CN108854595A - Modified PVDF plate membrane of a kind of nano biological charcoal and the preparation method and application thereof - Google Patents
Modified PVDF plate membrane of a kind of nano biological charcoal and the preparation method and application thereof Download PDFInfo
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- CN108854595A CN108854595A CN201810688330.2A CN201810688330A CN108854595A CN 108854595 A CN108854595 A CN 108854595A CN 201810688330 A CN201810688330 A CN 201810688330A CN 108854595 A CN108854595 A CN 108854595A
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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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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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
- B01D69/06—Flat membranes
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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Abstract
The invention belongs to the technical field of membrane separation in wastewater processing technology, and in particular to modified PVDF plate membrane of a kind of nano biological charcoal and the preparation method and application thereof.Nano biological charcoal is added in polymeric casting film liquid in film preparation and blending and modifying is carried out to PVDF the modified PVDF plate membrane of nano biological charcoal is prepared, PVDF plate membrane before modified is at loose porous spongy, and aperture is larger.Modified PVDF plate membrane fenestra hole count is reduced and aperture becomes smaller, i.e., the porosity and average number of pores of modified PVDF plate membrane reduce.The modified PVDF plate membrane of the nano biological charcoal can retain the dyestuff in removal water body, low in cost, high treating effect.It has reached 99.8% to methyl orange solution rejection, also has good development prospect for other dyestuffs.
Description
Technical field
The invention belongs to the technical field of membrane separation in wastewater processing technology, and in particular to a kind of nano biological charcoal is modified
PVDF plate membrane and the preparation method and application thereof.
Background technique
Membrane separation technique be considered as " 21 century is most promising, one of most promising great new and high technology, it
Strategic effect is played in industrial technology transformation ".Membrane separation technique plays the optimization of many traditional industries with transition critically important
Effect.There is scientist scholar even to show " who has grasped membrane technology, who has just grasped the future of chemical industry ".UF membrane skill
Art refers under the promotion of outside energy or chemical potential difference, by the osmosis of certain specific film, realizes to two kinds
The component even liquid or gas of various ingredients mixing are separated, are classified, purifying or the isolation technics of enrichment method.UF membrane skill
Art is the novel isolation technics just to grow up in recent decades.Membrane separation technique be widely used in medical treatment, pharmacy, biology,
The numerous areas such as electric power, beverage and food processing, petrochemical industry, bionical, degerming, water process and sea water desalination.
Kynoar (PVDF) is a kind of common membrane material, its antioxidant activity is strong, at room temperature not by
The corrosion of acid, alkali and the substances such as strong oxidizer and halogen, chemical resistance is excellent, and thermal stability is strong, and mechanical strength is big, film forming
Excellent performances can well be waited.It is set to be easy the dirt by other impurities in protein and water treatment system since hydrophobicity is strong
Dye leads to flux depression, and the service life of film reduces, and replacement cost increases.Therefore, PVDF it is modified have become one it is important
Research direction.
Pvdf membrane method of modifying mainly has modified surface, chemical modification and blending and modifying at present.But the modified coating in surface
Layer easily falls off from film surface, persistence is poor；Chemical modification can reduce film-strength and process is complicated；Blending and modifying is easy to operate and anti-
Mild condition is answered, therefore is compared with other methods with some superiority.The nano inoganic particle of blending and modifying has nanometer two at present
Titanium oxide (TiO2), nano aluminium oxide (Al2O3), nano silica (SiO2) etc. oxides, but their cost compares
It is high.
Charcoal is bio-organic materials (biomass) in anoxic or anoxybiotic environment, and what is generated after high temperature pyrolysis consolidates
State product.It can not only be used for the high-quality energy, soil conditioner, also can be used as reducing agent, fertilizer slow release carrier and carbon dioxide envelope
Agent etc. is deposited, carbon fixation and emission reduction, water source purifying, heavy metal adsorption and soil improvement etc. are widely used to.Charcoal is to micro in water
Organic pollutant has good adsorption capacity, good to the adsorption effect of industrial wastewater, and preparation is simple, cheap.So wide
It is general to be applied to all kinds of wastewater treatments.Charcoal is added in polymeric casting film liquid in film preparation, for improving hydrophily, resisting
Bacterium characteristic, permeability and mechanical strength.This provides new thinking for pvdf membrane modification.
Summary of the invention
The object of the present invention is to provide modified PVDF plate membranes of a kind of nano biological charcoal and the preparation method and application thereof.It will receive
Rice charcoal, which is added in polymeric casting film liquid in film preparation, to carry out blending and modifying to PVDF and nano biological charcoal is prepared changes
Property PVDF plate membrane, PVDF plate membrane before modified is at loose porous spongy, and aperture is larger.Modified PVDF plate membrane
Fenestra hole count is reduced and aperture becomes smaller, i.e., the porosity and average number of pores of modified PVDF plate membrane reduce.The nano biological charcoal
Modified PVDF plate membrane can retain the dyestuff in removal water body, low in cost, high treating effect.It is to methyl orange solution rejection
Reach 99.8%, has also had good development prospect for other dyestuffs.
The technical scheme is that：
A kind of preparation method of the modified PVDF plate membrane of nano biological charcoal, includes the following steps：
(1) n,N-Dimethylformamide (DMF) is added into nano biological charcoal, ultrasound is completely dispersed it after sealing, obtains
To active carbon nanoparticles-DMF dispersion；
(2) active carbon nanoparticles-DMF dispersion is added after taking Kynoar (PVDF) and polyethylene glycol (PEG) to mix
System, stirring to solution is in Uniform Flow petroleum shape under water bath condition, and sealing, which is placed on constant temperature in insulating box, escapes bubble
To casting solution；
(3) casting solution is poured on the glass plate of clean dried, carries out film using spreader；
(4) film is totally submerged in deionized water together with glass plate, after film is detached from glass plate and is fully formed,
Selection N/D part is cut into circular film, is placed in solution and impregnates, and finally impregnates in deionized water pvdf membrane, that is, makes
It is standby to obtain the modified PVDF plate membrane finished product of nano biological charcoal.
Preferably, the ratio of nano biological charcoal and DMF are 9~270g/20000~60000mL, ultrasound point in step (1)
Dissipating the time is 1~10h, and the diameter of circular film described in step (4) is greater than 10.2cm, and the solution refers to that mass concentration is 40
The ethanol water that~100% methanol aqueous solution or mass concentration is 40~100%, solution soaking time are 5~60min,
Last deionized water soaking time is 12~72h.
Preferably, the weight ratio that the molecular weight of PEG is 400~10000, PVDF and PEG in step (2) is 2~6:1~3.
It is highly preferred that the molecular weight of PEG is 400 in step (2).
Preferably, the weight ratio of nano biological charcoal and PVDF are 0.1~3% in step (2), and bath temperature is 50-80 DEG C,
Mixing time is 0.5~10h.
It is highly preferred that the weight ratio of nano biological charcoal and PVDF are 3% in step (2).
Preferably, coating thickness is 0.25~1mm in step (3).It is highly preferred that coating thickness is in step (3)
0.75mm。
The modified PVDF plate membrane of the nano biological charcoal that the above method is prepared.
Application of the modified PVDF plate membrane of above-mentioned nano biological charcoal in processing dyeing and printing sewage.
Beneficial effects of the present invention are as follows：
The modified PVDF plate membrane porosity peace of nano biological charcoal of the present invention hole count relative to significantly reducing before modified, energy
Dyestuff in retention removal water body, low in cost, high treating effect.It has reached 99.8% to methyl orange solution rejection, right
Also there is good development prospect in other dyestuffs.
Detailed description of the invention
Fig. 1 is the SEM figure of the PVDF plate membrane before being modified；
Fig. 2 is the SEM figure that the modified PVDF plate membrane of nano biological charcoal is prepared in embodiment 1；
Fig. 3 is the nano biological charcoal PVDF plate membrane of embodiment 1-4 to methyl orange solution rejection and membrane flux chart；
Fig. 4 is embodiment 1,4, the nano biological charcoal PVDF plate membrane of 7-9 to methyl orange solution rejection and membrane flux figure
Table；
Fig. 5 is embodiment 1, the nano biological charcoal PVDF plate membrane of 10-12 to methyl orange solution rejection and membrane flux figure
Table.
Specific embodiment
With reference to embodiment, technical solution of the present invention is described in further detail, but do not constituted pair
Any restrictions of the invention.
Embodiment 1
A kind of preparation method of the modified PVDF plate membrane of nano biological charcoal, includes the following steps：
(1) 1.35g nano biological charcoal is taken, is placed in 250mL conical flask, 250mLDMF is added, is sealed and is shaken with preservative film
It swings and shakes up, ultrasonic 2h is completely dispersed it, obtains active carbon nanoparticles-DMF dispersion；
(2) above-mentioned 250mL active carbon nanoparticles-DMF points are added after taking the PEG mixing that 45gPVDF and 20g molecular weight is 400
30min stirs to solution in Uniform Flow petroleum shape, at this time in solution with electric blender under 70 DEG C of water bath conditions in granular media system
A large amount of tiny bubbles are generated, are carefully sealed with preservative film, being placed in constant temperature in 70 DEG C of insulating boxs for 24 hours, makes bubble escape to obtain casting film
Liquid；
(3) casting solution is poured on the glass plate of clean dried, carries out film using spreader, control film thickness is
0.75mm；
(4) film is totally submerged in deionized water together with glass plate, after film is detached from glass plate and is fully formed,
Selection N/D part is cut into the circular film that diameter is slightly larger than 10.2cm, is placed in the ethanol water that mass concentration is 70%
Pvdf membrane is finally impregnated 48h displacement ethyl alcohol in deionized water by middle immersion 10min, that is, it is modified that nano biological charcoal is prepared
PVDF plate membrane finished product.
After tested, nano biological charcoal PVDF plate membrane manufactured in the present embodiment reaches the rejection of methyl orange solution
99.8%.
Embodiment 2
A kind of preparation method of the modified PVDF plate membrane of nano biological charcoal, includes the following steps：
(1) 0.9g nano biological charcoal is taken, is placed in 250mL conical flask, 250mLDMF is added, is sealed and is shaken with preservative film
It shakes up, ultrasonic 2h is completely dispersed it, obtains active carbon nanoparticles-DMF dispersion；
(2) above-mentioned 250mL active carbon nanoparticles-DMF points are added after taking the PEG mixing that 45gPVDF and 20g molecular weight is 400
30min stirs to solution in Uniform Flow petroleum shape, at this time in solution with electric blender under 70 DEG C of water bath conditions in granular media system
A large amount of tiny bubbles are generated, are carefully sealed with preservative film, being placed in constant temperature in 70 DEG C of insulating boxs for 24 hours, makes bubble escape to obtain casting film
Liquid；
(3) casting solution is poured on the glass plate of clean dried, carries out film using spreader, control film thickness is
0.75mm；
(4) film is totally submerged in deionized water together with glass plate, after film is detached from glass plate and is fully formed,
Selection N/D part is cut into the circular film that diameter is slightly larger than 10.2cm, is placed in the ethanol water that mass concentration is 70%
Pvdf membrane is finally impregnated 48h displacement ethyl alcohol in deionized water by middle immersion 10min, that is, it is modified that nano biological charcoal is prepared
PVDF plate membrane finished product.
Embodiment 3
A kind of preparation method of the modified PVDF plate membrane of nano biological charcoal, includes the following steps：
(1) 0.9g nano biological charcoal is taken, is placed in 250mL conical flask, 250mLDMF is added, is sealed and is shaken with preservative film
It shakes up, ultrasonic 2h is completely dispersed it, obtains active carbon nanoparticles-DMF dispersion；
(2) above-mentioned 250mL active carbon nanoparticles-DMF points are added after taking the PEG mixing that 45gPVDF and 20g molecular weight is 4000
30min stirs to solution in Uniform Flow petroleum shape, at this time in solution with electric blender under 70 DEG C of water bath conditions in granular media system
A large amount of tiny bubbles are generated, are carefully sealed with preservative film, being placed in constant temperature in 70 DEG C of insulating boxs for 24 hours, makes bubble escape to obtain casting film
Liquid；
(3) casting solution is poured on the glass plate of clean dried, carries out film using spreader, control film thickness is
0.75mm；
(4) film is totally submerged in deionized water together with glass plate, after film is detached from glass plate and is fully formed,
Selection N/D part is cut into the circular film that diameter is slightly larger than 10.2cm, is placed in the ethanol water that mass concentration is 70%
Pvdf membrane is finally impregnated 48h displacement ethyl alcohol in deionized water by middle immersion 10min, that is, it is modified that nano biological charcoal is prepared
PVDF plate membrane finished product.
Embodiment 4
A kind of preparation method of the modified PVDF plate membrane of nano biological charcoal, includes the following steps：
(1) 1.35g nano biological charcoal is taken, is placed in 250mL conical flask, 250mLDMF is added, is sealed and is shaken with preservative film
It swings and shakes up, ultrasonic 2h is completely dispersed it, obtains active carbon nanoparticles-DMF dispersion；
(2) above-mentioned 250mL active carbon nanoparticles-DMF points are added after taking the PEG mixing that 45gPVDF and 20g molecular weight is 4000
30min stirs to solution in Uniform Flow petroleum shape, at this time in solution with electric blender under 70 DEG C of water bath conditions in granular media system
A large amount of tiny bubbles are generated, are carefully sealed with preservative film, being placed in constant temperature in 70 DEG C of insulating boxs for 24 hours, makes bubble escape to obtain casting film
Liquid；
(3) casting solution is poured on the glass plate of clean dried, carries out film using spreader, control film thickness is
0.75mm；
(4) film is totally submerged in deionized water together with glass plate, after film is detached from glass plate and is fully formed,
Selection N/D part is cut into the circular film that diameter is slightly larger than 10.2cm, is placed in the ethanol water that mass concentration is 70%
Pvdf membrane is finally impregnated 48h displacement ethyl alcohol in deionized water by middle immersion 10min, that is, it is modified that nano biological charcoal is prepared
PVDF plate membrane finished product.
Embodiment 5
A kind of preparation method of the modified PVDF plate membrane of nano biological charcoal, includes the following steps：
(1) 0.9g nano biological charcoal is taken, is placed in 250mL conical flask, 250mLDMF is added, is sealed and is shaken with preservative film
It shakes up, ultrasonic 2h is completely dispersed it, obtains active carbon nanoparticles-DMF dispersion；
(2) above-mentioned 250mL active carbon nanoparticles-DMF is added after taking the PEG mixing that 45gPVDF and 20g molecular weight is 10000
Dispersion, under 70 DEG C of water bath conditions with electric blender stir 30min to solution be in Uniform Flow petroleum shape, at this time solution
It is middle to generate a large amount of tiny bubbles, it is carefully sealed with preservative film, being placed in constant temperature in 70 DEG C of insulating boxs for 24 hours, escapes bubble and cast
Film liquid；
(3) casting solution is poured on the glass plate of clean dried, carries out film using spreader, control film thickness is
0.75mm；
(4) film is totally submerged in deionized water together with glass plate, after film is detached from glass plate and is fully formed,
Selection N/D part is cut into the circular film that diameter is slightly larger than 10.2cm, is placed in the ethanol water that mass concentration is 70%
Pvdf membrane is finally impregnated 48h displacement ethyl alcohol in deionized water by middle immersion 10min, that is, it is modified that nano biological charcoal is prepared
PVDF plate membrane finished product.
Embodiment 6
A kind of preparation method of the modified PVDF plate membrane of nano biological charcoal, includes the following steps：
(1) 1.35g nano biological charcoal is taken, is placed in 250mL conical flask, 250mLDMF is added, is sealed and is shaken with preservative film
It swings and shakes up, ultrasonic 2h is completely dispersed it, obtains active carbon nanoparticles-DMF dispersion；
(2) above-mentioned 250mL active carbon nanoparticles-DMF is added after taking the PEG mixing that 45gPVDF and 20g molecular weight is 10000
Dispersion, under 70 DEG C of water bath conditions with electric blender stir 30min to solution be in Uniform Flow petroleum shape, at this time solution
It is middle to generate a large amount of tiny bubbles, it is carefully sealed with preservative film, being placed in constant temperature in 70 DEG C of insulating boxs for 24 hours, escapes bubble and cast
Film liquid；
(3) casting solution is poured on the glass plate of clean dried, carries out film using spreader, control film thickness is
0.75mm；
(4) film is totally submerged in deionized water together with glass plate, after film is detached from glass plate and is fully formed,
Selection N/D part is cut into the circular film that diameter is slightly larger than 10.2cm, is placed in the ethanol water that mass concentration is 70%
Pvdf membrane is finally impregnated 48h displacement ethyl alcohol in deionized water by middle immersion 10min, that is, it is modified that nano biological charcoal is prepared
PVDF plate membrane finished product.
Embodiment 7
A kind of preparation method of the modified PVDF plate membrane of nano biological charcoal, includes the following steps：
(1) 0.045g nano biological charcoal is taken, is placed in 250mL conical flask, 250mLDMF is added, is sealed and is shaken with preservative film
It swings and shakes up, ultrasonic 2h is completely dispersed it, obtains active carbon nanoparticles-DMF dispersion；
(2) above-mentioned 250mL active carbon nanoparticles-DMF points are added after taking the PEG mixing that 45gPVDF and 20g molecular weight is 400
30min stirs to solution in Uniform Flow petroleum shape, at this time in solution with electric blender under 70 DEG C of water bath conditions in granular media system
A large amount of tiny bubbles are generated, are carefully sealed with preservative film, being placed in constant temperature in 70 DEG C of insulating boxs for 24 hours, makes bubble escape to obtain casting film
Liquid；
(3) casting solution is poured on the glass plate of clean dried, carries out film using spreader, control film thickness is
0.75mm；
(4) film is totally submerged in deionized water together with glass plate, after film is detached from glass plate and is fully formed,
Selection N/D part is cut into the circular film that diameter is slightly larger than 10.2cm, is placed in the ethanol water that mass concentration is 70%
Pvdf membrane is finally impregnated 48h displacement ethyl alcohol in deionized water by middle immersion 10min, that is, it is modified that nano biological charcoal is prepared
PVDF plate membrane finished product.
Embodiment 8
A kind of preparation method of the modified PVDF plate membrane of nano biological charcoal, includes the following steps：
(1) 0.45g nano biological charcoal is taken, is placed in 250mL conical flask, 250mLDMF is added, is sealed and is shaken with preservative film
It swings and shakes up, ultrasonic 2h is completely dispersed it, obtains active carbon nanoparticles-DMF dispersion；
(2) above-mentioned 250mL active carbon nanoparticles-DMF points are added after taking the PEG mixing that 45gPVDF and 20g molecular weight is 400
30min stirs to solution in Uniform Flow petroleum shape, at this time in solution with electric blender under 70 DEG C of water bath conditions in granular media system
A large amount of tiny bubbles are generated, are carefully sealed with preservative film, being placed in constant temperature in 70 DEG C of insulating boxs for 24 hours, makes bubble escape to obtain casting film
Liquid；
(3) casting solution is poured on the glass plate of clean dried, carries out film using spreader, control film thickness is
0.75mm；
(4) film is totally submerged in deionized water together with glass plate, after film is detached from glass plate and is fully formed,
Selection N/D part is cut into the circular film that diameter is slightly larger than 10.2cm, is placed in the ethanol water that mass concentration is 70%
Pvdf membrane is finally impregnated 48h displacement ethyl alcohol in deionized water by middle immersion 10min, that is, it is modified that nano biological charcoal is prepared
PVDF plate membrane finished product.
Embodiment 9
A kind of preparation method of the modified PVDF plate membrane of nano biological charcoal, includes the following steps：
(1) 0.675g nano biological charcoal is taken, is placed in 250mL conical flask, 250mLDMF is added, is sealed and is shaken with preservative film
It swings and shakes up, ultrasonic 2h is completely dispersed it, obtains active carbon nanoparticles-DMF dispersion；
(2) above-mentioned 250mL active carbon nanoparticles-DMF points are added after taking the PEG mixing that 45gPVDF and 20g molecular weight is 400
30min stirs to solution in Uniform Flow petroleum shape, at this time in solution with electric blender under 70 DEG C of water bath conditions in granular media system
A large amount of tiny bubbles are generated, are carefully sealed with preservative film, being placed in constant temperature in 70 DEG C of insulating boxs for 24 hours, makes bubble escape to obtain casting film
Liquid；
(3) casting solution is poured on the glass plate of clean dried, carries out film using spreader, control film thickness is
0.75mm；
(4) film is totally submerged in deionized water together with glass plate, after film is detached from glass plate and is fully formed,
Selection N/D part is cut into the circular film that diameter is slightly larger than 10.2cm, is placed in the ethanol water that mass concentration is 70%
Pvdf membrane is finally impregnated 48h displacement ethyl alcohol in deionized water by middle immersion 10min, that is, it is modified that nano biological charcoal is prepared
PVDF plate membrane finished product.
Embodiment 10
A kind of preparation method of the modified PVDF plate membrane of nano biological charcoal, includes the following steps：
(1) 1.35g nano biological charcoal is taken, is placed in 250mL conical flask, 250mLDMF is added, is sealed and is shaken with preservative film
It swings and shakes up, ultrasonic 2h is completely dispersed it, obtains active carbon nanoparticles-DMF dispersion；
(2) above-mentioned 250mL active carbon nanoparticles-DMF points are added after taking the PEG mixing that 45gPVDF and 20g molecular weight is 400
30min stirs to solution in Uniform Flow petroleum shape, at this time in solution with electric blender under 70 DEG C of water bath conditions in granular media system
A large amount of tiny bubbles are generated, are carefully sealed with preservative film, being placed in constant temperature in 70 DEG C of insulating boxs for 24 hours, makes bubble escape to obtain casting film
Liquid；
(3) casting solution is poured on the glass plate of clean dried, carries out film using spreader, control film thickness is
0.25mm；
(4) film is totally submerged in deionized water together with glass plate, after film is detached from glass plate and is fully formed,
Selection N/D part is cut into the circular film that diameter is slightly larger than 10.2cm, is placed in the ethanol water that mass concentration is 70%
Pvdf membrane is finally impregnated 48h displacement ethyl alcohol in deionized water by middle immersion 10min, that is, it is modified that nano biological charcoal is prepared
PVDF plate membrane finished product.
Embodiment 11
A kind of preparation method of the modified PVDF plate membrane of nano biological charcoal, includes the following steps：
(1) 1.35g nano biological charcoal is taken, is placed in 250mL conical flask, 250mLDMF is added, is sealed and is shaken with preservative film
It swings and shakes up, ultrasonic 2h is completely dispersed it, obtains active carbon nanoparticles-DMF dispersion；
(2) above-mentioned 250mL active carbon nanoparticles-DMF points are added after taking the PEG mixing that 45gPVDF and 20g molecular weight is 400
30min stirs to solution in Uniform Flow petroleum shape, at this time in solution with electric blender under 70 DEG C of water bath conditions in granular media system
A large amount of tiny bubbles are generated, are carefully sealed with preservative film, being placed in constant temperature in 70 DEG C of insulating boxs for 24 hours, makes bubble escape to obtain casting film
Liquid；
(3) casting solution is poured on the glass plate of clean dried, carries out film using spreader, control film thickness is
0.5mm；
(4) film is totally submerged in deionized water together with glass plate, after film is detached from glass plate and is fully formed,
Selection N/D part is cut into the circular film that diameter is slightly larger than 10.2cm, is placed in the ethanol water that mass concentration is 70%
Pvdf membrane is finally impregnated 48h displacement ethyl alcohol in deionized water by middle immersion 10min, that is, it is modified that nano biological charcoal is prepared
PVDF plate membrane finished product.
Embodiment 12
A kind of preparation method of the modified PVDF plate membrane of nano biological charcoal, includes the following steps：
(1) 1.35g nano biological charcoal is taken, is placed in 250mL conical flask, 250mLDMF is added, is sealed and is shaken with preservative film
It swings and shakes up, ultrasonic 2h is completely dispersed it, obtains active carbon nanoparticles-DMF dispersion；
(2) above-mentioned 250mL active carbon nanoparticles-DMF points are added after taking the PEG mixing that 45gPVDF and 20g molecular weight is 400
30min stirs to solution in Uniform Flow petroleum shape, at this time in solution with electric blender under 70 DEG C of water bath conditions in granular media system
A large amount of tiny bubbles are generated, are carefully sealed with preservative film, being placed in constant temperature in 70 DEG C of insulating boxs for 24 hours, makes bubble escape to obtain casting film
Liquid；
(3) casting solution is poured on the glass plate of clean dried, carries out film using spreader, control film thickness is
1mm；
(4) film is totally submerged in deionized water together with glass plate, after film is detached from glass plate and is fully formed,
Selection N/D part is cut into the circular film that diameter is slightly larger than 10.2cm, is placed in the ethanol water that mass concentration is 70%
Pvdf membrane is finally impregnated 48h displacement ethyl alcohol in deionized water by middle immersion 10min, that is, it is modified that nano biological charcoal is prepared
PVDF plate membrane finished product.
Performance test
The modified PVDF plate membrane of nano biological charcoal prepared by embodiment 1~12 is tested it in batches and cut to methyl orange solution by this
Stay rate and membrane flux.
The SEM figure of the modified PVDF plate membrane of nano biological charcoal is prepared as shown in Fig. 2 in embodiment 1, before modified
The SEM figure of PVDF plate membrane as shown in Fig. 1, by the comparison of attached drawing 1 and attached drawing 2 as it can be seen that PVDF plate in attached drawing 1 before modified
Film is at loose porous spongy, and aperture is larger, the fibre structure " thicker " of the modified PVDF plate membrane of nano biological charcoal or
Some small gaps are filled up, so that fenestra hole count reduces and aperture becomes smaller, i.e., nano biological charcoal is modified PVDF plate membrane
Porosity and reduce with average number of pores.
Example 1, embodiment 2, the nano biological charcoal PVDF plate membrane of embodiment 3 and embodiment 4, it is right to test its respectively
Methyl orange solution rejection and membrane flux, when obtained different PEG molecular weight the rejection of nano biological charcoal PVDF plate membrane and
Membrane flux is as shown in Fig. 3.It is found that the film effect for preparing nano biological charcoal PVDF plate membrane is best when PEG molecular weight is 400.
Example 1, embodiment 2, embodiment 7, the nano biological charcoal PVDF plate membrane of embodiment 8 and embodiment 9, point
Do not test its methyl orange solution rejection and membrane flux to 19.958mg/L, 36.757mg/L, obtained nano biological charcoal with
The rejection of nano biological charcoal PVDF plate membrane and membrane flux are as shown in Fig. 4 when PVDF different weight ratio,.It is found that nanometer
When charcoal and PVDF weight ratio are 3%, the film effect for preparing nano biological charcoal PVDF plate membrane is best.
Example 1, embodiment 10, the nano biological charcoal PVDF plate membrane of embodiment 11 and embodiment 12, are tested respectively
Its to methyl orange solution rejection and membrane flux, when obtained different film thicknesses the rejection of nano biological charcoal PVDF plate membrane and
Membrane flux is as shown in Fig. 5.It is found that the film effect for preparing nano biological charcoal PVDF plate membrane is best when film thickness is 0.75mm.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of the modified PVDF plate membrane of nano biological charcoal, which is characterized in that include the following steps：
(1) DMF is added into nano biological charcoal, ultrasound is completely dispersed it after sealing, obtains active carbon nanoparticles-DMF dispersion
System；
(2) active carbon nanoparticles-DMF dispersion is added after taking PVDF and PEG to mix, stirring is to solution in equal under water bath condition
Even live oil shape, sealing, which is placed on constant temperature in insulating box, makes bubble escape to obtain casting solution；
(3) casting solution is poured on the glass plate of clean dried, carries out film using spreader；
(4) film is totally submerged in deionized water together with glass plate, after film is detached from glass plate and is fully formed, selection
N/D part is cut into circular film, is placed in solution and impregnates, and finally impregnates in deionized water pvdf membrane, that is, is prepared into
To the modified PVDF plate membrane finished product of nano biological charcoal.
2. a kind of preparation method of the modified PVDF plate membrane of nano biological charcoal according to claim 1, which is characterized in that step
Suddenly the ratio of nano biological charcoal and DMF are 9~270g/20000~60000mL in (1), and the ultrasonic disperse time is 1~10h, step
Suddenly the diameter of circular film described in (4) is greater than 10.2cm, and the methanol that the solution refers to that mass concentration is 40~100% is water-soluble
The ethanol water that liquid or mass concentration are 40~100%, solution soaking time is 5~60min, when last deionized water is impregnated
Between be 12~72h.
3. a kind of preparation method of the modified PVDF plate membrane of nano biological charcoal according to claim 1, which is characterized in that step
Suddenly the weight ratio that the molecular weight of PEG is 400~10000, PVDF and PEG in (2) is 2~6:1~3.
4. a kind of preparation method of the modified PVDF plate membrane of nano biological charcoal according to claim 1, which is characterized in that step
Suddenly the molecular weight of PEG is 400 in (2).
5. a kind of preparation method of the modified PVDF plate membrane of nano biological charcoal according to claim 1, which is characterized in that step
Suddenly in (2) weight ratio of nano biological charcoal and PVDF be 0.1~3%, bath temperature be 50-80 DEG C, mixing time be 0.5~
10h。
6. a kind of preparation method of the modified PVDF plate membrane of nano biological charcoal according to claim 1, which is characterized in that step
Suddenly the weight ratio of nano biological charcoal and PVDF are 3% in (2).
7. a kind of preparation method of the modified PVDF plate membrane of nano biological charcoal according to claim 1, which is characterized in that step
Suddenly coating thickness is 0.25~1mm in (3).
8. a kind of preparation method of the modified PVDF plate membrane of nano biological charcoal according to claim 1, which is characterized in that step
Suddenly coating thickness is 0.75mm in (3).
9. the modified PVDF plate membrane of the nano biological charcoal that any method described in claim 1 to 8 is prepared.
10. a kind of application of the modified PVDF plate membrane of nano biological charcoal as claimed in claim 9 in processing dyeing and printing sewage.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109806775A (en) * | 2019-03-08 | 2019-05-28 | 哈尔滨工业大学 | It is a kind of it is underwater it is superoleophobic and oily under super-hydrophobic seperation film and its preparation method and application |
| CN110496540A (en) * | 2019-08-20 | 2019-11-26 | 华南师范大学 | A kind of antipollution plate membrane and preparation method thereof of organic dyestuff removal function |
| CN112642308A (en) * | 2019-12-03 | 2021-04-13 | 贵州省材料技术创新基地 | Polysulfone-biochar blending separation membrane and preparation method thereof |
| CN113368702A (en) * | 2021-06-18 | 2021-09-10 | 常州大学 | Multifunctional ultrafiltration membrane and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102961972A (en) * | 2011-08-31 | 2013-03-13 | 李绩 | Preparation method of flat membrane for sewage treatment |
| CN104941466A (en) * | 2015-06-09 | 2015-09-30 | 同济大学 | Preparation method of mesoporous carbon organic composite film for removing macromolecular hepatotoxins in water |
| CN105903360A (en) * | 2016-06-17 | 2016-08-31 | 安庆市天虹新型材料科技有限公司 | Antibacterial stain-resistant polyvinylidene fluoride composite film |
| CN106345309A (en) * | 2016-10-20 | 2017-01-25 | 合肥创想能源环境科技有限公司 | PVDF organic membrane modifying method |
| CN106693726A (en) * | 2015-11-18 | 2017-05-24 | 天津工业大学 | Formula for preparing polyvinylidene fluoride and carbon nanotube composite film and preparation method of formula |
| CN107335341A (en) * | 2017-04-26 | 2017-11-10 | 浙江大学 | A kind of preparation method of biological carbon membrane |
| CN107998899A (en) * | 2017-12-08 | 2018-05-08 | 华北电力大学 | A kind of method for preparing PVDF blend films with activated carbon and crosslinking agent |
-
2018
- 2018-06-28 CN CN201810688330.2A patent/CN108854595A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102961972A (en) * | 2011-08-31 | 2013-03-13 | 李绩 | Preparation method of flat membrane for sewage treatment |
| CN104941466A (en) * | 2015-06-09 | 2015-09-30 | 同济大学 | Preparation method of mesoporous carbon organic composite film for removing macromolecular hepatotoxins in water |
| CN106693726A (en) * | 2015-11-18 | 2017-05-24 | 天津工业大学 | Formula for preparing polyvinylidene fluoride and carbon nanotube composite film and preparation method of formula |
| CN105903360A (en) * | 2016-06-17 | 2016-08-31 | 安庆市天虹新型材料科技有限公司 | Antibacterial stain-resistant polyvinylidene fluoride composite film |
| CN106345309A (en) * | 2016-10-20 | 2017-01-25 | 合肥创想能源环境科技有限公司 | PVDF organic membrane modifying method |
| CN107335341A (en) * | 2017-04-26 | 2017-11-10 | 浙江大学 | A kind of preparation method of biological carbon membrane |
| CN107998899A (en) * | 2017-12-08 | 2018-05-08 | 华北电力大学 | A kind of method for preparing PVDF blend films with activated carbon and crosslinking agent |
Non-Patent Citations (4)
| Title |
|---|
| ABDUL GHAFFAR等: "《Biochar composite membrane for high performance pollutant management: Fabrication, structural characteristics and synergistic mechanisms》", 《ENVIRONMENTAL POLLUTION》 * |
| 吕寅等: "《碳纳米管－聚偏氟乙烯共混超滤膜的制备及性能研究》", 《水处理技术》 * |
| 胡桢等编: "《新型高分子合成与制备工艺》", 31 May 2015, 哈尔滨工业大学出版社 * |
| 董秉直等著: "《饮用水膜法处理新技术》", 30 September 2015, 同济大学出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109806775A (en) * | 2019-03-08 | 2019-05-28 | 哈尔滨工业大学 | It is a kind of it is underwater it is superoleophobic and oily under super-hydrophobic seperation film and its preparation method and application |
| CN109806775B (en) * | 2019-03-08 | 2022-08-19 | 哈尔滨工业大学 | Underwater super-oleophobic and oil-super-hydrophobic separation membrane and preparation method and application thereof |
| CN110496540A (en) * | 2019-08-20 | 2019-11-26 | 华南师范大学 | A kind of antipollution plate membrane and preparation method thereof of organic dyestuff removal function |
| CN112642308A (en) * | 2019-12-03 | 2021-04-13 | 贵州省材料技术创新基地 | Polysulfone-biochar blending separation membrane and preparation method thereof |
| CN113368702A (en) * | 2021-06-18 | 2021-09-10 | 常州大学 | Multifunctional ultrafiltration membrane and preparation method and application thereof |
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