CN105854626A - Compound reverse osmosis film and preparation method thereof - Google Patents

Compound reverse osmosis film and preparation method thereof Download PDF

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Publication number
CN105854626A
CN105854626A CN201610282259.9A CN201610282259A CN105854626A CN 105854626 A CN105854626 A CN 105854626A CN 201610282259 A CN201610282259 A CN 201610282259A CN 105854626 A CN105854626 A CN 105854626A
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reverse osmosis
osmosis film
solution
film
graphene
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朱宏伟
胡蕊蕊
邓会
孙鹏展
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Tsinghua University
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Tsinghua University
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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
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • 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
    • B01D71/02—Inorganic material
    • B01D71/021—Carbon
    • 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
    • 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
    • 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

Abstract

The invention discloses a compound reverse osmosis film and a preparation method thereof, and belongs to the technical field of water treatment film preparation. The reverse osmosis film comprises a base supporting layer, a middle porous bearing layer and an ultra-thin compact separation layer. The ultra-thin compact separation layer is prepared from two-dimensional nanometer materials and aramide in a compounded mode. The two-dimensional nanometer materials comprise molybdenum disulfide or titanium dioxide or graphene capable of being functionalized. The two-dimensional nanometer materials are added into the compact separation layer through in-situ interfacial polymerization, the water yield, desalinization rate, antifouling property and chlorine resistance of the compound reverse osmosis film can be effectively improved, and meanwhile needed working pressure is lowered.

Description

A kind of compound reverse osmosis film and preparation method thereof
Technical field
The present invention relates to aromatic polyamides reverse osmosis film and the preparation method of a kind of modification, more specifically, be by two-dimensional nano material Material joins in the ultra-thin dense separation layers of reverse osmosis film, belongs to membrane for water treatment technical field.
Background technology
Along with industrial expansion, water pollutes and shortage of fresh water is one of maximum challenge of facing of the current whole world, current for solving Serious fresh water crisis, desalinization gets growing concern for.At present, main desalination technology has reverse osmosis, multiple-effect Distillation, multistage flash evaporation and electrodialysis.Wherein, the hyperfiltration of application reverse osmosis membrane is the most energy-conservation desalination technology.But, Currently used tradition polyamide macromolecule reverse osmosis membrane mainly plays the effect retaining salt ion by manufacture nano-pore, salt There is also many deficiencies on can, external pressure as more poor, required than relatively low, antipollution and anti-chlorine performance in the aquifer yield of film is relatively big, and de- Salt rate there is also certain room for promotion etc..
In recent years, research finds that some emerging two-dimension nano materials have many unique strainabilities.In terms of water transmission, Geim et al. report the thin film that graphene oxide (GO) constitutes steam is had ultrafast transmission characteristic (Nair R R, Wu H A, Jayaram P N,et al.Unimpeded permeation of water through helium-leak–tight graphene-based Membranes [J] .Science, 2012,335 (6067): 442-444), its reason is that GO synusia is stacked with defining nanometer capillary Network channel, and channel interior has ultralow flowage friction power due to the arrangement architecture that carbon atom is regular, thus the most ultrafast Water flow rate.Sun et al. further demonstrate that GO thin film has same characteristic (Sun P, Liu H, Wang K, et al. to aqueous water Ultrafast liquid water transport through graphene-based nanochannels measured by isotope labelling[J].Chemical Communications,2015,51(15):3251-3254).In terms of ion isolation, as a example by GO Some two-dimension nano materials there is the characteristic of ion selective.Mi and Sun et al. propose respectively dimensional effect ion get rid of and Ion rejection mechanism (the Mi B.Graphene oxide membranes for ionic and of the ionic interaction of electric charge regulation and control molecular sieving[J].Science,2014,343(6172):740-742；Sun P,Zhu M,Wang K,et al.Selective ion penetration of graphene oxide membranes[J].AcsNano,2012,7(1):428-437).At fouling membrane and chlorine Change effect aspect, two-dimension nano materials can change hydrophilic and hydrophobic by different functionalizations, thus improve anti-chlorine and the antipollution of thin film Performance, in addition, the introducing of two-dimension nano materials also contributes to protect the active reaction sites of chlorine on polyamide, thus further Stop the chlorination of thin film.Based on this, the two-dimension nano materials with regulatable multiple mass transfer mode has extensively at water process film applications Wealthy application prospect.
In order to solve conventional polymer reverse osmosis problem, in the present invention, two-dimension nano materials is dosed the ultra-thin cause of reverse osmosis membrane In close stratum disjunctum, improve the structure of reverse osmosis film, hydrophilic, water and ion transmission channel etc., thus it is thin to be effectively improved reverse osmosis The aquifer yield of film, salt rejection rate, antifouling property and anti-chlorine performance, reduce required operating pressure simultaneously, save energy consumption and reduce cost.
Summary of the invention
It is an object of the invention to provide a kind of compound reverse osmosis film, it has more excellent water flux, a salt rejection rate, antifouling property and Anti-chlorine performance, reduces required operating pressure simultaneously.
Technical scheme is as follows:
A kind of compound reverse osmosis film, containing base support layer, intermediate porous supporting layer and ultra-thin dense separation layers, it is characterised in that: Two-dimension nano materials is dosed to aromatic polyamides composition by original position interfacial polymerization by described ultra-thin dense separation layers.
Two-dimension nano materials of the present invention preferably employs the Graphene of molybdenum bisuphide, titanium dioxide or functionalization.Described sense The Graphene changed uses amination Graphene, hydroxylating Graphene or carboxylated graphene oxide.
Preferably, the thickness of ultra-thin dense separation layers of the present invention is 100-200nm.
Preferably, described intermediate porous supporting layer is polysulfones macromolecular material；Described base support layer is that water processes special nothing Spin cloth material.
The preparation method of a kind of compound reverse osmosis film that the present invention provides, it is characterised in that the method comprises the steps:
1) base support layer pretreatment: nonwoven surface is flattened with press；
2) polysulfones macromolecular material is dissolved in N-Methyl pyrrolidone solvent, prepares polysulfones solution；Will with automatic film applicator Polysulfones solution is coated uniformly on non-woven fabrics top layer, immerses film-forming after deionized water, and film thickness monitoring is in 50～200 μm；60～ It is dried 10～30min under the conditions of 80 DEG C, makes the non-woven fabrics being coated with polysulfone material；
3) being dispersed in by two-dimension nano materials in m-diaminobenzene. aqueous solution, this two-dimension nano materials content controls 0.005wt.%～0.03wt.%；
4) non-woven fabrics being coated with polysulfone material soaks 30min～1h in deionized water, is dipped in afterwards containing two dimension The m-diaminobenzene. aqueous solution of nano material keeps 5～10min, after taking-up, removes excess surface solution；Immerse equal benzene three formyl again Chlorine organic solution keeps 30s～2min；10min～30min it is dried under the conditions of 60～90 DEG C；I.e. prepare two-dimension nano materials Modified compound reverse osmosis film.
Preferably, step 3) described in the concentration of m-diaminobenzene. aqueous solution control at 0.5g/mL～3g/mL；Step 4) in The concentration of described pyromellitic trimethylsilyl chloride organic solution controls at 0.02g/mL～0.15g/mL.
The present invention compared with prior art, has the following advantages and the technique effect of salience: two-dimensional nano material prepared by the method The aromatic polyamide composite reverse osmosis membrane that material is modified, it is possible to utilize the nanometer network passage ultrafast transmission spy to water in two-dimension nano materials Property realizes the raising of reverse osmosis membrane water flux；The regulation and control to two-dimension nano materials charge characteristic are utilized to realize equipment with high desalinization；Utilize two dimension High capillary force in nano material internal capillary network reduces the external pressure needed for reverse osmosis, reduces energy consumption；By adding hydrophilic two Dimension nano material improves the hydrophilic of reverse osmosis membrane, improves the contamination resistance of reverse osmosis membrane；By adding two-dimension nano materials, protect Protect the active reaction sites of chlorine on aromatic polyamides, improve anti-chlorine performance.
Accompanying drawing explanation
The structural representation of the compound reverse osmosis film that accompanying drawing 1 provides for the present invention.
Detailed description of the invention
With embodiment, the present invention is further elaborated below in conjunction with the accompanying drawings.
As it is shown in figure 1, the one that the present invention provides is combined reverse osmosis film, containing base support layer 1, intermediate porous supporting layer 2 With ultra-thin dense separation layers 3, this ultra-thin dense separation layers is to be dosed two-dimension nano materials to fragrance polyamides by original position interfacial polymerization Amine is constituted.Base support layer 1 uses water to process special non-woven fabric, plays structure and supports and strengthen reverse osmosis membrane mechanical property Effect.Intermediate porous supporting layer 2 is polysulfones macromolecular material, forms loose structure, play the work of ultrafiltration at the bottom of nonwoven fabric base With.Ultra-thin dense separation layers 3 uses two-dimension nano materials and aromatic polyamides composite, and thickness is generally 100-200nm, rises To the effect removing salt ion.Its synthetic method is original position interfacial polymerization, and it is isophthalic two that the monomer used by interface polymerization reaction occurs Amine and pyromellitic trimethylsilyl chloride, described two-dimension nano materials generally comprises molybdenum bisuphide (MoS2), titanium dioxide (TiO2) or official The Graphene of energyization；The Graphene of described functionalization uses amination Graphene, hydroxylating Graphene or carboxylated graphene oxide. During desalination, hydrone can quickly pass through reverse osmosis film, and salt ion is effectively stopped.
The preparation method of compound reverse osmosis film that the present invention provides, it specifically includes following steps:
1) base support layer pretreatment: nonwoven surface is flattened with press；
2) polysulfones macromolecular material is dissolved in N-Methyl pyrrolidone solvent, prepares polysulfones solution；Will be poly-with automatic film applicator Sulfolane solution is coated uniformly on non-woven fabrics top layer, immerses film-forming after deionized water, and film thickness monitoring is in 50～200 μm；60～ It is dried 10～30min under the conditions of 80 DEG C, makes the non-woven fabrics being coated with polysulfone material；
3) two-dimension nano materials is dispersed in m-diaminobenzene. aqueous solution, two-dimension nano materials content control at 0.005wt.%～ 0.03wt.%；The concentration of described m-diaminobenzene. aqueous solution controls at 0.5g/mL～3g/mL；
4) non-woven fabrics being coated with polysulfone material soaks 30min～1h in deionized water, is dipped in afterwards containing two wieners The m-diaminobenzene. aqueous solution of rice material keeps 5～10min, after taking-up, removes excess surface solution；Immerse pyromellitic trimethylsilyl chloride again Organic solution keeps 30s～2min；10min～30min it is dried under the conditions of 60～90 DEG C；I.e. prepare two-dimension nano materials to change The compound reverse osmosis film of property.The concentration of described pyromellitic trimethylsilyl chloride organic solution controls at 0.02g/mL～0.15g/mL.
Enumerate several specific embodiment below to be further appreciated by being embodied as of the present invention.
Embodiment 1:
Step 1, the substrate pretreatment of reverse osmosis film: nonwoven surface is flattened with press；
Step 2, prepare the intermediate porous supporting layer of reverse osmosis film: this polysulfones (PSF) porous supporting layer preparation method includes Procedure below:
1) 20wt.%PSF solid particle and 80wt.%N-methyl pyrrolidone (NMP) solution are mixed, 50 DEG C of heating, Stirring 6h, forms the PSF/NMP solution of transparent and homogeneous；
2) PSF/NMP solution for vacuum degasification, until not having visible bubble in bubble；
3) PSF/NMP solution is made the nonwoven fabric base of pretreatment at the bottom of on to become with constant speed with thickness with automatic film applicator Film, film thickness monitoring is in 50 μm；
4) make PSF be solidified into porous structural film in deionized water the non-woven fabrics immersion of film immediately, keep 24h, In air atmosphere, 60 DEG C of dry 30min are stand-by；
Step 3, by molybdenum bisuphide (MoS2) nanometer sheet ultrasonic disperse is in m-diaminobenzene. (MPD) water that concentration is 0.5g/mL In solution, MoS2Content is 0.005wt.%；
Step 4, prepare ultra-thin dense separation layers.The preparation method of this stratum disjunctum includes procedure below:
1) non-woven fabrics of coating PSF porous supporting layer is soaked 30min in deionized water；
2) MOS is immersed2/ MPD aqueous solution keeps 5min, makes MoS2/ MPD aqueous solution is fully infiltrated into PSF loose structure Middle formation aqueous phase；
3) remove PSF excess surface solution with rubber cylinder, make surface there is no drop visible.The back side is wiped unnecessary molten with towel Liquid；
4) holding 1min in pyromellitic trimethylsilyl chloride (TMC)-hexane solution that concentration is 0.02g/mL is immersed, in aqueous phase MPD、MoS2Being diffused into organic facies interface occurs interface polymerization reaction in situ to form polyamide stratum disjunctum with TMC.
5) with hexane solution, the TMC monomer of residual is rinsed well, at 60 DEG C, be dried 30min.
6) MoS that will prepare2Modified compound reverse osmosis film deposit preserve in deionized water stand-by.
Embodiment 2:
Step 1, the substrate pretreatment of reverse osmosis film: nonwoven surface is flattened with press；
Step 2, prepare the intermediate porous supporting layer of reverse osmosis film: this polysulfones (PSF) porous supporting layer preparation method includes Procedure below:
1) 19wt.%PSF solid particle and 81wt.%N-methyl pyrrolidone (NMP) solution are mixed, 55 DEG C of heating Stirring 5h, forms the PSF/NMP solution of transparent and homogeneous；
2) PSF/NMP solution for vacuum degasification, until not having visible bubble in bubble；
3) PSF/NMP solution is made the nonwoven fabric base of pretreatment at the bottom of on to become with constant speed with thickness with automatic film applicator Film, film thickness monitoring is in 100 μm；
4) make PSF be solidified into porous structural film in deionized water the non-woven fabrics immersion of film immediately, keep 24h；
5) in air atmosphere, 70 DEG C of dry 20min are stand-by；
Step 3, by titanium dioxide (TiO2) to be scattered in concentration be in 1.0g/mL m-diaminobenzene. (MPD) aqueous solution to nanometer sheet, TiO2Content is 0.01wt.%；
Step 4, the preparation of ultra-thin dense separation layers: the preparation method of this stratum disjunctum includes procedure below:
1) non-woven fabrics of coating PSF porous supporting layer is soaked 45min in deionized water；
2) TiO is immersed2/ MPD aqueous solution keeps 7min, makes TiO2/ MPD aqueous solution is fully infiltrated into PSF loose structure Middle formation aqueous phase；
3) remove PSF excess surface solution with rubber cylinder, make surface there is no drop visible.The back side is wiped unnecessary with towel Solution；
4) holding 1min in pyromellitic trimethylsilyl chloride (TMC)-hexane solution that concentration is 0.05g/mL is immersed, in aqueous phase MPD、TiO2Being diffused into organic facies interface occurs interface polymerization reaction in situ to form polyamide stratum disjunctum with TMC；
5) with hexane solution, the TMC monomer of residual is rinsed well, at 70 DEG C, be dried 20min；
6) TiO that will prepare2Modified compound reverse osmosis film deposit preserve in deionized water stand-by.
Embodiment 3:
Step 1, the substrate pretreatment of reverse osmosis film: nonwoven surface is flattened with press；
Step 2, prepare the intermediate porous supporting layer of reverse osmosis film: this polysulfones (PSF) porous supporting layer preparation method includes
Procedure below:
1) 18wt.%PSF solid particle and 82wt.%N-methyl pyrrolidone (NMP) solution are mixed, 60 DEG C of heating Stirring 4h, forms transparent and homogeneous PSF/NMP solution；
2) PSF/NMP solution for vacuum degasification, until not having visible bubble in bubble；
3) PSF/NMP solution is made the nonwoven fabric base of pretreatment at the bottom of on to become with constant speed with thickness with automatic film applicator Film, film thickness monitoring is in 150 μm；
4) make PSF be solidified into porous structural film in deionized water the non-woven fabrics immersion of film immediately, keep 24h；
5) in air atmosphere, 80 DEG C of dry 10min are stand-by.
Step 3, the preparation of amination Graphene: this amination graphene preparation method includes procedure below:
1) 40mg graphene oxide (GO) and 5mL deionized water are mixed, ultrasonic 30min；
2) adding 40mL concentration is the ammonia solution of 20%, and in autoclave, 200 DEG C keep 10h；
3) clean with 0.1mol/L hydrochloric acid solution, then alternately rinse with deionized water and ethanol；
4) centrifugal rear taking precipitate is vacuum dried 24h under the conditions of 55 DEG C；
Step 4, by amination graphene dispersion in m-diaminobenzene. (MPD) aqueous solution that concentration is 1.5g/mL, amino fossil Ink alkene content is 0.01wt.%；
Step 5, the preparation of ultra-thin cause stratum disjunctum: the preparation method of this stratum disjunctum includes procedure below:
1) non-woven fabrics of film PSF porous supporting layer is soaked 1h in deionized water；
2) immerse in MPD and amination Graphene mixed solution and keep 10min, make mixed solution be fully infiltrated into PSF porous Structure is formed aqueous phase；
3) remove PSF excess surface solution with rubber cylinder, make surface there is no drop visible, wipe the back side with towel unnecessary Solution；
4) holding 1min, water in pyromellitic trimethylsilyl chloride (TMC)-normal hexane mixed solution that concentration is 0.07g/mL is immersed Mutually middle MPD, amination Graphene are diffused into organic facies interface and occur with TMC interface polymerization reaction formation polyamide in situ to separate Layer；
5) with hexane solution, the TMC monomer of residual is rinsed well, at 90 DEG C, be dried 10min；
6) compound reverse osmosis film modified for the amination Graphene prepared is deposited preserve in deionized water stand-by.
Embodiment 4:
Step 1, the substrate pretreatment of reverse osmosis film: nonwoven surface is flattened with press；
Step 2, prepare the intermediate porous supporting layer of reverse osmosis film: this polysulfones (PSF) porous supporting layer preparation method include with Lower process:
1) 18wt.%PSF solid particle and 82wt.%N-methyl pyrrolidone (NMP) solution are mixed, 50 DEG C of heating
Stirring 6h, forms transparent and homogeneous PSF/NMP solution；
2) PSF/NMP solution for vacuum degasification, until not having visible bubble in bubble；
3) PSF/NMP solution is made the nonwoven fabric base of pretreatment at the bottom of on to become with constant speed with thickness with automatic film applicator Film, film thickness monitoring is in 50 μm；
4) make PSF be solidified into porous structural film in deionized water the non-woven fabrics immersion of film immediately, keep 24h；
5) in air atmosphere, 60 DEG C of dry 20min are stand-by；
Step 3, the preparation of hydroxylating Graphene: this amination graphene preparation method includes procedure below:
1) 15mg graphite and 300mg potassium hydroxide (KOH) are mixed, mix with ball mill；
2) feed the mixture in 25mL deionized water, centrifugal 30min；
3) supernatant is transferred in bag filter, soak and remove foreign ion in deionized water；
Step 4, by hydroxylating graphene dispersion in m-diaminobenzene. (MPD) aqueous solution that concentration is 2g/mL, hydroxylating graphite Alkene content is 0.02wt.%；
Step 5, the preparation of ultra-thin dense separation layers: the preparation method of this stratum disjunctum includes procedure below:
1) non-woven fabrics of film PSF porous supporting layer is soaked 30min in deionized water；
2) immerse in MPD and hydroxylating Graphene mixed solution and keep 5min, make mixed solution be fully infiltrated into PSF porous Structure is formed aqueous phase；
3) remove PSF excess surface solution with rubber cylinder, make surface there is no drop visible.The back side is wiped unnecessary with towel Solution；
4) holding 1min, water in pyromellitic trimethylsilyl chloride (TMC)-normal hexane mixed solution that concentration is 0.1g/mL is immersed Mutually middle MPD, hydroxylating Graphene are diffused into organic facies interface and occur with TMC interface polymerization reaction formation polyamide in situ to separate Layer；
5) with hexane solution, the TMC monomer of residual is rinsed well, at 70 DEG C, be dried 20min；
6) compound reverse osmosis film modified for the hydroxylating Graphene prepared is deposited preserve in deionized water stand-by.
Embodiment 5:
Step 1, the substrate pretreatment of reverse osmosis film: nonwoven surface is flattened with press；
Step 2, prepare the intermediate porous supporting layer of reverse osmosis film.This polysulfones (PSF) porous supporting layer preparation method includes Procedure below:
1) 18wt.%PSF solid particle and 82wt.%N-methyl pyrrolidone (NMP) solution are mixed, 55 DEG C of heating Stirring 5h, forms transparent and homogeneous PSF/NMP solution；
2) PSF/NMP solution for vacuum degasification, until not having visible bubble in bubble；
3) PSF/NMP solution is made the nonwoven fabric base of pretreatment at the bottom of on to become with constant speed with thickness with automatic film applicator Film, film thickness monitoring is in 100 μm；
4) make PSF be solidified into porous structural film in deionized water the non-woven fabrics immersion of film immediately, keep 24h；
5) in air atmosphere, 70 DEG C of dry 15min are stand-by；
Step 3, the preparation of carboxylated graphene oxide: this amination graphene preparation method includes procedure below:
1) graphene oxide (GO) solution and 5mL hydrobromic acid (HBr) that 20mL concentration is 2mg/mL are mixed, Stirring 10h；
2) stirring 5h is continued after adding 1g oxalic acid；
3) under the conditions of 60 DEG C, it is vacuum dried 24h after being filtered by mixed solution；
Step 4, carboxylated graphene oxide is dispersed in m-diaminobenzene. (MPD) aqueous solution that concentration is 3g/mL, carboxyl
Changing graphene oxide content is 0.03wt.%；
Step 5, the preparation of ultra-thin dense separation layers: the preparation method of this stratum disjunctum includes procedure below:
1) non-woven fabrics of film PSF porous supporting layer is soaked 1h in deionized water；
2) immerse in MPD and hydroxylating graphene oxide mixed solution and keep 10min, make mixed solution be fully infiltrated into PSF Loose structure is formed aqueous phase；
3) remove PSF excess surface solution with rubber cylinder, make surface there is no drop visible.The back side is wiped unnecessary with towel Solution；
4) holding 1min, water in pyromellitic trimethylsilyl chloride (TMC)-normal hexane mixed solution that concentration is 0.15g/mL is immersed Mutually middle MPD, carboxylated graphene oxide are diffused into organic facies interface and occur interface polymerization reaction formation polyamide in situ to divide with TMC Absciss layer；
5) with hexane solution, the TMC monomer of residual is rinsed well, at 80 DEG C, be dried 15min；
6) compound reverse osmosis film modified for the carboxylated graphene oxide prepared is deposited preserve in deionized water.

Claims (8)

1. a compound reverse osmosis film, containing base support layer (1), intermediate porous supporting layer (2) and ultra-thin fine and close separation Layer (3), it is characterised in that: described ultra-thin dense separation layers is to be dosed two-dimension nano materials to virtue by original position interfacial polymerization Fragrant polyamide is constituted.
2. it is combined reverse osmosis film according to the one described in claim 1, it is characterised in that: described two-dimension nano materials uses The Graphene of molybdenum bisuphide, titanium dioxide or functionalization.
3. it is combined reverse osmosis film according to the one described in claim 2, it is characterised in that: the Graphene of described functionalization is adopted With amination Graphene, hydroxylating Graphene or carboxylated graphene oxide.
4. it is combined reverse osmosis film according to the one described in claim 1,2 or 3, it is characterised in that: described ultra-thin fine and close separation The thickness of layer is 100-200nm.
5. it is combined reverse osmosis film according to the one described in claim 1,2 or 3, it is characterised in that: described intermediate porous holds Torr layer is polysulfones macromolecular material.
6. it is combined reverse osmosis film according to the one described in claim 1,2 or 3, it is characterised in that: described base support layer Special non-woven fabric material is processed for water.
7. the preparation method of an a kind of compound reverse osmosis film as claimed in claim 1, it is characterised in that the method include as Lower step:
1) base support layer pretreatment: nonwoven surface is flattened with press；
2) polysulfones macromolecular material is dissolved in N-Methyl pyrrolidone solvent, prepares polysulfones solution；Will be poly-with automatic film applicator Sulfolane solution is coated uniformly on non-woven fabrics top layer, immerses film-forming after deionized water, and film thickness monitoring is in 50～200 μm；60～ It is dried 10～30min under the conditions of 80 DEG C, makes the non-woven fabrics being coated with polysulfone material；
3) two-dimension nano materials is dispersed in m-diaminobenzene. aqueous solution, two-dimension nano materials content control at 0.005wt.%～ 0.03wt.%；
4) non-woven fabrics being coated with polysulfone material soaks 30min～1h in deionized water, is dipped in afterwards containing two wieners The m-diaminobenzene. aqueous solution of rice material keeps 5～10min, after taking-up, removes excess surface solution；Immerse pyromellitic trimethylsilyl chloride again Organic solution keeps 30s～2min；10min～30min it is dried under the conditions of 60～90 DEG C；I.e. prepare two-dimension nano materials to change The compound reverse osmosis film of property.
The preparation method of a kind of compound reverse osmosis film the most as claimed in claim 7, it is characterised in that: step 3) described in The concentration of m-diaminobenzene. aqueous solution control at 0.5g/mL～3g/mL；Step 4) described in pyromellitic trimethylsilyl chloride organic solution Concentration controls at 0.02g/mL～0.15g/mL.
CN201610282259.9A 2016-04-29 2016-04-29 Compound reverse osmosis film and preparation method thereof Pending CN105854626A (en)

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CN108421422A (en) * 2018-01-18 2018-08-21 方大炭素新材料科技股份有限公司 A kind of Nano filtering composite membrane and preparation method thereof of selectivity ion isolation
CN109092087A (en) * 2018-09-28 2018-12-28 南京科技职业学院 A kind of graphene oxide modified polyamide composite nanometer filtering film and preparation method thereof
CN110141976A (en) * 2019-04-28 2019-08-20 浙江大学 Anti-chlorine, antibacterial molybdenum disulfide/crosslinked hyperbranched polyalcohol composite nano filter membrance with photothermal conversion effect and preparation method thereof
CN110180402A (en) * 2019-07-08 2019-08-30 清华大学 A method of loose nanofiltration membrane is prepared based on interfacial polymerization
CN110201544A (en) * 2019-06-17 2019-09-06 万华化学集团股份有限公司 A kind of highly selective nanofiltration membrane of high throughput and preparation method thereof
CN110545903A (en) * 2017-04-19 2019-12-06 香港大学 Membrane permeability-enhanced thin film composite membranes with nano-sized bubbles, methods of making and uses thereof
CN110559888A (en) * 2019-08-29 2019-12-13 浙江工业大学 Amphipathic graphene oxide modified ultrathin composite nanofiltration membrane as well as preparation method and application thereof
CN110975623A (en) * 2019-12-27 2020-04-10 厦门大学 Method for preparing reverse osmosis membrane by introducing carboxylated graphene oxide
CN113019147A (en) * 2021-04-08 2021-06-25 南阳师范学院 Preparation method of composite polyamide nanofiltration membrane
CN113713640A (en) * 2021-09-14 2021-11-30 江苏拓邦环保科技有限公司 High-flux alkali-washing-resistant reverse osmosis membrane and preparation method thereof
CN113797768A (en) * 2020-06-12 2021-12-17 三达膜科技（厦门）有限公司 Molybdenum oxide disulfide doped piperazine polyamide composite ceramic nanofiltration membrane and preparation method thereof
CN113797770A (en) * 2020-06-12 2021-12-17 三达膜科技（厦门）有限公司 Dopamine-modified molybdenum oxide-molybdenum disulfide-doped piperazine polyamide composite ceramic nanofiltration membrane and preparation method thereof
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CN110545903B (en) * 2017-04-19 2021-12-07 香港大学 Membrane permeability-enhanced thin film composite membranes with nano-sized bubbles, methods of making and uses thereof
CN110545903A (en) * 2017-04-19 2019-12-06 香港大学 Membrane permeability-enhanced thin film composite membranes with nano-sized bubbles, methods of making and uses thereof
CN108325399A (en) * 2018-01-12 2018-07-27 时代沃顿科技有限公司 A kind of preparation method of graphene polyamide reverse osmose membrane
CN108097059A (en) * 2018-01-15 2018-06-01 哈尔滨工业大学 A kind of method of modifying that aquaporin reinforced polyamide reverse osmosis membrane water flux is established using molybdenum disulfide
CN108421422A (en) * 2018-01-18 2018-08-21 方大炭素新材料科技股份有限公司 A kind of Nano filtering composite membrane and preparation method thereof of selectivity ion isolation
CN109092087A (en) * 2018-09-28 2018-12-28 南京科技职业学院 A kind of graphene oxide modified polyamide composite nanometer filtering film and preparation method thereof
CN110141976A (en) * 2019-04-28 2019-08-20 浙江大学 Anti-chlorine, antibacterial molybdenum disulfide/crosslinked hyperbranched polyalcohol composite nano filter membrance with photothermal conversion effect and preparation method thereof
CN110201544A (en) * 2019-06-17 2019-09-06 万华化学集团股份有限公司 A kind of highly selective nanofiltration membrane of high throughput and preparation method thereof
CN110201544B (en) * 2019-06-17 2022-01-07 万华化学集团股份有限公司 High-flux high-selectivity nanofiltration membrane and preparation method thereof
CN110180402A (en) * 2019-07-08 2019-08-30 清华大学 A method of loose nanofiltration membrane is prepared based on interfacial polymerization
CN110559888A (en) * 2019-08-29 2019-12-13 浙江工业大学 Amphipathic graphene oxide modified ultrathin composite nanofiltration membrane as well as preparation method and application thereof
CN110559888B (en) * 2019-08-29 2022-05-24 浙江工业大学 Amphipathic graphene oxide modified ultrathin composite nanofiltration membrane as well as preparation method and application thereof
CN110975623A (en) * 2019-12-27 2020-04-10 厦门大学 Method for preparing reverse osmosis membrane by introducing carboxylated graphene oxide
CN113797768A (en) * 2020-06-12 2021-12-17 三达膜科技（厦门）有限公司 Molybdenum oxide disulfide doped piperazine polyamide composite ceramic nanofiltration membrane and preparation method thereof
CN113797770A (en) * 2020-06-12 2021-12-17 三达膜科技（厦门）有限公司 Dopamine-modified molybdenum oxide-molybdenum disulfide-doped piperazine polyamide composite ceramic nanofiltration membrane and preparation method thereof
CN113797770B (en) * 2020-06-12 2023-04-14 三达膜科技（厦门）有限公司 Dopamine-modified molybdenum oxide-molybdenum disulfide-doped piperazine polyamide composite ceramic nanofiltration membrane and preparation method thereof
CN113797768B (en) * 2020-06-12 2023-04-14 三达膜科技（厦门）有限公司 Molybdenum disulfide oxide doped piperazine polyamide composite ceramic nanofiltration membrane and preparation method thereof
CN114130219A (en) * 2020-09-04 2022-03-04 三达膜科技（厦门）有限公司 Titanium dioxide loaded molybdenum disulfide oxide doped piperazine polyamide composite ceramic nanofiltration membrane and preparation method thereof
CN114130219B (en) * 2020-09-04 2023-04-14 三达膜科技（厦门）有限公司 Titanium dioxide-loaded molybdenum oxide disulfide-doped piperazine polyamide composite ceramic nanofiltration membrane and preparation method thereof
CN113019147A (en) * 2021-04-08 2021-06-25 南阳师范学院 Preparation method of composite polyamide nanofiltration membrane
CN113713640A (en) * 2021-09-14 2021-11-30 江苏拓邦环保科技有限公司 High-flux alkali-washing-resistant reverse osmosis membrane and preparation method thereof

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