrane of embodiment 2.Nano particle is dispersed in film surface, nothing Obvious agglomeration occurs.

Claims (7)

  1. A kind of 1. Kynoar/TiO2The preparation method of Nano sol composite hyperfiltration membrane, it is characterised in that comprise the following steps：
    (a) nano-TiO2The preparation of colloidal sol：By butyl titanate and absolute ethyl alcohol with 1:The volume ratio of (9 ~ 18) mixes 30min, obtain the precursors of clear homogeneous；By absolute ethyl alcohol and deionized water with 1:The volume ratio mixing composition of (6 ~ 12) Mixed solution, mechanical agitation 20min ~ 30min, and be 1 ~ 3 with the pH value of dust technology or watery hydrochloric acid regulation mixed solution, obtain Homogeneous transparent solution be reaction medium；Precursors are added dropwise in reaction medium in 40 DEG C ~ 60 DEG C water-baths, 1 ~ 2h of ultrasound is stirred, obtained faint yellow emulsion is nano-TiO2Sol solutionses；Control nano-TiO2The fourth of metatitanic acid four in sol solutionses The volume ratio of ester and deionized water is 1: (0.5~1.5)；
    (b) Kynoar/nano-TiO2The preparation of colloidal sol composite hyperfiltration membrane casting solution：Organic solvent is divided into two parts, used respectively In the preparation of pre- casting solution and containing nano-TiO2Sol solutionses disperse, and Kynoar is added to be had containing pore-foaming agent and part In the mixed liquor of solvent at 80 DEG C 3 ~ 5d of mechanical agitation, form the pre- casting solution of homogeneous；Then by ultrasonic disperse 20 ~ 30min's contains nano-TiO2The remainder organic solvent mixed liquor of sol solutionses is added to 1 ~ 2d of stirring, shape in pre- casting solution Into preparing Kynoar/nano-TiO2The casting solution of colloidal sol composite hyperfiltration membrane；Wherein：For disperseing TiO2The amount of sol solutionses with The volume ratio of total organic solvent amount is (0.15 ~ 0.35):1；
    (c) Kynoar/nano-TiO2The preparation of colloidal sol composite hyperfiltration membrane：Casting solution obtained by step (b) is cast in glass plate Or on non-woven fabrics, film is spread to, it is to make organic solvent evaporation under conditions of 45 ~ 70%, temperature is 15 DEG C ~ 40 DEG C in relative humidity 15 ~ 30s, glass plate or non-woven fabrics are then immersed into 0.5 ~ 24h in the coagulating bath that temperature is 20 DEG C ~ 25 DEG C, make its gel into Film, then filter membrane is taken out from coagulating bath, dry at room temperature, produce Kynoar/nano-TiO2Colloidal sol composite hyperfiltration membrane.
  2. 2. preparation method according to claim 1, it is characterised in that organic solvent is dimethyl sulfoxide, N, N- dimethylacetamides The combination of one or two kinds of arbitrary proportion in amine, DMF or 1-METHYLPYRROLIDONE.
  3. 3. preparation method according to claim 1, it is characterised in that in casting solution total organic solvent mass concentration be 65 ~ 85%。
  4. 4. preparation method according to claim 1, it is characterised in that pore-foaming agent is polyethylene glycol or polyvinylpyrrolidone One or both of arbitrary proportion combination, in casting solution mass concentration be 6 ~ 12%.
  5. 5. preparation method according to claim 1, it is characterised in that in casting solution Kynoar mass concentration be 8 ~ 16%。
  6. 6. preparation method according to claim 1, it is characterised in that coagulating bath be deionized water or deionized water with it is anhydrous The mixed liquor of ethanol arbitrary proportion.
  7. 7. preparation method according to claim 1, it is characterised in that knifing thickness control is 0.15 ~ 0.35 mm.
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WO2022104072A1 (en) * 2020-11-13 2022-05-19 Saudi Arabian Oil Company Desalination membranes
WO2022104089A1 (en) * 2020-11-13 2022-05-19 Saudi Arabian Oil Company Desalination membranes

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