CN104353423A - Novel preparation and application method of water treatment film doped with composite material with breath effect - Google Patents
Novel preparation and application method of water treatment film doped with composite material with breath effect Download PDFInfo
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- CN104353423A CN104353423A CN201410653261.3A CN201410653261A CN104353423A CN 104353423 A CN104353423 A CN 104353423A CN 201410653261 A CN201410653261 A CN 201410653261A CN 104353423 A CN104353423 A CN 104353423A
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- mil
- tio
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- composite material
- water treatment
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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
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
-
- 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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
Abstract
The invention relates to a novel preparation method and a novel application method of a water treatment film doped with a composite material with a breath effect. The method particularly comprises the following steps: after synthesizing flexible porous MIL-47 particles by using a hydrothermal method, loading nanometer titania in a duct of nanometer titania by using a sol-gel method to obtain a novel composite material, preparing the composite material as sol or suspension, directly filming or coating the surface of a PVDF film, and drying to obtain a novel water treatment film for sewage treatment. The method is simple in process and easy to operate. The absorption and degradation experiment indicates that the composite material prepared by the method is regular in structure, large in hole capacity and has good degrading effect on the organic matter; and therefore, a novel sewage organic matter absorption and degradation method is developed. By the method, the adding proportion of TiO2-MIL-47 and the polymer and the preparation ratio of the TiO2-MIL-47 suspension are free from any limitation, and the selection of the film material is free from any limitation and can be improved according to research demand or actual application demand.
Description
Technical field
The present invention relates to the preparations and applicatio new method that a kind of doping has the water treatment film of cell breath composite.This water treatment film doping advanced composite material (ACM), i.e. load titanium dioxide (TiO
2) the nanocrystalline MIL-47 flexible, porous nano particle with cell breath.After water heat transfer porous MIL-47 particle, 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.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.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-47 is the flexible back bone porous adsorbing material with cell breath that a class is formed by self assembly effect by metal ion and organic ligand.The well-regulated pore passage structure of MIL-47 tool, (BET specific surface area is up to 1000m for the specific area of super large
2/ g), the remarkable advantages such as good heat endurance and solvent stability, therefore, have been widely used in sample adsorption field.The present invention adopts this novel flexible, porous sorbing material of MIL-47 as adsorbent, comes for the preparation of enrichment and the organic advanced composite material (ACM) of catalytic degradation.
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 be there is cell breath flexible cellular material MIL-47 as binding matrix, after porous MIL-47 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.
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.
Summary of the invention
For realizing technical scheme provided by the present invention be:
Prepare MIL-47 porous adsorbing material with hydro-thermal method, through washing fully, purification, after activation, adopts mortar to be ground into the comparatively homogeneous MIL-47 powder of granularity.MIL-47 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-47.By composite wash, purification, after activation, namely obtain have cell breath for enrichment and the organic advanced composite material (ACM) of catalytic degradation.
Show through adsorption experiment, TiO prepared by this method
2-MIL-47 composite structure rule, pore capacities is large, to organic absorption and catalytic degradation functional.
Wherein, the hydrothermal synthesis method of porous adsorbing material MIL-47 is: by vanadium trichloride, and terephthalic acid (TPA) is dissolved in ultra-pure water, 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-47 composite: take a certain amount of MIL-47 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 thick white shape solid.
TiO
2the activation method of-MIL-47 composite: by the washing of above-mentioned thick white 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-47 composite water treatment film: by TiO
2-MIL-47 composite dissolves in polymer sol, and direct film is also dried, or by TiO
2-MIL-47 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 porous adsorbing 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-47 porous adsorbing material with hydro-thermal method, adopt sol method to be carried on by nano titanium oxide in MIL-47 sorbing material, composite is purified, after activation, is prepared into for enrichment and the organic advanced composite material (ACM) of catalytic degradation:
The hydrothermal synthesis method of porous adsorbing material MIL-47 is: by 1.5729 grams of vanadium trichlorides, 0.4153 gram of terephthalic acid (TPA) is dissolved in 18 milliliters of ultra-pure waters, after within ultrasonic 10 minutes, making it dissolve, mixed solution is placed in 30 milliliters of polytetrafluoroethylene (PTFE) reactors, 200 DEG C are reacted 96 hours.Question response still cools, and ultra-pure water, ethanolic solution washs obtained metallic organic framework sorbing material, 200 DEG C of dry for standby.
TiO
2the synthetic method of-MIL-47 composite: adopt mortar MIL-47 to be ground into the comparatively homogeneous powder of granularity.Take 50mg MIL-47 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 thick white shape solid.
TiO
2the activation method of-MIL-47 composite: by above-mentioned thick white 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-47 composite water treatment film: by 500mg TiO
2-MIL-47 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-47-polysulfone composite membrane; Or by 500mg TiO
2-MIL-47 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-47-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 porous adsorbing 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.
The above is only the preferred embodiment of the present invention, and for those skilled in the art, under the prerequisite not departing from inventive principle, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (6)
1. a MIL-47 porous adsorbent, it is characterized in that: it is the white solid particle adopting hydro-thermal method to prepare, this solid particle needs first repeatedly to clean with ultra-pure water, to remove unreacted slaine, repeatedly clean with ethanol again, remove unreacted terephthalic acid (TPA).
2. a MIL-47 adsorbent for high-specific surface area, good adsorption characteristic, is characterized in that: MIL-47 adsorbent according to claim 1 is needed 200 DEG C of high-temperature roasting a few hours.
3.TiO
2the synthetic method of-MIL-47 composite, is characterized in that: joined by the MIL-47 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-47 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-47 composite, is characterized in that: TiO
2without any restrictions with the adding proportion of MIL-47, can need to adopt any ratio to carry out load according to research needs or practical application.
6.TiO
2the preparation method of-MIL-47 composite water treatment film, is characterized in that: TiO
2the adding proportion of-MIL-47 and polymer and TiO
2the configuration proportion of-MIL-47 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105289510A (en) * | 2015-11-24 | 2016-02-03 | 天津工业大学 | Preparation method of core-shell structured composite material with breathable effect |
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| CN103240130A (en) * | 2013-05-21 | 2013-08-14 | 中国石油大学(北京) | TiO2 / MIL-101 composite catalyst for photocatalytic water splitting and preparation method and applications thereof |
| CN103272491A (en) * | 2013-06-19 | 2013-09-04 | 北京工业大学 | Preparation method for in situ self-assembled organic/inorganic hybrid membrane based on coordination |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105289510A (en) * | 2015-11-24 | 2016-02-03 | 天津工业大学 | Preparation method of core-shell structured composite material with breathable effect |
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Application publication date: 20150218 |