CN107297154A - A kind of carboxylated graphene oxide NF membrane and its preparation and application - Google Patents
A kind of carboxylated graphene oxide NF membrane and its preparation and application Download PDFInfo
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- CN107297154A CN107297154A CN201710413902.1A CN201710413902A CN107297154A CN 107297154 A CN107297154 A CN 107297154A CN 201710413902 A CN201710413902 A CN 201710413902A CN 107297154 A CN107297154 A CN 107297154A
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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
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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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
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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Abstract
The invention discloses a kind of carboxylated graphene oxide NF membrane and its preparation and application.The carboxylated graphene oxide NF membrane, it is that, using piperazine as aqueous phase monomers, pyromellitic trimethylsilyl chloride is oil phase monomer, and carboxylated graphene oxide is aqueous phase additive, forms active separating layer on polysulphone super-filter membrane using interfacial polymerization and prepares.The invention provides application of the described carboxylated graphene oxide NF membrane in dyestuff in monovalent salt removing.Carboxylated graphene oxide is incorporated into the active cortex of polyamide by the present invention by interfacial polymerization, significantly improve the flux of film, film has high rejection to dyestuffs such as new coccines simultaneously, has low rejection to monovalent salt, shows the huge applications prospect of dye desalination concentration；In addition, carboxylated graphene oxide NF membrane also shows good antifouling property.
Description
Technical field
The invention belongs to NF membrane preparing technical field, and in particular to a kind of its preparation of carboxylated graphene oxide NF membrane
Method and the application in dyestuff in monovalent salt removing.
Background technology
Most of dyestuffs can all add some additives in process of production, and it is small that such as NaCl and some other promotion are reacted
Molecule intermediate.However, these additives can have a strong impact on the quality of dyestuff.Nanofiltration is a kind of new pressure-driven UF membrane
Technology, between counter-infiltration (RO) and ultrafiltration (UF).Organic matter of the nanofiltration generally to monovalent ion and molecular weight less than 150 has
Relatively low rejection, and have higher rejection to the organic matter that divalence or multivalent ion and molecular weight are more than 300.Therefore,
Nanofiltration is widely used in the removing of monovalent salt in dyestuff.For example, business DK NF films can retain 96.5% reactive black 5, and it is right
NaCl retention only 21.1%.TFC PA membranes because its very thin active cortex and with very high separative efficiency, from into
For a kind of most widely used NF films, have broad application prospects in dye desalination concentration field.
In recent years, graphene oxide (GO) is always because of its special performance as a kind of single layer of carbon atom structural material
The focus of research.In UF membrane field, the presence of the upper a large amount of oxygen-containing functional groups of GO, such as internal hydroxyl and epoxy radicals and edge
Carboxyl, greatly strengthen hydrophily and the compatibility with film, so as to improve the performance of film.PA/GO film phases prepared by Bano et al.
PA films are compared to, with higher flux and antifouling property.Kim et al. improves the property of film each side by GO addition
Can, including permeance property, mechanical strength, durability and chlorine resistance.
However, once the GO contents in active layer reach certain value, reunion inevitably occurs, so as to influence the property of film
Energy.Therefore, when the GO or modified GO of higher amount are dispersed in polyamide active layer, film may have better performance.This hair
It is bright that carboxylated modification is carried out to GO to improve agglomerations of the GO in the active cortex of polyamide, prepare carboxylated oxidation stone
Black alkene polyamide nanofiltration membrane, while membrane flux is improved, more shows wide application prospect in dye desalination concentration.Separately
Outside, carboxylated graphene oxide NF membrane also shows good antifouling property.
The content of the invention
For the above-mentioned problems in the prior art, first purpose of the invention is to provide a kind of with high flux
With the carboxylated graphene oxide NF membrane of good antifouling property.
Second object of the present invention is to provide a kind of preparation method of the carboxylated graphene oxide NF membrane.
Third object of the present invention is to provide carboxylated graphene oxide NF membrane monovalent salt in dyestuff and removed
In application.
For achieving the above object, the present invention is adopted the following technical scheme that：
A kind of carboxylated graphene oxide NF membrane, it is that, using piperazine as aqueous phase monomers, pyromellitic trimethylsilyl chloride is oil phase list
Body, carboxylated graphene oxide is aqueous phase additive, form on polysulphone super-filter membrane active separating layer using interfacial polymerization and
Prepare.
A kind of preparation method of the carboxylated graphene oxide NF membrane, comprises the following steps：
(1) using polysulphone super-filter membrane as porous support layer, with aqueous phase solution impregnating porous support layer surface, the aqueous phase solution
In contain carboxylated graphene oxide, piperazine and hydrochloric acid-sodium phosphate, wherein carboxylated graphene oxide and piperazine concentration difference
For 0.01~0.1g/100mL and 0.1~0.5g/100mL, the addition of hydrochloric acid-sodium phosphate causes the pH value of aqueous phase solution 8
~11, remove unnecessary solution after standing 1~10min；
(2) under the conditions of normal pressure, temperature is 15~30 DEG C, with the oil-phase solution immersion step (1) containing pyromellitic trimethylsilyl chloride
Open support layer surface after processing, make two kinds of activated monomer piperazines and pyromellitic trimethylsilyl chloride two-phase interface polymerisation 30~
500s；The oil-phase solution is using n-hexane as solvent, and wherein the concentration of pyromellitic trimethylsilyl chloride is 0.05~0.2g/100mL, and is made
Concentration of the piperazine in aqueous phase solution is pyromellitic trimethylsilyl chloride 1~5 times of concentration in oil-phase solution；
(3) film for obtaining step (2) is heat-treated 5~20min at 50~100 DEG C；
(4) it is cooled to after room temperature, obtains carboxylated graphene oxide NF membrane.The carboxylated graphene oxide NF membrane
It can be stored in deionized water.
Further, described carboxylated graphene oxide can be prepared via a method which：In graphene oxide water solution
Hydrobromic acid and stirring reaction are added, oxalic acid is added and continues stirring reaction, impurity is removed after completion of the reaction carboxylated oxidation is made
Graphene.
Further, per 0.1g graphene oxides addition 0.4~4g hydrobromic acids, the addition of oxalic acid is 2~5g.Wherein hydrogen
Bromic acid can be added in the form of hydrobromic acid aqueous solution.
Further, in graphene oxide solution add hydrobromic acid after, be preferable over 20~30 DEG C of stirring reactions 10~
20h, adds 3~5h of oxalic acid stirring reaction.
Present invention also offers application of the carboxylated graphene oxide NF membrane in dyestuff in monovalent salt removing.
Further, described dyestuff is new coccine.
Further, described monovalent salt is sodium chloride.
Compared with prior art, the beneficial effects of the present invention are：
Carboxylated graphene oxide is incorporated into the active cortex of polyamide by the present invention by interfacial polymerization, compared to drawing
Enter graphene oxide, significantly improve the flux of film, while film has high rejection to dyestuffs such as new coccines, have to monovalent salt
There is low rejection, show the huge applications prospect of dye desalination concentration.In addition, composite membrane resistance tocrocking can be shown that, carboxylated
Graphene oxide NF membrane also shows good antifouling property.
Brief description of the drawings
Fig. 1 is carboxylated graphene oxide preparation process figure of the present invention；
Fig. 2 is carboxylated graphene oxide NF membrane preparation process general thought schematic diagram of the present invention；
Fig. 3 is the scanning electron microscope (SEM) photograph of various films, and wherein a is PS membrane surface electron microscope, and b is PA surfaces electron microscope, and c is
CFGO/PA surfaces electron microscope, d is GO/PA surfaces electron microscope；
Fig. 4 be different films to NaCl removal effects figure in new coccine, wherein a is PA films, and b is GO/PA films, and c is
CFGO/PA films.
Fig. 5 a, 5b, 5c are the antipollution curve of each film prepared by embodiment 1, and wherein 5a is each film in humic acid solution
Time changing curve, 5b be time changing curve of each film in sodium alginate soln, 5c for each film pure water flux at any time
Between change curve.
Embodiment
The preferred embodiments of the present invention are described in detail below, so that present disclosure feature is easy to by this area
In researcher understand, so as to make more full and accurate define to protection scope of the present invention.
Embodiment 1
Mass fraction is added in expansible graphite for 98% concentrated sulfuric acid in 0 DEG C of ice-water bath, height is slowly added
Violent acid potassium, the uniform stirring at 20 DEG C；It is placed on again in water bath with thermostatic control and is heated to 35 DEG C of holding 1h；40mL is added dropwise
Deionized water, temperature rises to 98 DEG C and is stirred for 30min；Mass fraction is added for 30% hydrogenperoxide steam generator to solution to be changed into
The suspension of glassy yellow, is staticly settled, and takes precipitation addition deionized water centrifuge washing to neutrality, then freeze-dried is aoxidized
Graphene powder.
Carboxylated graphene oxide preparation process is carried out as shown in figure 1, gained graphene oxide powder is added into ultra-pure water
Ultrasonic disperse, and add ultra-pure water and be diluted to 2.5mg/mL, 60mL is taken, 10mL mass fractions are added water-soluble for 40% hydrobromic acid
Liquid, is stirred vigorously 12h at 25 DEG C, adds 3.024g oxalic acid stirring 4h.Dialysis removes impurity, obtains carboxylated graphite oxide
Alkene.
Carboxylated graphene oxide NF membrane preparation process general thought is as shown in Fig. 2 using polysulphone super-filter membrane as porous branch
Support layer, by the graphene oxide containing 0.05g/100mL, 0.2g/100mL piperazines and hydrochloric acid-sodium phosphate buffer agent (regulation pH to
10) aqueous phase solution and the carboxylated graphene oxide containing 0.05g/100mL, 0.2g/100mL piperazines and hydrochloric acid-sodium phosphate
The aqueous phase solution of buffer (regulation pH to 10) infiltrates in open support layer surface respectively, stand removed after 5min it is unnecessary molten
Liquid；Then under the conditions of normal pressure, temperature is 25 DEG C, infiltrated with the n-hexane oil-phase solution of the pyromellitic trimethylsilyl chloride containing 0.1g/100mL
Supporting layer, makes two kinds of activated monomers in two-phase interface polymerisation 60s；Film is heat-treated 10min for 80 DEG C in drying box again；It is cold
But to after room temperature, storage in deionized water, respectively obtains graphene oxide NF membrane (GO/PA films) and carboxylated graphite oxide
Alkene NF membrane (CFGO/PA films).
Using polysulphone super-filter membrane as porous support layer, 0.2g/100mL piperazines and the (regulation of hydrochloric acid-sodium phosphate buffer agent will be contained
In open support layer surface, unnecessary solution is removed after standing 5min to aqueous phase solution infiltration 10) by pH；Then in normal pressure, temperature
Spend under the conditions of 25 DEG C, to infiltrate supporting layer with the n-hexane oil-phase solution of the pyromellitic trimethylsilyl chloride containing 0.1g/100mL, make two kinds of work
Property monomer is in two-phase interface polymerisation 60s；Film is heat-treated 10min for 80 DEG C in drying box again；It is cooled to after room temperature, stores
In deionized water, obtain being not added with the NF membrane (PA films) of nano particle.
And then, three kinds of film PA films, the removings of GO/PA films, CFGO/PA films all to NaCl in new coccine are tested.
The desalination and concentration experiment of dyestuff is simulated with 500ppm NaCl and 500ppm new coccine mixed liquors, and test temperature is 25 DEG C,
Pressure is 1Mpa.As a result as schemed, more than 97%, 30% or so, difference are trapped in NaCl to new coccine for three kinds of films
Less, it is notable that either graphene oxide or carboxylated graphene oxide all greatly enhance film and led to
Amount, the flux of PA films is 30.5L/m2The flux of/h, GO/PA film is 75.5L/m2The flux of/h, CFGO/PA film is 90.8L/m2/
H, the flux of carboxylated graphene oxide NF membrane is maximum.
Also, choose humic acid (HA) aqueous solution and sodium alginate (SA) aqueous solution as simulating pollution thing system, evaluate PA,
GO/PA and CFGO, PA composite membrane antifouling property.Operating pressure is set as in 1MPa, the HA aqueous solution that HA concentration is 500ppm,
SA concentration is 500ppm in the SA aqueous solution.As a result as shown in figure 5, carboxylated graphene oxide NF membrane shows good anti-soil
Metachromia energy.
Embodiment 2
The concentration of piperazine in examples detailed above 1 is changed to 0.5g/100mL, other steps are constant, respectively obtain CFGO/PA
Film, GO/PA films and PA films.
Embodiment 3
By the concentration 0.15g/100mL of the pyromellitic trimethylsilyl chloride in examples detailed above 1, other steps are constant, respectively obtain
CFGO/PA films, GO/PA films and PA films.
Embodiment 4
The median surface polymerization reaction time of examples detailed above 1 is changed to 120s, other steps are constant, respectively obtain CFGO/PA films,
GO/PA films and PA films.
Embodiment 5
The heat treatment temperature of film in an oven in examples detailed above 1 is changed to 100 DEG C, other steps are constant, respectively obtain
CFGO/PA films, GO/PA films and PA films.
Embodiment 6
The heat treatment time of film in an oven in examples detailed above 1 is changed to 20min, other steps are constant, respectively obtain
CFGO/PA films, GO/PA films and PA films.
Embodiment 7
The graphene oxide concentration added in examples detailed above 1 is changed to 0.1g/100mL, other steps are constant, obtain GO/
PA films.
Embodiment 8
The carboxylated graphene oxide concentration added in examples detailed above 1 is changed to 0.1g/100mL, other steps are constant, obtain
To CFGO/PA films.
CFGO/PA films, GO/PA films and PA films are to new coccine, NaCl rejection and pure water made from above-described embodiment
Flux data is as shown in the table：
Table 1.
Claims (8)
1. a kind of carboxylated graphene oxide NF membrane, it is that, using piperazine as aqueous phase monomers, pyromellitic trimethylsilyl chloride is oil phase monomer,
Carboxylated graphene oxide is aqueous phase additive, forms active separating layer on polysulphone super-filter membrane using interfacial polymerization and prepares
Obtain.
2. a kind of preparation method of carboxylated graphene oxide NF membrane as claimed in claim 1, comprises the following steps：
(1) using polysulphone super-filter membrane as porous support layer, with aqueous phase solution impregnating porous support layer surface, contain in the aqueous phase solution
There are carboxylated graphene oxide, piperazine and hydrochloric acid-sodium phosphate, the concentration of wherein carboxylated graphene oxide and piperazine is respectively
0.01~0.1g/100mL and 0.1~0.5g/100mL, the addition of hydrochloric acid-sodium phosphate cause the pH value of aqueous phase solution 8~
11, remove unnecessary solution after standing 1~10min；
(2) under the conditions of normal pressure, temperature is 15~30 DEG C, handled with the oil-phase solution immersion step (1) containing pyromellitic trimethylsilyl chloride
Open support layer surface afterwards, make two kinds of activated monomer piperazines and pyromellitic trimethylsilyl chloride two-phase interface polymerisation 30~
500s；The oil-phase solution is using n-hexane as solvent, and wherein the concentration of pyromellitic trimethylsilyl chloride is 0.05~0.2g/100mL, and is made
Concentration of the piperazine in aqueous phase solution is pyromellitic trimethylsilyl chloride 1~5 times of concentration in oil-phase solution；
(3) film for obtaining step (2) is heat-treated 5~20min at 50~100 DEG C；
(4) it is cooled to after room temperature, obtains carboxylated graphene oxide NF membrane.The carboxylated graphene oxide NF membrane can store
Deposit in deionized water.
3. preparation method as claimed in claim 2, it is characterised in that：Described carboxylated graphene oxide is by the following method
Prepare：Hydrobromic acid and stirring reaction are added in graphene oxide water solution, oxalic acid is added and continues stirring reaction, reaction is finished
Impurity is removed afterwards, and carboxylated graphene oxide is made.
4. preparation method as claimed in claim 3, it is characterised in that：Per 0.1g graphene oxides addition 0.4~4g hydrobromic acids,
The addition of oxalic acid is 2~5g.
5. preparation method as claimed in claim 4, it is characterised in that：Added in graphene oxide solution after hydrobromic acid, in
20~30 DEG C of 10~20h of stirring reaction, add 3~5h of oxalic acid stirring reaction.
6. application of the carboxylated graphene oxide NF membrane as claimed in claim 1 in dyestuff in monovalent salt removing.
7. application as claimed in claim 6, it is characterised in that：Described dyestuff is new coccine.
8. application as claimed in claim 6, it is characterised in that：Described monovalent salt is sodium chloride.
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| CN108404688A (en) * | 2018-03-29 | 2018-08-17 | 同济大学 | A kind of modified semi-aromatic polyamide film and preparation method thereof |
| 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 |
| CN108786499A (en) * | 2018-06-15 | 2018-11-13 | 武汉工程大学 | The preparation method of the controllable carboxylated graphene oxide NF membrane of flux |
| CN109772177A (en) * | 2019-03-12 | 2019-05-21 | 江西理工大学 | A kind of preparation method and application of the modified nanofiltration membrane of graphene oxide |
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| CN108786499A (en) * | 2018-06-15 | 2018-11-13 | 武汉工程大学 | The preparation method of the controllable carboxylated graphene oxide NF membrane of flux |
| CN110385047A (en) * | 2018-12-30 | 2019-10-29 | 启成（江苏）净化科技有限公司 | A method of high-flux reverse osmosis membrane is prepared with graphene oxide chloride product |
| CN109772177A (en) * | 2019-03-12 | 2019-05-21 | 江西理工大学 | A kind of preparation method and application of the modified nanofiltration membrane of graphene oxide |
| CN110773000B (en) * | 2019-11-08 | 2021-09-24 | 成都石大力盾科技有限公司 | Efficient and anti-pollution carboxylated graphene oxide nanofiltration membrane, and preparation method and application thereof |
| CN110773000A (en) * | 2019-11-08 | 2020-02-11 | 成都石大力盾科技有限公司 | Efficient and anti-pollution carboxylated graphene oxide nanofiltration membrane, and preparation method and application thereof |
| CN110975620A (en) * | 2019-12-25 | 2020-04-10 | 恩泰环保科技（常州）有限公司 | Nanofiltration membrane based on weak base buffer system and preparation method thereof |
| CN110975623A (en) * | 2019-12-27 | 2020-04-10 | 厦门大学 | Method for preparing reverse osmosis membrane by introducing carboxylated graphene oxide |
| CN113797771A (en) * | 2020-06-12 | 2021-12-17 | 三达膜科技（厦门）有限公司 | Graphene oxide-titanium dioxide-silver doped piperazine polyamide composite nanofiltration membrane and preparation method thereof |
| CN113797769A (en) * | 2020-06-12 | 2021-12-17 | 三达膜科技（厦门）有限公司 | Dopamine-modified titanium dioxide graphene oxide polyamide nanofiltration membrane and preparation method thereof |
| CN113797771B (en) * | 2020-06-12 | 2023-04-14 | 三达膜科技（厦门）有限公司 | Graphene oxide-titanium dioxide-silver doped piperazine polyamide composite nanofiltration membrane and preparation method thereof |
| CN113797769B (en) * | 2020-06-12 | 2023-05-23 | 三达膜科技（厦门）有限公司 | Dopamine modified titanium dioxide graphene oxide polyamide nanofiltration membrane and preparation method thereof |
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