CN104324696A - Novel preparation and application method of water treatment thin film doped with mesoporous composite material - Google Patents
Novel preparation and application method of water treatment thin film doped with mesoporous composite material Download PDFInfo
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- CN104324696A CN104324696A CN201410653357.XA CN201410653357A CN104324696A CN 104324696 A CN104324696 A CN 104324696A CN 201410653357 A CN201410653357 A CN 201410653357A CN 104324696 A CN104324696 A CN 104324696A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
Abstract
The invention relates to a novel preparation and application method of a water treatment thin film doped with an SOD zeolite configuration composite material. The method specifically comprises the following steps: synthesizing mesoporous MIL-101 particles by using a hydrothermal method, then loading nano titanium dioxide into pore channels of the particles by using a sol-gel method to obtain a novel composite material, preparing sol or a suspension liquid from the composite material, directly coating a film or coating on the surface of a PVDF film, and drying to obtain a novel water treatment thin film for sewage treatment. The method disclosed by the invention is simple in process and easy to operate. Adsorption and degradation experiments show that the composite material prepared by using the method disclosed by the invention is regular in structure and large in pore volume, and has a good degradation effect on organic matters, and thus a novel method for adsorbing and degrading the organic matters in sewage can be developed. According to the method, the adding proportion of TiO2-MIL-101 to a polymer and the preparation proportion of a TiO2-MIL-101 suspension liquid do not have any limits, and the selection of film materials also does not have any limits, so that the method can be improved according to the research needs or practical application.
Description
Technical field
The present invention relates to a kind of preparations and applicatio new method of water treatment film of doped meso-porous composite.This water treatment film doping advanced composite material (ACM), i.e. load titanium dioxide (TiO
2) nanocrystalline mesoporous MIL-101 nano particle.After the mesoporous MIL-101 particle of water heat transfer, sol method is adopted to be carried on by nano titanium oxide in its duct, obtain advanced composite material (ACM), above-mentioned composite is prepared into colloidal sol or suspension, direct film or be coated in pvdf membrane surface, and dry, the new type water process film for sewage disposal can be obtained, and finally developed Adsorption of Organic and degraded new method in a kind of sewage.
Background technology
At present, bioanalysis, oxidizing process and physico-chemical process etc. are mainly contained to the processing method of organic wastewater both at home and abroad.Bioanalysis is current most widely used a kind of method for processing organic wastewater, mainly utilizes the metabolism of microorganism, the organic matter be used in degradation of sewage by the cohesion, absorption, oxidation Decomposition etc. of microorganism.But when being difficult to the organic matter of degrading containing noxious material or biology in waste water, Biochemical method less effective, even can not process.Chemical oxidation techniques is usually used in the pretreatment process of carrying out a biological disposal upon, and is generally with chemical oxidizing agent process organic wastewater, to improve the biodegradability of waste water, or the organic matter in direct oxidation degrading waste water.But oxidizing process not only needs to consume a large amount of oxidant, and along with the kind of industrial wastewater and composition day by day complicated, the oxidability that conventional oxidant shows is strong, is difficult to reach actual requirement, constrains the extensive use of the method.Physico-chemical process process organic pollution mainly contains absorption method, extraction, various membrane technologies etc.Wherein, Membrane Separation for Water Treatment is being most widely used in recent years.
MIL-101 is the rigid backbone mesoporous adsorption material with special cage structure that a class is formed by self assembly effect by metal ion and organic ligand.MIL-101 is the well-regulated pore passage structure of tool not only, good heat endurance and solvent stability, and its maximum feature has mesoporous cage structure exactly, and the specific area of super large (BET specific surface area is up to 4500m
2/ g), therefore, MIL-101 has been widely used in sample adsorption field.The present invention adopts this novel mesoporous adsorption material of MIL-101 as adsorbent, prepares the mesoporous composite material with absorption and catalytic degradation activity.
Be used for since catalytic degradation organic matter makes a breakthrough from semi-conducting material, titanium dioxide because its catalytic activity is high, chemistry and biologically inert is good, to human non-toxic, the particular advantages such as inexpensive, become the most active catalysis material of Recent study.Compared with the titanium dioxide of stock size, nano titanium oxide has higher catalytic activity and selective, can form Strong oxdiative-reduction system, decomposed by substance oxidation that is not oxidizable or that be difficult to degrade, this technology has been widely used in the organic wastewater processing the generation of the industry such as dyestuff, papermaking.But because particle diameter is minimum, nano titanium oxide very easily runs off in oxidizing process, therefore, find the carrier can fixing nano titanium oxide, absorption, oxidation Decomposition are combined, is just more conducive to the extensive use in actual production.
The composite that sewerage disposing film of the present invention adulterates is using mesoporous MIL-101 material as binding matrix, after mesoporous MIL-101 materials synthesis, adopt sol method to have the nano titanium oxide of catalytic degradation activity at its duct internal burden, finally make the composite that can be doped in water treatment film.But above-mentioned composite is dispergated fine solid powder, and it has certain limitation in actual water treatment applications, therefore the present invention is intended to the preparation of above-mentioned composite to become form of film, to expand its application in actual water treatment.
Summary of the invention
For realizing technical scheme provided by the present invention be:
Prepare MIL-101 mesoporous adsorption material with hydro-thermal method, through washing fully, purification, after activation, adopts mortar to be ground into the comparatively homogeneous MIL-101 powder of granularity.MIL-101 powder after overactivation is joined in the ethanolic solution of butyl titanate, drips hydrolyzate and constantly stir, the composite of synthesis of nano titanium dioxide and MIL-101.Composite is washed, purification, after activation, namely obtain the mesoporous composite material with absorption and catalytic degradation activity.
Show through adsorption experiment, TiO prepared by this method
2-MIL-101 composite structure rule, pore capacities is large, to organic absorption and catalytic degradation functional.
Wherein, the hydrothermal synthesis method of mesoporous adsorption material MIL-101 is: by chromic nitrate, and terephthalic acid (TPA) is dissolved in high purity water, add hydrofluoric acid solution, ultrasonic make it dissolve after, mixed solution is placed in polytetrafluoroethylene (PTFE) reactor, carries out pyroreaction in an oven.After reaction terminates, reactor is cooled, the solid matter in reactor is carried out repeatedly, repeatedly washs, with being placed on dry for standby in baking oven.
TiO
2the synthetic method of-MIL-101 composite: take a certain amount of MIL-101 powder, join butyl titanate, in the mixed liquor of ethanol, and stir.Under magnetic agitation condition, in above-mentioned mixed liquor, slowly drip ethanol, water, the mixed liquor of nitric acid, drip and terminate rear continuation stirring some hours.After reaction terminates, centrifugally can obtain green viscous shape solid.
TiO
2the activation method of-MIL-101 composite: by the washing of above-mentioned green viscous shape solid ethanol for several times, and solid is placed in baking oven dries, subsequently high-temperature activation a few hours in an oven.
TiO
2the preparation method of-MIL-101 composite water treatment film: by TiO
2-MIL-101 composite dissolves in polymer sol, and direct film is also dried, or by TiO
2-MIL-101 composite dissolves in organic solvent, is coated on pvdf membrane surface, and dries, and can obtain the new type water process film for sewage disposal.
The using method of composite water treatment film: the film of preparation is arranged on supporter in the form of an array, and be placed in cesspool or sewage draining exit, by the mesoporous adsorption material in film, fast enriching is carried out to the organic matter in sewage, by the TiO of load
2material realizes organic degraded.Meanwhile, sewage sample can carry out sampling monitoring at any time, measures content of organics wherein.
Detailed description of the invention
For better understanding the present invention, below in conjunction with embodiment the present invention done and describe in detail further, but the scope of protection of present invention being not limited to the scope that embodiment represents.
Embodiment:
Prepare MIL-101 mesoporous adsorption material with hydro-thermal method, adopt sol method to be carried on by nano titanium oxide in MIL-101 sorbing material, composite is purified, after activation, be prepared into the mesoporous composite material with absorption and catalytic degradation activity:
The hydrothermal synthesis method of mesoporous adsorption material MIL-101 is: by 0.325 gram of chromic nitrate, 0.410 gram of terephthalic acid (TPA) is dissolved in 20 milliliters of high purity waters, add 1 milliliter of hydrofluoric acid solution, after within ultrasonic 10 minutes, making it dissolve, mixed solution is placed in 35 milliliters of polytetrafluoroethylene (PTFE) reactors, 220 DEG C are reacted 8 hours.Question response still cools, and adopt water, ethanolic solution washs obtained metallic organic framework sorbing material, 200 DEG C of dry for standby.
TiO
2the synthetic method of-MIL-101 composite: adopt mortar MIL-101 to be ground into the comparatively homogeneous powder of granularity.Take 50mg MIL-101 powder, join 25ml butyl titanate, in the mixed liquor of 10ml ethanol, stirred at ambient temperature 1 hour.Under magnetic agitation condition, with the speed of 1ml/min, in above-mentioned mixed liquor, drip 10ml ethanol, 4ml water, the mixed liquor of 1ml nitric acid, drip and terminate rear stirring 12 hours.Centrifugally can obtain green viscous shape solid.
TiO
2the activation method of-MIL-101 composite: by above-mentioned green viscous shape solid ethanol washing for several times, and solid is placed in the oven dry of 60 DEG C, baking oven, activates 3 hours subsequently in 200 DEG C of baking ovens.
TiO
2the preparation method of-MIL-101 composite water treatment film: by 500mg TiO
2-MIL-101 composite dissolves in 10ml polysulfones colloidal sol, colloidal sol is poured into cleaned glass plate surface, adopts glass bar knifing and being placed in infrared drying oven to dry, can obtain TiO
2-MIL-101-polysulfone composite membrane; Or by 500mg TiO
2-MIL-101 composite is scattered in 5ml ethanolic solution, and is poured into pvdf membrane surface, adopts glass bar that dissolution homogeneity is coated on pvdf membrane surface, then pvdf membrane is placed in baking oven dry, can obtains TiO
2-MIL-101-PVDF composite membrane.
The using method of composite water treatment film: by the film of preparation to be arranged on supporter, and be placed in cesspool, carries out fast enriching by the mesoporous adsorption material in film to the organic matter in sewage, by the TiO of load
2material realizes organic degraded.Meanwhile, sewage sample carries out sampling monitoring at any time, measures content of organics wherein.
This patent system state natural sciences fund (No.21305102), national Students' Innovation foundation drill program (No.201410058026), Tianjin S & T Developmentin High Institutions fund plan (No.2013512), outer academic scientific and technological works contest (No.2014341) funded projects of Tianjin University of Technology's students in class.
Claims (6)
1. a MIL-101 mesoporous adsorbent, it is characterized in that: adopt hydro-thermal method to prepare green solid particle, this solid particle needs first repeatedly to clean with distilled water, to remove unreacted slaine, repeatedly clean with ethanol again, remove unreacted terephthalic acid (TPA).
2. a MIL-101 adsorbent for high-specific surface area, good adsorption characteristic, is characterized in that: MIL-101 adsorbent according to claim 1 is needed 200 DEG C of high-temperature roasting a few hours.
3.TiO
2the synthetic method of-MIL-101 composite, is characterized in that: joined by the MIL-101 be ground into powder in ethanol (or other solvents) solution of butyl titanate, after fully stirring and evenly mixing, then drip hydrolyzate.
4.TiO
2the activation method of-MIL-101 composite, is characterized in that: gained composite need wash for several times with ethanol, and to remove unreacted butyl titanate, the composite after purification needs 200 DEG C of high-temperature roasting a few hours with activated nano TiO
2catalytic activity.
5. TiO according to claim 3
2the synthetic method of-MIL-101 composite, is characterized in that: TiO
2without any restrictions with the adding proportion of MIL-101, can need to adopt any ratio to carry out load according to research needs or practical application.
6.TiO
2the preparation method of-MIL-101 composite water treatment film, is characterized in that: TiO
2the adding proportion of-MIL-101 and polymer and TiO
2the configuration proportion of-MIL-101 suspension is without any restrictions, and the selection of membrane material is without any restrictions, can need to improve according to research needs or practical application.
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Cited By (3)
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| CN105251435A (en) * | 2015-11-24 | 2016-01-20 | 天津工业大学 | Preparation method of core-shell type composite material with MTN zeolite configuration |
| CN109569739A (en) * | 2016-12-28 | 2019-04-05 | 苏州大学 | Double layer hollow material based on titanium dioxide and its application in hydrogen sulfide photocatalysis treatment |
| CN109603762A (en) * | 2018-12-27 | 2019-04-12 | 南京大学 | A kind of adsorbed film based on metal-organic framework materials, preparation method and application |
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| CN109569739A (en) * | 2016-12-28 | 2019-04-05 | 苏州大学 | Double layer hollow material based on titanium dioxide and its application in hydrogen sulfide photocatalysis treatment |
| CN109569739B (en) * | 2016-12-28 | 2020-12-08 | 苏州大学 | Double-layer hollow material based on titanium dioxide and application thereof in hydrogen sulfide photocatalytic treatment |
| CN109603762A (en) * | 2018-12-27 | 2019-04-12 | 南京大学 | A kind of adsorbed film based on metal-organic framework materials, preparation method and application |
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