CN107158960A - A kind of preparation method of high flux and resistant to pollution poly NF membrane - Google Patents

A kind of preparation method of high flux and resistant to pollution poly NF membrane Download PDF

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Publication number
CN107158960A
CN107158960A CN201710568824.2A CN201710568824A CN107158960A CN 107158960 A CN107158960 A CN 107158960A CN 201710568824 A CN201710568824 A CN 201710568824A CN 107158960 A CN107158960 A CN 107158960A
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China
Prior art keywords
ether
ketone
membrane
sulfonated polyether
polyether
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CN201710568824.2A
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Chinese (zh)
Inventor
赵长伟
杨梅
俞灵
王军
曹爱新
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Research Center for Eco Environmental Sciences of CAS
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Research Center for Eco Environmental Sciences of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—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
    • 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
    • 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
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/36—Hydrophilic membranes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2461/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Water Supply & Treatment (AREA)
  • Dispersion Chemistry (AREA)
  • Materials Engineering (AREA)
  • Polyethers (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention discloses a kind of high flux and the preparation method of resistant to pollution poly NF membrane, belong to membrane preparation technology field.This method is that the polyether-ether-ketone concentrated sulfuric acid is carried out into sulfonation, cleans to neutrality, is dried to obtain sulfonated polyether-ether-ketone；Then by the 0.01 1wt% graphene oxides handled well add with 0.01 10wt% sulfonated polyether-ether-ketones to N, in N dimethyl acetamides (DMAC), be put into processing in cell disruptor, obtain dispersion liquid；Additive is added to the dispersion liquid of graphene oxide and sulfonated polyether-ether-ketone again, stirring is subsequently added dried PMIA, in being dissolved at 80 DEG C, vacuum defoamation is standby after mechanical agitation, striking film forming.Present invention process is simple to operate, and using the method for the present invention, in the case where keeping rejection to rise, prepared NF membrane contact angle is reduced to 45 ° or so from original 78 ° or so, substantially increases the hydrophily and antifouling property of film.

Description

A kind of preparation of high flux and resistant to pollution poly NF membrane Method
Technical field
Pass through graphene oxide and sulfonated polyether-ether-ketone the present invention relates to a kind of NF membrane method of modifying, more particularly to one kind The method for acting synergistically to prepare high flux and resistant to pollution poly NF membrane, belongs to membrane preparation technology Field.
Background technology
Nanofiltration is more and more paid close attention to its unique stalling characteristic by people, and NF membrane is in performance between counter-infiltration Between milipore filter, it is pollutant and divalence, high price inorganic salts etc. in the range of 200-1000 to be particularly suitable for separation molecular weight, and The part ion beneficial to human body can be retained.In drink water purifying, wastewater treatment, the classification of biogenetic products and concentration, food work The various fields such as industry play oneself unique effect, show good application prospect.
The flux and contamination resistance for how improving film are one of membrane material modified subject matter, graphene oxide (GO) It because it contains substantial amounts of hydrophilic functional group, can improve the hydrophily on film surface, and then strengthen the antifouling property of film, into For the study hotspot in membrane material modified field.To solve the compatibility of graphene oxide and coating solution, sulfonated polyether-ether-ketone (SPEEK) because hydrogen bond can be formed between GO containing sulfonic acid group (- SO3H), graphene is improved scattered in film liquid Property.Meanwhile, sulfonated polyether-ether-ketone (SPEEK) because the introducing of sulfonic acid group (- SO3H) can also greatly reinforce film hydrophily and It is charge.CN104826505A is disclosed by the way that the membrane material such as graphene oxide and polysulfones, polyether sulfone addition solvent is blended To casting solution, the nano graphene oxide Modified Membrane product with loose structure can be obtained, membrane flux and antipollution is improved Property.CN104275100A is disclosed deposits one layer by graphene and the compound assembling of cyclodextrin by uniform in PVDF ultrafiltration membrane Composite nanometer filtering film, improve its contamination resistance.At present, the special of modified NF membrane is prepared by adding graphene oxide Sharp a lot, although the addition of graphene oxide improves the flux of film, but the retention of film can also be affected,
The content of the invention
The invention aims to overcome the deficiencies in the prior art there is provided one kind to pass through graphene oxide and sulfonated polyether The method that ether ketone acts synergistically to prepare high flux and resistant to pollution poly NF membrane.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：
A kind of preparation method of high flux and resistant to pollution poly NF membrane, its step is as follows：
(1) preparation of sulfonated polyether-ether-ketone
The polyether-ether-ketone concentrated sulfuric acid is subjected to sulfonation, cleans to neutrality, is dried to obtain sulfonated polyether-ether-ketone；
(2) 0.01-1wt% graphene oxides are added and 0.01-10wt% sulfonated polyether-ether-ketones to N, N- dimethylacetamides In amine (DMAC), processing in cell disruptor is put into, dispersion liquid is obtained；
(3) additive is added to the dispersion liquid of graphene oxide and sulfonated polyether-ether-ketone, stirring is subsequently added dry Good PMIA, in being dissolved at 80 DEG C, vacuum defoamation is standby after mechanical agitation, striking film forming, obtains described high flux and anti-soil The poly NF membrane of dye.
The present invention propose to improve both graphene oxide and sulfonated polyether-ether-ketone synergy it is poly- between phenyl-diformyl The flux and antifouling property of phenylenediamine NF membrane, with preferable application prospect.
Using the method for the present invention, in the case where keeping rejection to rise, prepared NF membrane contact angle is from original 78 ° or so be reduced to 45 ° or so, membrane flux is by original 62.05L/m2/ h brings up to 89.12L/m2/h-125.76L/m2/ H, rejection brings up to 55% or so by original 44%, substantially increases the hydrophily and antifouling property of film.
Embodiment
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit Determine the scope of the present invention.
Embodiment 1
A kind of preparation method of high flux and resistant to pollution poly NF membrane：
(1) preparation of sulfonated polyether-ether-ketone, sulfonation is carried out by the polyether-ether-ketone concentrated sulfuric acid, is cleaned to neutrality, is dried to obtain sulphur Change polyether-ether-ketone.
(2) 0.05wt% graphene oxide and 1wt% sulfonated polyether-ether-ketones are added to DMA (DMAC) in, it is put into processing in cell disruptor.5% LiCl is added into the scattered of graphene oxide and sulfonated polyether-ether-ketone Liquid, stirring, is subsequently added 20% dried PMIA, and in being dissolved at 80 DEG C, vacuum defoamation is standby after mechanical agitation, scrapes Film is made.Obtained modification nanofiltration membrane flux is by original 62.05L/m2/ h brings up to 89.12L/m2/ h, rejection is by original 44% brings up to 55%, and contact angle drops to 58 ° by original 78 °.
Embodiment 2
A kind of preparation method of high flux and resistant to pollution poly NF membrane：
(1) preparation of sulfonated polyether-ether-ketone, sulfonation is carried out by the polyether-ether-ketone concentrated sulfuric acid, is cleaned to neutrality, is dried to obtain sulphur Change polyether-ether-ketone.
(2) 0.1wt% graphene oxide and 2wt% sulfonated polyether-ether-ketones are added to DMA (DMAC) in, it is put into processing in cell disruptor.5% LiCl is added into the scattered of graphene oxide and sulfonated polyether-ether-ketone Liquid, stirring, is subsequently added 20% dried PMIA, and in being dissolved at 80 DEG C, vacuum defoamation is standby after mechanical agitation, scrapes Film is made.Obtained modification nanofiltration membrane flux is by original 62.05L/m2/ h brings up to 119.12L/m2/ h, rejection is by original 44% bring up to 58%, contact angle drops to 53 ° by original 78 °.
Embodiment 3
A kind of preparation method of high flux and resistant to pollution poly NF membrane：
(1) preparation of sulfonated polyether-ether-ketone, sulfonation is carried out by the polyether-ether-ketone concentrated sulfuric acid, is cleaned to neutrality, is dried to obtain sulphur Change polyether-ether-ketone.
(2) 0.1wt% graphene oxide and 1wt% sulfonated polyether-ether-ketones are added to DMA (DMAC) in, it is put into processing in cell disruptor.5% LiCl is added into the scattered of graphene oxide and sulfonated polyether-ether-ketone Liquid, stirring, is subsequently added 20% dried PMIA, and in being dissolved at 80 DEG C, vacuum defoamation is standby after mechanical agitation, scrapes Film is made.Obtained modification nanofiltration membrane flux is by original 62.05L/m2/ h brings up to 125.76L/m2/ h, rejection is by original 44% bring up to 55%, contact angle drops to 45 ° by original 78 °.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto, Any one skilled in the art the invention discloses technical scope in, the change or replacement that can be readily occurred in, It should all be included within the scope of the present invention.

Claims (1)

1. the preparation method of a kind of high flux and resistant to pollution poly NF membrane, it is characterised in that should Method is achieved by the steps of：
(1) preparation of sulfonated polyether-ether-ketone
The polyether-ether-ketone concentrated sulfuric acid is subjected to sulfonation, cleans to neutrality, is dried to obtain sulfonated polyether-ether-ketone；
(2) 0.01-1wt% graphene oxides are added and 0.01-10wt% sulfonated polyether-ether-ketones to DMA (DMAC) in, processing in cell disruptor is put into, dispersion liquid is obtained；
(3) additive lithium chloride is added to the dispersion liquid of graphene oxide and sulfonated polyether-ether-ketone, stirring is subsequently added and done Dry good PMIA polies (PMIA), in being dissolved at 80 DEG C, vacuum defoamation is standby after mechanical agitation, striking Film forming, obtains described high flux and resistant to pollution poly NF membrane.
CN201710568824.2A 2017-07-13 2017-07-13 A kind of preparation method of high flux and resistant to pollution poly NF membrane Pending CN107158960A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112755821A (en) * 2020-12-15 2021-05-07 上海应用技术大学 PMIA mixed matrix ultrafiltration membrane with high flux and anti-pollution performance and preparation application thereof
CN114887501A (en) * 2022-06-22 2022-08-12 苏州聚维元创生物科技有限公司 Nano sulfonated polyether-ether-ketone modified polyether sulfone material separation membrane

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EP2722100A2 (en) * 2011-06-20 2014-04-23 LG Chem, Ltd. Reverse osmosis membrane having superior salt rejection and permeate flow, and method for manufacturing same
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CN105013354A (en) * 2014-04-30 2015-11-04 华北电力大学 Composite membrane used for gathering water vapor in smoke of thermal power plant and preparation method thereof
CN105413500A (en) * 2015-11-26 2016-03-23 中国科学院生态环境研究中心 Preparation method for polyisophthaloyl metaphenylene diamine nanofiltration membrane
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112755821A (en) * 2020-12-15 2021-05-07 上海应用技术大学 PMIA mixed matrix ultrafiltration membrane with high flux and anti-pollution performance and preparation application thereof
CN114887501A (en) * 2022-06-22 2022-08-12 苏州聚维元创生物科技有限公司 Nano sulfonated polyether-ether-ketone modified polyether sulfone material separation membrane
CN114887501B (en) * 2022-06-22 2023-10-24 苏州聚维元创生物科技有限公司 Nano sulfonated polyether-ether-ketone modified polyether sulfone material separation membrane

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