CN107261871A - A kind of preparation method of polyethyleneimine/sodium lignin sulfonate composite membrane - Google Patents

A kind of preparation method of polyethyleneimine/sodium lignin sulfonate composite membrane Download PDF

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Publication number
CN107261871A
CN107261871A CN201710668477.0A CN201710668477A CN107261871A CN 107261871 A CN107261871 A CN 107261871A CN 201710668477 A CN201710668477 A CN 201710668477A CN 107261871 A CN107261871 A CN 107261871A
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membrane
preparation
composite
filtering film
nanometer filtering
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代娟
刘旺衢
王璐莹
雷建都
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Beijing Forestry University
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Beijing Forestry 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
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • 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
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • 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
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • 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
    • 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
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
    • 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
    • B01D71/74—Natural macromolecular material or derivatives thereof

Abstract

The invention discloses a kind of preparation method of polyethyleneimine/sodium lignin sulfonate composite membrane.The preparation of the composite membrane is to use surface in electronegative polysulphone super-filter membrane as basement membrane, and thereon, self assembly polyethyleneimine and sodium lignin sulfonate form self assembly composite bed successively, form it into constitutionally stable composite bed by glutaraldehyde cross-linking afterwards.It is an advantage of the invention that using the electrostatic interaction between the electrolyte with different electric charges, zwitterion polyelectrolyte successively can be adsorbed on the surface of polysulphone super-filter membrane, so as to realize the LBL self-assembly of polyelectrolyte.When the double-deck number of polyelectrolyte is 7 layers, composite nanometer filtering film shows preferable separating property.

Description

A kind of preparation method of polyethyleneimine/sodium lignin sulfonate composite membrane
Technical field
The present invention relates to a kind of LBL self-assembly polyethyleneimine/sodium lignin sulfonate composite nanometer filtering film and its preparation side Method, belongs to separation technical field of membrane.
Background technology
Membrane separation technique is a kind of emerging mixture isolation technics, and it is saturating using selection of the film to each component in mixture The property crossed separates, purifies, concentrates and is enriched with purpose product using outside energy or chemical potential difference as driving force.Compared to can be traditional Separation means, membrane separation technique has that separation condition is gentle, energy consumption is low, can realize and continuously separates, is easy to industry amplification, operation The advantageous characteristic such as easy, operation stability is high, pollution-free.Membrane separation technique classification is various, and particle diameter is retained from big according to film It can be divided into micro-filtration, ultrafiltration, nanofiltration and counter-infiltration to small.The retention particle diameter of NF membrane between ultrafiltration and counter-infiltration, Therefore nanofiltration can be realized to macromolecular or high valence ion under relatively low operating pressure and retained, and at the same time be also ensured Higher flux.This special selective cutoff performance of NF membrane makes it have special advantage in some separation processes, Such as drinking water softening, sewage disposal, food engineering, bioengineering.
NF membrane is from after being developed the eighties twentieth century, and Many researchers had done abundant research, most Main research is exactly to develop and prepare new membrane material.Current NF membrane can be divided into organic nanofiltration membrane, Inorganic Nanofiltration Membranes And composite nanofiltration membrane.Organic polymer films are the higher class NF membranes of current degree of commercialization, its material substantially with Reverse osmosis membrane materials are similar, mainly there is SPSF class NF membrane, polyamide-based NF membrane, cellulose NF membrane etc..It is inorganic to receive Filter membrane mainly has ceramic membrane, metal oxide film etc. at present, and it has extremely good chemical stability, mechanical strength and biological tolerance Property, but big, the elastic small, price of organic nanofiltration membrane fragility is high, therefore to be widely used.In recent years, with organic nanofiltration membrane Correlative study with the composite nanofiltration membrane developed based on Inorganic Nanofiltration Membranes has become a heat of NF membrane preparation research Door topic.
By polyelectrolyte, self-assembly method can be prepared with specific function or high flux, compound the receiving of height retention layer by layer Filter membrane.Its separating layer is fine and close than more uniform, and arrangement assembling is more neat, and biggest advantage is exactly that individual layer film thickness monitoring can exist Nanoscale, can control the composition of film, structure on a molecular scale, and then change its separation property by changing self assembly condition Energy.Polyelectrolyte refers to the polymer on monomer with charged group, the when meeting that such polymer dissolves in polar solvent Zwitterion corresponding with charged group is ionized out, so as to take electric charge.Therefore, using between the electrolyte with different electric charges Electrostatic interaction, zwitterion polyelectrolyte can be successively adsorbed on the surface of base material, so as to realize poly- electricity Solve the LBL self-assembly of matter.
Lignin is a kind of noncrystalline, three-dimensional netted phenols complicated natural polymerses, lignin and fibre Dimension element, hemicellulose are the key components for constituting higher plant cell wall.Lignin is only second to cellulose, and reserves are the richest Rich natural polymer.Sodium lignin sulfonate（SL）It can mainly be extracted from sulphite process mashing off papermaking wastewater Come, i.e., the black liquor that the red liquid and soda pulping process that acid polishing is produced are produced can also be made by alkali lignin sulfonation.It is wooden The solvent of plain sodium sulfonate is the bases such as hydrogen, methoxyl group, hydroxyl on benzyl propane derivative, the phenyl ring or side chain of lignin Group is replaced by sulfonic group and generates lignosulfonates, and common lignosulfonates are yellowish-brown powder.Lignin sulfonic acid The relative molecular weight distribution of sodium is very uneven, and the difference with source raw material and pulping process has very big difference, and common is wooden Plain sodium sulfonate molecular weight is in more than 3500-15000 Da.The solvent of sodium lignosulfonate is benzyl propane derivative, is tool There is nonpolar aromatic group, while the hydrophilic radical such as its sulfonic group containing polarized, hydroxyl, carboxyl, therefore its hydrophily It is very strong, and lipophile is weaker, it is soluble in water, but insoluble in organic solvents such as acetone, ethanol.Therefore sodium lignin sulfonate has well Surface-active, a kind of anion surfactant can be used as.
If by polyethyleneimine（Polyethyleneimine,PEI）It is used as polycation electrolyte and lignin sulfonic acid Sodium（Sodium Ligninsulfonate,SL）Self assembly is formed as polyanion electrolyte on polysulphone super-filter membrane surface to be combined Layer, forms it into constitutionally stable composite bed, so that the poly- electricity with good separation performance is made by glutaraldehyde cross-linking afterwards Solve matter LBL self-assembly NF membrane.
The content of the invention
It is an object of the invention to provide a kind of LBL self-assembly polyethyleneimine/sodium lignin sulfonate composite nanometer filtering film Preparation method, by between the positive and negative electrolyte that the surface of polysulphone super-filter membrane utilizes between polyethyleneimine and sodium lignin sulfonate Electrostatic force suction-operated forms self assembly composite bed, forms it into constitutionally stable composite bed by glutaraldehyde cross-linking afterwards, carries The selection performance of high NF membrane.
In order to achieve the above object, the invention provides a kind of LBL self-assembly polyethyleneimine/sodium lignin sulfonate is multiple The preparation method of NF membrane is closed, it comprises the following steps：
1）The pretreatment of basement membrane, using polysulfones（PSF）Milipore filter soaks in deionization as basement membrane, by it and soaked after certain time Enter in the NaOH aqueous solution, water bath with thermostatic control is for a period of time；Take the film out, be washed with deionized water to neutrality afterwards；
2) preparation of composite nanometer filtering film, immerses certain time in polyethylenimine solution by polysulfones basement membrane, PEI solution is poured out, With deionized water rinsing for several times；The time same in lignin sulfonic acid sodium solution then is dipped in, deionized water rinsing number is used It is secondary；So far double-deck self assembly is completed, is repeated the above steps repeatedly, can obtain being combined the NF membrane of the different numbers of plies；
3）The crosslinking of composite nanometer filtering film, the composite nanometer filtering film of the different numbers of plies is immersed in glutaraldehyde water solution and stood after a period of time It is drawn off, composite membrane is cleaned with deionized water for several times, completes crosslinking.
As preferred：
The step 1）In, soak time is 6 ~ 24 h to basement membrane in deionized water, and NaOH aqueous solution mass concentration is 0.2 ~ 1.0 Wt%, the temperature of water bath with thermostatic control is 30 ~ 60 DEG C, and the time is 15 ~ 60 min.
The step 2）In, the time that polysulfones basement membrane is stood in polyelectrolyte solution is 10 ~ 60 min, and deionized water is clear Wash is 5 ~ 10 times for several times.
The step 2）In, the mass concentration of aq. polyethyleneimine is 0.1 ~ 1.0 wt%, the matter of sodium lignin sulfonate Amount concentration is 0.1 ~ 1.6 wt%, the double-deck numerical digit 2 ~ 12 of self assembly.
The step 3）In, the mass concentration of glutaraldehyde water solution is 0.2 ~ 2.0 wt%, and composite nanometer filtering film is in glutaraldehyde water Time of repose is 0.5 ~ 4.5 h in solution, and deionized water wash number is 5 ~ 15 times.
Beneficial effect：
Self assembly is formed by electrostatic force suction-operated between the positive and negative electrolyte between polyethyleneimine and sodium lignin sulfonate to answer Layer is closed, constitutionally stable composite bed is formed it into by glutaraldehyde cross-linking afterwards.Polyethyleneimine/lignin prepared by the present invention The MgSO that sodium sulfonate composite nanometer filtering film is used in nanofiltration water separating membrane solution4, excellent separating property can be shown.The present invention's Filming technology is simple, the separating property lifting of made composite nanometer filtering film, the separative efficiency of nanofiltration can be improved, with great development Potentiality.
Brief description of the drawings
Fig. 1 is that electron microscope is swept on the surface of polysulfones basement membrane and seven layers of composite membrane.
Embodiment
The present invention provides a kind of for nanofiltration separation MgSO4Polyethyleneimine/sodium lignin sulfonate of the aqueous solution is compound to be received Filter membrane and preparation method thereof, with reference to embodiment, the present invention is further illustrated, but it is not intended that to the present invention's Can practical range restriction.
Separating property is evaluated and tested：Received using Flat Membrane performance evaluating apparatus measure polyethyleneimine/sodium lignin sulfonate is compound Filter membrane separates the nanofiltration separation performance of water solution system：Feed concentration is 2.0 g/L MgSO4The aqueous solution, 25 °C of operation temperature, Nanofiltration operation pressure difference is 1.0 MPa.
The permeation flux and rejection of the evaluation of nanofiltration separation performance, i.e. film；
1）Permeation flux（J）, permeability of the membrane is reacted, its definition is：J = M / (A · t) orJ = V / (A · t)
In formula,MWithV distinguishesTo penetrate the penetrating fluid quality of film（kg）And volume（m3）；AFor membrane area, m2；tDuring for operation Between, h；
2）Rejection（R）, the selectivity of reaction film, its definition is：R = (C f – C p ) / C f × 100%
In formula,C f WithC p Respectively concentration of the solute component in feed liquid and penetrating fluid.
Embodiment 1 ~ 5
The pretreatment of basement membrane：PS membrane is cut to 14 × 14 cm sizes, 12 h are soaked in deionization.Soaked after the completion of immersion In the NaOH aqueous solution for entering 0.5 wt%, in 50 DEG C of h of water bath with thermostatic control 1.Take the film out, be washed with deionized water to neutrality afterwards.In advance Basement membrane after processing drenches seals that to put refrigerator cold-storage standby with valve bag after deionized water；
The self assembly of polyelectrolyte composite bed：Four angles of polysulfones basement membrane are fixed on culture dish bottom surface with adhesive waterproof tape, used Deionized water cleans basement membrane.About appropriate 0.15 wt% PEI solution is poured into culture dish, 30 min are stood.PEI solution is fallen Go out, except the unnecessary polyelectrolyte that weak force is adsorbed is leaned on striping surface with deionized water rinsing for several times.It is then poured into about appropriate 0.2 wt% SL solution, pours out SL solution, after standing 30 min with deionized water rinsing for several times.So far complete one it is double-deck from Assembling, repeats the above steps repeatedly, obtains the composite nanometer filtering film that double-deck number is respectively 1,3,5,7,11；
The crosslinking of polyelectrolyte multilayer film：After above-mentioned composite membrane is cleaned with deionized water, appropriate 1.0 are poured into surface plate Wt% glutaraldehyde water solution, stands 1 h.Glutaraldehyde water solution is poured out afterwards, composite membrane is cleaned with ionized water for several times, is crosslinked Complete.For separating MgSO4The aqueous solution, separating property is shown in Table 1.
The permeation flux of polyethyleneimine/sodium lignin sulfonate composite membrane is with the increase of film layer number as seen from Table 1 Reduction, its reason, which is probably that separating layer is thickening, makes feed liquid be increasingly difficult to through caused.And composite membrane cutoff performance when starting with film The number of plies rises, and is gradually tended towards stability afterwards to 7 layers.In order to take into account flux and cutoff performance, it is believed that polyethyleneimine/lignin The more excellent number of plies of sodium sulfonate composite membrane self assembly is 7 bilayers.The surface for 7 layers of composite membrane that the result and SEM are observed is the most It is smooth, it is fine and close consistent, because smooth fine and close surface separation layer can provide good separating effect.
The separating property of 1 polyethyleneimine of table/sodium lignin sulfonate composite nanometer filtering film

Claims (8)

1. a kind of preparation of polyethyleneimine/sodium lignin sulfonate composite membrane, preparation method comprises the following steps：
1）The pretreatment of basement membrane, using polysulfones（PSF）Milipore filter soaks in deionization as basement membrane, by it and soaked after certain time Enter in the NaOH aqueous solution, water bath with thermostatic control is for a period of time；Take the film out, be washed with deionized water to neutrality afterwards；
2）The preparation of composite nanometer filtering film, immerses certain time in polyethylenimine solution by polysulfones basement membrane, PEI solution is poured out, With deionized water rinsing for several times；The time same in lignin sulfonic acid sodium solution then is dipped in, deionized water rinsing number is used It is secondary；So far double-deck self assembly is completed, is repeated the above steps repeatedly, can obtain being combined the NF membrane of the different numbers of plies；
3）The crosslinking of composite nanometer filtering film, the composite nanometer filtering film of the different numbers of plies is immersed in glutaraldehyde water solution and stood after a period of time It is drawn off, composite membrane is cleaned with deionized water for several times, completes crosslinking.
2. the pretreatment of basement membrane according to claim 1, it is characterised in that：Soak time is 6 ~ 24 to basement membrane in deionized water H, the NaOH aqueous solution mass concentration are 0.2 ~ 1.0 wt%.
3. the pretreatment of basement membrane according to claim 1, it is characterised in that：The temperature of water bath with thermostatic control is 30 ~ 60 DEG C, and the time is 15~60 min。
4. the preparation of composite nanometer filtering film according to claim 1, it is characterised in that：Polysulfones basement membrane is quiet in polyelectrolyte solution The time put is 10 ~ 60 min, and deionized water cleaning is 5 ~ 10 times for several times.
5. the preparation of composite nanometer filtering film according to claim 1, it is characterised in that：The mass concentration of aq. polyethyleneimine For 0.1 ~ 1.0 wt%, the mass concentration of sodium lignin sulfonate is 0.1 ~ 1.6 wt%.
6. the preparation of composite nanometer filtering film according to claim 1, it is characterised in that：The double-deck numerical digit 0.5 ~ 10 of self assembly.
7. the crosslinking of composite nanometer filtering film according to claim 1, it is characterised in that：The mass concentration of glutaraldehyde water solution is 0.2~2.0 wt%。
8. the crosslinking of composite nanometer filtering film according to claim 1, it is characterised in that：Composite nanometer filtering film is in glutaraldehyde water solution Time of repose is 0.5 ~ 4.5 h, and deionized water wash number is 5 ~ 15 times.
CN201710668477.0A 2017-08-08 2017-08-08 A kind of preparation method of polyethyleneimine/sodium lignin sulfonate composite membrane Pending CN107261871A (en)

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Cited By (8)

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Publication number Priority date Publication date Assignee Title
CN108905642A (en) * 2018-09-17 2018-11-30 北京林业大学 A kind of sodium lignosulfonate being preferentially dehydrated/sodium alginate blending infiltrating and vaporizing membrane
CN109126743A (en) * 2018-09-19 2019-01-04 鲁东大学 A kind of preparation method of polyurethane foam adsorbent material
FR3078267A1 (en) * 2018-02-27 2019-08-30 Li Shengmin ULTRAFILTRATION MEMBRANE AND METHOD FOR PREPARING THE SAME
CN110438805A (en) * 2019-07-29 2019-11-12 武汉纺织大学 A kind of hydrophobically modified method of layer-by-layer to surface of cotton fabric
CN111437740A (en) * 2020-03-09 2020-07-24 哈尔滨工业大学 Preparation method of sodium lignosulphonate-based high-flux high-interception nanofiltration membrane
CN111659268A (en) * 2020-06-17 2020-09-15 埃隆水处理技术(上海)有限公司 Preparation method of low-pressure multi-electrolyte-layer hollow fiber nanofiltration membrane
CN111992041A (en) * 2020-09-10 2020-11-27 德州学院 Lignin-based polyelectrolyte nanofiltration membrane and preparation method thereof
CN112263918A (en) * 2020-10-19 2021-01-26 天津工业大学 Preparation method of oxalic acid crosslinked layer-by-layer self-assembled hydrogel filtering membrane and application of filtering membrane in molecular ion separation

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3078267A1 (en) * 2018-02-27 2019-08-30 Li Shengmin ULTRAFILTRATION MEMBRANE AND METHOD FOR PREPARING THE SAME
CN108905642A (en) * 2018-09-17 2018-11-30 北京林业大学 A kind of sodium lignosulfonate being preferentially dehydrated/sodium alginate blending infiltrating and vaporizing membrane
CN109126743A (en) * 2018-09-19 2019-01-04 鲁东大学 A kind of preparation method of polyurethane foam adsorbent material
CN109126743B (en) * 2018-09-19 2021-12-24 鲁东大学 Preparation method of polyurethane foam adsorption material
CN110438805A (en) * 2019-07-29 2019-11-12 武汉纺织大学 A kind of hydrophobically modified method of layer-by-layer to surface of cotton fabric
CN111437740A (en) * 2020-03-09 2020-07-24 哈尔滨工业大学 Preparation method of sodium lignosulphonate-based high-flux high-interception nanofiltration membrane
CN111437740B (en) * 2020-03-09 2022-07-01 哈尔滨工业大学 Preparation method of sodium lignosulfonate-based high-flux high-interception nanofiltration membrane
CN111659268A (en) * 2020-06-17 2020-09-15 埃隆水处理技术(上海)有限公司 Preparation method of low-pressure multi-electrolyte-layer hollow fiber nanofiltration membrane
CN111992041A (en) * 2020-09-10 2020-11-27 德州学院 Lignin-based polyelectrolyte nanofiltration membrane and preparation method thereof
CN112263918A (en) * 2020-10-19 2021-01-26 天津工业大学 Preparation method of oxalic acid crosslinked layer-by-layer self-assembled hydrogel filtering membrane and application of filtering membrane in molecular ion separation

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