CN107875862A - The preparation method of graphene oxide Ceramic Composite NF membrane - Google Patents

The preparation method of graphene oxide Ceramic Composite NF membrane Download PDF

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Publication number
CN107875862A
CN107875862A CN201710995672.4A CN201710995672A CN107875862A CN 107875862 A CN107875862 A CN 107875862A CN 201710995672 A CN201710995672 A CN 201710995672A CN 107875862 A CN107875862 A CN 107875862A
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Prior art keywords
membrane
graphene oxide
solution
ceramic membrane
tubular ceramic
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CN201710995672.4A
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Chinese (zh)
Inventor
王耀斌
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Shaanxi Shengmai Petroleum Co Ltd
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Shaanxi Shengmai Petroleum Co Ltd
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Priority to CN201710995672.4A priority Critical patent/CN107875862A/en
Publication of CN107875862A publication Critical patent/CN107875862A/en
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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
    • B01D71/02—Inorganic material
    • B01D71/024—Oxides
    • 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
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0044—Inorganic membrane manufacture by 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
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/009—After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
    • 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
    • B01D69/04—Tubular membranes
    • 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
    • B01D71/02—Inorganic material
    • B01D71/021—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/16—Membrane materials having positively charged functional groups

Abstract

The present invention discloses a kind of preparation method of graphene oxide Ceramic Composite NF membrane, comprises the following steps：（1）It is Al with air gun purging inwall2O3Tubular ceramic membrane surface, be ultrasonically treated, drying；（2）It is immersed in the aqueous solution of 3 aminopropyl triethoxysilanes, with deionized water rinsing, drying；（3）The concentrated sulfuric acid and concentrated phosphoric acid are added into graphite powder, stirring, adds potassium permanganate, is stirred, cooling, adds hydrogen peroxide solution, stirring；（4）The pH for adjusting solution is 67, and ultrasound, centrifugation, it is graphene oxide solution to obtain upper strata centrifugate；（5）Graphene oxide solution tank is entered in the pipe of tubular ceramic membrane, cleaned with deionized water after taking-up solution, purged again with air gun successively；（6）Aq. polyethyleneimine is poured into the pipe of tubular ceramic membrane, cleaned with deionized water after taking-up solution, purged again with air gun successively.The film that the present invention is prepared is big to rejection height, the permeation flux of inorganic salts.

Description

The preparation method of graphene oxide-Ceramic Composite NF membrane
Technical field
The invention belongs to membrane preparation technology field, and in particular to a kind of preparation of graphene oxide-Ceramic Composite NF membrane Method.
Background technology
Nanofiltration（Nanofiltration, NF）It is between counter-infiltration（Reverseosmosis, RO）And ultrafiltration （Ultrafiltration, UF）Between membrane separation technique.NF membrane tool nanoscale aperture, molecular cut off exist
, can be effective compared with being carried out under low operating pressure to divalence, multivalent ion and small organic molecule between 200~1000 Retention, has huge applications prospect in the field such as environment water process, water desalination, pharmacy and biotechnology, food industry.Porous Pass through dip-coating on basement membrane（ dip-coating ）, surface aggregate（ interfacial polymerization ）, layer by layer from group Dress（ layer-by-layerself-assembly）Film layer Deng deposition compact is to prepare the common method of NF membrane.Layer by layer certainly Assembling is that driving force promotes poly- zwitterion electrolyte to certainly with electrostatic interaction, hydrogen bond, coordinate bond, covalent bond, electric charge transfer etc. Row assembling, easy to operate, the adjustable self assembly number of plies adjust the structure of film and performance, are more and more applied.
Graphene oxide（GO）The oxygen-containing functional groups such as the COOH contained by lamella, ionization can occur in aqueous and with negative Electric charge, thus GO can realize LBL self-assembly with the polycation electrolyte of positively charged by electrostatic interaction, so as to make Standby such as nanofiltration, infiltrating and vaporizing membrane, gas barrier film and other kinds of film layer.
But also there is the defects of rejection is low, permeation flux is small in existing graphene-tubular ceramic membrane.
The content of the invention
For it is existing the defects of, the present invention provides a kind of preparation method of graphene oxide-Ceramic Composite NF membrane.
The preparation method of graphene oxide-Ceramic Composite NF membrane, comprises the following steps：
（1）It is Al by inwall2O3Tubular ceramic membrane be cut into 22 cm length, described tubular ceramic membrane table is purged with air gun Face, after 1 h is then handled in supersonic generator, 1.5 h are dried at 110 DEG C；
（2）By step（1）Treated tubular ceramic membrane is immersed in the aqueous solution of 3- aminopropyl triethoxysilanes, Ran Houyong Deionized water rinsing 3 times, 2h is dried in 110 DEG C of baking oven；
（3）The concentrated sulfuric acid and concentrated phosphoric acid are added into graphite powder, stirring, adds potassium permanganate, then the stirring reaction 10- at 50 DEG C 15h, room temperature is naturally cooled to, then add the hydrogen peroxide solution that mass concentration is 30%, stir 30-50min；
（4）The pH for adjusting solution is 6-7, the ultrasonic reaction 1h under power 200W, is then centrifuged under 4000r/min rotating speed 10-20min, obtained upper strata centrifugate is graphene oxide solution；
（5）By step（4）Obtained graphene oxide solution tank enters step（2）In the pipe of obtained tubular ceramic membrane, 15min will Graphene oxide solution is taken out, and the inwall 2min of tubular ceramic membrane is cleaned with deionized water, then purge tubular ceramic membrane with air gun Inwall；
（6）Aq. polyethyleneimine is poured into step（5）In the pipe of obtained tubular ceramic membrane, 15min is by polyethyleneimine The aqueous solution takes out, and the inwall 2min of tubular ceramic membrane is cleaned with deionized water, then purge tubular ceramic membrane inwall with air gun.
Preferably, step（1）In in ultrasonic wave generation the condition that handles be that the power being ultrasonically treated is 100-200W.
Preferably, step（2）Described in the mass concentrations of the aqueous solution of 3- aminopropyl triethoxysilanes be 8-10g/L.
Preferably, step（3）Middle graphite powder, the concentrated sulfuric acid, concentrated phosphoric acid, potassium permanganate, the adding proportion of hydrogen peroxide solution are： 6g:720mL:80mL：36g：800mL.
Preferably, step（6）The mass concentration of middle aq. polyethyleneimine is 5g/L.
Advantages of the present invention：
Method provided by the invention, the graphene oxide being prepared-Ceramic Composite NF membrane is high to the rejections of inorganic salts, oozes Saturating flux is big, and the rejection for the magnesium chloride solution for being 2g/L to concentration is 97.54%, meets typical positive charge NF membrane feature.
Embodiment
Embodiment 1
The preparation method of graphene oxide-Ceramic Composite NF membrane, comprises the following steps：
（1）It is Al by inwall2O3Tubular ceramic membrane be cut into 22 cm length, described tubular ceramic membrane table is purged with air gun Face, after then handling 1 h in the supersonic generator that power is 100W, 1.5 h are dried at 110 DEG C；
（2）By step（1）Treated tubular ceramic membrane is immersed in the 3- aminopropyl triethoxysilanes that mass concentration is 8g/L The aqueous solution in, then with deionized water rinsing 3 times, 2h is dried in 110 DEG C of baking oven；
（3）The concentrated sulfuric acid and concentrated phosphoric acid are added into graphite powder, stirring, adds potassium permanganate, then the stirring reaction at 50 DEG C 10h, room temperature is naturally cooled to, then add the hydrogen peroxide solution that mass concentration is 30%, stir 30min；Wherein, graphite powder, dense Sulfuric acid, concentrated phosphoric acid, potassium permanganate, the adding proportion of hydrogen peroxide solution are：6g:720mL:80mL：36g：800mL；
（4）The pH for adjusting solution is 6, the ultrasonic reaction 1h under power 200W, is then centrifuged under 4000r/min rotating speed 10min, obtained upper strata centrifugate is graphene oxide solution；
（5）By step（4）Obtained graphene oxide solution tank enters step（2）In the pipe of obtained tubular ceramic membrane, 15min will Graphene oxide solution is taken out, and the inwall 2min of tubular ceramic membrane is cleaned with deionized water, then purge tubular ceramic membrane with air gun Inwall；
（6）The aq. polyethyleneimine that mass concentration is 5g/L is poured into step（5）In the pipe of obtained tubular ceramic membrane, 15min takes out aq. polyethyleneimine, cleans the inwall 2min of tubular ceramic membrane with deionized water, then with air gun scavenging conduit Formula ceramic membrane inwall.
Embodiment 2
The preparation method of graphene oxide-Ceramic Composite NF membrane, comprises the following steps：
（1）It is Al by inwall2O3Tubular ceramic membrane be cut into 22 cm length, described tubular ceramic membrane table is purged with air gun Face, after then handling 1 h in the supersonic generator that power is 200W, 1.5 h are dried at 110 DEG C；
（2）By step（1）Treated tubular ceramic membrane is immersed in the 3- aminopropyl triethoxysilanes that mass concentration is 10g/L The aqueous solution in, then with deionized water rinsing 3 times, 2h is dried in 110 DEG C of baking oven；
（3）The concentrated sulfuric acid and concentrated phosphoric acid are added into graphite powder, stirring, adds potassium permanganate, then the stirring reaction at 50 DEG C 15h, room temperature is naturally cooled to, then add the hydrogen peroxide solution that mass concentration is 30%, stir 50min；Wherein, graphite powder, dense Sulfuric acid, concentrated phosphoric acid, potassium permanganate, the adding proportion of hydrogen peroxide solution are：6g:720mL:80mL：36g：800mL；
（4）The pH for adjusting solution is 7, the ultrasonic reaction 1h under power 200W, is then centrifuged under 4000r/min rotating speed 20min, obtained upper strata centrifugate is graphene oxide solution；
（5）By step（4）Obtained graphene oxide solution tank enters step（2）In the pipe of obtained tubular ceramic membrane, 15min will Graphene oxide solution is taken out, and the inwall 2min of tubular ceramic membrane is cleaned with deionized water, then purge tubular ceramic membrane with air gun Inwall；
（6）The aq. polyethyleneimine that mass concentration is 5g/L is poured into step（5）In the pipe of obtained tubular ceramic membrane, 15min takes out aq. polyethyleneimine, cleans the inwall 2min of tubular ceramic membrane with deionized water, then with air gun scavenging conduit Formula ceramic membrane inwall.
Embodiment 3
The preparation method of graphene oxide-Ceramic Composite NF membrane, comprises the following steps：
（1）It is Al by inwall2O3Tubular ceramic membrane be cut into 22 cm length, described tubular ceramic membrane table is purged with air gun Face, after then handling 1 h in the supersonic generator that power is 100W, 1.5 h are dried at 110 DEG C；
（2）By step（1）Treated tubular ceramic membrane is immersed in the 3- aminopropyl triethoxysilanes that mass concentration is 9g/L The aqueous solution in, then with deionized water rinsing 3 times, 2h is dried in 110 DEG C of baking oven；
（3）The concentrated sulfuric acid and concentrated phosphoric acid are added into graphite powder, stirring, adds potassium permanganate, then the stirring reaction at 50 DEG C 12h, room temperature is naturally cooled to, then add the hydrogen peroxide solution that mass concentration is 30%, stir 40min；Wherein, graphite powder, dense Sulfuric acid, concentrated phosphoric acid, potassium permanganate, the adding proportion of hydrogen peroxide solution are：6g:720mL:80mL：36g：800mL；
（4）The pH for adjusting solution is 7, the ultrasonic reaction 1h under power 200W, is then centrifuged under 4000r/min rotating speed 15min, obtained upper strata centrifugate is graphene oxide solution；
（5）By step（4）Obtained graphene oxide solution tank enters step（2）In the pipe of obtained tubular ceramic membrane, 15min will Graphene oxide solution is taken out, and the inwall 2min of tubular ceramic membrane is cleaned with deionized water, then purge tubular ceramic membrane with air gun Inwall；
（6）The aq. polyethyleneimine that mass concentration is 5g/L is poured into step（5）In the pipe of obtained tubular ceramic membrane, 15min takes out aq. polyethyleneimine, cleans the inwall 2min of tubular ceramic membrane with deionized water, then with air gun scavenging conduit Formula ceramic membrane inwall.

Claims (5)

1. the preparation method of graphene oxide-Ceramic Composite NF membrane, it is characterised in that：Comprise the following steps：
（1）It is Al by inwall2O3Tubular ceramic membrane be cut into 22 cm length, described tubular ceramic membrane table is purged with air gun Face, after 1 h is then handled in supersonic generator, 1.5 h are dried at 110 DEG C；
（2）By step（1）Treated tubular ceramic membrane is immersed in the aqueous solution of 3- aminopropyl triethoxysilanes, Ran Houyong Deionized water rinsing 3 times, 2h is dried in 110 DEG C of baking oven；
（3）The concentrated sulfuric acid and concentrated phosphoric acid are added into graphite powder, stirring, adds potassium permanganate, then the stirring reaction 10- at 50 DEG C 15h, room temperature is naturally cooled to, then add the hydrogen peroxide solution that mass concentration is 30%, stir 30-50min；
（4）The pH for adjusting solution is 6-7, the ultrasonic reaction 1h under power 200W, is then centrifuged under 4000r/min rotating speed 10-20min, obtained upper strata centrifugate is graphene oxide solution；
（5）By step（4）Obtained graphene oxide solution tank enters step（2）In the pipe of obtained tubular ceramic membrane, 15min will Graphene oxide solution is taken out, and the inwall 2min of tubular ceramic membrane is cleaned with deionized water, then purge tubular ceramic membrane with air gun Inwall；
（6）Aq. polyethyleneimine is poured into step（5）In the pipe of obtained tubular ceramic membrane, 15min is by polyethyleneimine The aqueous solution takes out, and the inwall 2min of tubular ceramic membrane is cleaned with deionized water, then purge tubular ceramic membrane inwall with air gun.
2. the preparation method of graphene oxide according to claim 1-Ceramic Composite NF membrane, it is characterised in that：Step （1）In in ultrasonic wave generation the condition that handles be that the power being ultrasonically treated is 100-200W.
3. the preparation method of graphene oxide according to claim 1-Ceramic Composite NF membrane, it is characterised in that：Step （2）Described in the mass concentrations of the aqueous solution of 3- aminopropyl triethoxysilanes be 8-10g/L.
4. the preparation method of graphene oxide according to claim 1-Ceramic Composite NF membrane, it is characterised in that：Step （3）Middle graphite powder, the concentrated sulfuric acid, concentrated phosphoric acid, potassium permanganate, the adding proportion of hydrogen peroxide solution are：6g:720mL:80mL：36g： 800mL。
5. the preparation method of graphene oxide according to claim 1-Ceramic Composite NF membrane, it is characterised in that：Step （6）The mass concentration of middle aq. polyethyleneimine is 5g/L.
CN201710995672.4A 2017-10-23 2017-10-23 The preparation method of graphene oxide Ceramic Composite NF membrane Withdrawn CN107875862A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109966931A (en) * 2019-04-07 2019-07-05 北京化工大学 A kind of preparation method of graphene oxide/attapulgite/polyvinyl alcohol ceramic matrix composite membrane
CN113797773A (en) * 2020-06-12 2021-12-17 三达膜科技（厦门）有限公司 Molybdenum disulfide oxide-graphene oxide-PEI composite ceramic nanofiltration membrane and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160038885A1 (en) * 2014-08-08 2016-02-11 University Of Southern California High performance membranes for water reclamation using polymeric and nanomaterials
CN105536563A (en) * 2015-12-14 2016-05-04 北京工业大学 Preparation method of high-performance oxidized graphene tubular nanofiltration membrane and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160038885A1 (en) * 2014-08-08 2016-02-11 University Of Southern California High performance membranes for water reclamation using polymeric and nanomaterials
CN105536563A (en) * 2015-12-14 2016-05-04 北京工业大学 Preparation method of high-performance oxidized graphene tubular nanofiltration membrane and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
高亮等: "氧化石墨烯-陶瓷复合纳滤膜的层层自组装制备及其性能", 《化工学报》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109966931A (en) * 2019-04-07 2019-07-05 北京化工大学 A kind of preparation method of graphene oxide/attapulgite/polyvinyl alcohol ceramic matrix composite membrane
CN113797773A (en) * 2020-06-12 2021-12-17 三达膜科技（厦门）有限公司 Molybdenum disulfide oxide-graphene oxide-PEI composite ceramic nanofiltration membrane and preparation method thereof
CN113797773B (en) * 2020-06-12 2023-04-14 三达膜科技（厦门）有限公司 Molybdenum disulfide oxide-graphene oxide-PEI composite ceramic nanofiltration membrane and preparation method thereof

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