CN102107927B - Photocatalytic degradation treatment device of wastewater with organic pollutants - Google Patents
Photocatalytic degradation treatment device of wastewater with organic pollutants Download PDFInfo
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Abstract
The invention relates to a photocatalytic degradation treatment device of the wastewater with organic pollutants. The treatment device contains a box. The treatment device is characterized in that the inside of the box is provided with a plurality of relatively independent baffled chambers which are connnected end to end; the both ends of the box are separately provided with a water inlet and a water outlet; in each baffled chamber, a plurality of three-dimensional reticular bodies with immobilized catalyst are stacked at intervals, the center of each three-dimensional reticular body is provided with a through hole, a ultraviolet light source is inserted in the through hole, and an aeration pipe is arranged at the bottom of the baffled chambers; and each three-dimensional reticular body is formed by stacking several layers of reticular carrier, the space between the layers of reticular carrier is 1-3 times of the reticular width, the periphery of the reticular carrier is bent to the bottom surface relatively, the center of the reticular carrier is provided with an I-shaped notch, and the notch is bent to the bottom surface. An illumination device is inserted in the notch. By adopting the device of the invention, the organic matter in wastewater can be decomposed to a large extent.
Description
The original bill application number: 200910303709.8,
The applying date: on June 26th, 2009,
Denomination of invention: the manufacturing method of netted catalyst of organic pollutant and organic pollutant in the photocatalytic degradation waste water
Wastewater treatment equipment
Technical field
The present invention relates to the working method of the netted catalyst of organic pollutant in a kind of photocatalytic degradation waste water and use the organic pollutant wastewater treating device of this netted catalyst.
Background technology
China's detergent industry development in recent years is rapid, and its output increases year by year.China's synthetic detergent output was 5,100,000 tons in 2005, and 2006 is 5,500,000 tons, reached 6,000,000 tons in 2007, was expected to be 6,500,000 tons in 2008.China uses many tensio-active agents at present has: AS (is main with linear alkylbenzene sulphonic acid LAS) accounts for 70% of total amount; Nonionogenic tenside accounts for 20% of total amount; Other account for 10%.Synthetic detergent is of many uses, almost relates to all respects of family life, industrial and agricultural production.
Photocatalysis oxidation technique is the seventies in last century new developing technology, a novel method in the last thirty years.Photochemical catalysis is when being mapped to semiconductor catalyst through ultraviolet lighting; The electronics (e) that is in valence band will be excited on the conduction band; Valence band generates hole (h+), thereby it is right on valence band and conduction band, to produce highly active light induced electron-photohole respectively, and the thorough mineralising of multiple organic pollutant is removed.Photocatalysis oxidation technique is the removal of the hazardous and noxious substances of various organic pollutants and reducing inorganic pollutent, particularly difficult for biological degradation, and the environmental pollution that has future advanced purification technology is provided.Simultaneously because advantages such as its processing cost is low, complete decomposition, non-secondary pollution have caused the concern in contemporary science and technology field.
But photocatalysis oxidation technique exists many deficiencies and restraining factors in practical application:
The first, the quantum benefit is low, simple TiO
2The height of recombination rate again that the light induced electron-space of photocatalyst is right, photocatalysis performance is outstanding.Lower photo-quantum efficiency has limited the industrial applications of photochemical catalytic oxidation.
The second, TiO
2Select adsorptivity poor, the product C O of light-catalyzed reaction process
2Very easily be adsorbed on catalyst surface and greatly reduce the speed and the selectivity of light-catalyzed reaction.
The 3rd, the organic pollutant degradation intermediate product is complicated, and actual waste water is of a great variety; All kinds of water quality differ greatly, and the contaminant degradation complexity differs, and mechanism is different; There is competing reaction between the component, restricted the commercial application of photocatalysis technology to a certain extent.
The 4th, effective distribution of photocatalyst and ultraviolet source and fusion problem.
Below what time be technology and the technological problems of realizing that photocatalysis oxidation technique industrial applications institute must solution.So the catalyst distribution system is optimized in research and develop high efficiency have industry synthesizing new carrier and catalyzer or it is modified targetedly, to improve the effective rate of utilization of light and catalyzer, significantly improves the efficient of photocatalytic oxidation degradation; The coupling of exploitation photocatalysis oxidation technique and other technologies, the new technology of preparing such as restriction that overcome unfavorable factor from technology are the mainstream development directions of photocatalysis technology.Also be to carry out the major subjects of commercial application research and exploitation and the key issue place that needs to solve at present both at home and abroad.
At home and abroad in the photocatalysis technology patent; The nano titanium oxide that is used for photocatalytic degradation mostly adopts suspension or its appendix is that hollow glass ball, porous plastics, resin, wood are cut, processes floated or fixed-bed type photochemical catalysis system on the helical spring structure carrier, ceramic foam, fine microfilament; Its dual mode all exists catalyzer and can not fully effectively contact and fusion with UV-light; Can not make that fluid catalyst contacts uniformly and effectively in the whole catalystsystem, be unfavorable for system's fully reaction uniformly and effectively.No matter be suspended state or filling type fixed bed catalyst and since fluid through or air-flow stir and all can cause catalyzer to damage because of collision, make catalyst loss.Thereby can't satisfy the industriallization application in industry of photocatalysis oxidation technique.
Summary of the invention
The problem that the present invention solved is to overcome above deficiency, and provides a kind of duration of service longer, the photocatalysis degradation organic contaminant wastewater treatment equipment of better effects if.
In order to reach above purpose, the organic pollutant wastewater treating device of this application netted catalyst of the present invention comprises casing; It is characterized in that: be provided with a plurality of relatively independent and end to end successively baffling chambers in the casing; Two ends are respectively equipped with water-in and water outlet, and the baffling partition stacks some solid netted bodies that are solidified with catalyzer, have through hole in the middle of the solid netted body; Ultraviolet source is inserted in the through hole, and aeration tube is located at bottom, baffling chamber.
Solid netted body is to be formed by stacking with the several layers mesh carrier, and each layer mesh carrier spacing is 1-3 a times of mesh width.
Can the mesh carrier periphery be bent to the bottom surface relatively, middle cut notched cut, and to the bottom surface turnover, intermediate formation is used for inserting the through hole of ultraviolet source; Perhaps, be fixed on the indoor support of baffling, be superimposed as solid netted body with mesh carrier mesh width 1-3 distance doubly between shelf layer after direct punching in the middle of the mesh carrier or cutting the hole.
Advantage that the present invention and prior art relatively have and advance:
1, propose with transition metal to the nano titanic oxide catalyst modification technique; Making catalyst surface produce defective or changing its percent crystallinity becomes the right shallow gesture in light induced electron-space and catches trap; Make the titanium dioxide nanocrystalline electrode demonstrate p-n junction photoresponse coexistence phenomenon, prolong the recombination time in electronics and space, reduce recombination rate; Photochemical catalytic oxidation activity and benefit are improved, have solved the active Enhancement problem of catalyst.
2, form catalyst system on the solid netted body that titanium deoxide catalyst is attached to rule that proposes.Utilize the high-intensity organic binder bond will be on the solid netted body that is made into rule through the catalyst-coated after modifying; Realized the catalyzer uniform distribution; Catalyzer can evenly and be distributed in the Processing Equipment fully, make UV-light fusion sufficient with it.Form the syzygy of uniform catalyst and UV-light.Make reaction uniform and stable, efficient is improved.Having overcome its appendix of catalyzer simultaneously is to process on hollow glass ball, porous plastics, resin and the wood chip in the floated photochemical catalysis system catalyzer and damages losing issue because of collision causes.Comparing with the packed bed catalyst system, is that the specific surface area aspect of catalyzer all has growth at double in effective utilization or the unit volume of light.
What 3, propose lets the fluid deflector type, and the photocatalysis oxidation reaction device of flowing through has solved fluidic back-mixing problem in the treating processes.Owing to the fusion sufficient of reactor drum medium ultraviolet light, form the syzygy of uniform catalyst and UV-light simultaneously, the waste water that needs to handle is among the uniform reaction system all the time with it.Make the manufacturability issues of continuous industrial application in industry be able to solve.
4, propose with in photochemical catalytic oxidation and the catalytic oxidation coupling technique, (oxygenant commonly used adds O to additional oxidizer
2, add Fe
3+, H
2O
2) method.These oxygenants itself are a kind of good electron receptors, can reduce right compound in electronics and space, and catalytic activity is improved.In realizing industrial applications, often do extra catalyst with the air of cheapness, the effect of airborne oxygen in catalystic converter system, one increases the concentration (O in the electron reduction sewage of photocatalytic degradation reacting middle catalyst conduction band of oxygen in water
2Molecule is the decisive step of speed of response, O
2Superoxide radical or hydroxyl radical free radical that molecule is accepted to form behind the electronics have very strong oxidation capacity, can organism thoroughly be degraded).Two have solved the mass transfer problem between fluid, make between the reactant and can fully contact and react.Simultaneously the product C O2 of alleviating and eliminate the light-catalyzed reaction process is adsorbed on the speed of the light-catalyzed reaction that catalyst surface causes and the problem of selectivity reduction.
Description of drawings
Fig. 1 is an organic pollutant wastewater treating device structural representation of the present invention.
Fig. 2 is the nickel coated iron wire web frame synoptic diagram that is applied to wastewater treatment equipment.
Embodiment
To combine embodiment that the present invention is done further explanation below:
Embodiment 1
The manufacturing method of netted catalyst of organic pollutant in this photocatalytic degradation waste water, step is following:
(1), select for use 8 purpose stainless (steel) wires to be cut into dice; Soak with diluted acid; Here with Hydrogen chloride comparatively commonly used, treat its corrosion, take out with flushing with clean water to there not being residual acid to end; The normal temperature airing keeps online rust staining (rust staining is the compound of elements such as each transition metal Cr, Ni, Fe in the stainless steel composition).
(2), by weight getting 1 part of nano-TiO
2With 4 parts of acetone dispersed with stirring, get 2 parts of epoxy resin, 2 parts of solidifying agent and a little softening agent again, add acetone and TiO
2Dispersion system in, thorough mixing grinds evenly.
(3), will grind the uniform catalyst jelly is coated on the stainless (steel) wire.Rust staining in the coating procedure on the stainless (steel) wire (compounds of elements such as each transition metal Cr, Ni, Fe) will be dissolved in the catalyzer jelly system; To dissolve in the coating procedure as far as possible and be coated on again on the stainless (steel) wire after the rust staining (compounds of elements such as each transition metal Cr, Ni, Fe) that gets off stirs with catalyzer, and place the 150C baking oven to solidify coated mesh load catalyzer.
(4), again be placed in the acetone and soaked 60 minutes, destroy fine and close superficial film, to increase specific surface area of catalyst.
Promptly obtain to be applied to the netted catalyst carrier of organic pollutant wastewater treating device through above step.
The organic pollutant wastewater treating device structure of using above netted catalyst carrier is as shown in Figure 1; Comprise casing 1, be provided with a plurality of relatively independent and end to end successively baffling chambers 2 in the casing 1, stack the mesh carrier 3 that several layers is solidified with catalyzer in each baffling chamber 2 at interval; Have through hole in the middle of the mesh carrier 3; Ultraviolet source is that ultraviolet light 4 is planted wherein, and 2 bottoms, baffling chamber are provided with aeration tube 5, and air injects air to the baffling chamber from the through hole that aeration tube has.As shown in Figure 2 again; The nickel-clad iron silk screen that is applied to wastewater treatment equipment promptly is solidified with the mesh carrier 3 of catalyzer, and operation for ease bends (also can will bend to the bottom surface at four angle kerves earlier) with its both sides 6 all around to the bottom surface relatively; " worker " notched cut is cut in the centre; Two otch 7 and to the bottom surface turnover, intermediate formation is used for inserting the through hole 8 of ultraviolet source, and a plurality of mesh carriers 3 through bending are stacked and placed on and form solid netted body in the baffling chamber 2; The spacing of each layer wire netting doubly is advisable with the 1-3 of mesh carrier mesh width, and ultraviolet source 4 (fluorescent tube) inserts in the through hole 8.When wastewater treatment; Sewage gets into from casing water-in 8, and through current downflow on each baffling chamber 2, air is from aeration tube 5 air inlets of each bottom, baffling chamber; Under the effect of UV-light; Sewage passes the mesh carrier generation Decomposition that is solidified with catalyzer, reaches the purpose of photocatalysis Decomposition wastewater through organic matter, and discharges from water outlet 10.The equipment of this structure has strengthened contacting of sewage and catalyzer, makes full use of the irradiation of UV-light simultaneously, thereby quickens organic decomposition, and rate of decomposition is further improved.
The manufacturing method of netted catalyst of organic pollutant in the present embodiment photocatalytic degradation waste water is different from embodiment 1 and is:
(1), select 1/4 purpose common iron wire net for use, through electro-plating method nickel plating, the nickel plating amount is less than 5% of net surface of the base body and gets final product; It is subsequent use to be cut into certain specification then; Soak with Hydrogen chloride, treat its corrosion, take out with flushing with clean water to there not being residual acid to end; The normal temperature airing keeps online rust staining (rust staining is the compound of elements such as transition metal Ni, Fe).
(2), by weight getting 1 part of nano-TiO
2With 4 parts of acetone dispersed with stirring, get 6 parts of epoxy resin, 6 parts of solidifying agent and a little softening agent again, add acetone and TiO
2Dispersion system in, thorough mixing grinds evenly.
(3), coated mesh load catalyzer is placed on spontaneous curing under the normal temperature.
(4), again be placed in the acetone and soaked 3 minutes, destroy fine and close superficial film, to increase specific surface area of catalyst.
Other are identical with embodiment 1.
The manufacturing method of netted catalyst of organic pollutant in the present embodiment photocatalytic degradation waste water is different from embodiment 1 and is:
(1), selects 4 purpose stainless (steel) wires for use.
(2), get 1 part of nano-TiO
2Add dispersed with stirring in 3 parts of acetone, add 1 again and get a part epoxy resin, 1 part of solidifying agent and the grinding of a little softening agent thorough mixing evenly.
(3), place acetone to soak after 15 minutes to take out, destroy fine and close superficial film, to increase specific surface area of catalyst.
Other are identical with embodiment 1.
The waste water of discharging detects after above 3 are implemented to handle, and the clearance of the essential substance tensio-active agent LAS in the organic cpds is more than 90%, and water outlet meets design requirement fully, is higher than the standard of the general less than 50% of existing clearance far away.And the mesh carrier mesh width is more little, helps contacting of sewage and catalyzer more, but will weaken the exposure rate of UV-light, and through repeatedly test contrast, the mesh carrier grid is advisable between the 1/4-8 order.
Claims (1)
1. photocatalysis degradation organic contaminant wastewater treatment equipment; Comprise casing, be provided with a plurality of relatively independent and end to end successively baffling chambers in the casing, two ends are respectively equipped with water-in and water outlet; It is characterized in that: the baffling partition stacks the solid netted body that is solidified with catalyzer; Have through hole in the middle of the solid netted body, ultraviolet source is inserted in the through hole, and aeration tube is located at bottom, baffling chamber; Said solid netted body is to be formed by stacking with the several layers mesh carrier, and each layer mesh carrier spacing is mesh width 1-3 times; Said mesh carrier periphery bends to the bottom surface relatively; Middle cut notched cut; And turn down to the bottom surface; In the middle of the perhaps said mesh carrier directly punching or cut the hole after, be fixed on the indoor support of baffling, the mesh width 1-3 distance doubly with mesh carrier between shelf layer is superimposed as solid netted carrier.
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| CN201110000895A CN102107927B (en) | 2009-06-26 | 2009-06-26 | Photocatalytic degradation treatment device of wastewater with organic pollutants |
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|---|---|---|---|
| CN201110000895A CN102107927B (en) | 2009-06-26 | 2009-06-26 | Photocatalytic degradation treatment device of wastewater with organic pollutants |
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| CN2009103037098A Division CN101584996B (en) | 2009-06-26 | 2009-06-26 | Manufacturing method of netted catalyst for degrading organic pollutant in wastewater by photocatalysis |
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| CN103663869A (en) * | 2013-12-05 | 2014-03-26 | 武汉宏澳绿色能源工程有限责任公司 | Device and method for treating high density organic waste water by multiphase photocatalysis combined film bioreactor |
| CN104310523A (en) * | 2014-05-06 | 2015-01-28 | 河北科技大学 | Method for processing wastewater by using photocatalytic reaction, and photocatalytic reactor |
| CN107340255B (en) * | 2017-03-29 | 2019-11-29 | 宁波方太厨具有限公司 | Cleaning machine |
| CN112010388A (en) * | 2020-08-18 | 2020-12-01 | 天津市职业大学 | Wastewater treatment device for photocatalytic degradation of organic pollutants for laboratory and use method thereof |
| CN113526757B (en) * | 2021-08-27 | 2022-11-22 | 安徽工业大学 | Wastewater treatment device and method |
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|---|---|---|---|---|
| CN1864843A (en) * | 2006-04-21 | 2006-11-22 | 太原理工大学 | Labyrinth type current-crossing and bubbling photocatalytic reaction device and method for treating organic waste water thereby |
| CN201024117Y (en) * | 2007-04-17 | 2008-02-20 | 任应刚 | Device for processing waste water surfactant by photocatalytic oxidation |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1864843A (en) * | 2006-04-21 | 2006-11-22 | 太原理工大学 | Labyrinth type current-crossing and bubbling photocatalytic reaction device and method for treating organic waste water thereby |
| CN201024117Y (en) * | 2007-04-17 | 2008-02-20 | 任应刚 | Device for processing waste water surfactant by photocatalytic oxidation |
Non-Patent Citations (1)
| Title |
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| 陈胜等.新型内折流光催化反应器连续降解气相中甲苯的研究.《全国太阳能光化学与光催化学术会议专辑》.2004, * |
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