CN104475029A - Novel preparation and application methods of mesoporous composite material with adsorption and catalytic degradation activity - Google Patents
Novel preparation and application methods of mesoporous composite material with adsorption and catalytic degradation activity Download PDFInfo
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- CN104475029A CN104475029A CN201410653356.5A CN201410653356A CN104475029A CN 104475029 A CN104475029 A CN 104475029A CN 201410653356 A CN201410653356 A CN 201410653356A CN 104475029 A CN104475029 A CN 104475029A
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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
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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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
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
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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
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Abstract
The invention relates to novel preparation and application methods of a mesoporous composite material with adsorption and catalytic degradation activity. The preparation method specifically comprises the steps of preparing a MIL-101 mesoporous adsorption material by a hydrothermal method, adequately washing, purifying and activating, then, adding the MIL-101 mesoporous adsorption material into an ethanol solution of butyl titanate, dropwise adding a hydrolysis solution and continuously stirring, thereby finally preparing the mesoporous TiO2-MIL-101 composite material with adsorption and catalytic degradation activity. The method is simple in process and easy in operation. Shown by adsorption and degradation experiments, the composite material prepared by the method is regular in structure and large in pore capacity and has a good degradation effect on organics. According to the method, the added ratio of TiO2 and MIL-101 is free from any restriction, and TiO2 and MIL-101 of any ratio can be loaded according to research needs or practical application needs.
Description
Technical field
The present invention relates to a kind of mesoporous composite material with absorption and catalytic degradation activity, this composite is carried titanium dioxide (TiO
2) nanocrystalline mesoporous MIL-101 particle, after water heat transfer MIL-101 particle, adopt sol method to be carried on by nano titanium oxide in mesoporous MIL-101 duct, finally obtain New Type of Mesoporous composite, and develop a kind of fast simple Adsorption of Organic and degraded new method with this.
Background technology
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.
Advanced composite material (ACM) designed by the present invention adopts mesoporous material MIL-101 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 novel mesoporous composite material with absorption and catalytic degradation activity.The object of the invention is in conjunction with above-mentioned bi-material characteristics and advantages separately, prepare a kind of novel Mobyneb composite, and to be applied in sewage or waste water in organic absorption and degradation process.
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 using method of-MIL-101 composite: will through washing, dry, composite after activation joins in the waste water containing organic matter or organic dyestuff, mechanical agitation is carried out to sample solution simultaneously, composite is contacted fully with sample solution, with high-pressure sodium lamp, sample solution is irradiated simultaneously.Meanwhile, can gas chromatography be adopted, liquid chromatography, spectra methods etc., the content of organic matter in sample solution or organic dyestuff is measured.
The present invention adopts New Type of Mesoporous material MIL-101 as binding matrix, has the TiO of catalytic organism degrading activity at its duct internal burden
2nanocrystalline, make the novel mesoporous composite material with absorption and catalytic degradation activity.Advanced composite material (ACM) involved in the present invention has good absorption and degradation effect to the organic matter in sewage or waste water, can be with a wide range of applications in actual production or life.
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 using method of-MIL-101 composite: will through washing, dry, composite after activation joins in the waste water containing organic matter or organic dyestuff, mechanical agitation is carried out to sample solution simultaneously, composite is contacted fully with sample solution, with high-pressure sodium lamp, sample solution is irradiated simultaneously.Meanwhile, can gas chromatography be adopted, liquid chromatography, spectra methods etc., the content of organic matter in sample solution or organic dyestuff is measured.
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 (5)
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.
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| CN201410653356.5A CN104475029A (en) | 2014-11-11 | 2014-11-11 | Novel preparation and application methods of mesoporous composite material with adsorption and catalytic degradation activity |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105289509A (en) * | 2015-11-24 | 2016-02-03 | 天津工业大学 | Preparation method of mesoporous composite material with core-shell structure |
| CN107519841A (en) * | 2016-11-17 | 2017-12-29 | 天津工业大学 | The mesoporous composite material with absorption and catalytic degradation activity is prepared using " one kettle way " |
| CN107529451A (en) * | 2016-11-17 | 2018-01-02 | 天津工业大学 | The advanced composite material (ACM) with one-dimensional channels and catalytic activity is prepared using " one kettle way " |
| CN108483556A (en) * | 2018-03-05 | 2018-09-04 | 昆明理工大学 | A method of degradation antibiotic |
| CN115960366A (en) * | 2022-12-21 | 2023-04-14 | 浙江工商大学 | Method for preparing MOF material by using waste PET and stainless steel pickling wastewater and application |
-
2014
- 2014-11-11 CN CN201410653356.5A patent/CN104475029A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105289509A (en) * | 2015-11-24 | 2016-02-03 | 天津工业大学 | Preparation method of mesoporous composite material with core-shell structure |
| CN107519841A (en) * | 2016-11-17 | 2017-12-29 | 天津工业大学 | The mesoporous composite material with absorption and catalytic degradation activity is prepared using " one kettle way " |
| CN107529451A (en) * | 2016-11-17 | 2018-01-02 | 天津工业大学 | The advanced composite material (ACM) with one-dimensional channels and catalytic activity is prepared using " one kettle way " |
| CN108483556A (en) * | 2018-03-05 | 2018-09-04 | 昆明理工大学 | A method of degradation antibiotic |
| CN115960366A (en) * | 2022-12-21 | 2023-04-14 | 浙江工商大学 | Method for preparing MOF material by using waste PET and stainless steel pickling wastewater and application |
| CN115960366B (en) * | 2022-12-21 | 2024-03-19 | 浙江工商大学 | Method for preparing MOF material by utilizing waste PET and stainless steel pickling wastewater and application |
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Application publication date: 20150401 |