CN106040015A - High-throughput multilayer composite nano-filtration membrane and preparation method thereof - Google Patents

High-throughput multilayer composite nano-filtration membrane and preparation method thereof Download PDF

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Publication number
CN106040015A
CN106040015A CN201610520302.0A CN201610520302A CN106040015A CN 106040015 A CN106040015 A CN 106040015A CN 201610520302 A CN201610520302 A CN 201610520302A CN 106040015 A CN106040015 A CN 106040015A
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membrane
multilayer composite
nanocrystalline cellulose
preparation
aqueous phase
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徐志康
林福文
王静静
郭毅
吴铭榜
杨皓程
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Zhejiang University ZJU
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Zhejiang University ZJU
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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
    • 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
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • 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
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/105—Support pretreatment

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

Abstract

The invention discloses a high-throughput multilayer composite nano-filtration membrane and a preparation method thereof. The high-throughput multilayer composite nano-filtration membrane is obtained by loading a nanocrystalline cellulose support layer on a porous support membrane and forming a layer of polymer functional cortex on the nanocrystalline cellulose support layer through the interfacial polymerization of water-phase monomer and oil-phase monomer. Due to the fact that nanocrystalline cellulose has high hydrophilicity, the prepared multilayer composite nano-filtration membrane has the feature of high throughput. By the nanocrystalline support layer, the surface of the porous support membrane is flat, and the defects of the functional cortex of the prepared multilayer composite nano-filtration membrane are few. The macroporous structure on the surface of the porous support membrane is replaced by the nanocrystalline cellulose support layer, so that the pressure of the cortex of the composite nano-filtration membrane is dispersed under filtration operations, and structural damage cannot occur easily.

Description

A kind of high flux MULTILAYER COMPOSITE NF membrane and preparation method thereof
Technical field
The present invention relates to technical field of membrane, particularly relate to a kind of high flux MULTILAYER COMPOSITE NF membrane and preparation method thereof.
Background technology
Nanofiltration is a kind of novel membrane separation technique, and the aperture of NF membrane is in the range of Nano grade.Composite nanometer filtering film master Will be made up of stratum disjunctum, supporting layer and basement membrane three part, stratum disjunctum is to play the functional layer of centrifugation.Composite nanometer filtering film can be answered For fields such as water demineralization, food processing, Dye Removal, waste water process, have broad application prospects, cause membrane material Manufacturing enterprise and research institution extensive concern.
The Chinese patent literature of Publication No. CN102890315A disclose carbon nano tube-polymer composite nanofiltration membrane and Preparation method, is immersed in porous support membrane containing in oil phase monomer solution, is then immersed in containing reaction monomers and hydroxylating carbon In the aqueous phase solution of nanotube, then it is immersed in containing in oil phase monomer solution, prepares carbon nano tube-polymer composite nanofiltration Film.This composite membrane water flux and salt rejection rate increase, but due to porous support membrane surface irregularity, the method passes through interface The mechanical strength of the polymers function cortex of polymerization preparation is the highest, the most damaged.
Meanwhile, in composite nanometer filtering film field, the water flux of NF membrane is on the low side, and the water flux how improving NF membrane remains This field a great problem.In nanometer filtering film water processing procedure, water flux is on the low side often results in high energy consumption and high running cost etc. How problem, therefore, improve the water flux of composite nanometer filtering film and make it keep higher salt rejection rate to be always composite nanometer filter simultaneously One of research emphasis of film preparation.
Nanocrystalline cellulose is nano level cellulose crystals, can by cellulose being carried out enzyme hydrolysis or acid hydrolysis and Obtain.Acid hydrolysis is simple, and can be recycled residual acid by methods such as dialysis, is a kind of green ring The method protected.Strong acid makes the amorphous region in cellulose dissolve after mainly acting on cellulose, and remaining crystal region, thus The nanocrystalline cellulose high to degree of crystallinity, crystalline texture is complete.This crystal length is 10nm～1 μm, and cross sectional dimensions is only Having 5～50nm, the ratio of length and cross sectional dimensions is 1～100.Nanocrystalline cellulose has numerous excellent performance, as height is tied Crystalline substance degree, high-hydrophilic, high Young's modulus, high intensity, hyperfine structure etc..
Summary of the invention
It is an object of the invention to provide a kind of high flux MULTILAYER COMPOSITE NF membrane and preparation method thereof, this MULTILAYER COMPOSITE is received Filter membrane has and is better than the tradition high flux of NF membrane, equipment with high desalinization performance, and its preparation method operating process is simple, reacts bar Part is gentle, and production cost is relatively low.
The invention provides a kind of high flux MULTILAYER COMPOSITE NF membrane, this MULTILAYER COMPOSITE NF membrane is by open support Loaded nano crystal cellulose support layer on film, then by aqueous phase monomers and oil phase monomer interfacial polymerization, prop up in nanocrystalline cellulose Form one layer of polymeric Motor cortex on support layer and obtain.
The present invention forms nanocrystalline cellulose supporting layer by negative pressure leaching method on perforated membrane, then by interfacial polymerization work Skill produces polymers function cortex on nanocrystalline cellulose supporting layer and obtains MULTILAYER COMPOSITE NF membrane.Due to nanocrystalline fiber Element has stronger hydrophilic so that prepared MULTILAYER COMPOSITE NF membrane has high-throughout characteristic；Simultaneously because it is nanocrystalline Cellulose surface is with hydrophilic hydroxyl functional groups, and in interfacial polymerization process, nanocrystalline cellulose supporting layer makes aqueous phase list The speed that body spreads to interface is accelerated, so that interfacial polymerization is rapidly completed, the Motor cortex of generation is thinner, and due to nanometer The existence of brilliant supporting layer makes porous support membrane surface more smooth, and the MULTILAYER COMPOSITE NF membrane Motor cortex defect of preparation is more Few, the macroporous structure on porous support membrane surface is replaced by nanocrystalline cellulose supporting layer, has disperseed compound receiving under filter operation The pressure of filter membrane cortex, the breakage being not susceptible in structure.
Present invention also offers the preparation method of above-mentioned MULTILAYER COMPOSITE NF membrane, comprise the following steps:
(1) by the suspension sucking filtration of nanocrystalline cellulose to porous support membrane, it is vacuum dried under the conditions of 40～90 DEG C, Obtain the perforated membrane being loaded with nanocrystalline cellulose supporting layer；
(2) perforated membrane being loaded with nanocrystalline cellulose supporting layer is directly immersed in the aqueous phase solution containing aqueous phase monomers In, impregnate 1～10min, take out and drain the aqueous phase solution of its surface excess；
(3) it is then immersed in the oil-phase solution containing oil phase monomer, reacts 1～10min, take out and drain its surface mistake The oil-phase solution of amount, obtains MULTILAYER COMPOSITE NF membrane after last dried；
Being loaded with the load capacity of nanocrystalline cellulose in the perforated membrane of nanocrystalline cellulose supporting layer is 0.01～10g/m2；
Interfacial reaction is by the reaction occurred between polyamine compounds and many chloride compounds, in the present invention:
In aqueous phase solution, described aqueous phase monomers be o-phenylenediamine, m-diaminobenzene., diethylenetriamine, triethylene tetramine, three At least one in ethanolamine, methyl diethanolamine, piperazine, the concentration of aqueous phase monomers is 0.01～1g/L；
In oil-phase solution, described oil phase monomer is o-phthaloyl chloride, m-phthaloyl chloride, paraphthaloyl chloride, all At least one in benzene three formyl chloride, the concentration of oil phase monomer is 0.01～1g/L.
The water flux of NF membrane can be affected, along with aqueous phase monomers and oil phase list when aqueous phase monomers and oil phase monomer excessive concentration The reduction of bulk concentration, the water flux of NF membrane raises, but its salt rejection rate reduces；The load capacity impact of nanocrystalline cellulose is compound to be received The water flux of filter membrane and salt rejection rate, as preferably, be loaded with nanocrystalline cellulose in the perforated membrane of nanocrystalline cellulose supporting layer Load capacity be 0.01～1g/m2；
In aqueous phase solution, the concentration of aqueous phase monomers is 0.1～1g/L；In oil-phase solution, the concentration of oil phase monomer be 0.1～ 1g/L。
It is further preferred that be loaded with the load capacity of nanocrystalline cellulose in the perforated membrane of nanocrystalline cellulose supporting layer it is 0.1～1g/m2；
In aqueous phase solution, described aqueous phase monomers is piperazine, and the concentration of aqueous phase monomers is 0.1～1g/L；
In oil-phase solution, described oil phase monomer is pyromellitic trimethylsilyl chloride, and the concentration of oil phase monomer is 0.1～1g/L.
In oil-phase solution, oil phase monomer is many chloride compounds, so the solvent of oil-phase solution is many acyl chlorides in the present invention The good solvent of compound, as preferably, in described oil-phase solution, solvent is trifluorotrichloroethane, normal hexane, hexamethylene, heptan At least one in alkane.Most preferably, solvent is normal hexane.
Porous support membrane in the present invention is Hydrophilized porous membrane, and as preferably, described porous support membrane is that polysulfones surpasses One in filter membrane, poly (ether-sulfone) ultrafiltration membrane, polypropylene micro-filtration membrane, cellulose-acetafolic, polyether sulfone micro-filtration membrane.Most preferably , described porous support membrane is polysulphones hyperfiltration membrane.
Nanocrystalline cellulose is nano level cellulose crystals, can by cellulose being carried out enzyme hydrolysis or acid hydrolysis and Obtain.As preferably, the nanocrystalline cellulose in the present invention is prepared by acid hydrolysis microcrystalline Cellulose, and hydrolysis temperature is 25～75 DEG C, hydrolysis time is 1～10h.
Acid hydrolysis is simple, and can be recycled residual acid by methods such as dialysis, is a kind of green The method that colour circle is protected.Strong acid makes the amorphous region in cellulose dissolve after mainly acting on cellulose, and remaining crystal region, from And obtain the nanocrystalline cellulose that degree of crystallinity is high, crystalline texture is complete.
Nanocrystalline cellulose has numerous excellent performance, as high-crystallinity, high-hydrophilic, high Young's modulus, high intensity, Hyperfine structures etc., load to be formed on porous support membrane nanocrystalline cellulose supporting layer by nanocrystalline cellulose, are improving film Its hydrophilic can be improved again while the mechanical strength of material, thus its water flux is provided.
As preferably, described acid is sulphuric acid, and its mass concentration is 40～80%.
As preferably, in step (1), preparation is loaded with the method for the perforated membrane of nanocrystalline cellulose supporting layer: by porous Support membrane is layed in buchner funnel, is poured into by nanocrystalline cellulose suspension, sucking filtration, vacuum drying, it is thus achieved that be loaded with nanometer The perforated membrane of crystalline cellulose supporting layer.
Sucking filtration operation can make nanocrystalline cellulose form one layer of compacted zone on porous support membrane surface, and do one's duty or coat not This effect can be reached.
Compared with prior art, the invention have the benefit that
1, due to nanocrystalline cellulose, there is stronger hydrophilic so that prepared MULTILAYER COMPOSITE NF membrane has high pass The characteristic of amount；
2, owing to nanocrystalline cellulose surface is with hydrophilic hydroxyl functional groups, in interfacial polymerization process, nanocrystalline The speed that cellulose support layer makes aqueous phase monomers spread to interface is accelerated, so that interfacial polymerization is rapidly completed, and the merit of generation Energy cortex is thinner, and owing to the existence of nanocrystalline supporting layer makes porous support membrane surface more smooth, the MULTILAYER COMPOSITE of preparation NF membrane Motor cortex defect is less, and the macroporous structure on porous support membrane surface is replaced by nanocrystalline cellulose supporting layer, in mistake The pressure of composite nanometer filtering film cortex, the breakage being not susceptible in structure has been disperseed under filter operation.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the MULTILAYER COMPOSITE NF membrane of embodiment 4 preparation；
Fig. 2 is the scanning electron microscope (SEM) photograph of the cross section of the MULTILAYER COMPOSITE NF membrane of embodiment 4 preparation.
Detailed description of the invention
Composite nanometer filtering film prepared by the present invention is used for desalination, and salt rejection rate and water flux are two of evaluating combined NF membrane Important parameter.Wherein, salt rejection rate is defined as:
R ( % ) = ( 1 - C p C f ) × 100
Wherein, CfExpression processes the concentration of salt ion in front water；CpThe concentration of salt ion in solution after expression process.
The definition of water flux is: under certain operation pressure condition, pass through the body of the water of per membrane area in the unit interval Long-pending, its unit is L m-2·h-1, formula is:
F = V A · t
Wherein, V represents the volume of the solution passed through, and unit is L；A represents effective film area, and unit is m2；When t represents Between, unit is h.
Embodiment 1
Take 2g microcrystalline Cellulose to be placed in container, in microcrystalline Cellulose, drip the sulphuric acid water that 20mL mass concentration is 64% Solution, keeping mixture temperature in ice bath is 0 DEG C, with water bath with thermostatic control, mixture is warming up to 45 DEG C, stirs after completion of dropwise addition Mix reaction 4h.
Above-mentioned reacted mixture is slowly poured in the ultra-pure water that decaploid is long-pending and dilute, and carry out centrifuge washing three Secondary, products therefrom through bag filter dialysis to solution be neutrality, the most freeze-dried, obtain nanocrystalline cellulose powder.
Being distributed in water by nano-grade cellulosic powder and ultrasonic disperse 2h, the nanocrystalline cellulose obtaining 0.08g/L is hanged Supernatant liquid.
Polysulphones hyperfiltration membrane is layed in buchner funnel, by the nanocrystalline cellulose suspension that 10mL concentration is 0.08g/L Pour into, sucking filtration, then be vacuum dried at 25 DEG C, it is thus achieved that surface is the perforated membrane of nanocrystalline cellulose supporting layer, and this film surface is received The load capacity of rice crystalline cellulose is 0.64g/m2。
Being immersed in the aqueous phase solution that concentration is 1g/L by the above-mentioned perforated membrane prepared, aqueous phase solution is that piperazine is water-soluble Liquid, removes aqueous phase solution after 2min, get rid of the aqueous phase droplets of support membrane surface excess, after the most fully drying again by leaching Entering in the oil-phase solution that concentration is 1g/L, oil-phase solution is the hexane solution of pyromellitic trimethylsilyl chloride, reacts 2min, then will Film is put into and is processed 30min in baking oven at 60 DEG C, finally gives many with nanocrystalline cellulose as supporting layer after ultra-pure water cleans Layer composite nanometer filtering film.
Embodiment 2～4
Regulation aqueous phase monomers piperazine and the concentration of oil phase monomer pyromellitic trimethylsilyl chloride, remaining condition is with embodiment 1.
Comparative example 1
In aqueous phase solution, piperazine concentration is 0.1g/L, and in oil-phase solution, pyromellitic trimethylsilyl chloride concentration is 0.1g/L, and not Loaded nano crystal cellulose support layer, remaining condition is with embodiment 1.
Embodiment 5～8
The nanocrystalline fibre of porous film surface is regulated by the usage amount of nanocrystalline cellulose suspension during regulation sucking filtration The load capacity of dimension element, in aqueous phase solution, piperazine concentration is 0.3g/L, and in oil-phase solution, pyromellitic trimethylsilyl chloride concentration is 0.3g/L, its Remaining condition is with embodiment 1.
Test case 1
MULTILAYER COMPOSITE NF membrane prepared by comparative example 1 and embodiment 1～8 is carried out water flux and the survey of sodium sulfate salt rejection rate Examination, result is as shown in table 1.
The water flux of the MULTILAYER COMPOSITE NF membrane of table 1 embodiment 1～8 preparation and salt rejection rate
From data in table 1, water flux and the salt rejection rate of the MULTILAYER COMPOSITE NF membrane of preparation are the highest, along with aqueous phase list Body and the reduction of oil phase monomer concentration, water flux significantly improves, and water flux increases, and the salt rejection rate of NF membrane the most significantly drops Low；Compared with comparative example 1, there is the MULTILAYER COMPOSITE nanometer filtering film water flux of embodiment 1～8 preparation of nanocrystalline cellulose supporting layer It is obtained for significantly raising with salt rejection rate, embodies the high pass of the MULTILAYER COMPOSITE NF membrane with nanocrystalline cellulose supporting layer Amount, the performance of equipment with high desalinization.
As depicted in figs. 1 and 2, the Motor cortex of the MULTILAYER COMPOSITE NF membrane of embodiment 4 preparation is relatively thin and the most smooth.By In nanocrystalline cellulose surface with hydrophilic hydroxyl functional groups, in interfacial polymerization process, nanocrystalline cellulose supporting layer The speed making aqueous phase monomers spread to interface is accelerated, so that interfacial polymerization is rapidly completed, the Motor cortex of generation is thinner, and Owing to the existence of nanocrystalline supporting layer makes porous support membrane surface more smooth, the MULTILAYER COMPOSITE NF membrane Motor cortex of preparation Defect is less, and the macroporous structure on porous support membrane surface is replaced by nanocrystalline cellulose supporting layer, disperses under filter operation The pressure of composite nanometer filtering film cortex, the breakage being not susceptible in structure.
Test case 2
Magnesium sulfate, sodium sulfate, magnesium chloride, sodium chloride are carried out by MULTILAYER COMPOSITE NF membrane respectively that prepared by embodiment 3 Salt rejection rate is tested, and structure is as shown in table 2.
The salt rejection rate of the MULTILAYER COMPOSITE NF membrane of table 2 embodiment 3 preparation
Sequence number Salt Concentration (mg/L) Salt rejection rate (%)
1 Na2SO4 1.0 99.2
2 MgSO4 1.0 96.4
3 MgCl2 1.0 60.7
4 NaCl2 1.0 22.1
From the data of table 2, there is the desalination to divalent salts of the MULTILAYER COMPOSITE NF membrane of nanocrystalline cellulose supporting layer Rate is preferable, it is adaptable to the removing of divalent salts in water, such as sulfate.

Claims (10)

1. a high flux MULTILAYER COMPOSITE NF membrane, it is characterised in that by loaded nano crystal cellulose on porous support membrane Supporting layer, then by aqueous phase monomers and oil phase monomer interfacial polymerization, nanocrystalline cellulose supporting layer forms one layer of polymeric Motor cortex and obtain.
The preparation method of MULTILAYER COMPOSITE NF membrane the most according to claim 1, it is characterised in that comprise the following steps:
(1) by the suspension sucking filtration of nanocrystalline cellulose to porous support membrane, it is vacuum dried under the conditions of 40～90 DEG C, it is thus achieved that It is loaded with the perforated membrane of nanocrystalline cellulose supporting layer；
(2) perforated membrane being loaded with nanocrystalline cellulose supporting layer is directly immersed in the aqueous phase solution containing aqueous phase monomers, leaching Stain 1～10min, takes out and drains the aqueous phase solution of its surface excess；
(3) it is then immersed in the oil-phase solution containing oil phase monomer, reacts 1～10min, take out and drain its surface excess Oil-phase solution, obtains MULTILAYER COMPOSITE NF membrane after last dried；
Being loaded with the load capacity of nanocrystalline cellulose in the perforated membrane of nanocrystalline cellulose supporting layer is 0.01～10g/m2:
In aqueous phase solution, described aqueous phase monomers is o-phenylenediamine, m-diaminobenzene., diethylenetriamine, triethylene tetramine, three ethanol At least one in amine, methyl diethanolamine, piperazine, the concentration of aqueous phase monomers is 0.01～1g/L；
In oil-phase solution, described oil phase monomer is o-phthaloyl chloride, m-phthaloyl chloride, paraphthaloyl chloride, equal benzene three At least one in formyl chloride, the concentration of oil phase monomer is 0.01～1g/L.
The preparation method of MULTILAYER COMPOSITE NF membrane the most according to claim 2, it is characterised in that described porous support membrane is One in polysulphones hyperfiltration membrane, poly (ether-sulfone) ultrafiltration membrane, polypropylene micro-filtration membrane, cellulose-acetafolic, polyether sulfone micro-filtration membrane.
The preparation method of MULTILAYER COMPOSITE NF membrane the most according to claim 2, it is characterised in that described nanocrystalline cellulose is led to Peracid hydrolyzing microcrystalline cellulose prepares, and hydrolysis temperature is 25～75 DEG C, and hydrolysis time is 1～10h.
The preparation method of MULTILAYER COMPOSITE NF membrane the most according to claim 2, it is characterised in that described acid is sulphuric acid, its Mass concentration is 40～80%.
The preparation method of MULTILAYER COMPOSITE NF membrane the most according to claim 2, it is characterised in that be loaded with nanocrystalline cellulose In the perforated membrane of supporting layer, the load capacity of nanocrystalline cellulose is 0.01～1g/m2；
In aqueous phase solution, the concentration of aqueous phase monomers is 0.1～1g/L；In oil-phase solution, the concentration of oil phase monomer is 0.1～1g/ L。
The preparation method of MULTILAYER COMPOSITE NF membrane the most according to claim 2, it is characterised in that be loaded with nanocrystalline cellulose In the perforated membrane of supporting layer, the load capacity of nanocrystalline cellulose is 0.1～1g/m2；
In aqueous phase solution, described aqueous phase monomers is piperazine, and the concentration of aqueous phase monomers is 0.1～1g/L；
In oil-phase solution, described oil phase monomer is pyromellitic trimethylsilyl chloride, and the concentration of oil phase monomer is 0.1～1g/L.
The preparation method of MULTILAYER COMPOSITE NF membrane the most according to claim 2, it is characterised in that in described oil-phase solution, Solvent is at least one in trifluorotrichloroethane, normal hexane, hexamethylene, heptane.
The preparation method of MULTILAYER COMPOSITE NF membrane the most according to claim 2, it is characterised in that described porous support membrane is Polysulphones hyperfiltration membrane.
The most according to claim 2, the preparation method of MULTILAYER COMPOSITE NF membrane, it is characterised in that in step (1), preparation is negative The method being loaded with the perforated membrane of nanocrystalline cellulose supporting layer: be layed in buchner funnel by porous support membrane, by nanocrystalline fibre Dimension element suspension is poured into, sucking filtration, vacuum drying, it is thus achieved that be loaded with the perforated membrane of nanocrystalline cellulose supporting layer.
CN201610520302.0A 2016-06-29 2016-06-29 High-throughput multilayer composite nano-filtration membrane and preparation method thereof Pending CN106040015A (en)

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CN110327794A (en) * 2019-06-28 2019-10-15 杭州天创环境科技股份有限公司 A kind of preparation method of nanofiltration membrane
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