CN106606931B - High stability sea water desalination membrane and its preparation method and application - Google Patents
High stability sea water desalination membrane and its preparation method and application Download PDFInfo
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- CN106606931B CN106606931B CN201510710485.8A CN201510710485A CN106606931B CN 106606931 B CN106606931 B CN 106606931B CN 201510710485 A CN201510710485 A CN 201510710485A CN 106606931 B CN106606931 B CN 106606931B
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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
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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
- B01D67/0039—Inorganic membrane manufacture
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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
- B01D71/021—Carbon
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The present invention relates to a kind of high stability sea water desalination membrane and its preparation method and applications, more particularly to it is a kind of by the amine-modified solid phase carrier technique of DOPA to prepare even compact, the graphene oxide membrane with high stability, high sea water desalination performance, and the preparation method that a kind of graphene oxide membrane is provided and its application in sea water desalination.
Description
Technical field
The present invention relates to a kind of high stability sea water desalination membrane and its preparation method and applications, pass through DOPA more particularly to one kind
Amine-modified solid phase carrier technique to prepare even compact, the graphene oxide membrane with high stability, high sea water desalination performance, and
The preparation method that a kind of graphene oxide membrane is provided and its application in sea water desalination.
Background technique
One of substance necessary to water is the mankind and biology is depended on for existence, however, as modernization industry in recent years is built
If development, water pollution degree increasingly sharpens, and China western city and many outlying districts are faced with shortage of water resources
Crisis.The water shortage situation of such sternness is faced, China takes a series of mitigation strategies, such as increases income and decreases expenditure, scientific application of irrigation, life
State protection reduces waste and prevents and remedies pollution.People have found that this big precious deposits of seawater resources when very early, according to statistics,
Earth Shanghai ocean surface product accounts for about 71% or so of earth total surface area, it may be said that is an inexhaustible resource.In vastness
Inside ocean, not only there are the chemical resources such as minerals abundant, but also fresh water danger can also be solved by conversion, development and utilization
Machine.When 16th century, people have begun to the research and probe that seawater is converted into fresh water, until 20th century mid-term, seawater
Desalination technology has obtained quick development.So far, people develop more than 20 desalination technologies, mainly have reverse osmosis
Method, solar energy method, low-temperature multi-effect, multistage flash distillation, electrodialysis, pressure steam distillation etc..And desalination be in entire desalting process most
For the part of core, the method that people often use UF membrane reaches this purpose.
Membrane seawater desalination technology be using permeable membrane differential permeability by seawater salinity and hydrone separate, from
And achieve the purpose that seawater desalination.The membrane material of early stage is mostly high-molecular organic material, these membrane materials preparation process is simple,
It is easy molding, it is cheap, there is very high desalting performance, however organic film is easy to be influenced by organic solvent, and it is perishable, it uses
Service life is short, needs frequent clean and replacement, thus increases the cost of reverse osmosis legal system water.It is inorganic compared with organic film material
Membrane material (such as zeolite molecular sieve film) has many advantages, such as good thermal stability and chemical stability and longer service life,
The deficiency of existing organic film material can effectively be made up.Although inoranic membrane can effectively overcome the shortcomings of organic film, inoranic membrane
Material fragility is big, elasticity is small, it is difficult to machine-shaping and apparatus components.
Film layer is formed on certain special materials for sea water desalination, still in conclusion having been reported in the prior art
The film of formation is poor in briny environment stability inferior.Therefore, more excellent, structure novel is badly in need of developing a kind of performance in this field, point
Cloth uniformly can be used for the novel sea water desalinization membrane material that the film layer of sea water desalination, especially stability are high and salt rejection rate is high.
Summary of the invention
The purpose of the present invention is to provide a kind of stability is high and salt rejection rate is high novel sea water desalinization membrane materials and its system
Method and application.
In the first aspect of the present invention, a kind of graphene oxide composite membrane is provided, the composite membrane includes:
(1) solid phase carrier layer, the solid phase carrier is inorganic carrier, wherein the solid phase carrier has at least one through repairing
Adorn the main surface of agent modification；With
(2) graphene oxide layer combined with the main surface through dressing agent modification,
Wherein, the dressing agent is the molecule with two or more functional groups selected from the group below: amino, quinonyl, hydroxyl
Base, or combinations thereof.
In another preferred example, the solid phase carrier is porous carrier.
In another preferred example, the solid phase carrier includes that ceramic monolith, metal oxide carrier and/or metal carry
Body.
In another preferred example, the solid phase carrier is selected from the group: porous alumina carrier.
In another preferred example, the solid phase carrier is selected from the group: porous alumina ceramic, poriferous titanium dioxide pottery
Porcelain, porous stainless steel or combinations thereof.
In another preferred example, the graphene oxide layer with a thickness of 100-1000nm, preferably 200-600nm,
More preferably 250-500nm.
In another preferred example, the solid phase carrier layer with a thickness of 0.1-10mm, preferably 0.2-5mm, more preferably
0.5-2.5mm, most preferably about 1mm.
In another preferred example, the dressing agent is while having the molecule of amino and hydroxy functional group.
In another preferred example, the dressing agent is polyhydroxy single-amino compound or its polymer.
In another preferred example, the dressing agent includes dopamine, poly-dopamine or combinations thereof.
In another preferred example, in the graphene oxide composite membrane, the content of dressing agent is 10g/m2Film surface, or
5g/m2Graphene, wherein dressing agent is by the dressing agent meter before modification.
In another preferred example, the graphene oxide composite membrane has the following performance:
(a) salt rejection rate: >=95%, preferably >=99%, more preferably >=99.5%；
(b) water penetration: water penetration >=2kg/ (m at 70-90 DEG C (being preferably about 75 DEG C)2H) (such as 2-100kg/
(m2H)), preferably >=5kg/ (m2H), more preferably >=10kg/ (m2·h)；(such as 20-100kg/ (m2·h))
(c) stability: at 75 DEG C, in 2 weeks, water flux keep constant it is constant (or amplitude of variation be ± 10% within, compared with
Goodly within ± 5%), stablize in 2-100kg/ (m2H) (preferably 5-100kg/ (m between2H) between, more preferably 20-
100kg/(m2H) between), and salt rejection rate is >=95%, preferably >=99%, more preferably >=99.5%.
Test method: salt rejection rate and water flux reflect the interception capacity and water-yielding capacity of sea water desalination membrane, its calculating
It can be reflected using conductivity meter.The calculation formula of salt rejection rate:Pass through measurement feeding liquid and infiltration
The conductivity for producing water thoroughly brings formula calculating into.
Water flux calculation formula:Pass through the graphene oxide membrane for being A by area in measurement certain time △ t
Infiltration produces the quality W of water, calculates and obtains.
GB5749-2006 standards for drinking water quality does not provide conductivity indices, but has dissolubility always solid in standard
Body and total hardness index, 2 times for being estimated as total dissolved solid or so that conductivity can be rough, that is, 2000us/cm are left
The right side, water source of the conductivity lower than 800us/cm are considered as preferable water quality.
In another preferred example, the graphene oxide composite membrane is the method system described in second aspect of the present invention
It is standby.
In the second aspect of the present invention, a kind of preparation method of composite membrane as described in the first aspect of the invention is provided,
It comprises the steps of:
(1) solid phase carrier is provided；
(2) functional modification is carried out at least one main surface of the solid phase carrier, thus solid phase carrier extremely
A few main surface introduces and the covalently bound dressing agent of the main surface, the carrier surface modified, wherein the modification
Agent be with the molecule for being two or more functional groups selected from the group below: amino, quinonyl, hydroxyl, or combinations thereof；
(3) on the modified carrier surface of step (2) preparation, deposited oxide graphene particles, thus formation and institute
State the graphene oxide layer that the main surface through dressing agent modification combines.
In another preferred example, the partial size of the graphene oxide particle is size at 0.2-5 microns, preferably
0.5-3 microns, be more preferably 0.55-1.5 microns.
In another preferred example, in step (3), the deposition under the conditions of vacuum filtration comprising steps of deposited.
In another preferred example, in step (2), the dressing agent is (a) dopamine and/or poly-dopamine；(b)
The mixture of trishydroxymethylaminomethane.
In another preferred example, in the mixture, component (a) dopamine and/or poly-dopamine and three hydroxyl first of component (b)
The weight ratio of base aminomethane is 0.5-5:1-10, preferably 1:1-10, is more preferably 1:2-5.
In another preferred example, the method comprises the steps of:
(1) functional modification is carried out to the surface of solid phase carriers using dopamine, thus poly- more in carrier surface building
Bar amine chemistry reaction platform；
(2) the surface of solid phase carriers deposited oxide graphene film surface-functionalized in poly-dopamine by vacuum filtration method；
(3) after being filtered by vacuum, solidify 5-24h, the graphene oxide membrane of even compact is prepared；
(4) the sea water desalination performance of graphene oxide membrane is tested by pervaporation method.
In another preferred example, in step (1), the solid phase carrier is immersed in dopamine hydrochloride and three (methylols)
In the mixed solution of aminomethane, a strata dopamine is modified in the surface of solid phase carriers after submergence a period of time.
In another preferred example, the amine-modified temperature of DOPA is room temperature in the step (1).
In another preferred example, the pH of aqueous dopamine solution is 7.5-9.5, preferably 8.0- in the step (1)
9.0, it is more preferably 8.2-8.9.
In another preferred example, the aqueous dopamine solution adjusts pH value: trishydroxymethylaminomethane with following substance.
In another preferred example, in the mixed solution, the weight of dopamine hydrochloride and three (methylol) aminomethanes
Than for 1:10 to 10:1, preferably 1:1 to 1:5.
In another preferred example, the graphene oxide of vacuum filtration deposited oxide graphene film suspends in the step (2)
Liquid concentration is 0.01-2.0mg/mL, preferably 0.01-1.0mg/mL.
In another preferred example, vacuum filtration pressure is 0.1Mpa in the step (2).
In another preferred example, solidification temperature is 10-150 DEG C, preferably 40-100 DEG C in the step (3).
In another preferred example, in the step (3), after vacuum filtration, solidify 5-24h at a temperature of 40-100 DEG C.
In the third aspect of the present invention, a kind of desalination plant is provided, the device includes of the invention first
Graphene oxide composite membrane described in aspect.
In the fourth aspect of the present invention, graphene oxide composite membrane described in a kind of the first aspect of the present invention is provided
Purposes is used for sea water desalination.
In the fifth aspect of the invention, the method that a kind of pair of seawater carries out desalination and/or prepare fresh water, including step are provided
Rapid: for seawater to be diluted, the graphene oxide composite membrane described in the first aspect of the present invention is handled, thus to sea
Water carries out desalination, and obtains fresh water.
In another preferred example, the processing includes: infiltration evaporation or hyperfiltration.
In another preferred example, operation temperature is 20-100 DEG C, preferably 30 DEG C, 45 DEG C, 60 DEG C, 75 DEG C or 90 DEG C.
It should be understood that above-mentioned each technical characteristic of the invention and having in below (eg embodiment) within the scope of the present invention
It can be combined with each other between each technical characteristic of body description, to form a new or preferred technical solution.As space is limited, In
This no longer tires out one by one states.
Detailed description of the invention
Fig. 1 shows the SEM photograph in the graphene oxide membrane of the porous alumina carrier surface synthesis of PDA modification.
Fig. 2 shows the side SEM in the graphene oxide membrane for the porous alumina carrier surface synthesis modified without PDA
Photo.
Fig. 3 is shown modifying without PDA and the graphene oxide of the porous alumina carrier surface synthesis through PDA modification
Film impregnates the photo after seawater.
Fig. 4 is shown in the graphene oxide membrane for the porous alumina carrier surface synthesis modified through PDA in 30-90 DEG C of temperature
Sea water desalination performance schematic diagram under degree.
Specific embodiment
The present inventor is obtained by extensive and in-depth research by the way that a large amount of different materials are combined and are screened for the first time
It obtained a kind of with high stability, the graphene oxide composite membrane that preparation method is simple, sea water desalination performance is high.Specifically, of the invention
Graphene oxide composite membrane be in the inorganic solid phase carrier (such as α-Al modified through specific modification agent2O3Equal porous carriers)
Upper deposited oxide graphene particles and prepare.On this basis, inventor completes the present invention.
Experiment shows the graphene oxide composite membrane of high stability of the invention, high sea water desalination performance, and not only solid phase carries
Body layer is highly stable, and graphene oxide layer is also highly stable, be both not easy to fall off in the complex environment of sea water desalination,
Corrugation or fracture, and the channel that there is the graphene oxide composite film aperture to be suitable for, have high water flux and salt rejection rate
(especially there is more preferably high water flux at high temperature).Therefore, it is particularly suitable for heavy industrialization application.
Before describing the present invention, it should be understood that the present invention is not limited to the specific method and experiment conditions, because this
Class method and condition can change.It should also be understood that its purpose of the term as used herein is only that description specific embodiment, and
And it is not intended to be restrictive, the scope of the present invention will be limited only by the claims which follow.
Term
As used herein, term " containing ", "comprising" or " comprising " refer to " having ", " containing ", " substantially by ... structure
At " and " by ... constitute (or composition) ".In other words, these terms can be open, be also possible to enclosed.
Graphene oxide
Graphene is a kind of monoatomic layer material of two-dimensional carbon hexatomic ring array arrangement by SP2 hydridization, because its is excellent
The performances such as machinery, electronics and optics more and widely paid close attention to and studied.Although the monoatomic layer thickness of graphene film is
Membrane material prepares pursued target, but ideal regular graphene film is that compact film can not penetrate any gas and liquid
Body.
Graphene energy of oxidation is accessed into graphene oxide.It is formed on the carbocyclic ring and edge of graphene after oxidation a variety of oxygen-containing
Group, material are transformed into hydrophily by hydrophobicity, and the distance of interlayer increases by 0.34nm to 0.6-0.7nm, therefore has very
Big separation application potential.
Graphene is concerned because of its distinctive structure, superior performance and broad application prospect.Graphite oxide
Alkene is the oxidation product of graphene, and it is new that the functional groups such as-COOH ,-OH and C-O-C possessed in surface of graphene oxide assign it
Chemical property, by film made of graphene oxide have preferable hydrophily, chemical stability and pollution resistance.Graphite oxide
Alkene can be by drop coating, spin coating, and the technologies such as dip-coating and vacuum filtration method, which are supported in organic or inorganic substrate, forms one layer of densification
Film, and be widely used in liquid separation, gas separation etc. separation fields application.
Graphene oxide membrane can also be divided into symmetry film and asymmetric membrane as membrane material, and wherein symmetric membrane is not need
Substrate carrier support, it is also self-supported membrane, the composition of entire film is pure stannic oxide/graphene nano lamellar structure, rather than right
Claiming film is the graphene oxide laminate structure formed on the support carrier.Self-supported membrane usually requires to be made into thicker graphite oxide
Alkene film could be applied, and the thickness of anisotropic membrane layer is up to nanoscale.Substrate used by common anisotropic membrane is organic nothing
Woven fabric material or porous inorganic material, the mechanical strength of organic non-woven fabric carrier, resistance to stability are often all good not as good as inorganic material,
Therefore it is also limited as substrate carrying body.Porous inorganic material is most commonly that alumina ceramic carrier, but common oxidation
Bond strength is inadequate between aluminium and graphene oxide layer, and the stability of graphene oxide film layer structure in aqueous solution is poor, such as
Graphene oxide film is directly supported on the porous carriers such as aluminium oxide and is used for sea water desalination by fruit, since graphene oxide is readily soluble
Yu Shui, graphene oxide membrane can then be easy to wrinkle and gradually split away off from carrier.
It is suitable for the invention graphene oxide to be not particularly limited, may include a variety of different graphene oxides, example
Such as using the graphene oxide or commercially available graphene oxide of conventional method preparation.
When using the method for the present invention, graphene oxide can be easy and fine and close and firm connection is efficiently formed in load
Graphene oxide membrane on body material, to have excellent desalting performance.
Porous carrier
As used in the present invention, the porous carrier includes ceramic monolith, metal oxide carrier and/or metallic carrier.
In another preferred example, the solid phase carrier is selected from the group: porous alumina carrier.
In another preferred example, the solid phase carrier is selected from the group: porous alumina ceramic, poriferous titanium dioxide pottery
Porcelain, porous stainless steel or combinations thereof.
Dressing agent
As used in the present invention, the dressing agent is connect with carrier surface, is while having amino and hydroxy functional group
Molecule.
In another preferred example, the dressing agent is polyhydroxy single-amino compound or its polymer.
In another preferred example, the dressing agent includes dopamine, poly-dopamine, trishydroxymethylaminomethane or its group
It closes, the functional modification includes: to carry out functional modification to solid carrier with dopamine.
Graphene oxide composite membrane
The present invention provides a kind of poly-dopamine-graphene oxide composite membrane, the composite membrane includes:
(1) solid phase carrier layer, the solid phase carrier is inorganic carrier, wherein the solid phase carrier has at least one through repairing
Adorn the main surface of agent modification；With
(2) graphene oxide layer combined with the main surface through dressing agent modification,
Wherein, the dressing agent is the molecule with two or more functional groups selected from the group below: amino, quinonyl, hydroxyl
Base, or combinations thereof.
It should be understood that the present invention is not limited by specific theory or mechanism.However, to facilitate the understanding of the present invention, the present invention
People provides following mechanism: in the present invention, graphene oxide layer be although formed in such a way that similar physical deposits, but
In deposition process, the graphene oxide particle not only mutual mode self assembly, but also for example, by α-Al2O3Etc. nothings
In dressing agent present on machine porous carrier (preferably polyhydroxy single-amino compound, especially dopamine or poly-dopamine) simultaneously
Liang Zhong functional group (such as OH and-NH2) interaction, thus by graphene oxide layer and solid phase carrier layer by covalently and/or
The mode precision that non-covalent bond combines combines.In addition, the structures such as phenyl ring in the molecules such as dopamine, can also with further with oxygen
The effect of graphite alkene layer, it is further provided the stability of graphene oxide composite membrane in water, to help to realize oxidation stone
Application of the black alkene film in desalting process.
The preparation of composite membrane
(1) the modified adhesion property to enhance carrier and graphene oxide of carrier modification
Porous carrier (such as porous alumina carrier) is immersed into the mixing dissolved with dressing agent (such as dopamine hydrochloride) solution
In solution, under certain temperature (such as 20-40 DEG C) processing a period of time (such as 0.5-100 hours, preferably 10-72 hours, more preferably
Ground 20-48 hours), thus in matrix surface introducing-NH2, the organo-functional groups such as-OH, enhance the adhesion strength of porous carrier.
(2) preparation of graphene oxide membrane
By graphene oxide slurry be dissolved in water be made into a certain concentration (such as 0.01-5mg/mL, preferably 0.05-1mg/mL, more
Good ground 0.10-0.5mg/mL) graphene oxide suspension, and ultrasonic disperse, substrate carrier is fixed on vacuum after PDA is modified
In Suction filtration device component, vacuum pump is opened, under negative pressure of vacuum, stannic oxide/graphene nano sector-meeting is gradually covered in carrier table
Face forms one layer of fine and close film layer.Suction filtration finishes, and graphene oxide membrane is dried and/or is solidified, such as is placed in 40-100
It is dried in DEG C baking oven and solidifies 5-24h.
It should be understood that the graphene oxide membrane preparation step can be repeated optionally, such as repeat 1-3 times.
(3) graphene oxide membrane is used for sea water desalination
The graphene oxide membrane of preparation is sealed in osmotic cell, the seawater of graphene oxide membrane is investigated by infiltration evaporation
Desalinate performance.Raw material cavity conveying of the pre-heated seawater from magnetic force circulating pump from raw material tank to osmotic cell；Thermostatic water bath control
The temperature of material liquid and osmotic cell；Permeation chamber is vacuumized with mechanical pump；Liquid nitrogen cold trap is used to collect penetrating fluid.When being spaced certain
Between sampling, weighing, analysis composition.The conductivity of material liquid and penetrating fluid measures the seawater of graphene oxide membrane by conductivity meter
Desalinate performance by water penetration and salt rejection rate by evaluating.Water penetration J and salt rejection rate R is following is determined by formula:
Effective infiltration that wherein quality (Kg) of W penetrating fluid, Δ t are sample interval (h), A is graphene oxide membrane
Area (m2)、κfConductivity, κ for material liquidpFor the conductivity of penetrating fluid.
The graphene oxide membrane even compact prepared using the method for the present invention, thickness is controllable, and stability is good in aqueous solution.
Show closely to cover one layer of smooth continuous graphene oxide film of densification, thickness in alumina carrier surface through SEM detection
Uniform, the average thickness of graphene oxide film about 100-1000nm, preferably 200-600nm, is more preferably 250-500nm.
The stability of the graphene oxide membrane for the porous carrier surface preparation modified using the method for the present invention in PDA in water
It is fabulous, any variation does not occur.
Sea water desalination is used for by infiltration evaporation using graphene oxide membrane prepared by the present invention, the results showed that, it is operating
When temperature is 30,45,60,75 and 90 DEG C, the water flux of most of graphene oxide membranes prepared by the present invention is 10-50kg/
(m2H), salt rejection rate is all larger than 99%, has very high sea water desalination performance.
Purposes
As used in the present invention, it forms a film in the surface of solid phase carriers modified with modified with functional group agent, height can be prepared
The graphene oxide membrane of performance, obtained graphene oxide membrane has good separating property, suitable for plurality of liquid
Separation, is used especially for sea water desalination.
Main advantages of the present invention include:
(1) stability: the stability of combined oxidation graphene film of the invention in aqueous solution is good, is being used for sea water desalination
In, it is not easy to it wrinkles, will not be split away off from carrier.
(2) organic film that co-occurrence has been reported that is compared with inorganic material film, and combined oxidation graphene film flux of the invention is more
Height, selectivity is higher, and performance is more excellent, has more preferably sea water desalination performance.
(3) graphene oxide membrane of the present invention maintains fabulous salt rejection rate within the scope of very wide temperature.
(4) the method for the present invention is easy to operate, and the repeatability that forms a film is high, function admirable, is suitable for industry amplification.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to conventional strip
Part, or according to the normal condition proposed by manufacturer.Unless otherwise stated, otherwise percentage and number are weight percent and weight
Number.
Embodiment 1: preparation graphene oxide membrane
(1) PDA functional modification porous flake alumina substrate
Porous aluminas chip carrier (2.5cm × 2.5cm) is put into dissolved with 0.3g dopamine hydrochloride (dressing agent)
In the mixed solution of 60g deionized water (0.6g tri- (methylol) aminomethane wherein, is added in the mixed solution, thus
PH is adjusted to about 8.4-8.6), it is handled for 24 hours at 25 DEG C, thus in matrix surface introducing-NH2, the organo-functional groups such as-OH,
Enhance the bioadhesion performance of carrier.
(2) vacuum filtration method prepares graphene oxide membrane
The GO slurry of 2.5wt% is dissolved in the graphene oxide suspension and ultrasonic disperse that water is made into 1.0mg/mL, by PDA
The aluminium oxide chip carrier of modification is fixed in vacuum plant component, open vacuum pump, take 2mL graphene oxide suspension drop in
Aluminium oxide chip carrier front surface, under vacuum, the water in suspension can be extracted out through carrier inside and from the back side, oxidation
Graphene nano lamella then gradually can form one layer of fine and close film layer in carrier surface by uniform fold, and suction filtration is finished, will be aoxidized
Graphene film, which is placed in 60 DEG C of baking ovens, to be dried and takes out after solidifying 10h, for characterizing and subsequent performance test.
Embodiment 2: preparation graphene oxide membrane
(1) PDA functional modification porous flake alumina substrate
By porous aluminas chip carrier be put into dissolved with 0.3g dopamine hydrochloride, (methylol) aminomethane of 0.6g tri- and
In the mixed solution of 60g deionized water, 48h is handled at 25 DEG C, thus in matrix surface introducing-NH2, the organic functionals such as-OH
Group, enhances the bioadhesion performance of carrier.
(2) vacuum filtration method prepares graphene oxide membrane
With embodiment 1.
Embodiment 3: preparation graphene oxide membrane
(1) PDA functional modification porous flake alumina substrate
With embodiment 1.
(2) vacuum filtration method prepares graphene oxide membrane
The GO slurry of 2.5wt% is dissolved in the graphene oxide suspension and ultrasonic disperse that water is made into 0.5mg/mL, by PDA
The aluminium oxide chip carrier of modification is fixed in vacuum plant component, open vacuum pump, take 2mL graphene oxide suspension drop in
Aluminium oxide chip carrier front surface, under vacuum, the water in suspension can be extracted out through carrier inside and from the back side, oxidation
Graphene nano lamella then gradually can form one layer of fine and close film layer in carrier surface by uniform fold, and suction filtration is finished, will be aoxidized
Graphene film, which is placed in 60 DEG C of baking ovens, to be dried and takes out after solidifying 10h, for characterizing and subsequent performance test.
Embodiment 4: preparation graphene oxide membrane
(1) PDA functional modification porous flake alumina substrate
With embodiment 1.
(2) vacuum filtration method prepares graphene oxide membrane
The GO slurry of 2.5wt% is dissolved in the graphene oxide suspension and ultrasonic disperse that water is made into 0.25mg/mL, it will
The aluminium oxide chip carrier of PDA modification is fixed in vacuum plant component, is opened vacuum pump, is taken 2mL graphene oxide suspension
It drips in aluminium oxide chip carrier front surface, under vacuum, the water in suspension can be extracted out through carrier inside and from the back side,
Stannic oxide/graphene nano lamella then gradually can form one layer of fine and close film layer in carrier surface by uniform fold, and suction filtration finishes, will
Graphene oxide membrane, which is placed in 60 DEG C of baking ovens, to be dried and takes out after solidifying 10h, for characterizing and subsequent performance test.
Embodiment 5: preparation graphene oxide membrane
(1) PDA functional modification porous flake alumina substrate
With embodiment 1.
(2) vacuum filtration method prepares graphene oxide membrane
The GO slurry of 2.5wt% is dissolved in the graphene oxide suspension and ultrasonic disperse that water is made into 0.1mg/mL, by PDA
The aluminium oxide chip carrier of modification is fixed in vacuum plant component, open vacuum pump, take 2mL graphene oxide suspension drop in
Aluminium oxide chip carrier front surface, under vacuum, the water in suspension can be extracted out through carrier inside and from the back side, oxidation
Graphene nano lamella then gradually can form one layer of fine and close film layer in carrier surface by uniform fold, and suction filtration is finished, will be aoxidized
Graphene film, which is placed in 60 DEG C of baking ovens, to be dried and takes out after solidifying 10h, for characterizing and subsequent performance test.
Embodiment 6: preparation graphene oxide membrane
(1) PDA functional modification porous flake alumina substrate
With embodiment 1.
(2) vacuum filtration method prepares graphene oxide membrane
The GO slurry of 2.5wt% is dissolved in the graphene oxide suspension and ultrasonic disperse that water is made into 0.05mg/mL, it will
The aluminium oxide chip carrier of PDA modification is fixed in vacuum plant component, is opened vacuum pump, is taken 2mL graphene oxide suspension
It drips in aluminium oxide chip carrier front surface, under vacuum, the water in suspension can be extracted out through carrier inside and from the back side,
Stannic oxide/graphene nano lamella then gradually can form one layer of fine and close film layer in carrier surface by uniform fold, and suction filtration finishes, will
Graphene oxide membrane, which is placed in 60 DEG C of baking ovens, to be dried and takes out after solidifying 10h, for characterizing and subsequent performance test.
Embodiment 7: preparation graphene oxide membrane
(1) PDA functional modification porous flake alumina substrate
With embodiment 1.
(2) vacuum filtration method prepares graphene oxide membrane
The GO slurry of 2.5wt% is dissolved in the graphene oxide suspension and ultrasonic disperse that water is made into 0.25mg/mL, it will
The aluminium oxide chip carrier of PDA modification is fixed in vacuum plant component, is opened vacuum pump, is taken 2mL graphene oxide suspension
It drips in aluminium oxide chip carrier front surface, under vacuum, the water in suspension can be extracted out through carrier inside and from the back side,
Stannic oxide/graphene nano lamella then gradually can form one layer of fine and close film layer in carrier surface by uniform fold, and suction filtration finishes, will
Graphene oxide membrane, which is placed in 60 DEG C of baking ovens, to be dried and takes out after solidifying 10h, for characterizing and subsequent performance test.
Embodiment 8: preparation graphene oxide membrane
(1) PDA functional modification porous flake alumina substrate
With embodiment 1.
(2) vacuum filtration method prepares graphene oxide membrane
The GO slurry (graphene oxide slurry) of 2.5wt% is dissolved in the graphene oxide suspension that water is made into 0.08mg/mL
The PDA aluminium oxide chip carrier modified is fixed in vacuum plant component, opens vacuum pump, take 2mL oxygen by liquid and ultrasonic disperse
Graphite alkene hanging drop is in aluminium oxide chip carrier front surface, and under vacuum, the water in suspension can be through in carrier
Portion and extracted out from the back side, stannic oxide/graphene nano lamella then can gradually uniform fold in carrier surface, formed one layer it is fine and close
Film layer, suction filtration finish, and graphene oxide membrane is placed in 60 DEG C of baking ovens and dries and takes out after solidifying 10h, are used to characterize and subsequent
Performance test.
Embodiment 9: preparation graphene oxide membrane
(1) PDA functional modification perforated tubular alumina substrate
By porous aluminas tubular carrier be put into dissolved with 0.3g dopamine hydrochloride, (methylol) aminomethane of 0.6g tri- and
It in the mixed solution of 60g deionized water, is handled for 24 hours at 25 DEG C, thus in matrix surface introducing-NH2, the organic functionals such as-OH
Group, enhances the bioadhesion performance of carrier.
(2) vacuum filtration method prepares graphene oxide membrane
The GO slurry of 2.5wt% is dissolved in the graphene oxide suspension and ultrasonic disperse that water is made into 0.25mg/mL, it will
The aluminium oxide tubular carrier of PDA modification is fixed in vacuum plant component, unlatching vacuum pump, after 30min, under vacuum,
Water in suspension can be extracted out through outside tubular carrier from inside, and stannic oxide/graphene nano lamella then gradually can uniformly cover
It covers in carrier outer surface, forms one layer of fine and close film layer, suction filtration finishes, and graphene oxide membrane is placed in 60 DEG C of baking ovens and is dried simultaneously
It is taken out after solidification 10h, for characterizing and subsequent performance test.
Embodiment 10: preparation graphene oxide membrane
(1) PDA functional modification porous titanium dioxide ceramic matrix
Porous titanium dioxide ceramic carrier is put into dissolved with 0.3g dopamine hydrochloride, 0.6g tri- (methylol) aminomethane
It in the mixed solution of 60g deionized water, is handled for 24 hours at 25 DEG C, thus in matrix surface introducing-NH2, organic official such as-OH
It can roll into a ball, enhance the bioadhesion performance of carrier.
(2) vacuum filtration method prepares graphene oxide membrane
The GO slurry of 2.5wt% is dissolved in the graphene oxide suspension and ultrasonic disperse that water is made into 0.25mg/mL, it will
The porous titanium dioxide ceramic carrier of PDA modification is fixed in vacuum plant component, is opened vacuum pump, is taken 2mL graphene oxide
Hanging drop is in titanium dioxide chip carrier front surface, under vacuum, water in suspension can through carrier inside and from
Back side extraction, stannic oxide/graphene nano lamella then gradually can form one layer of fine and close film layer in carrier surface by uniform fold, take out
Filter finishes, and graphene oxide membrane is placed in 60 DEG C of baking ovens and dries and takes out after solidifying 10h, surveys for characterizing with subsequent performance
Examination.
Embodiment 11: preparation graphene oxide membrane
(1) PDA functional modification porous zirconia ceramic matrix
By porous zirconia ceramic monolith be put into dissolved with 0.3g dopamine hydrochloride, (methylol) aminomethane of 0.6g tri- and
It in the mixed solution of 60g deionized water, is handled for 24 hours at 25 DEG C, thus in matrix surface introducing-NH2, the organic functionals such as-OH
Group, enhances the bioadhesion performance of carrier.
(2) vacuum filtration method prepares graphene oxide membrane
The GO slurry of 2.5wt% is dissolved in the graphene oxide suspension and ultrasonic disperse that water is made into 0.25mg/mL, it will
The porous zirconia ceramic monolith of PDA modification is fixed in vacuum plant component, opens vacuum pump, takes 2mL graphene oxide outstanding
Supernatant liquid is dripped in zirconium oxide chip carrier front surface, and under vacuum, water in suspension can be through carrier inside and from the back side
Extraction, stannic oxide/graphene nano lamella then gradually uniform fold can form one layer of fine and close film layer, filter in carrier surface
Finish, graphene oxide membrane is placed in 60 DEG C of baking ovens and dries and is taken out after solidifying 10h, for characterizing and subsequent performance test.
Embodiment 12:
The Microstructure characterization and seawater performance detection of graphene oxide
It is characterized using graphene oxide membrane surface microscopic topographic and its thickness of the FESEM (S-4800) to preparation；It adopts
Graphene oxide membrane structure composition is analyzed with XRD (Bruker D8ADVANCE).
The sea water desalination method for testing performance of graphene oxide membrane sees below technical solution.By pre-heated seawater by magnetic
Raw material cavity conveying of the power circulating pump from raw material tank to osmotic cell, permeation chamber are vacuumized with mechanical pump.Thermostatic water bath controls material liquid
With the temperature of osmotic cell, liquid nitrogen cold trap is used to collect penetrating fluid.Between sample at regular intervals, weigh, analyze composition.Material liquid
It is measured with the conductivity of penetrating fluid by conductivity meter.The sea water desalination performance of graphene oxide membrane by water penetration and salt rejection rate by
Evaluation.Water penetration J and salt rejection rate R is following is determined by formula:
Effective infiltration that wherein quality (Kg) of W penetrating fluid, Δ t are sample interval (h), A is graphene oxide membrane
Area (m2)、κfConductivity, κ for material liquidfFor the conductivity of penetrating fluid.
Measurement result shows that the salt rejection rate of the graphene oxide membrane of the synthesis of embodiment 1-11 is all larger than 95%, absolutely mostly
Number >=99%, and most of its permeable amount is in 2-70Kgm-2·h-1In range, meet industrial application requirement.
In addition, also having carried out stability test to the graphene oxide membrane of embodiment 2,4,5 and 8, i.e., put when at 75 DEG C
It is placed in seawater 2 weeks, is then measured.Swelling corrugation or obscission do not occur for measurement result, graphene oxide membrane, and
Water flux and salt rejection rate have no significant change (amplitude of variation≤± 5%).
The part measurement result of embodiment 1-11 and comparative example is as shown in table 1.
Sea water desalination performance of the graphene oxide membrane of 1 above-described embodiment of table synthesis at a temperature of 75 DEG C
| Embodiment | Permeable amount (Kgm-2·h-1) | Salt rejection rate (%) |
| 1 | 5.9 | 99.7 |
| 2 | 4.3 | 99.6 |
| 3 | 16.2 | 99.7 |
| 4 | 31.3 | 99.8 |
| 5 | 49.3 | 95.7 |
| 7 | 6.5 | 99.4 |
| 8 | 9.0 | 99.2 |
| 9 | 2.8 | 99.8 |
| 10 | 27.2 | 99.3 |
| 11 | 34.1 | 99.7 |
| Comparative example 1 | 75.6 | 52.1 |
| Comparative example 2 | 2443 | 3.15 |
| Comparative example 3 | 2261 | 2.32 |
The part measurement result of embodiment 4 is as shown in Fig. 1 (graphene oxide membrane is with a thickness of about 400nm) and Fig. 4.From Fig. 4
As can be seen that graphene oxide membrane of the present invention is within the scope of very wide temperature, maintain fabulous salt rejection rate (embodiment 2,
5 is similar with 8 result).
Comparative example 1
Repeat embodiment 1, the difference lies in that omit with the mixed solution containing inorganic agent to porous aluminas chip carrier into
Row processing step directly carries out vacuum filtration preparation graphene oxide membrane with unmodified aluminium oxide.
As a result: porous oxidation aluminium surface does not deposit poly-dopamine active layer, after the graphene oxide membrane of vacuum filtration is dry
It wrinkles, in desalting process, film layer gradually ruptures, and permeable amount is caused to increase, and (only about 50%) is greatly reduced in salt rejection rate.
The permeable amount of the film is about 75.6Kgm-2·h-1。
It is not close in conjunction with carrier in graphene oxide membrane prepared by unmodified oxidation aluminium surface through analyzing, exist compared with
Big gap (Fig. 2).
In addition, aoxidizing stone after the graphene oxide membrane for the porous carrier surface preparation modified without PDA is impregnated in water
Swelling corrugation and obscission (Fig. 3) can occur for black alkene film.
Comparative example 2
Test method is with embodiment 1, the difference lies in that saving with inorganic agent to porous aluminas chip carrier processing step
And the step of omitting preparation graphene oxide membrane, and directly sea water desalination performance test is carried out with the aluminium oxide.
As a result: porous alumina carrier is directly used in desalting process, and water flux is very big, salt rejection rate < 5%, close to
0, no sea water desalination performance.
The permeable amount of the film is about 2443Kgm-2·h-1, show that there are a certain amount of channels for being directed through seawater.
Comparative example 3
Embodiment 1 is repeated, the difference lies in that omitting " vacuum filtration method preparation graphene oxide membrane " step, uses modification instead
The processed aluminium oxide of agent carries out sea water desalination performance test.
As a result: the porous aluminas after poly-dopamine is modified is used for desalting process, and water flux is very big, salt rejection rate <
3% (close to 0), close with comparative example 2, the carrier after showing poly-dopamine modification does not have sea water desalination performance.
The permeable amount of the film is about 2261Kgm-2·h-1, show that there are a certain amount of channels for being directed through seawater.
All references mentioned in the present invention is incorporated herein by reference, independent just as each document
It is incorporated as with reference to such.In addition, it should also be understood that, after reading the above teachings of the present invention, those skilled in the art can
To make various changes or modifications to the present invention, such equivalent forms equally fall within model defined by the application the appended claims
It encloses.
Claims (10)
1. a kind of graphene oxide composite membrane, which is characterized in that the composite membrane includes:
(1) solid phase carrier layer, the solid phase carrier is inorganic carrier, wherein the solid phase carrier has at least one through dressing agent
The main surface of modification；With
(2) graphene oxide layer combined with the main surface through dressing agent modification, the graphene oxide layer are oxidation
Graphene film；
Wherein, the dressing agent be the molecule with two or more functional groups selected from the group below: amino, quinonyl, hydroxyl or
A combination thereof；
And the dressing agent is selected from the group: dopamine, poly-dopamine, or combinations thereof；
The graphene oxide layer with a thickness of 100-1000nm；
The composite membrane is prepared as follows:
(1) solid phase carrier is provided；
(2) functional modification is carried out at least one main surface of the solid phase carrier, thus at least the one of solid phase carrier
A main surface introduces and the covalently bound dressing agent of the main surface, the carrier surface modified, wherein the dressing agent is
With the molecule for being two or more functional groups selected from the group below: amino, quinonyl, hydroxyl, or combinations thereof；
(3) on the modified carrier surface of step (2) preparation, deposited oxide graphene particles, to be formed and the warp
The graphene oxide layer that the main surface of dressing agent modification combines；
And in step (3), the deposition under the conditions of vacuum filtration comprising steps of deposited.
2. graphene oxide composite membrane as described in claim 1, which is characterized in that the solid phase carrier is porous carrier.
3. graphene oxide composite membrane as described in claim 1, which is characterized in that the graphene oxide layer with a thickness of
100-600nm。
4. graphene oxide composite membrane as described in claim 1, which is characterized in that in the graphene oxide composite membrane,
The content of dressing agent is 10g/m2Film surface or 5g/m2Graphene, wherein dressing agent is by the dressing agent meter before modification.
5. graphene oxide composite membrane as described in claim 1, which is characterized in that the graphene oxide layer with a thickness of
100-500nm。
6. graphene oxide composite membrane as claimed in claim 5, which is characterized in that the graphene oxide layer with a thickness of
100-250nm。
7. a kind of preparation method of composite membrane described in claim 1, which comprises the following steps:
(1) solid phase carrier is provided；
(2) functional modification is carried out at least one main surface of the solid phase carrier, thus at least the one of solid phase carrier
A main surface introduces and the covalently bound dressing agent of the main surface, the carrier surface modified, wherein the dressing agent is
With the molecule for being two or more functional groups selected from the group below: amino, quinonyl, hydroxyl, or combinations thereof；
(3) on the modified carrier surface of step (2) preparation, deposited oxide graphene particles, to be formed and the warp
The graphene oxide layer that the main surface of dressing agent modification combines；
Also, in step (3), the deposition under the conditions of vacuum filtration comprising steps of deposited.
8. a kind of desalination plant, which is characterized in that the device includes that graphene oxide described in claim 1 is compound
Film.
9. a kind of purposes of graphene oxide composite membrane described in claim 1, which is characterized in that be used for sea water desalination.
10. the method that a kind of pair of seawater carries out desalination and/or prepare fresh water, which is characterized in that comprising steps of for be diluted
Seawater is handled with graphene oxide composite membrane described in claim 1, to carry out desalination to seawater, and obtains fresh water.
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