CN105498478B - A kind of method and device of gas phase photolysis-liquid phase photochemical catalytic oxidation purifying volatile organic matter - Google Patents

A kind of method and device of gas phase photolysis-liquid phase photochemical catalytic oxidation purifying volatile organic matter Download PDF

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CN105498478B
CN105498478B CN201511014772.1A CN201511014772A CN105498478B CN 105498478 B CN105498478 B CN 105498478B CN 201511014772 A CN201511014772 A CN 201511014772A CN 105498478 B CN105498478 B CN 105498478B
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gas
liquid phase
photolysis
liquid
gas phase
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CN105498478A (en
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黄海保
占玉杰
刘高源
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GUANGDONG LVMEI ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd.
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National Sun Yat-sen University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/75Multi-step processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/76Gas phase processes, e.g. by using aerosols
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77Liquid phase processes
    • B01D53/78Liquid phase processes with gas-liquid contact
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8678Removing components of undefined structure
    • B01D53/8687Organic components
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/20Metals or compounds thereof
    • B01D2255/207Transition metals
    • B01D2255/20707Titanium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/80Type of catalytic reaction
    • B01D2255/802Photocatalytic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/70Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708Volatile organic compounds V.O.C.'s
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/06Polluted air

Abstract

The invention discloses a kind of method and apparatus of gas phase photolysis liquid phase photochemical catalytic oxidation purifying volatile organic matter.The method of the present invention includes the following steps:S1. gas phase photolysis:Volatile organic matter is irradiated under ultraviolet light conditions, photolysis period < 1s, reaction generates the residual gas composition gaseous mixture after ozone, with photodissociation;S2. liquid phase photocatalysis:The gaseous mixture that S1 is obtained carries out reverse gas-liquid contact with catalyst slurry, fully reacts, and gaseous mixture is converted into CO2And H2O.The present invention effectively combines gas phase photolysis with liquid phase photochemical catalytic oxidation, and two steps influence each other, and synergistic effect can not be divided.The method fundamentally solves the problems such as catalyst inactivation caused by gas-solid photocatalytic surfaces intermediate product deposition and low VOCs liquid phase scrubbing efficiency, it is acted synergistically by various procedures such as high energy ultraviolet photodissociation, liquid phase photocatalysis and catalytic ozonations, the generation and accumulation of intermediate product are reduced, realizes the degradation of organic exhaust gas efficient stable.

Description

A kind of method of gas phase photolysis-liquid phase photochemical catalytic oxidation purifying volatile organic matter and Device
Technical field
The invention belongs to gas pollutant process fields, and in particular, to a kind of gas phase photolysis-liquid phase photochemical catalytic oxidation is net Change the method and device of volatile organic matter.
Background technology
With quickly propelling for Chinese Urbanization and process of industrialization, the discharge capacity of organic exhaust gas is increasing, and air is dirty Dye is on the rise, the volatile organic matter in surrounding air(VOCs)It is substantially improved.Volatile organic matter(VOCs)It is that China is big Gas key pollutants PM2.5 and O3The important as precursors object of formation, easily intercouples with other atmosphere pollutions, is formed by new dirt Dye object is difficult to natural decomposition, and harm is more lasting.In addition, it can also participate in photochemical reaction, lead to photochemical pollution.Have Machine exhaust gas not only has stimulation, but also have certain toxicity often with stench to human body and various sense organs, strong to human body Health causes great harm.The elimination improvement of organic exhaust gas is a urgent and important job, becomes the difficult point of current research With hot spot.
There are still a foregone conclusions in actual use for the more technique of application such as activated carbon adsorption at present, catalysis burning etc. Limit, it is difficult to meet an urgent demand of increasingly strict emission regulation and the people to improvement air quality.Not such as absorption method Can fundamentally eliminate pollutant, desorption equipment, control system and desorption operating cost are high, needed after adsorbent saturation regeneration or Person replaces.Catalysis burning is of high cost usually using noble metal as catalyst;Carry out that there are security risk and catalyst in hot environment Easy in inactivation;Organic exhaust gas concentration is relatively low to need outside heat to maintain to burn.
Photocatalysis technology is to obtain extensive concern in recent years, can light at room temperature photograph under decomposing organic matter, have oxidability The advantages such as by force, reaction condition is mild, are a kind of more promising technologies.However common gas/solid photochemical catalytic oxidation volatility The intermediate products such as aldehyde, ketone, acid and ester are will produce during organic matter, not only cause secondary pollution, but also intermediate product is covered in Catalytic active site can cause catalyst efficiency to decline even complete deactivation, and the by-products such as gas residual ozone after purification.These Problem, which becomes, restricts the bottleneck that the technology further develops and applies.To improve photocatalytic degradation efficiency, effectively solving catalyst Inactivation and elimination ozonation by-product, need to change gas/solid photochemical catalytic oxidation organic exhaust gas system.
Invention content
The present invention is proposed for the deficiency of VOCs treatment technology in the prior art on the basis of gas/solid light-catalysed A kind of new method of gas phase photolysis-liquid phase photochemical catalytic oxidation purifying volatile organic matter, this method is by gas phase photolysis and liquid phase light Catalysis effectively combines, by the way that catalyst is added in the liquid phase so that volatile organic matter enters in liquid phase and occurred after photodissociation The reactions such as photochemical catalytic oxidation, ozone oxidation, the final degradation for realizing organic exhaust gas efficient stable.
Another object of the present invention is to provide a kind of gas phase photolysis-liquid phase photochemical catalytic oxidation purifying volatile organic matters Device.
The above-mentioned purpose of the present invention is achieved by the following technical programs.
A kind of method of gas phase photolysis-liquid phase photochemical catalytic oxidation purifying volatile organic matter, includes the following steps:
S1. gas phase photolysis:Volatile organic matter is irradiated under ultraviolet light conditions, photolysis period < 1s, reaction generates smelly Residual gas after oxygen, with photodissociation forms gaseous mixture;
S2. liquid phase photocatalysis:The gaseous mixture that S1 is obtained carries out reverse gas-liquid contact with catalyst slurry, fully reacts, Gaseous mixture is converted into CO2And H2O;
TiO is added using water as medium in the catalyst slurry2Or through transient metal Mn, Cu, Co or Ni modified TiO2; Wherein, transition metal modified TiO2Method be:Using the salt containing transition metal as presoma, using infusion process, by its aqueous solution With TiO2After the aqueous solution mixing of powder, then 80 ~ 120 DEG C of drying roast under conditions of 300 ~ 550 DEG C, obtain described change Property TiO2
It is existing studies have shown that aqueous-phase photo-catalysis degradation Organic substance in water is organic compared to gas-solid light catalytic purifying volatility Object, catalytic stability are good.This may be because catalyst surface keeps higher activity due to washing effect in liquid phase.It is single Gas phase photolysis is solely used, volatile organic matter degradation efficiency is low, and generates a large amount of intermediate products, the ozone direct emission meeting of generation It pollutes, and processing of the liquid phase photocatalysis for volatile organic matter in waste water is more, gaseous volatile organic matter is mainly used Gas-solid photocatalysis combines the two the degradation rate allowed in liquid phase to be higher than gas phase, and some photolytic products are soluble easily in water, Furthermore the catalyst in liquid phase since washing effect, intermediate product will not be accumulated in catalyst surface as gas-solid photocatalysis, Lead to catalyst inactivation.
Volatile organic matter carries out high energy ultraviolet photodissociation first under action of ultraviolet light, and a part of volatile organic matter is by light Solution, while the process generates a certain amount of O3, wherein including aldehyde, acid by the photolytic product of a part of volatile organic matter of photodissociation Equal intermediate products;Gaseous mixture after photodissociation(Including volatile organic matter, photolytic product, ozone)With catalyst slurry into promoting the circulation of qi Liquid contacts, and volatile organic matter and its product can also be made other than being shifted into liquid phase due to the absorption of catalyst slurry at this time It is spread into solution and catalyst solid particle with quickening, then under the action of ultraviolet light, photochemical catalyst and ozone, volatility The processes such as photochemical catalytic oxidation and catalytic ozonation occur in the liquid phase for organic matter and its intermediate product, are finally changed into CO2 And H2O is discharged.The liquid phase photochemical catalytic oxidation step for the ozone energy strengthening subsequent that step S1 ultraviolet photolysis generates generates more high Active oxygen species, and then improve volatile organic matter purification efficiency and delay catalyst inactivation, it reduces real while ozone pollution Ozone utilization is showed, has turned harm into good;Due to the presence of degradation during step S2, the volatile organic matter in liquid phase is not It is disconnected to be degraded, volatile organic matter can be effectively facilitated and shifted into liquid phase, the absorption efficiency of liquid phase is accelerated, it is final to realize volatilization The high-efficient purification of property organic matter.
The present invention effectively combines gas phase photolysis with liquid phase photochemical catalytic oxidation, and two steps influence each other, and collaboration is made With can not divide.The method fundamentally solve catalyst inactivation caused by gas-solid photocatalytic surfaces intermediate product deposition with And VOCs liquid phase scrubbing efficiency it is low the problems such as, pass through a variety of mistakes such as high energy ultraviolet photodissociation, liquid phase photocatalysis and catalytic ozonation Journey acts synergistically, and reduces the generation and accumulation of intermediate product, realizes the degradation of organic exhaust gas efficient stable.In addition, this method is filled Dividing makes it using ultraviolet luminous energy while providing energy for gas phase photolysis, liquid phase photochemical catalytic oxidation, and is produced during gas phase photolysis Raw ozone can also strengthen VOCs oxidations under liquid-phase catalyst effect.
The catalyst slurry is added titanium dioxide or the titanium dioxide after transition metal modified mixes using water as medium It closes, there is stronger photocatalytic activity than common titanium dioxide, catalyst and water can generate more under ultraviolet lamp excitation The free radical of more strong oxidizing properties, improve system oxidability, can decompose to non-selectivity Recalcitrant chemicals be carbon dioxide and Water has strong organic exhaust gas adsorption performance, high ozone utilization ratio and highlight catalytic active.There is the method for the present invention purification to imitate Rate is high, reaction is mild, process is simple, performance is stable and it is economical many advantages, such as, can be that volatile organic matter improvement provide A kind of solution of new high-efficiency and economic.
Preferably, the catalyst slurry after S2 uses regenerates use after collection.
Preferably, the salt containing transition metal is organic acetate or mineral sulfates.
Preferably, the load capacity of the transition metal is 1% ~ 5%.
Preferably, the wavelength of ultraviolet light described in S1 is 185nm.
The present invention also provides a kind of gas phase photolysis based on the above method-liquid phase photocatalysis apparatus, including gas phase photolysis room, Liquid phase photocatalysis spray column and liquids recovery regenerate case, be provided, in sequence from bottom to top, in the liquid phase photocatalysis spray column exhaust gas into Device of air, filter bulb layer, absorbing liquid spray equipment and gas discharge outlet, the lower part of the liquid phase photocatalysis spray column and liquids recovery The top for regenerating case is connected, and the liquids recovery regeneration case is connected by liquor charging pipeline, circulating pump with absorbing liquid spray equipment;Institute It states and is additionally provided with ultraviolet lamp and gas phase photolysis cell in liquid phase photocatalysis spray column, the ultraviolet lamp in liquid phase photocatalysis spray column is set to Between filter bulb layer and gas discharge outlet, the end of the absorbing liquid spray equipment is equipped with several atomizers, the gas phase light Solution room includes quartz glass sleeve and sets ultraviolet lamp in the inner, the quartz glass sleeve respectively with air inlet and gas inlet Device is connected.
In use, being equipped with catalyst slurry in liquids recovery regeneration case, which passes through circulating pump, liquor charging pipeline It is sprayed with Sprayable at the top of liquid phase photocatalysis spray column with absorbing liquid spray equipment.When exhaust gas from air inlet through gas phase photolysis After the photodissociation of room, then through gas inlet device it is passed through liquid phase photocatalysis spray column, is inversely contacted with spraying by the exhaust gas of filter bulb layer, Liquid phase photochemical catalytic oxidation step is carried out, most of exhaust gas is switched to harmless micromolecular compound, the transfer of fraction intermediate product To catalyst by man of wild origin, the further exhaustive oxidation degradation of liquid phase photocatalysis, and in-situ synchronization is handled in liquids recovery regeneration case Catalyst slurry afterwards continues cycling through use.The liquid phase photocatalysis spray column and gas phase photolysis chamber are equipped with ultraviolet lamp, gas The ultraviolet lamp of phase photolysis chamber cannot be only used for gas phase photolysis, since gas phase photolysis room is quartz glass sleeve, interior ultraviolet lamp It can also play a role to the liquid phase photocatalytic process in liquid phase photocatalysis spray column, to conducive to the quantity of ultraviolet lamp is reduced, save It can be efficiently.
Preferably, the liquid phase photocatalysis spray column, the indoor ultraviolet lamp of gas phase photolysis are equipped with several, are The vacuum UV lamp of 185nm.
Preferably, the ultraviolet lamp in the liquid phase photocatalysis spray column is distributed in a ring.It is highly preferred that liquid phase photocatalysis is sprayed Ultraviolet lamp in leaching tower forms one or more levels annular array, you can one or more layers annular, outermost layer are formed in spray column Ultraviolet lamp along spray inner wall of tower be uniformly distributed.
Preferably, the gas phase photolysis room is equipped with several quartz glass sleeves for being mutually parallel, quartz glass sleeve it Between be connected to by pipeline, be inside respectively equipped with ultraviolet lamp.
Preferably, the gas phase photolysis room is set in gas inlet device.
Preferably, the absorbing liquid spray equipment includes several solution branch pipes, the solution branch pipe with liquor charging pipeline Connection.It is highly preferred that the solution branch pipe is equipped with branch pipe control valve, the flow for controlling the absorbing liquid spray equipment is big Small and atomizing effect.
Preferably, the atomizer uses stainless steel precision high-dispersion noz(zle), atomizing particle to reach 50-100 μm, can also prevent Absorbed liquid is corroded.According to the type of exhaust gas, water solubility, flow and concentration etc., it is preferable that the bore of the atomizer is 1- 3mm ensures that catalyst granules is passed through without blocking.Preferably, the atomizer is equipped with radial injection spray pipe Road, radial ejection of spraying, more conducively comes into full contact with exhaust gas.
Preferably, the gas inlet device is equipped with several outlet passageways, and the outlet passageway is sprayed with the atomization The position of mouth is corresponding.The outlet passageway is face atomizer upward, or consistent with the direction of atomizer downward.As A kind of embodiment, the outlet passageway are venthole, and the venthole is equal with the quantity of the atomizer, and position is opposite It answers.As another embodiment, the gas inlet device be equipped with tubaeform air-guide disk, the air-guide disk it is opening down and If inside setting dried layer outlet passageway.
Preferably, the ultraviolet lamp length in the liquid phase photocatalysis spray column is 1200mm-1800mm, according to the spray The height of tower is adjusted, and ensure that comprehensive by ultraviolet light in the spray column.
Preferably, the filter bulb layer is highly 10cm-30cm using polypropylene filter bulb as filler.
Preferably, the top of the absorbing liquid spray equipment is equipped with demister, and the demister uses spiral-flow plate-type demisting Device or Flat defroster.
Preferably, the liquor charging pipeline is equipped with liquor charging control valve.
Preferably, the liquid phase photocatalysis spray column is equipped with access panel.
Compared with prior art, advantageous effect of the present invention is:Gas phase photolysis is combined by the present invention with liquid phase photocatalysis, Wherein gas phase photolysis can also generate ozone for ozone oxidation degradation organic waste gas, carry other than a part of organic exhaust gas of degrading The degradation rate of high organic exhaust gas, the intermediate product that photodissociation generates in addition is solubility, is conducive to it and further degrades.And liquid phase light Catalysis overcomes the problem of catalyst easy in inactivation in the gas/solid light-catalyzed reaction of tradition, due to the washing effect in liquid phase, centre production Object washing is detached from catalyst surface so that photocatalysis efficient stable carries out, in addition strong adsorptivity in liquid phase, high ozone utilization rate and The degradation of volatile organic matter organic exhaust gas efficient stable can be achieved in the use of highlight catalytic active catalyst, finally realizes and waves Hair property organic matter can be realized innoxious.And can be carried out under this method room temperature, reaction process is mild and simple, has higher warp Ji benefit.
Description of the drawings
Fig. 1 is the overall structure diagram of 3 device of embodiment.
Fig. 2 is the air-guide disk of gas inlet device described in embodiment 3.
Air-guide disk described in Fig. 3 exports upward view.
Fig. 4 is the overall structure diagram of 4 device of embodiment.
Caption:1- liquid phase photocatalysis spray columns;2- circulating pumps;3- gas phase photolysis room;4- photolysis cell ultraviolet lamps;5- liquid pushing tubes Road;6- liquor charging control valves;7- access panels;8- spray column ultraviolet lamps;9- absorbing liquid spray equipments;10- atomizers;11- filter bulbs Layer;12- demisters;13- gas inlet devices;14- gas discharge outlets;15- liquids recoveries regenerate case;16- air-guide disks.
Specific implementation mode
The present invention is described in further details with specific embodiment with reference to the accompanying drawings of the specification, but embodiment is not The present invention is limited in any form.Unless stated otherwise, the present invention uses reagent, method and apparatus is the art Conventional reagent, method and apparatus.Wherein, the drawings are for illustrative purposes only and are merely schematic diagrams rather than pictorial diagram, no It can be understood as a limitation of this patent;Embodiment in order to better illustrate the present invention, the certain components of attached drawing have omission, amplification Or reduce, do not represent the size of actual product;It will be understood by those skilled in the art that certain known features and its explanation in attached drawing It may omit and will be understood by.
Embodiment 1
A kind of method of gas phase photolysis-liquid phase photochemical catalytic oxidation purifying volatile organic matter, includes the following steps:
S1. experiment uses 1 ultraviolet lamp, and the volatile organic matter benzene of a concentration of 15 ~ 50ppm is pressed flow velocity 1L/min, wet 50%, the gas phase photolysis 0.5s under the conditions of ultra violet lamp of 185nm wavelength are spent, reaction generates the residue gas after ozone, with photodissociation Body forms gaseous mixture;
S2. the gaseous mixture through gas phase photolysis is passed through liquid phase photocatalysis spray column, catalyst slurry TiO2(P25)From upper Downwards, from bottom to top, the two inversely carries out gas-liquid contact to gaseous mixture, by liquid phase scrubbing, purple under the irradiation of vacuum UV lamp Outer photochemical catalytic oxidation, catalytic ozonation process, VOCs are eventually converted to CO2And H2O is discharged through gas outlet, in gas outlet pair Benzene and CO2Concentration is detected.
After testing, the degradation efficiency of benzene is 84% after reaction, mineralization rate 79%, the exit concentration of ozone less than 100ppm, Reach 150ppm or more only with its outlet ozone concentration when liquid phase photocatalysis, and its degradation rate and mineralization rate are below gas phase light Solution-liquid phase light catalytic purifying volatile organic matter.
Embodiment 2
A kind of method of gas phase photolysis-liquid phase photochemical catalytic oxidation purifying volatile organic matter, includes the following steps:
S1. experiment uses 1 ultraviolet lamp, wet by the volatile organic matter benzene of a concentration of 15 ~ 50ppm by flow velocity 1L/min Degree is 50%, the gas phase photolysis 0.8s under the vacuum UV lamp irradiation condition of 254nm wavelength, after reaction generates ozone, with photodissociation Residual gas forms gaseous mixture;
S2. the gaseous mixture through gas phase photolysis is passed through liquid phase photocatalysis spray column, catalyst slurry is modified by Mn TiO2(P25)(Mn load capacity is respectively 0.1%, 1%, 3% and 5%), catalyst slurry from the top down, gaseous mixture from bottom to top, The two inversely carries out gas-liquid contact, by liquid phase scrubbing, ultraviolet catalytic oxidation, ozone catalytic under the irradiation of vacuum UV lamp Oxidation process, VOCs are eventually converted to CO2And H2O is discharged through gas outlet, in gas outlet to benzene and CO2Concentration is detected.
After testing, when Mn load capacity is 0.1%, the optimal degradation efficiency of benzene is 89%, mineralization rate 85%, but is gone out at this time Halitosis oxygen concentration is higher.Integrated survey photochemical catalytic oxidation clean-up effect and the concentration for exporting ozone, Mn load capacity is respectively 1 ~ 3% It is more suitable.When Mn load capacity is 3%, the exit concentration of ozone is minimum, is 50ppm.
Embodiment 3
The present embodiment provides a kind of, and the gas phase photolysis based on the above method-liquid phase photocatalysis apparatus is wrapped as shown in Fig. 1 ~ 3 It is interior under to include gas phase photolysis room 3, liquid phase photocatalysis spray column 1 and liquids recovery regeneration case 15, the liquid phase photocatalysis spray column 1 Gas inlet device 13, filter bulb layer 11, absorbing liquid spray equipment 9, demister 12 and gas discharge outlet 14, institute are equipped on and successively The lower part for stating liquid phase photocatalysis spray column 1 is connected with the top of liquids recovery regeneration case 15, and the liquids recovery regeneration case 15 is logical Cross liquor charging pipeline 5, circulating pump 2 is connected with absorbing liquid spray equipment 9.The absorbing liquid spray equipment 9 includes several solution branch Pipe, the solution branch pipe are connected to liquor charging pipeline 5, and the solution branch pipe is equipped with branch pipe control valve, for controlling the suction Receive the uninterrupted and atomizing effect of liquid spray equipment.The end of the absorbing liquid spray equipment 9 is equipped with several stainless steel precisions High-dispersion noz(zle) 10, atomizing particle reach 50-100 μm, can also prevent absorbed liquid from corroding.The gas inlet device 13 is equipped with loudspeaker The air-guide disk 16 of shape, if the air-guide disk 16 is opening down and internal setting dried layer outlet passageway.The outlet passageway is court It is lower consistent with the direction of atomizer 10.The filter bulb layer 11 is highly 10cm-30cm using polypropylene filter bulb as filler.It is described Liquor charging pipeline 5 is equipped with liquor charging control valve 6.The liquid phase photocatalysis spray column 1 is equipped with access panel 7.
More specifically, the gas inlet device 13 includes interconnected air inlet, quartz glass sleeve and air-guide disk 16.The gas phase photolysis room 3 is set between filter bulb floor 11 and liquids recovery regeneration case 15, by quartz glass sleeve and is set in the inner Several horizontal 185nm photolysis cells ultraviolet lamps 4 form.Several are also equipped in the liquid phase photocatalysis spray column 1 vertically 185nm spray columns ultraviolet lamp 8, spray column ultraviolet lamp 8 is set between filter bulb layer 11 and gas discharge outlet 14.The liquid phase light is urged 8 length of spray column ultraviolet lamp changed in spray column 1 is 1200mm-1800mm, is adjusted according to the height of the spray column, is protected It has demonstrate,proved comprehensive by ultraviolet light in the spray column.
In use, exhaust gas enters gas phase photolysis room 3 by the air inlet of gas inlet device 13, by photolysis cell ultraviolet lamp After 4 gas phase photolysis effect, then by the entrance liquid phase photocatalysis of air-guide disk 16 spray column 1, spraying with catalyst slurry reverse Contact carries out liquid phase photochemical catalytic oxidation step.It is equipped with ultraviolet lamp in the liquid phase photocatalysis spray column 1 and gas phase photolysis cell 3, Photolysis cell ultraviolet lamp 4 in gas phase photolysis room 3 cannot be only used for gas phase photolysis, since gas phase photolysis room 3 is quartz glass sleeve, Its interior ultraviolet lamp can also play a role to the liquid phase photocatalytic process in liquid phase photocatalysis spray column 1, to ultraviolet conducive to reducing The quantity of lamp, it is energy-efficient.
Embodiment 4
Gas phase photolysis provided in this embodiment-liquid phase photocatalysis apparatus is substantially same as Example 3, as shown in figure 4, different Place is that the quartz glass sleeve and photolysis cell ultraviolet lamp 4 are vertically arranged, there are two the gas phase photolysis room 3 is set The quartz glass sleeve being mutually parallel, between be connected to by pipeline, it is ultraviolet to be respectively equipped with photolysis cell in two quartz glass sleeves Lamp 4 is connected between quartz glass sleeve by pipeline, is inside respectively equipped with photolysis cell ultraviolet lamp 4.
Obviously, the above embodiment of the present invention is just for the sake of clearly demonstrating examples made by the present invention, and is not Restriction to embodiments of the present invention.For those of ordinary skill in the art, on the basis of the above description also It can make other variations or changes in different ways, there is no necessity and possibility to exhaust all the enbodiments.It is all All any modification, equivalent and improvement made by within the scope of the spirit and principles in the present invention etc. should be included in power of the present invention Within the protection domain that profit requires.

Claims (9)

1. a kind of method of gas phase photolysis-liquid phase photochemical catalytic oxidation purifying volatile organic matter, which is characterized in that including walking as follows Suddenly:
S1. gas phase photolysis:Volatile organic matter to be irradiated under ultraviolet light conditions, photolysis period < 1s, reaction generates ozone, Gaseous mixture is formed with the residual gas after photodissociation;
S2. liquid phase photocatalysis:The gaseous mixture that S1 is obtained carries out reverse gas-liquid contact with catalyst slurry, in ozone, ultraviolet light It is reacted under the collective effect of catalyst, gaseous mixture is converted into CO2And H2O;
The catalyst slurry is added using water as medium through transient metal Mn, Cu, Co or Ni modified TiO2, wherein transition Metal-modified TiO2Method be:Using the salt containing transition metal as presoma, using infusion process, by its aqueous solution and TiO2Powder Aqueous solution mixing after, 80 ~ 120 DEG C drying, then roasted under conditions of 300 ~ 550 DEG C, obtain the modified TiO2;It is described The load capacity of transition metal is 1% ~ 5%.
2. a kind of gas phase photolysis based on claim 1 the method-liquid phase photocatalysis apparatus, including gas phase photolysis room, liquid phase Photocatalysis spray column and liquids recovery regenerate case, which is characterized in that are set successively from bottom to top in the liquid phase photocatalysis spray column Have gas inlet device, filter bulb layer, absorbing liquid spray equipment and a gas discharge outlet, the lower part of the liquid phase photocatalysis spray column with The top that liquids recovery regenerates case is connected, and the liquids recovery regeneration case is sprayed by liquor charging pipeline, circulating pump and absorbing liquid to be filled It sets connected;Ultraviolet lamp and gas phase photolysis cell, the purple in liquid phase photocatalysis spray column are additionally provided in the liquid phase photocatalysis spray column Outer lamp is set between filter bulb layer and gas discharge outlet, and the end of the absorbing liquid spray equipment is equipped with several atomizers, The gas phase photolysis room includes quartz glass sleeve and sets ultraviolet lamp in the inner, the quartz glass sleeve respectively with air inlet And gas inlet device is connected.
3. the apparatus of claim 2, which is characterized in that the liquid phase photocatalysis spray column, gas phase photolysis are indoor Ultraviolet lamp is equipped with several, is the vacuum UV lamp of 185nm.
4. device according to claim 3, which is characterized in that the ultraviolet lamp in the liquid phase photocatalysis spray column is in a ring Distribution.
5. device according to claim 3, which is characterized in that the gas phase photolysis room is equipped with several stones being mutually parallel English glass bushing is connected between quartz glass sleeve by pipeline, is inside respectively equipped with ultraviolet lamp.
6. the apparatus of claim 2, which is characterized in that the atomizer uses stainless steel precision high-dispersion noz(zle).
7. the apparatus of claim 2, which is characterized in that the gas inlet device is logical equipped with several outlets Road, the outlet passageway are corresponding with the position of the atomizer.
8. the apparatus of claim 2, which is characterized in that the top of the absorbing liquid spray equipment is equipped with demister, The demister uses spiral-flow plate-type demister or Flat defroster.
9. the apparatus of claim 2, which is characterized in that the liquor charging pipeline is equipped with liquor charging control valve.
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