CN107021583A - A kind of ozonation aerated device of POROUS TITANIUM for having ozone heterocatalysis-electro-catalysis function concurrently - Google Patents

A kind of ozonation aerated device of POROUS TITANIUM for having ozone heterocatalysis-electro-catalysis function concurrently Download PDF

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CN107021583A
CN107021583A CN201610071158.7A CN201610071158A CN107021583A CN 107021583 A CN107021583 A CN 107021583A CN 201610071158 A CN201610071158 A CN 201610071158A CN 107021583 A CN107021583 A CN 107021583A
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porous titanium
ozone
ozonation aerated
heterocatalysis
aerated device
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CN201610071158.7A
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CN107021583B (en
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李新洋
郑建中
刘桂成
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University of Chinese Academy of Sciences
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University of Chinese Academy of Sciences
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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
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C02F2001/46142—Catalytic coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents

Abstract

A kind of ozonation aerated device of POROUS TITANIUM for having ozone heterocatalysis electro-catalysis function concurrently.The ozonation aerated device is made up of porous Titanium base and the Catalytic Layer being supported on matrix.Described Catalytic Layer is the compound of the oxides such as Ti, Mn, Ce, Cu, Fe, Ni, Sn, Sb, Pb or above-mentioned metal oxide, and its oxide pattern can be nano flower, nano wire, nanometer rods and nanotube.The present invention assigns POROUS TITANIUM aerator the concerted catalysis ability of ozone heterocatalysis and electrocatalytic oxidation, can reach the efficient catalytic reaction of pollutant gas, solid, liquid three-phase in aerator, reach the efficient mineralization of target contaminant and the purpose of removal.The present invention the ozonation aerated device of POROUS TITANIUM be used for drinking water treatment, wastewater treatment and other use ozone occasion, with oxidability is strong, reaction speed is fast, treatment effect is stable, service life length, small investment, it is applied widely the features such as, with good application prospect.

Description

A kind of ozonation aerated device of POROUS TITANIUM for having ozone heterocatalysis-electro-catalysis function concurrently
It is more particularly to a kind of to be loaded with catalyst coatings and while there is the ozonation aerated device of POROUS TITANIUM of ozone heterocatalysis-electro-catalysis function the present invention relates to a kind of ozonation aerated device of POROUS TITANIUM for having ozone heterocatalysis-electro-catalysis function concurrently.Gas-liquid-solid three phase catalytic reaction can effectively be realized on POROUS TITANIUM aerator surface by the catalyst synergic catalytic effect, promote the decomposition of target contaminant in waste water.The invention belongs to the field of ozonation aerated device technology in water treatment procedure.
Background technology
Ozone has been widely used in sterilization, decolouring, organic matter degradation, deodorization and the field such as eliminated the unusual smell.In addition, ozone in the processing procedure of target contaminant by direct oxidation to mainly being reacted, generally wherein directly reaction refers to that ozone directly reacts with organic matter, this mode has stronger selectivity, it is generally more effective to unsaturated aliphatic hydrocarbon and compound fragrant hydrocarbon, therefore it is more effective to the scission of link of pollutant such as organic pollution, open loop, decomposition, but the mineralization effect to organic pollution is not notable.Therefore, it is certain by metal oxide by being added in ozone system（TixOy、MnxOy、CuxOy、CexOyDeng）The solid catalyst of composition, the stronger oxidant hydroxyl radical free radical of catalysis ozone generation oxidability, the mineralising organic matter of non-selectivity realizes that reinforcing pollutant mineralising is arisen at the historic moment with the ozonation technology-out-phase catalytic ozonation technology removed.Compared to traditional ozone oxidation, the technology has the features such as oxidability is strong, pollutant mineralization degree is complete.For the technology, usually used catalyst is powdered or graininess（It is supported on particulate vector such as activated carbon or aluminum oxide）.Ozone is passed through in the fluid bed or fixed bed of filling above-mentioned catalyst by aerator, and organic pollution reacts in catalyst surface generation gas, solid, liquid triphase catalytic oxidation and is mineralized decomposition.But powder or particulate load type catalyst are present：1）Fine catalyst hardly possible is reclaimed, number of dropouts is big; 2）The easy phase mutual friction of beaded catalyst, efflorescence.It is important that, ozone in the packed bed of particulate load type catalyst, especially stacking bed inside is difficult to reach the uniform diffusion of ozone, target contaminant in particle catalyst surface, and resistance to mass tranfer is big, reduce the effective rate of utilization of catalyst.In addition, conventional ozonation aerated device is made up of materials such as inorganic sandstone, stainless steels, but have that oxidation resistance is poor, resistance to acids and bases is poor, easily oozes out residuals and ion, cause secondary pollution problems.
In recent years, POROUS TITANIUM using the features such as its excellent corrosion resistance, inoxidizability, resistance to acids and bases, safe non-secondary pollution as ozonation aerated device by progressively be used for the process using ozone such as Chemical Manufacture, drinking water and wastewater treatment and food processing.According to the requirement of aeration bubbles size, POROUS TITANIUM aerator can be customized according to different pore size size specification, thus application flexibility is strong, applied widely.Particularly, porous titanium material is in view of its excellent three-dimensional porous structure, specific surface area height, are a kind of preferable catalyst carrier materials.Therefore, using POROUS TITANIUM aerator as carrier, thereon load with ozone out-phase urge and electro-catalysis dual purpose catalyst, so can not only give full play to POROUS TITANIUM itself three-dimensional, continuous, loose structure can provide more loaded areas for the structure of active layer, promote the raising of the degradation efficiency of catalytic activity and target contaminant, while the flow trough configuration and Hole bottom cavity blast of POROUS TITANIUM itself, promote air-liquid abundant mass transfer in the Catalytic Layer on POROUS TITANIUM surface by forced convertion effect, so as to reach efficient gas, solid, liquid three phase catalytic reaction efficiency.Ozone-elctro-catalyst of load is combined closely with POROUS TITANIUM simultaneously, equally with three-dimensional porous construction, therefore also efficiently solves powder catalyst loss and beaded catalyst efflorescence, the problems such as mass transfer is not good.
Although the existing Patents CN202465355U report ozonation aerated devices of POROUS TITANIUM, its focus is to improve the aeration effect of ozone by the improvement of the construction of profile, strengthen the compressive resistance of aerator.About POROUS TITANIUM aerator to be assigned to certain catalytic capability especially ozone heterocatalysis and electro-catalysis capability study, there is not yet relevant report.
The content of the invention
It is an object of the invention to provide a kind of ozonation aerated device of POROUS TITANIUM for having ozone heterocatalysis-electro-catalysis function concurrently, POROUS TITANIUM aerator is assigned to the function of ozone heterocatalysis and electro-catalysis simultaneously.In addition, making full use of POROUS TITANIUM itself three-dimensional, continuous, loose structure to provide more loaded areas for the structure of catalyst, promote the raising of the degradation efficiency of catalytic activity and target contaminant.While the flow trough configuration and Hole bottom cavity blast of POROUS TITANIUM itself, promote air-liquid abundant mass transfer in the Catalytic Layer on POROUS TITANIUM surface by forced convertion effect, so as to reach efficient gas, solid, liquid three phase catalytic reaction efficiency, efficient mineralization and the removal of target contaminant are realized.Ozone-elctro-catalyst of load is combined closely with POROUS TITANIUM and has three-dimensional porous construction, can efficiently solve powder catalyst loss, the problems such as mass transfer is not good.
Technical scheme is as follows：
A kind of ozonation aerated device of POROUS TITANIUM for having ozone heterocatalysis-electro-catalysis function concurrently, it is characterised in that ozonation aerated device is made up of porous Titanium base and the Catalytic Layer being supported on matrix.Described Catalytic Layer is the compound of the oxides such as Ti, Mn, Ce, Cu, Fe, Ni, Sn, Sb, Pb or above-mentioned metal oxide, and its shape can be nanosphere, nano wire, nanometer rods and nanotube.
A kind of ozonation aerated device of POROUS TITANIUM for having ozone heterocatalysis-electro-catalysis function concurrently of the present invention, it is characterised in that：Ozonation aerated device is tabular, tubulose, spherical POROUS TITANIUM, and average pore size scope is 2 μm~200 μm.
A kind of carrying method for having the Catalytic Layer described in the ozonation aerated device of POROUS TITANIUM of ozone heterocatalysis-electro-catalysis function concurrently of the present invention is hydro-thermal method, the hot method of alcohol, anodizing, infusion process-sintering process, sol-gel process thermal decomposition method and electrodeposition process.
Brief description of the drawings
Fig. 1 is the ozonation aerated device ozone catalytic-electrocatalysis oxidation reaction schematic device of POROUS TITANIUM
Fig. 2 is the stereoscan photograph of example 2.
Fig. 3 is the stereoscan photograph of example 3.
Embodiment
Embodiment 1：A kind of ozonation aerated device of POROUS TITANIUM for having ozone heterocatalysis-electro-catalysis function concurrently of the present embodiment, selection average pore size is that 55 μm of tubular porous titanium is matrix, and TiO is loaded by hydro-thermal method2Catalytic Layer is in porous titanium substrate, wherein TiO2Pattern is into nano flower array.
Embodiment 2：A kind of ozonation aerated device of POROUS TITANIUM for having ozone heterocatalysis-electro-catalysis function concurrently of the present embodiment, selection average pore size is that 45 μm of tubular porous titanium is matrix, and MnO is loaded by hydro-thermal method2Catalytic Layer is in porous titanium substrate, wherein MnO2Pattern is into nanometer stick array.
Embodiment 3：A kind of ozonation aerated device of POROUS TITANIUM for having ozone heterocatalysis-electro-catalysis function concurrently of the present embodiment, selection average pore size is that 50 μm of tubular porous titanium is matrix, and TiO is loaded by hydro-thermal method-sol-gal process2-SnO2Composite catalytic layer is in porous titanium substrate, wherein TiO2-SnO2Composite catalytic layer pattern is into nano flower array.
Embodiment 4：A kind of ozone catalytic-electrochemical oxidation effect test of the ozonation aerated device of POROUS TITANIUM for having ozone heterocatalysis-electro-catalysis function concurrently of the present embodiment.The ozonation aerated device of the POROUS TITANIUM prepared in embodiment 1-3 is placed in glass reactor and carries out processing rhdamine B electrolytic trial（COD:1000 mg/L, pH=3）, wherein electrolyte Na2SO4Concentration is 0.1M.Using the ozonation aerated device of POROUS TITANIUM as anode, platinum electrode is negative electrode.It is 15 mA/cm to apply current density to the ozonation aerated device of POROUS TITANIUM in experiment2Constant current be passed through 8 mg/L ozone gas simultaneously, react 2.5 hours, determine COD clearances and be used as evaluation index.
Removal effect of the ozonation aerated device of POROUS TITANIUM prepared in the embodiment of the present invention of table 1 for pollutant
Embodiment 1 2 3
COD average removal rates (%) 81% 95% 99%
From table 1 it follows that a kind of ozonation aerated device of POROUS TITANIUM for having ozone heterocatalysis-electro-catalysis function concurrently prepared by the present invention has higher clearance to organic pollution rhodamine B in ozone-electrocatalytic oxidation experiment, catalytic effect is excellent.

Claims (4)

1. a kind of ozonation aerated device of POROUS TITANIUM for having ozone heterocatalysis-electro-catalysis function concurrently, it is characterised in that ozonation aerated device is made up of porous Titanium base and the Catalytic Layer being supported on matrix.
2. according to the compound that the Catalytic Layer described in claim 1 is the oxides such as Ti, Mn, Ce, Cu, Fe, Ni, Sn, Sb, Pb or above-mentioned metal oxide, its shape can be nanosphere, nano wire, nanometer rods and nanotube.
3. according to a kind of ozonation aerated device of POROUS TITANIUM for having ozone heterocatalysis-electro-catalysis function concurrently described in claim 1, it is characterised in that：Ozonation aerated device is tabular, tubulose, spherical POROUS TITANIUM, and average pore size scope is 2 μm~200 μm.
4. according to a kind of ozonation aerated device of POROUS TITANIUM for having ozone heterocatalysis-electro-catalysis function concurrently described in claim 1, it is characterised in that：The carrying method of described Catalytic Layer is hydro-thermal method, the hot method of alcohol, anodizing, infusion process-sintering process, sol-gel process thermal decomposition method and electrodeposition process.
CN201610071158.7A 2016-02-02 2016-02-02 Porous titanium ozone aerator with ozone heterogeneous catalysis-electrocatalysis function Active CN107021583B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108046380A (en) * 2017-12-13 2018-05-18 东华大学 A kind of titanium-based Sn-Sb-Ce oxide electrodes and its preparation method and application
CN108358350A (en) * 2018-02-07 2018-08-03 北京交通大学 The advanced treatment apparatus and method of high ferro defecate collection waste water
CN110357242A (en) * 2018-04-10 2019-10-22 中国石油化工股份有限公司 A kind of processing method of fluidized catalytic oxidation treatment device and saline sewage

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04243597A (en) * 1991-01-25 1992-08-31 Matsushita Electric Ind Co Ltd Ozone water producing apparatus
CN1429773A (en) * 2001-12-31 2003-07-16 中国科学院大连化学物理研究所 Method of treating oil field waste water by electric-multiphase catalytic reaction and its special equipment
US20110150734A1 (en) * 2008-08-18 2011-06-23 Sinvent As Photo-Catalytic Membrane Reactor
CN102730856A (en) * 2012-07-16 2012-10-17 江苏丰源环保科技工程有限公司 Titanium micro-pore aerator disc
CN204454721U (en) * 2015-04-30 2015-07-08 上海自来水投资建设有限公司 A kind of ozone catalytic dissolved air release

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04243597A (en) * 1991-01-25 1992-08-31 Matsushita Electric Ind Co Ltd Ozone water producing apparatus
CN1429773A (en) * 2001-12-31 2003-07-16 中国科学院大连化学物理研究所 Method of treating oil field waste water by electric-multiphase catalytic reaction and its special equipment
US20110150734A1 (en) * 2008-08-18 2011-06-23 Sinvent As Photo-Catalytic Membrane Reactor
CN102730856A (en) * 2012-07-16 2012-10-17 江苏丰源环保科技工程有限公司 Titanium micro-pore aerator disc
CN204454721U (en) * 2015-04-30 2015-07-08 上海自来水投资建设有限公司 A kind of ozone catalytic dissolved air release

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108046380A (en) * 2017-12-13 2018-05-18 东华大学 A kind of titanium-based Sn-Sb-Ce oxide electrodes and its preparation method and application
CN108358350A (en) * 2018-02-07 2018-08-03 北京交通大学 The advanced treatment apparatus and method of high ferro defecate collection waste water
CN108358350B (en) * 2018-02-07 2020-12-22 北京交通大学 Advanced treatment device and method for high-speed rail excrement collecting wastewater
CN110357242A (en) * 2018-04-10 2019-10-22 中国石油化工股份有限公司 A kind of processing method of fluidized catalytic oxidation treatment device and saline sewage
CN110357242B (en) * 2018-04-10 2022-11-15 中国石油化工股份有限公司 Fluidized catalytic oxidation treatment device and method for treating salt-containing sewage

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