CN106039953A - Method for treating VOCs waste gas in petrochemical industry through normal-temperature high-efficiency catalytic degradation - Google Patents

Method for treating VOCs waste gas in petrochemical industry through normal-temperature high-efficiency catalytic degradation Download PDF

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CN106039953A
CN106039953A CN201610505613.XA CN201610505613A CN106039953A CN 106039953 A CN106039953 A CN 106039953A CN 201610505613 A CN201610505613 A CN 201610505613A CN 106039953 A CN106039953 A CN 106039953A
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waste gas
tio
nano
cemno
catalyst
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李其忠
丁辉
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Zibo Baoquan Environmental Engineering Co., Ltd.
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/75—Multi-step processes
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D—SEPARATION
    • B01D53/00—Separation 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/38—Removing components of undefined structure
    • B01D53/40—Acidic components
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2255/00—Catalysts
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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Abstract

The invention discloses a method for treating VOCs waste gas in petrochemical industry through normal-temperature high-efficiency catalytic degradation and belongs to the technical field of waste gas treatment. The method disclosed by the invention comprises the following steps of: enabling waste gas to enter a first spraying tower from the bottom, collide relative to each other with alkaline spraying liquid sprayed from top to bottom and neutralize acid ingredients to form salt, trapping dust, discharging from the bottom, and enabling the waste gas to be discharged from the top; enabling the waste gas to enter a second spraying tower from the bottom, collide relative to each other with spraying liquid sprayed from top to bottom and dissolve soluble ingredients to form a dissolved solution, discharging from the bottom, introducing ozone into the waste gas discharged from the top, and carrying out oxidation reduction reaction under the action of a CeMnO3/TiO2@SiO2 catalyst to generate CO2 and H2O, so that waste gas treatment is completed. The treatment method disclosed by the invention has the advantages that a large number of 'gas state' hydroxyl free radicals are produced and released and are fully contacted with gas state VOCs molecules as no interphase resistance exists, so that efficiency of treating 'gas' with 'gas' is greatly improved, and VOCs are rapidly and efficiently degraded into micromolecules such as CO2 and H2O and extremely small amount of inorganic salt.

Description

A kind of method of normal-temperature efficient catalytic degradation petroleum chemical industry VOCs waste gas
Technical field
The invention belongs to waste gas pollution control and treatment technical field, be specifically related to a kind of normal-temperature efficient catalytic degradation petroleum chemical industry The method of VOCs waste gas.
Background technology
Petroleum chemical industry is one column support type industry of China, its through atmospheric and vacuum distillation, catalytic cracking, delayed coking, The a series of technical processs such as the processing of catalytic reforming, gas and product purification, are processed into various oil product crude oil.Oil refines The primary raw material of enterprise processed is the element such as Hydrocarbon and the sulfur of part trace, nitrogen, and has substantial amounts of in Hydrocarbon Alkane, and a small amount of aromatic hydrocarbon and cycloalkane.So, petroleum refining process can discharge benzene class, phenols, organic sulfur compound With volatile organic matters (VOCs) such as organic chlorides.
According to the investigation of 2011 of regional planning agency of national environmental protection portion, national petroleum refining, petrochemical industry in 2009 Industry VOCs total amount accounts for the 8.73% of whole nation VOCs total emission volumn, has become as the emphasis source of VOCs discharge.VOCs is the biggest Most poisonous, there is carcinogenecity；Can also react with nitrogen oxides in air, generate photochemical fog, to plant growing and Human respiratory damages；Halogenated hydrocarbon in VOCs also can damage the ozone layer, and causes earth surface temperature to raise.To ring Border and human body cause great bodily injury.
In order to strengthen the improvement to petroleum chemical industry VOCs, the environmental protection Room is at " prevention and control of air pollution action plan " (promulgated by the State Council (2013) No. 37) on the basis of, tailor " petrochemical industry volatile organic matter comprehensive improvement scheme " (environment-development (2014) No. 177), accelerate the Environmental Management Work of Sinopec industry volatile organic matter comprehensive improvement, promote that atmosphere quality changes Kind.Various VOCs treatment technologies meet the tendency and are progressively developed.
At present, it is possible to the technology effectively administering petroleum chemical industry VOCs waste gas is the most less.China's Application No. The utility model patent of 201520418663.5 discloses a kind of room temperature and processes the device of VOCs, uses biological oxidation+hypochlorous acid The PROCESS FOR TREATMENT VOCs waste gas of sodium catalysis oxidation, capital equipment is biological contact oxidation tower and sodium hypochlorite catalysis oxidizing tower.Double Organic substance in VOCs " is classified " process by oxidation technology, improves treatment effeciency, it can be ensured that the tail gas qualified discharge after process.So And, no matter biological contact oxidation tower or sodium hypochlorite catalysis oxidizing tower, all can produce a large amount of waste liquid, purify the same of waste gas Time create waste liquor contamination.
The utility model patent of China's Application No. 201520594899.4 also discloses a kind of use catalytic combustion method Process the device of VOCs.Including catalytic tower, in catalytic tower, it is simultaneously provided with low-temperature catalyzed oxidant layer and high temperature catalyst Layer, through the effect of two-layer catalyst, can obtain good VOCs removal effect.But, still need to add hot waste gas, improve useless The temperature of gas, energy expenditure is big；Additionally, catalytic tower internal structure is complicated, two kinds of catalytic bed are set in same tower, to tower Require height, be unfavorable for industrial popularization and application.
Summary of the invention
The technical problem to be solved is to provide a kind of normal-temperature efficient catalytic degradation petroleum chemical industry VOCs and gives up The method of gas, it is possible to improve governance quality waste gas produced in petroleum refining production process under normal temperature environment.
For solving above-mentioned technical problem, the technical scheme is that a kind of normal-temperature efficient catalytic degradation oil of invention The method of industrial and commercial bank's industry VOCs waste gas, it is characterised in that: comprise the steps:
(1) waste gas is entered the first spray column from bottom, with the spray of alkalescence under spray from top to bottom in the first spray column Drench liquid phase acid ingredient in collision, spray liquid and in waste gas and form salt, and trap dust, arrange from the bottom of the first spray column Going out, the waste gas after process is discharged from the top of the first spray column；
The waste gas that (2) first spray columns are discharged enters the second spray column from bottom, with from top to bottom in the second spray column Spray liquid under Pen Lin collides in opposite directions, dissolves the solvable composition in waste gas and forms lysate, and the bottom of the second spray column is discharged molten Solve liquid, the waste gas after spray processes is discharged at top；
The waste gas that (3) second spray columns are discharged is passed through ozone, at the CeMnO of nucleocapsid micro nano structure3/TiO2@@SiO2 Under catalyst action, ozone and the reaction of moisture in waste gas, the O of generation2Anti-with hydroxyl radical free radical and waste gas generation oxidoreduction Should, generate CO2And H2O, completes the process of waste gas；Described Cu-Cr-O/TiO2@@SiO2Catalyst prepares through following method:
A, under agitation carried out gelation reaction by tetrabutyl titanate, ethanol, hydrochloric acid and water, prepare TiO2Nano-carrier, Speed of agitator is 300～600r/min；It is as follows that the quality of each raw material consumes number:
B, the TiO that will prepare in step a2Nano-carrier is dispersed in water, and adds in the Acetate Solution of Mn and Ce, solution Middle Mn ion and Ce ionic adsorption are at TiO2On nano-carrier, so centrifugal that to be adsorbed with Cu ion and the TiO of Cr ion2Nano-carrier, In the vacuum environment that temperature is 150 DEG C, it is dried 3h, prepares nanoscale CeMnO3/TiO2, nanoscale CeMnO3/TiO2Middle CeMnO3 Mass loading amount be 4～8%；
The nanoscale CeMnO obtained in c, ultraviolet irradiation step b using wavelength to be 200～275nm3/TiO210min, Then clean with water and prepare nano Ce MnO3/TiO2Catalyst；
D, the nano Ce MnO that will prepare in step c3/TiO2Catalyst is hydro-thermal reaction 5～10h in glucose solution, Nano Ce MnO3/TiO2Catalyst surface cladding carbon-coating, carbon layers having thicknesses is 2～4nm, and carbon-coating accounts for nano Ce MnO after cladding3/TiO2 The 2～5% of catalyst gross mass.
E, mixed to obtain mixed liquor by tetraethyl orthosilicate, ammonia and ethanol, step d will prepare the nanometer being coated with carbon-coating CeMnO3/TiO2Catalyst adds in mixed liquor, uses sol-gal process at nano Ce MnO3/TiO2The Surface coating of catalyst Silicon layer, silicon layer accounts for CeMnO after cladding3/TiO2The 20～40% of catalyst gross mass, calcining prepares for 3 hours the most in atmosphere CeMnO3/TiO2@@SiO2。
Preferably, in step (3), described CeMnO3/TiO2@@SiO2Catalyst is supported on filler.
Preferably, described step (3) is carried out in airtight oxidizing tower, and described filler is arranged on the middle part in oxidizing tower, The connection ozonator of the bottom of oxidizing tower and the top of the second spray column, top connection aiutage.
Preferably, described filler is Raschig ring filler, saddle filler, many spheres filler, screen waviness packings, perforated plate corrugated Filler or grid packing.
Preferably, TiO in step a2The particle diameter of nano-carrier is 20～50nm.
Preferably, in described step c, clean to impurity content in filtrate less than 1%.
Preferably, in described step d, the temperature of hydro-thermal reaction is 180 DEG C.
Preferably, in described step e, calcining heat is 500 DEG C.
Compared with prior art, the invention has the beneficial effects as follows:
1, the present invention uses sol-gal process to prepare nanoscale perovskite catalyst CeMnO3/TiO2, then with CeMnO3/ TiO2For raw material, hydro-thermal reaction method and sol-gal process is used to prepare nucleocapsid micro nano structure catalyst CeMnO3/TiO2@@ SiO2.This composite catalyst chemically and thermally good stability, catalysis activity is high, and sulfur resistive, halogen-resistant poisoning capability are strong, and service life is long More than 3 years.
2, the present invention is in numerous metal-oxides, selects TiO2As nano-carrier, TiO2Not only there is nontoxic, character The advantage such as stable, anticorrosive and cheap, also has a dispersibility at a relatively high with aluminium oxide, high porosity and to active component The most loading, and TiO2Itself having certain catalysis activity, it can promote catalysis together with active component synergism Degraded VOCs waste gas, enhances the catalytic capability of catalyst.
3, used by the present invention, the kernel of nucleocapsid micro nano structure catalyst is CeMnO3/TiO2Nanoparticle, shell is porous Property SiO2, the gap of kernel and shell is about 3nm, effectively prevent nano-perovskite catalyst and filling carrier contact with And the agglomeration of self, greatly increase the specific surface area of perovskite catalyst, reduce the load of perovskite catalyst Amount, enhances stability, and catalysis activity is greatly improved.
4, the nucleocapsid micro nano structure perovskite catalyst of the present invention can be by the ozone molecule of gaseous state in the condition of steam Under change into substantial amounts of hydroxyl radical free radical, the catalysis VOCs degraded of strong oxidizing property that hydroxyl radical free radical has；Composite catalyst can also Reduce reaction activity, improve reaction rate, accelerate VOCs degradation reaction speed, both combinations can the most quickly incite somebody to action VOCs degrades, it is to avoid the deficiency of existing catalytic combustion process.
5, nucleocapsid micro nano structure catalyst ozone produces the hydroxyl radical free radical release of a large amount of " gaseous state ", because of without any Alternate resistance, is fully contacted with gaseous state VOCs molecule so that controls the efficiency amplification of " gas " with " gas ", thus fast and efficiently will VOCs clears up into little molecule CO2、H2O and very small amount inorganic salt.Practical Project runs and shows: gas is being existed by reaction zone speed Good treatment effect, complete qualified discharge just can be reached between 1-11m/s.
6, there are not naked light, bright electricity, at normal temperatures efficient catalytic pollutant in this technology, it is not necessary to high temperature, without electrion, Without pulse, without strengthening means such as ultraviolet lights so that it is there is not inflammable and explosive potential safety hazard.Avoid prior art medium Gas ions eliminates VOCs technology needs the danger of electrion.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is described in further detail.
Embodiment one
The step that the present invention administers petroleum refining process generation waste gas is as follows:
(1) waste gas is entered the first spray column from bottom, with the spray of alkalescence under spray from top to bottom in the first spray column Drench liquid phase acid ingredient in collision, spray liquid and in waste gas and form salt, and trap dust, arrange from the bottom of the first spray column Going out, the waste gas after process is discharged from the top of the first spray column；
The waste gas that (2) first spray columns are discharged enters the second spray column from bottom, with from top to bottom in the second spray column Spray liquid under Pen Lin collides in opposite directions, dissolves the solvable composition in waste gas and forms lysate, and the bottom of the second spray column is discharged molten Solve liquid, the waste gas after spray processes is discharged at top；
The waste gas that (3) second spray columns are discharged is passed through in airtight oxidizing tower from bottom, and the bottom of oxidizing tower also connects smelly Oxygen Generator, the middle part in oxidizing tower arranges packing layer, and the filler in packing layer is Raschig ring filler, negative on Raschig ring filler Carry CeMnO3/TiO2@@SiO2Catalyst, the top connection aiutage of oxidizing tower.CeMnO at nucleocapsid micro nano structure3/ TiO2@@SiO2Under the effect of catalyst, ozone and the reaction of moisture in waste gas, the O of generation2Produce with waste gas with hydroxyl radical free radical Redox reaction, generates CO2And H2O, completes the process of waste gas, and the waste gas after process is discharged from aiutage.
Above-mentioned CeMnO3/TiO2@@SiO2Catalyst prepares through following method:
A, under the stirring that rotating speed is 300r/min, carried out gelation reaction by tetrabutyl titanate, ethanol, hydrochloric acid and water, system Obtaining particle diameter is the TiO of 20nm2Nano-carrier；It is as follows that the quality of each raw material consumes number:
B, the TiO that will prepare in step a2Nano-carrier is dispersed in water, and adds in the Acetate Solution of Mn and Ce, solution Middle Mn ion and Ce ionic adsorption are at TiO2On nano-carrier, so centrifugal that to be adsorbed with Cu ion and the TiO of Cr ion2Nano-carrier, In the vacuum environment that temperature is 150 DEG C, it is dried 3h, prepares nanoscale CeMnO3/TiO2, nanoscale CeMnO3/TiO2Middle CeMnO3 Mass loading amount be 4%；
C, employing wavelength are the nanoscale CeMnO obtained in ultraviolet irradiation step b of 200nm3/TiO210min, then Clean with water and prepare nano Ce MnO3/TiO2Catalyst；
D, the nano Ce MnO that will prepare in step c3/TiO2Catalyst is hydro-thermal reaction 5h in glucose solution, and hydro-thermal is anti- The temperature answered is 180 DEG C, at nano Ce MnO3/TiO2Catalyst surface cladding carbon-coating, carbon layers having thicknesses is 2nm, after carbon-coating accounts for cladding Nano Ce MnO3/TiO2The 2% of catalyst gross mass.
E, mixed to obtain mixed liquor by tetraethyl orthosilicate, ammonia and ethanol, step d will prepare the nanometer being coated with carbon-coating CeMnO3/TiO2Catalyst adds in mixed liquor, uses sol-gal process at nano Ce MnO3/TiO2The Surface coating of catalyst Silicon layer, the thickness of silicon layer is about 10nm, and silicon layer accounts for CeMnO after cladding3/TiO2The 20% of catalyst gross mass, the most in atmosphere Calcine 3 hours prepared CeMnO3/TiO2@@SiO2, calcining heat is 500 DEG C.
In oxidizing tower, VOCs gas catalysis mechanism of degradation is as follows.
(1), hydroxyl radical free radical mechanism of production.VOCs gas after spray contains water vapour, with ozone at CeMnO3/ TiO2@@SiO2React generation hydroxyl radical free radical with steam under catalyst action.Mechanism is as follows:
(2), catalysis oxidation mechanism in oxidizing tower.For the VOCs gas of hydrocarbon compound, waste gas is at catalyst and hydroxyl Generating water and carbon dioxide under base free radical dual function, reaction mechanism is as follows:
VOCs+activesite→[VOCs]
[VOCs]+·OH→CO2+H2O
Nucleocapsid micro nano structure spinel catalyst and hydroxyl radical free radical can also process chloride VOCs gas very well, i.e. CVOCs gas.Mechanism is as follows: how many according to amount of chlorine atom purpose in chlorohydrocarbon, along with the generation of dealuminated USY cataluyst phenomenon. First CVOCs waste gas adsorb in the active sites of nano spinel catalyst, and occurs dealuminated USY cataluyst to react, and sloughs chlorine element, The chloride formed has been retained on filling carrier.Aldehyde, carboxylic acid and hydrocarbon after dechlorination are in hydroxyl radical free radical effect Under, become CO by exhaustive oxidation2And H2O, completes waste gas purification processing procedure.
Above-mentioned filler can also select saddle filler, many spheres filler, screen waviness packings, perforated plate corrugated filler or lattice Grid filler.
Embodiment two
The present embodiment is with the difference of embodiment one: CeMnO3/TiO2@@SiO2The concrete preparation technology of catalyst Condition is different.Particularly as follows:
In step a, the rotating speed of stirring is 450r/min；Nanoscale CeMnO in step b3/TiO2Middle CeMnO3Mass loading Amount is 6%；The wavelength 240nm of step c medium ultraviolet light；The time of hydro-thermal reaction in step c is 8h by step d, carbon layers having thicknesses For 3nm, carbon-coating accounts for nano Ce MnO after cladding3/TiO2The 4% of catalyst gross mass；CeMnO after silicon layer accounts for cladding in step e3/ TiO2The 30% of catalyst gross mass.
Embodiment three
The present embodiment is with the difference of embodiment one: CeMnO3/TiO2@@SiO2The concrete preparation technology of catalyst Condition is different.Particularly as follows:
In step a, the rotating speed of stirring is 600r/min；Nanoscale CeMnO in step b3/TiO2Middle CeMnO3Mass loading Amount is 8%；The wavelength 275nm of step c medium ultraviolet light；The time of hydro-thermal reaction in step c is 10h by step d, carbon layers having thicknesses For 4nm, carbon-coating accounts for nano Ce MnO after cladding3/TiO2The 5% of catalyst gross mass；CeMnO after silicon layer accounts for cladding in step e3/ TiO2The 40% of catalyst gross mass.
Making in aforementioned manners, petrochemical plant VOCs contrasts before and after processing, and result see table:
By VOCs content balance before and after processing it can be seen that the nucleocapsid micro nano structure spinelle of present invention design is catalyzed Agent is strong with hydroxyl radical free radical coefficient catalyzing oxidizing degrading VOCs waste gas ability, and every clearance all reaches more than 90%； React under room temperature, save energy resources and heat transmission equipment, it also avoid the catalyst failure that high temperature causes simultaneously, extend The service life of device.Through actual verification, catalysis oxidizing tower still has stronger catalytic capability after using 3 years.
The above, be only presently preferred embodiments of the present invention, is not the restriction that the present invention makees other form, appoints What those skilled in the art is combined possibly also with the technology contents of the disclosure above, changes or retrofits and is the present invention Equivalent embodiments.But every without departing from technical solution of the present invention content, implement above according to the technical spirit of the present invention Any simple modification, equivalent variations and the remodeling that example is made, still falls within the protection domain of technical solution of the present invention.

Claims (8)

1. the method for a normal-temperature efficient catalytic degradation petroleum chemical industry VOCs waste gas, it is characterised in that: comprise the steps:
(1) waste gas is entered the first spray column from bottom, with the spray liquid of alkalescence under spray from top to bottom in the first spray column Colliding in opposite directions, the acid ingredient in spray liquid and in waste gas forms salt, and traps dust, discharges from the bottom of the first spray column, Waste gas after process is discharged from the top of the first spray column；
(2) first spray columns discharge waste gas enter the second spray column from bottom, in the second spray column with spray from top to bottom Under spray liquid collide in opposite directions, dissolve the solvable composition in waste gas and form lysate, the bottom of the second spray column discharge lysate, The waste gas after spray processes is discharged at top；
The waste gas that (3) second spray columns are discharged is passed through ozone, at the CeMnO of nucleocapsid micro nano structure3/TiO2@@SiO2Catalysis Under agent effect, ozone and the reaction of moisture in waste gas, the O of generation2Redox reaction is produced with hydroxyl radical free radical and waste gas, raw Become CO2And H2O, completes the process of waste gas；Described Cu-Cr-O/TiO2@@SiO2Catalyst prepares through following method:
A, under agitation carried out gelation reaction by tetrabutyl titanate, ethanol, hydrochloric acid and water, prepare TiO2Nano-carrier, stirring turns Speed is 300～600r/min；It is as follows that the quality of each raw material consumes number:
B, the TiO that will prepare in step a2Nano-carrier is dispersed in water, and adds in the Acetate Solution of Mn and Ce, Mn in solution Ion and Ce ionic adsorption are at TiO2On nano-carrier, so centrifugal that to be adsorbed with Cu ion and the TiO of Cr ion2Nano-carrier, in temperature Degree is to be dried 3h in the vacuum environment of 150 DEG C, prepares nanoscale CeMnO3/TiO2, nanoscale CeMnO3/TiO2Middle CeMnO3Matter Amount load capacity is 4～8%；
The nanoscale CeMnO obtained in c, ultraviolet irradiation step b using wavelength to be 200～275nm3/TiO210min, then Clean with water and prepare nano Ce MnO3/TiO2Catalyst；
D, the nano Ce MnO that will prepare in step c3/TiO2Catalyst is hydro-thermal reaction 5～10h in glucose solution, in nanometer CeMnO3/TiO2Catalyst surface cladding carbon-coating, carbon layers having thicknesses is 2～4nm, and carbon-coating accounts for nano Ce MnO after cladding3/TiO2Catalysis The 2～5% of agent gross mass.
E, mixed to obtain mixed liquor by tetraethyl orthosilicate, ammonia and ethanol, step d will prepare the nano Ce MnO being coated with carbon-coating3/ TiO2Catalyst adds in mixed liquor, uses sol-gal process at nano Ce MnO3/TiO2The Surface coating silicon layer of catalyst, silicon Layer accounts for CeMnO after cladding3/TiO2The 20～40% of catalyst gross mass, the most in atmosphere 3 hours prepared CeMnO of calcining3/ TiO2@@SiO2。
The method of normal-temperature efficient catalytic degradation petroleum chemical industry VOCs waste gas the most according to claim 1, its feature exists In: in step (3), described CeMnO3/TiO2@@SiO2Catalyst is supported on filler.
The method of normal-temperature efficient catalytic degradation petroleum chemical industry VOCs waste gas the most according to claim 2, its feature exists In: described step (3) is carried out in airtight oxidizing tower, and described filler is arranged on the middle part in oxidizing tower, the bottom of oxidizing tower Connection ozonator and the top of the second spray column, top connection aiutage.
The method of normal-temperature efficient catalytic degradation petroleum chemical industry VOCs waste gas the most according to claim 3, its feature exists In: described filler is Raschig ring filler, saddle filler, many spheres filler, screen waviness packings, perforated plate corrugated filler or grid Filler.
5. according to the method for the arbitrary described normal-temperature efficient catalytic degradation petroleum chemical industry VOCs waste gas of Claims 1-4, its It is characterised by: TiO in step a2The particle diameter of nano-carrier is 20～50nm.
The method of normal-temperature efficient catalytic degradation petroleum chemical industry VOCs waste gas the most according to claim 5, its feature exists In: in described step c, clean to impurity content in filtrate less than 1%.
The method of normal-temperature efficient catalytic degradation petroleum chemical industry VOCs waste gas the most according to claim 6, its feature exists In: in described step d, the temperature of hydro-thermal reaction is 180 DEG C.
The method of normal-temperature efficient catalytic degradation petroleum chemical industry VOCs waste gas the most according to claim 7, its feature exists In: in described step e, calcining heat is 500 DEG C.
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