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 PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
biological charcoal
nano biological
plate membrane
pvdf
membrane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201810688330.2A
Other languages
Chinese (zh)
Inventor
郑刘春
阳月贝
黄嘉颖
许宗林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China Normal University
Original Assignee
South China Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by South China Normal University filed Critical South China Normal University
Priority to CN201810688330.2A priority Critical patent/CN108854595A/en
Publication of CN108854595A publication Critical patent/CN108854595A/en
Pending legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/30Polyalkenyl halides
    • B01D71/32Polyalkenyl halides containing fluorine atoms
    • B01D71/34Polyvinylidene fluoride
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D67/00Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079Manufacture of membranes comprising organic and inorganic components
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/06Flat membranes
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/308Dyes; Colorants; Fluorescent agents

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

Modified PVDF plate membrane of a kind of nano biological charcoal and the preparation method and application thereof
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.
CN201810688330.2A 2018-06-28 2018-06-28 Modified PVDF plate membrane of a kind of nano biological charcoal and the preparation method and application thereof Pending CN108854595A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810688330.2A CN108854595A (en) 2018-06-28 2018-06-28 Modified PVDF plate membrane of a kind of nano biological charcoal and the preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810688330.2A CN108854595A (en) 2018-06-28 2018-06-28 Modified PVDF plate membrane of a kind of nano biological charcoal and the preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN108854595A true CN108854595A (en) 2018-11-23

Family

ID=64296381

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810688330.2A Pending CN108854595A (en) 2018-06-28 2018-06-28 Modified PVDF plate membrane of a kind of nano biological charcoal and the preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN108854595A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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

Patent Citations (7)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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

Similar Documents

Publication Publication Date Title
CN108854595A (en) Modified PVDF plate membrane of a kind of nano biological charcoal and the preparation method and application thereof
CN103446899B (en) Organic and inorganic surface chemically-crosslinked alginate-based hybrid hydrogel filter membrane, and preparation method thereof
CN100584437C (en) Hydrophilic polyvinylidene fluoride hollow fiber microporous membrane and preparation method thereof
CN103446898B (en) Alginate-base organic-inorganic composite hydrogel filtering membrane and preparation method thereof
CN106237869B (en) A kind of polyphenol coating hydrophilic method of modified hydrophobic type polymeric membrane
CN103464004B (en) high-strength nano modified ultrafiltration membrane and preparation method thereof
CN110787645B (en) Visible light photocatalyst modified PVDF ultrafiltration membrane as well as preparation method and application thereof
CN106731886B (en) Preparation method of mesoporous composite membrane
CN112387131B (en) Polymer microporous membrane, preparation method and application thereof
CN105214511A (en) A kind of Nano Silver/Graphene/Kynoar hybrid membranes and preparation method thereof
CN103861476A (en) Preparation method of polyvinylidene fluoride (PVDF) composite mesoporous membrane
CN106902645A (en) A kind of preparation method of the super hydrophilic ceramic membrane with photocatalysis performance
CN106955603B (en) Surface segregation functionalized anti-pollution polymer separation membrane and preparation method thereof
CN104258738A (en) Forward osmosis organic-inorganic composite membrane and preparation method thereof
CN112691560A (en) Preparation method of MOFs-PVDF composite ultrafiltration membrane
CN111701465A (en) Super hydrophilic SiO2Preparation of/PDAus/PVDF composite membrane
CN113509847A (en) Method for preparing porous nano particle/polydimethylsiloxane membrane by spreading on water surface
CN103657433A (en) Forward-osmosis organic-inorganic composite membrane and preparation method thereof
CN113289657B (en) Preparation method and application of nitrogen-doped graphene catalytic membrane
CN108079798B (en) Preparation method of super-hydrophilic organic membrane based on nano hydrotalcite-like compound
CN112090296A (en) Based on F-TiO2/Fe-g-C3N4Self-cleaning flat plate type PVDF ultrafiltration membrane and preparation method thereof
CN117181004A (en) Hydrophilic anti-pollution MXene/PVDF composite membrane and preparation method and application thereof
CN112588127A (en) Method for modifying polymer porous membrane through diffusion reaction
CN103752185A (en) Magnetic-induction charged ceramic ultra-filtration membrane and preparation method thereof
CN115350589A (en) Polymeric nanofiltration membrane and preparation and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination