CN107162167A

CN107162167A - The technique and device of a kind of catalytic ozonation processing organic wastewater

Info

Publication number: CN107162167A
Application number: CN201710583328.4A
Authority: CN
Inventors: 王军; 张勇; 侯得印; 赵长伟; 曹爱新
Original assignee: Research Center for Eco Environmental Sciences of CAS
Current assignee: Research Center for Eco Environmental Sciences of CAS
Priority date: 2017-07-18
Filing date: 2017-07-18
Publication date: 2017-09-15
Anticipated expiration: 2037-07-18
Also published as: CN107162167B

Abstract

The technique and device of a kind of catalytic ozonation processing organic wastewater.The present invention will be full of the polytetrafluoroethylmaterial material of perfluoro alkane solvent as the catalyst of ozone oxidation process by the use of porous Teflon material as the carrier of perfluoro alkane solution in above-mentioned hole.And then, the catalyst is added in the ozonation aerated device of microbubble, or the polytetrafluoroethylene (PTFE) catalysis material of hollow fiber type is processed as membrane module form, form two kinds of device for catalyzing and oxidating ozone.Perfluoro alkane solvent forms high local concentrations reaction substrate, so as to improve ozone oxidation speed to ozone and some organic matter preferential absorptions.This method and device can effectively improve the utilization ratio of ozone, reduce the loss of perfluoro alkane solvent, and reduce equipment volume.This method is applied to the ozone oxidation degradation technique of the higher organic matter of Organic substance in water, especially octanol water partition coefficient.

Description

The technique and device of a kind of catalytic ozonation processing organic wastewater

Technical field

The present invention relates to the technique and dress of sewage treatment area, more particularly to a kind of catalytic ozonation processing organic wastewater Put.

Background technology

The a large amount of organic wastewaters of the industries such as chemical industry, papermaking, weaving, coking, cultivation discharge, these waste water presentation complicated components, The features such as concentration height, many salinities, difficult degradation.No matter under the conditions of nature or artificial-strengthening, being difficult to using conventional microbial method Such waste water is effectively handled, need to generally be handled with reference to physico-chemical process.Chemical oxidization method is a kind of conventional physical chemistry method, suitably Complicated organic wastewater system for above-mentioned difficult for biological degradation.Acted on, the organic matter of difficult degradation can be decomposed by chemical oxidation It is carbon dioxide and water for small-molecule substance, or even mineralising.In chemical oxidation method, Ozonation oxidability is strong, work Skill is simple, and source of the gas is easy to get, using safety, is a kind of technology of economical and efficient.The oxidation-reduction potential of ozone is 2.07eV, is higher than The common oxidants such as chlorine, hydrogen peroxide.Organic matter degradation effect to Organic substance in water especially containing unsaturated bond is good.Especially Combined catalyst, ultraviolet or hydrogen peroxide ozone high grade oxidation technology, its application is wider, and effect is more notable.

However, salinity present in waste water and various organic matters can influence ozone oxidation process, utilizing for reduction ozone is imitated Rate.At the same time, existing ozone contact device poor, the problems such as equipment volume is larger that also there is mass transfer effect.

The content of the invention

In consideration of it, the present invention proposes the technique and device of a kind of catalytic ozonation processing organic wastewater, it is intended in solution State problem.The present invention's is accomplished in the following manner：

A kind of method that catalytic ozonation handles organic wastewater, it is characterised in that this method comprises the following steps：To be many Hole polytetrafluoroethylmaterial material perfluoro alkane solvent fully soaks；It is hollow with above-mentioned porous material filling micro-hole aerator or composition Fiber film component, builds ozone catalytic reactor, and ozone and waste water by ozone catalytic reactor bottom enter, and tail gas is through handling heel row Sky, produces water autoreactor collected overhead.It is preferred that, the used a diameter of 1mm-5mm of polytetrafluoroethylmaterial material, length is 1mm- 0.1m, porosity is 30%-60%；Used polytetrafluoroethylmaterial material is line style or doughnut/cast.

It is preferred that, used perfluoro alkane solvent is the mixture or pure substance of perfluor amine substance.

It is preferred that, the ozone catalytic reactor includes two kinds of micro-pore aeration type and hollow fiber film assembly type.

It is preferred that, the fine bubble diffuser type ozone catalytic reactor is by housing, micro-pore aeration plate and line style polytetrafluoro Ethylene catalyst material is constituted.

It is preferred that, aeration panel aperture is 10 μm -100 μm, and Air Bubble Size is 0.1mm-1mm.

It is preferred that, the hollow fiber film assembly type ozone catalytic reactor is by membrane module polytetrafluoroethylhollow hollow fiber membrane Composition is loaded, loading density is 10%-50%.

It is preferred that, the mass transport process of ozone is carried out with non-vesicular forms, in operating process, and gaseous pressure is less than liquid phase pressure.

Beneficial effects of the present invention are：

Using perfluoro alkane solvent as the medium of ozone oxidation process, perfluoro alkane solvent is to ozone and partial organic substances Optionally it is enriched with, reaction substrate is concentrated in perfluoro alkane phase, ozone oxidation speed is improved.

Using porous Teflon material as the backing material of perfluoro alkane solvent, water, ozone and perfluor can be improved The contact area of alkane solution, while reducing loss of the perfluoro alkane solution under hydraulic blow.

Film forming haptoreaction component is prepared using hollow polytetrafluoroethylene fibre/tubular material, the component has ozone Distribution and ozone catalytic dual-use function, reactor are compacter.

Ozone mass transport process bubble-free in hollow-fibre membrane contact reactor produces, it is to avoid the liquid of traditional reactor The problems such as general and foam, meanwhile, its mass-transfer efficiency is higher, the small volume of reactor.

Brief description of the drawings

A kind of two kinds of unit configuration signals of correspondence of Fig. 1 techniques of catalytic ozonation processing organic wastewater of the present invention Figure.

Fig. 2 is a kind of molecular formula of representative perfluor alkane solvent of the present invention.

Fig. 3 is the surface texture electromicroscopic photograph of polytetrafluoroethylmaterial material of the present invention, under 10,000 times.

Fig. 4 is the cross section structure electromicroscopic photograph of polytetrafluoroethylmaterial material of the present invention, under 500 times.

Fig. 5 is embodiment the method for the invention to diisobutyl phthalate degradation effect figure.

Embodiment

The present invention is described in further detail below.

Embodiment 1

Diisobutyl phthalate is a kind of common plasticizer, be plastic processing enterprise discharge waste water in it is common Component, it is easily enriched with, and bio-toxicity is big.The present embodiment is contacted by comparing the independent ozone oxidation of Bubbling method and hollow-fibre membrane Perfluoro alkane dicyandiamide solution O3 catalytic oxidation method degraded diisobutyl phthalate under device, to illustrate the feasible of the invention Property.

Supporting substrates are used as from polytetrafluoroethylhollow hollow fiber membrane.The hollow-fibre membrane external diameter 1.6mm, internal diameter 0.8mm, 0.2 μm of average pore size, porosity 45%.The material has pattern such as Fig. 3 of the pore space structure of abundant insertion, its surface and section With shown in Fig. 4.The hollow-fibre membrane is loaded as in putamina body, blocked using epoxide-resin glue, membrane contactor being made.Should Membrane contactor loads film silk 20, and internal diameter is 15mm, and effective length is 100mm.Its basic configuration such as Fig. 1, shown in form 2.

As a comparison, while having made fine bubble diffuser, such as Fig. 1, shown in form 1.Aerator internal diameter 15mm, effectively Height 100mm.Aerator bottom is provided with micro-pore aeration titanium plate, and aeration titanium plate average pore size is 50 μm, prepared bubble diameter For 0.1mm-1mm.

Diisobutyl phthalate concentration of aqueous solution is 5ppm, and volume is 1L, is by the flow velocity of aerator 100ml/min, reaction temperature is 20 DEG C, and the reaction time is 30min.

The effect that it contrasts oxidation is as shown in Figure 5.By the 30min reaction time, the degradation rate of independent ozone oxidation is 16%, and the degradation rate of O3 catalytic oxidation is 47%.By contrast, the ozone utilization ratio and pollutant of O3 catalytic oxidation Degradation rate is obviously improved.

The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and Within principle, any modification, equivalent substitution and improvements made etc. should be included in the scope of the protection.

Claims

1. a kind of method that catalytic ozonation handles organic wastewater, it is characterised in that this method comprises the following steps：Will be porous Polytetrafluoroethylmaterial material perfluoro alkane solvent fully soaks；With above-mentioned porous material filling micro-hole aerator or hollow fibre is made Membrane module is tieed up, ozone catalytic reactor is formed；Ozone and waste water enter from ozone catalytic reactor bottom, and tail gas is through handling heel row Sky, produces water autoreactor collected overhead.

2. the method that catalytic ozonation according to claim 1 handles organic wastewater, it is characterised in that：It is used poly- Tetrafluoroethene material diameter is 1mm-5mm, and length is 1mm-0.1m, and porosity is 30%-60%；Used polytetrafluoroethylene (PTFE) Material is line style or doughnut/cast.

3. the method that catalytic ozonation according to claim 1 handles organic wastewater, it is characterised in that：It is used complete Fluothane hydrocarbon solvent is the mixture or pure substance of perfluor amine substance.

4. the method that catalytic ozonation according to claim 1 handles organic wastewater, it is characterised in that：The ozone is urged Changing reactor includes two kinds of micro-pore aeration type and hollow fiber film assembly type.

5. the method that catalytic ozonation according to claim 4 handles organic wastewater, it is characterised in that：The microbubble Aeration type ozone catalytic reactor is made up of housing, micro-pore aeration plate and line style polytetrafluoroethylene (PTFE) catalysis material.

6. the method that catalytic ozonation according to claim 5 handles organic wastewater, it is characterised in that：It is aerated panel aperture For 10 μm -100 μm, Air Bubble Size is 0.1mm-1mm.

7. the method that catalytic ozonation according to claim 4 handles organic wastewater, it is characterised in that：The hollow fibre Dimension membrane module type ozone catalytic reactor is loaded by membrane module polytetrafluoroethylhollow hollow fiber membrane and constituted, and loading density is 10%- 50%.

8. the method that catalytic ozonation according to claim 1 handles organic wastewater, it is characterised in that：The mass transfer of ozone Process is carried out with non-vesicular forms, in operating process, and gaseous pressure is less than liquid phase pressure.