CN106166442A - A kind of room temperature clears up the nano rare earth catalytic ozonation method of volatile organic matter - Google Patents

A kind of room temperature clears up the nano rare earth catalytic ozonation method of volatile organic matter Download PDF

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CN106166442A
CN106166442A CN201610624429.7A CN201610624429A CN106166442A CN 106166442 A CN106166442 A CN 106166442A CN 201610624429 A CN201610624429 A CN 201610624429A CN 106166442 A CN106166442 A CN 106166442A
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rare earth
catalyst
nano
volatile organic
room temperature
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丁辉
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Tianjin University
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Abstract

The invention discloses a kind of room temperature and clear up the nano rare earth catalytic ozonation method of volatile organic matter, it comprises the following steps: (1) loads the nano rare earth unit element coating as auxiliary agent the most on a catalyst support, the nano spinel of the active component as catalyst is coated again on the carrier loaded rare earth element, finally by the catalyst carrier calcining of load auxiliary agent and active component, at catalyst support surface and be internally formed substantial amounts of micropore, obtain final catalyst with holes；(2) prepared final catalyst is fixed in the catalytic bed of catalysis oxidizing tower, start ozonator, then it is passed through through pretreatment in catalysis oxidizing tower, remove contained acid, alkaline gas and other dust and the volatile organic compounds of granule, under the room temperature of 10～40 DEG C, volatile organic matter deep oxidation is generated nontoxic scentless material.VOCs complete oxidation the most just can be generated carbon dioxide and water, thus operation safety and energy consumption is low by this method.

Description

A kind of room temperature clears up the nano rare earth catalytic ozonation method of volatile organic matter
Technical field
The invention belongs to waste gas pollution control and treatment technical field, be specifically related to a kind of room temperature (-10～40 DEG C) efficient digestion volatility The preparation method of the nano rare earth catalytic ozonation catalyst with holes of Organic substance (VOCs).
Background technology
Volatile organic matter (Volatile Organic Compounds), is called for short VOCs, refers to atmospheric boiling point at 50- The saturated vapor pressure organic general name more than 133.32Pa between 260 DEG C, under room temperature.VOCs be mainly derived from petrochemical industry, The waste gas of the industry discharges such as pharmaceuticals industry, printing industry, coating adnornment industry, surface anticorrosion and vehicle exhaust.Tie according to chemistry The difference of structure, can be divided into eight classes by VOCs: fats hydrocarbon compound (butane, gasoline etc.), arene compounds (benzene, Toluene, dimethylbenzene), halohydrocarbon compound (chloromethanes, ethyl chloride, chloroform, freon etc.), aldehyde, ketone, alcohol multicomponent alcoholics compound (formaldehyde, acetaldehyde, acetone, butanol), ether, phenol, epoxy compounds (ether, phenol, oxirane), ester, acid compounds (second Acetoacetic ester, butyl acetate, acetic acid), amine, nitrile compounds (dimethylformamide, acrylonitrile), other (Chlorofluorocarbons (CFCs), chlorine Fluorohydrocarbon, methyl bromide).VOCs itself is poisonous, and human body Long Term Contact can cause internal organs and neural infringement.Benzene in VOCs The harm being thing is especially serious, respiratory tract enter human body, damage hematopoietic cell and liver by metabolism.In international cancer research Benzene is confirmed as carcinogen by the heart (IARC).Benzene homologues poisoning is attributed to three kinds to the harm of health: carcinogenic, disable, teratogenesis Tire.It addition, as forming ozone and the forerunner of PM2.5, VOCs issues third contact of a total solar or lunar eclipse chemical reaction in illumination effect and causes photochemistry dirty Dye；Fluorine chlorohydrocarbon in VOCs then can cause Ozone hole.
In recent years, along with developing rapidly of China's industry, the discharge capacity of VOCs is also riseing year by year, and these will certainly be to the mankind Existence cause huge threat, therefore the improvement to VOCs is extremely urgent.
For the severe situation of China's atmospheric pollution, national correlation department has put into effect various waste gas emission standard and improvement is arranged Execute.Not long ago the national efforts at environmental protection meeting closed is revealed, VOCs includes in major pollutants overall control scope, current environmental protection Portion has put into effect the series standard of VOCs, Specifications of Monitoring Technology, analysis method etc., and the Monitor examination reduced discharging for " 13 " VOCs is established Determine basis.Relevant enterprise it is also proposed the treatment technology scheme of various VOCs, achieves certain achievement.At present, main Administering method has: activated carbon adsorption, burning, precious metal catalyst oxidation etc..
There is the defect that adsorbance is limited in activated carbon adsorption, needs to regularly replace activated carbon, and adsorb the work of full waste gas Property charcoal need to do the desorption in later stage and process, and if not doing desorption for unworthy adsorbed gas and process and be likely to result in secondary Pollute.Burning method can cause secondary pollution equally, and energy consumption is bigger.Then there is relatively costly and catalyst in precious metal catalyst oxidation The problems such as the phenomenon being easily poisoned, thus range of application is limited.
Patent CN1488435 is open a kind of with block ceramic honey comb as carrier, lives at its surface coating coatings and noble metal Property component.Coating is Al2O3、SiO2The composite oxides composition being collectively forming with one or more alkali metal oxides.Patent CN102441379A is open a kind of with ceramic honeycomb as carrier, surface-coated SiO2And CeO2Coating, coating surface carried noble metal Pt and transition metal Zr and rare earth element are as active component.Patent CN1415410A disclose a kind of catalyst for catalytic combustion and Its preparation method.This patent, with precious metals pt as active component, is carried on carrier surface by the way of organic acid competitive Adsorption, Carrier surface first coats Al2O3、TiO2、CeO2、ZrO2Coating.Above patent all with noble metal as active component, prepared catalysis The most chloride common contaminants is gone to dechlorinate the highest by agent, but is of limited application, easy in inactivation, is applied to the catalysis burning of VOCs Process is it is generally required to be heated to more than 200 DEG C, and energy consumption is of a relatively high, and owing to there is structural stability difference etc. with pottery for carrier Shortcoming.
Summary of the invention
It is an object of the invention to the shortcoming overcome in prior art, propose a kind of can under the room temperature of-10～40 DEG C Efficiently by VOCs completely, the room temperature cleared up of the degree of depth clear up the nano rare earth catalytic ozonation method of volatile organic matter.This Method operation safety, energy consumption is low, low cost and will not produce secondary pollution.
For solving above-mentioned technical problem, the technical scheme is that
The room temperature that the present invention proposes clears up the nano rare earth catalytic ozonation method of volatile organic matter, and it includes following step Rapid:
(1) load the nano rare earth unit element coating as auxiliary agent the most on a catalyst support, then load rare earth unit The nano spinel of the active component as catalyst is coated, finally by load auxiliary agent and the catalysis of active component on the carrier of element Agent carrier is calcined, and at catalyst support surface and be internally formed substantial amounts of micropore, obtains final catalyst with holes；
(2) prepared final catalyst is fixed in the catalytic bed of catalysis oxidizing tower, starts ozonator, then Being passed through through pretreatment in catalysis oxidizing tower, the volatility removing contained acid, alkaline gas and other dust and granule has Machine thing waste gas, generates nontoxic scentless material by volatile organic matter deep oxidation under the room temperature of-10～40 DEG C.
Compared with prior art, present invention have the advantage that
1. carrier attapulgite is cheap and easy to get, has the appearance of high specific surface area and pore structure, load active component and auxiliary agent Amount is big.The prominent good characteristic that the ball shaped nano attapulgite carrier of activation has:
A specific surface area that () is the biggest, effectively dispersed catalyst active component, it is possible to active component negative is greatly decreased Carrying capacity, ensures catalytic performance while reducing cost；
B () surface has a lot of active center, also be able to play the effect of O3 catalytic oxidation to a certain extent；
C () itself has stronger oxidation activity, can play the effect of oxidation Decomposition VOCs to a certain extent.
2. China's rare earth resources is of a great variety, rich reserves, low price.Nano rare earth element as catalyst promoter, The catalytic performance of catalyst activity component can be effectively improved, moreover it is possible to changed by the valence state of nano rare earth ion and store and release Oxygen.
3. before waste gas enters to be catalyzed oxidizing tower, first by its pretreatment, on the one hand, remove acid and alkaline gas and dust granules Deng, reach effect of preliminary purification；On the other hand, can prevent these acidity, alkaline gas, dust granules etc. from entering catalysis oxidation Tower, it is to avoid cause equipment corrosion, the blocking in catalyst duct and the inactivation of catalyst activity component, with extension device and catalysis The service life of agent.
4. the performance of catalyst activity component nano spinel O3 catalytic oxidation highlights, it is possible to by ozone and pollutant VOCs is adsorbed onto catalyst surface simultaneously, and effective generation catalyst-pollutant VOCs in combination, catalyst-ozone are multiple Close intermediate product.On the one hand, the catalyst of generation-pollutant VOCs is combined intermediate product and can be decomposed by ozone the efficient oxidation； On the other hand, ozone occurs a series of radical chain reaction to decompose the substantial amounts of hydroxyl radical free radical of generation under the effect of catalyst, Due to the oxidizing potential that hydroxyl radical free radical is the highest, under room temperature (-10～40 DEG C), just can decompose VOCs by deep oxidation, it is also possible to Cyclic compound ring-opening oxidation is decomposed into carbon dioxide and water.
5. the cavernous structure of catalyst surface and inside considerably increases its absorption ozone and ability of VOCs, thus is catalyzed Performance is greatly improved.
6. it is nano material due to catalyst carrier, auxiliary agent and active component, thus compared with non-nano catalyst, than Surface area is big, active component dispersion is high, and catalytic performance is greatly improved, and catalyst activity component not easy in inactivation, service life Long.
7., due to the strong oxidizing property of hydroxyl radical free radical, just VOCs complete oxidation can be generated under room temperature (-10～40 DEG C) Carbon dioxide and water, thus operation safety and energy consumption are low.
8. the equipment that the present invention relates to and operate safe and simple, the rich reserves of synthetic catalyst raw material, originate wide and honest and clean Valency is easy to get, and does not use noble metal, thus low cost；And under room temperature, just can obtain the high clearance of VOCs, regulation effect is excellent, easily In industrial large-scale promotion and application.This method can be widely used in the improvement of high, medium and low concentration VOCs.
Accompanying drawing explanation
Fig. 1 is the stream that room temperature of the present invention clears up the device of the nano rare earth catalytic ozonation method employing of volatile organic matter Journey schematic diagram.
Detailed description of the invention
Below in conjunction with the drawings and the specific embodiments, the present invention is elaborated:
The room temperature that the present invention proposes clears up the nano rare earth catalytic ozonation method of volatile organic matter, and it includes following step Rapid:
(1) load the oxide nano rare earth coating as auxiliary agent the most on a catalyst support, then load rare earth The active component nano spinel as catalyst is coated, finally urging load auxiliary agent and active component on the carrier of oxide Agent carrier is calcined, and at catalyst support surface and be internally formed substantial amounts of micropore, obtains final catalyst with holes；
(2) prepared final catalyst is fixed in the catalytic bed of catalysis oxidizing tower 2, starts ozonator 4, so It is passed through through pretreatment in backward catalysis oxidizing tower, removes contained acid, alkaline gas and other dust and the volatility of granule Organic compounds VOCs, it is not necessary to additionally heat, generates nothing by volatile organic matter deep oxidation under the room temperature of-10～40 DEG C The scentless material of poison.
The detailed process of the most described step (1) is:
A catalyst carrier is immersed in the nitrate solution adding nano rare earth element by (), then dry, roasting, is urging Agent carrier surface covers oxide nano rare earth auxiliary agent, and dry run can be carried out in 100 DEG C～200 DEG C of temperature ranges, Roasting process can continue 0.5h～2h in 350 DEG C～550 DEG C of temperature ranges；
(b) surface has been covered the catalyst carrier of oxide nano rare earth auxiliary agent add by divalent transition metal solution and The Mixed bittern saline solution that trivalent transition metal solution is mixed into, stirring makes its mix homogeneously, in described Mixed bittern saline solution In two kinds of transition metal ionss, trivalent transition metal ion is 2:1 with the mol ratio of divalent transition metal ion；Described mixing Two kinds of transition metal solutions in halide salt solution can be CoCl3Solution, MnCl3Solution or CrCl3In a kind of solution and CuCl2、MnCl2Or CrCl2A kind of solution in three kinds mixes.
C () adds sodium hydroxide solution in the Mixed bittern saline solution of transition metal, regulation solution ph is 7, and room temperature is quiet Putting 6h～8h, sucking filtration, washing, check halogen-free ionic to cleaning mixture, carrier surface loads one layer of nano spinel active component, then It calcines at 300～500 DEG C 2～4h make its surface and be internally formed a large amount of micropore, obtain catalyst with holes.This target Catalyst surface and internal aperture are in nano-scale range.
As preferably, using the ball shaped nano attapulgite of activation as catalyst carrier.Obtaining catalyst with holes is nanometer The ball shaped nano attapulgite of spinelle/oxide nano rare earth-activation.
The ball shaped nano attapulgite of activation is first made spherical by the attapulgite powder bought, then obtains through microwave activation Method.Activation method may refer to that Lv Dongqin, Zhou Shixue delivered in 2010 etc. entitled " proposition of attapulgite and modification are to it The impact of absorption property " document.Described catalyst carrier can also select activated carbon or aluminium oxide, and follow-up auxiliary agent, The load process of active component is identical with the preparation technology as carrier of the ball shaped nano attapulgite to activate.
Described nano rare earth element can be nano level lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), the one in europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho) or erbium (Er).
The preprocessing process of the described volatile organic compounds in step (2) is: be passed through from the bottom of spray column by waste gas Spray column 1, waste gas enters in spray column, up by inner-tower filling material layer in tower, fully connects with spray liquid on packing layer surface Touch, make the acidity in waste gas and alkaline gas fully be neutralized.Dust contained in waste gas and granule are then by descending drop Catch and remove, it is achieved pretreatment and the preliminary purification to waste gas.Described packing layer can use the glass spring filler of scattered heap.
As a kind of system realizing being catalyzed the preparation method of the catalyst that volatile organic matter ozonisation is decomposed under room temperature, This system includes many spray columns 1 being sequentially connected, the tower top gas outlet of the most previous seat spray column 1 by pipeline with latter one Air inlet at the bottom of the tower of spray column is connected, and the several concrete condition according to pending waste gas of actual table of spray column determines, at each seat The tower internal upper part of described spray column 1 is provided with spray arm 6 in the horizontal direction, sprays equipped with multiple seedpod of the lotus on described spray arm 6 Pouring 7, in each spray column, spray arm is additionally arranged below with supporting plate 8 with holes, is placed with filler on described supporting plate with holes Layer 9.The gas outlet, top of described last spray column in many spray columns 1 is by the tower of pipeline with catalysis oxidizing tower 2 First air inlet is connected at the end, and the described catalysis the second air inlet at the bottom of oxidizing tower 2 tower is smelly by pipeline and ozonator 4 Oxygen gas outlet connects, and the steam vent of the tower top of described catalysis oxidizing tower has exhaustor and the aerofluxus cigarette of air-introduced machine 3 by connection Cylinder 5 is connected.In described catalysis oxidizing tower 2, bottom is provided with web plate 10 with holes, is placed with catalysis on described web plate with holes The ball shaped nano attapulgite of agent nano spinel/nano rare earth element oxide-activation.Described web plate with holes will be catalyzed oxidizing tower Inside is divided into the discharge chamber on top and the ozone of bottom and volatile organic matter inlet chamber.
So react under catalysis oxidizing tower inner catalyst effect through the pretreated waste gas of spray and ozone, wave The property sent out Organic substance is broken down into carbon dioxide and other non-toxic gas and water；The non-toxic gas ultimately generated is by catalysis oxidizing tower The exhaustor on top is extracted into aerofluxus chimney 5 by air-introduced machine 3, finally has aerofluxus chimney top to discharge, and the most whole process completes.
Described spray column and catalysis oxidizing tower can use existing structure, the spray column that the present invention uses and catalysis oxidation Tower is improvement on an existing structure.
As preferably, above the steam vent away from catalysis oxidizing tower 2 of aerofluxus chimney 5 top 15 meters.
Embodiment 1
(1) preparing final catalyst, detailed process is as follows:
(a) using activation ball shaped nano attapulgite as catalyst carrier, catalyst carrier is immersed in interpolation nanoscale The nitrate solution of cerium, be then dried, roasting, cover oxide nano rare earth auxiliary agent at catalyst support surface, be dried temperature Degree is 100 DEG C, and sintering temperature is 550 DEG C and lasting 0.5h；
B surface has been covered the catalyst carrier of oxide nano rare earth auxiliary agent and has added by MnCl by ()3Solution and CuCl2Molten The Mixed bittern saline solution that liquid is mixed into, stirring makes its mix homogeneously, the described manganese ion in Mixed bittern saline solution and copper ion Mol ratio be 2:1；
C () then adds sodium hydroxide solution in the Mixed bittern saline solution of transition metal, regulation solution ph is 7, room The gentle and quiet 6h that puts, sucking filtration, washing, check halogen-free ionic to cleaning mixture, carrier surface loads one layer of nano spinel active component, then Make its surface by calcining 4h at its 400 DEG C and be internally formed a large amount of micropore, obtaining catalyst with holes.This final catalyst surface It is in nano-scale range with internal aperture.
(2) prepared final catalyst is fixed in the catalytic bed of catalysis oxidizing tower 2, starts ozonator 4, so Be passed through through pretreatment waste gas in backward catalysis oxidizing tower, the VOCs component not removed by spray column (be mainly composed of normal butane, Pentane, normal hexane, normal octane and n-nonane etc.) with ozone is adsorbed together with in catalysis oxidizing tower is enriched in catalyst and (receives Rice CuMn2O4/ nano Ce O2The ball shaped nano attapulgite of-activation) surface, decomposed by deep oxidation under the room temperature of-10 DEG C and generate Carbon dioxide and water.Preprocessing process is: by waste gas from being passed through spray column 1 at the bottom of spray column, and waste gas enters in spray column, in tower Up it is fully contacted with spray liquid on packing layer surface by inner-tower filling material layer, makes the acidity in waste gas and alkaline gas be filled Divide and neutralize.Dust contained in waste gas and granule are then caught by descending drop and remove, it is achieved to the pretreatment of waste gas and just Step purifies.Described packing layer can use the glass spring filler of scattered heap.
Catalytic oxidation effect is checked
The waste gas that catalysis oxidizing tower is discharged is sent into aerofluxus chimney 5, the aerofluxus away from catalysis oxidizing tower 2 of aerofluxus chimney 5 top Above hole 15 meters, gather aerofluxus chimney 5 expellant gas, in 1 hour, gather 3 sample detection with constant duration, and count Calculate each VOCs concentration of component meansigma methods.Testing result is listed in table 1:
Table 1 is catalyzed oxidizing tower aerofluxus testing result
Consult country's discharge standard of air pollutants to understand, when aerofluxus chimney 5 top is away from the aerofluxus being catalyzed oxidizing tower 2 Above hole when 15 meters, the highest permission concentration of emission of NMHC compounds is 120mg/m3。
By the chimney concentration of emission of normal butane, pentane, normal hexane, normal octane and n-nonane in table 1 is added and, permissible Finding, waste gas VOCs is after spray column, catalysis oxidizing tower process, and the total of the NMHC compounds of aerofluxus chimney discharges Concentration is well below the highest permission discharge value of national regulation.Embodiment is only listed to normal butane, pentane, normal hexane, just Octane, the treatment effect of n-nonane, actually catalyst (nanometer CuMn2O4/ nano Ce O2The ball shaped nano attapulgite of-activation) The ozone oxidation of all of carbon hydrocarbon compounds such as methane, ethane, n-propane, iso-butane, isopentane, Pentamethylene., hexamethylene is divided Solve effect the most highly desirable, and every discharge parameter after treatment is well below the discharge index of national regulation.It addition, urge Agent is the most highly desirable in the effect of removal VOCs running more than 5 years and every discharge parameter is far below national regulation equally The highest permission discharge value.
Embodiment 2
(1) preparing final catalyst, detailed process is as follows:
(a) using activation ball shaped nano attapulgite as catalyst carrier, catalyst carrier is immersed in interpolation nanoscale The nitrate solution of lanthanum, be then dried, roasting, cover oxide nano rare earth auxiliary agent at catalyst support surface, be dried temperature Degree is 200 DEG C, and sintering temperature is 350 DEG C and lasting 2h；
B surface has been covered the catalyst carrier of oxide nano rare earth auxiliary agent and has added by CrCl by ()3Solution and CuCl2Molten The Mixed bittern saline solution that liquid is mixed into, stirring makes its mix homogeneously, the described chromium ion in Mixed bittern saline solution and copper ion Mol ratio be 2:1；
C () then adds sodium hydroxide solution in transition metal Mixed bittern saline solution, regulation solution ph is 7, room temperature Standing 8h, sucking filtration, washing, check halogen-free ionic to cleaning mixture, carrier surface loads one layer of nano spinel active component, then will Calcine 2h at its 500 DEG C make its surface and be internally formed a large amount of micropore, obtain catalyst with holes.This final catalyst surface and Internal aperture is in nano-scale range.
(2) prepared final catalyst is fixed in the catalytic bed of catalysis oxidizing tower 2, starts ozonator 4, so Being passed through through pretreatment waste gas in backward catalysis oxidizing tower, the VOCs component not removed by spray column (is mainly composed of benzene, first Benzene, o-Dimethylbenzene etc.) it is adsorbed being enriched in catalyst (nanometer CuCr together with in catalysis oxidizing tower with ozone2O4/ nanometer LaO2- The ball shaped nano attapulgite of activation) surface, decomposed by deep oxidation under the room temperature of 40 DEG C and generate carbon dioxide and water.Pretreatment Process is: by waste gas from being passed through spray column 1 at the bottom of spray column, and waste gas enters in spray column, up by inner-tower filling material layer in tower, It is fully contacted with spray liquid on packing layer surface, makes the acidity in waste gas and alkaline gas fully be neutralized.And it is contained in waste gas Dust and granule then caught by descending drop and remove, it is achieved pretreatment and the preliminary purification to waste gas.Described packing layer The glass spring filler of scattered heap can be used.
Catalytic oxidation effect is checked:
The waste gas that catalysis oxidizing tower is discharged is sent into aerofluxus chimney 5, the aerofluxus away from catalysis oxidizing tower 2 of aerofluxus chimney 5 top Above hole 15 meters, gather aerofluxus chimney 5 expellant gas, in 1 hour, gather 3 sample detection with constant duration, and count Calculate each VOCs concentration of component meansigma methods.Testing result is listed in table 2:
Table 2 is catalyzed oxidizing tower aerofluxus testing result
Consult country's discharge standard of air pollutants, when on the steam vent away from catalysis oxidizing tower 2 of aerofluxus chimney 5 top During 15 meters, side, the highest permission concentration of emission of benzene,toluene,xylene is listed in table 3:
The maximum permissible concentration of table 3 benzene,toluene,xylene
Contrast table 2, table 3, it appeared that waste gas VOCs is after spray column, catalysis oxidizing tower process, every discharge parameter The highest permission discharge value well below national regulation.Embodiment is only listed to benzene, toluene, the treatment effect of o-Dimethylbenzene, Actually catalyst (nanometer CuCr2O4/ nanometer LaO2The ball shaped nano attapulgite of-activation) to meta-xylene, xylol, second The ozone oxidation discomposing effect of all of compound fragrant hydrocarbons such as benzene, biphenyl, naphthalene, anthracene, phenanthrene, a species of orchid is the most highly desirable, and passes through Every discharge parameter after process is well below the discharge index of national regulation.It addition, catalyst is in the removal running more than 5 years The effect of VOCs is the most highly desirable and every discharge parameter is equally far below the highest permission discharge value of national regulation.
Embodiment 3
(1) preparing final catalyst, detailed process is as follows:
(a) using activation ball shaped nano attapulgite as catalyst carrier, catalyst carrier is immersed in interpolation nanoscale The nitrate solution of erbium, then dry, roasting, covers oxide nano rare earth auxiliary agent, baking temperature at catalyst support surface Being 150 DEG C, sintering temperature is 350 DEG C and lasting 2h；
B surface has been covered the catalyst carrier of oxide nano rare earth auxiliary agent and has added by MnCl by ()3Solution and CrCl2Molten The Mixed bittern saline solution that liquid is mixed into, stirring makes its mix homogeneously, the described manganese ion in Mixed bittern saline solution and chromium ion Mol ratio be 2:1；
C () then adds sodium hydroxide solution in the Mixed bittern saline solution of transition metal, regulation solution ph is 7, room The gentle and quiet 8h that puts, sucking filtration, washing, check halogen-free ionic to cleaning mixture, carrier surface loads one layer of nano spinel active component, then Make its surface by calcining 3h at its 500 DEG C and be internally formed a large amount of micropore, obtaining catalyst with holes.This final catalyst surface It is in nano-scale range with internal aperture.
(2) prepared final catalyst is fixed in the catalytic bed of catalysis oxidizing tower 2, starts ozonator 4, so Being passed through through pretreatment waste gas in backward catalysis oxidizing tower, the VOCs component not removed by spray column (is mainly composed of a chloromethane Alkane, monochlorethane, chloroform etc.) it is adsorbed being enriched in catalyst (nanometer CrMn together with in catalysis oxidizing tower with ozone2O4/ nanometer ErO2The ball shaped nano attapulgite of-activation) surface, decomposed by deep oxidation under the room temperature of 40 DEG C and generate carbon dioxide and water. Preprocessing process is: by waste gas from being passed through spray column 1 at the bottom of spray column, and waste gas enters in spray column, up by tower in tower Packing layer, is fully contacted with spray liquid on packing layer surface, makes the acidity in waste gas and alkaline gas fully be neutralized.And waste gas Dust and granule contained by are then caught by descending drop and remove, it is achieved pretreatment and the preliminary purification to waste gas.Described Packing layer can use the glass spring filler of scattered heap.
Catalytic oxidation effect is checked:
The waste gas that catalysis oxidizing tower is discharged is sent into aerofluxus chimney 5, the aerofluxus away from catalysis oxidizing tower 2 of aerofluxus chimney 5 top Above hole 15 meters, gather aerofluxus chimney 5 expellant gas, in 1 hour, gather 3 sample detection with constant duration, and count Calculate each VOCs concentration of component meansigma methods.Testing result is listed in table 4:
Table 4 is catalyzed oxidizing tower aerofluxus testing result
Consult country's discharge standard of air pollutants and the working space maximum permissible concentration of VOCs, when aerofluxus chimney Above the steam vent away from catalysis oxidizing tower 2 of 5 tops when 15 meters, chloromethanes, ethyl chloride, the highest permission concentration of emission of chloroform are listed in Table 5:
Table 5 chloromethanes, ethyl chloride, chloroform the highest permission concentration of emission
Contrast table 4, table 5, it appeared that waste gas VOCs is after spray column, catalysis oxidizing tower process, every discharge parameter The highest permission discharge value well below national regulation.Embodiment is only listed to monochloro methane, monochlorethane, the process of chloroform Effect, actually catalyst (nanometer CrMn2O4/ nanometer ErO2The ball shaped nano attapulgite of-activation) to dichloromethane, dibromo second The all of halocarbons such as alkane, trichloroethane, trichloro ethylene, dichloroethanes, Monocyclohexane, vinyl chloride, iodoform, benzyl chloride, chlorobenzene The ozone oxidation discomposing effect of compounds is the most highly desirable, and every discharge parameter after treatment is well below state's domestic discipline and family rules Fixed discharge index.It addition, catalyst in the effect of removal VOCs running more than 5 years the most highly desirable and every discharge parameter The same the highest permission discharge value far below national regulation.
Embodiment 4
(1) preparing final catalyst, detailed process is as follows:
(a) using activation ball shaped nano attapulgite as catalyst carrier, catalyst carrier is immersed in interpolation nanoscale The nitrate solution of holmium, be then dried, roasting, cover oxide nano rare earth auxiliary agent at catalyst support surface, be dried temperature Degree is 200 DEG C, and sintering temperature is 350 DEG C and lasting 2h；
B surface has been covered the catalyst carrier of oxide nano rare earth auxiliary agent and has added by CoCl by ()3Solution and MnCl2Molten The Mixed bittern saline solution that liquid is mixed into, stirring makes its mix homogeneously, the described cobalt ion in Mixed bittern saline solution and manganese ion Mol ratio be 2:1；
C () then adds sodium hydroxide solution in the Mixed bittern saline solution of transition metal, regulation solution ph is 7, room The gentle and quiet 7h that puts, sucking filtration, washing, check halogen-free ionic to cleaning mixture, carrier surface loads one layer of nano spinel active component, then Make its surface by calcining 2h at its 500 DEG C and be internally formed a large amount of micropore, obtaining catalyst with holes.This final catalyst surface It is in nano-scale range with internal aperture.
(2) prepared final catalyst is fixed in the catalytic bed of catalysis oxidizing tower 2, starts ozonator 4, so Being passed through through pretreatment waste gas in backward catalysis oxidizing tower, the VOCs component not removed by spray column (is mainly composed of dichloro four Fluoroethane, dichlorodifluoromethane, methyl bromide etc.) it is adsorbed being enriched in catalyst (nanometer together with in catalysis oxidizing tower with ozone MnCo2O4/ nanometer HoO2The ball shaped nano attapulgite of-activation) surface, under the room temperature of 40 DEG C, decomposed generation two by deep oxidation Carbonoxide and water.Preprocessing process is: by waste gas from being passed through spray column 1 at the bottom of spray column, and waste gas enters in spray column, in tower on Row, by inner-tower filling material layer, is fully contacted with spray liquid on packing layer surface, makes the acidity in waste gas and alkaline gas by fully Neutralize.Dust contained in waste gas and granule are then caught by descending drop and remove, it is achieved to the pretreatment of waste gas and preliminary Purify.Described packing layer can use the glass spring filler of scattered heap.
Catalytic oxidation effect is checked:
The waste gas that catalysis oxidizing tower is discharged is sent into aerofluxus chimney 5, the aerofluxus away from catalysis oxidizing tower 2 of aerofluxus chimney 5 top Above hole 15 meters, gather aerofluxus chimney 5 expellant gas, in 1 hour, gather 3 sample detection with constant duration, and count Calculate each VOCs concentration of component meansigma methods.Testing result is listed in table 6:
Table 6 is catalyzed oxidizing tower aerofluxus testing result
Consult country's discharge standard of air pollutants and the working space maximum permissible concentration of VOCs, when aerofluxus chimney Above the steam vent away from catalysis oxidizing tower 2 of 5 tops when 15 meters, dichlorotetra-fluoroethane, dichlorodifluoromethane, the highest permission of methyl bromide Concentration of emission is listed in table 7:
Table 7 dichlorotetra-fluoroethane, dichlorodifluoromethane, the highest permission concentration of emission of methyl bromide
Contrast table 6, table 7, it appeared that waste gas VOCs is after spray column, catalysis oxidizing tower process, every discharge parameter The highest permission discharge value well below national regulation.Embodiment is only listed dichlorotetra-fluoroethane, F-22, first The treatment effect of bromide, actually catalyst (nanometer MnCo2O4/ nanometer HoO2The ball shaped nano attapulgite of-activation) to difluoro two All polyhalohydrocarbon compounds such as chloromethanes, isceon, trichorotrifluoroethane, a chloropentafluoroethane, Perfluorocyclobutane Ozone oxidation discomposing effect the most highly desirable, and every discharge parameter after treatment is well below the discharge of national regulation Index.It addition, catalyst is the most highly desirable in the effect of removal VOCs running more than 5 years and every discharge parameter is the lowest The highest permission discharge value in national regulation.
Above detailed description of the invention method to the present invention has carried out concrete description, but content of the present invention It is not restricted to above case study on implementation, as long as without departing from the main scope of the present invention, experiment condition and method can be entered Row changes flexibly.

Claims (7)

1. a room temperature clears up the nano rare earth catalytic ozonation method of volatile organic matter, it is characterised in that it includes following Step:
(1) load the nano rare earth unit element coating as auxiliary agent the most on a catalyst support, then load rare earth element Coat the nano spinel of the active component as catalyst on carrier, finally the catalyst of load auxiliary agent and active component is carried Body is calcined, and at catalyst support surface and be internally formed substantial amounts of micropore, obtains final catalyst with holes；
(2) prepared final catalyst is fixed in the catalytic bed of catalysis oxidizing tower, starts ozonator, then to urging It is passed through in changing oxidizing tower through pretreatment, removes contained acid, alkaline gas and other dust and the volatile organic matter of granule Waste gas, generates nontoxic scentless material by volatile organic matter deep oxidation under the room temperature of-10～40 DEG C.
Room temperature the most according to claim 1 clears up the nano rare earth catalytic ozonation method of volatile organic matter, its feature It is: the detailed process of described step (1) is:
A catalyst carrier is immersed in the nitrate solution adding nano rare earth element, then dry, roasting by (), at catalyst Carrier surface covers oxide nano rare earth auxiliary agent；
B surface has been covered the catalyst carrier of oxide nano rare earth auxiliary agent and has added by divalent transition metal solution and trivalent by () The Mixed bittern saline solution that transition metal solution is mixed into, stirring makes its mix homogeneously, described two kinds in Mixed bittern saline solution In transition metal ions, trivalent transition metal ion is 2:1 with the mol ratio of divalent transition metal ion；
C () adds sodium hydroxide solution in the Mixed bittern saline solution of transition metal, regulation solution ph is 7, and room temperature stands 6h ～8h, sucking filtration, washing, check halogen-free ionic to cleaning mixture, carrier surface loads one layer of nano spinel active component, then by it Calcining 2～4h at 300～500 DEG C make its surface and be internally formed a large amount of micropore, obtain catalyst with holes, this is intended catalyzed Agent surface and internal aperture are in nano-scale range.
Room temperature the most according to claim 2 clears up the nano rare earth catalytic ozonation method of volatile organic matter, its feature Be: the described dry run in step (a) is carried out in 100 DEG C～200 DEG C of temperature ranges, roasting process at 350 DEG C～ 0.5h～2h is continued in 550 DEG C of temperature ranges.
4. the nano rare earth catalytic ozonation method of volatile organic matter is cleared up according to the room temperature described in claim 2 or 3, its It is characterised by: two kinds of transition metal solutions in described Mixed bittern saline solution are CoCl3Solution, MnCl3Solution or CrCl3In A kind of solution and CuCl2、MnCl2Or CrCl2A kind of solution in three kinds mixes.
5. the nano rare earth catalytic ozonation method of volatile organic matter is cleared up according to the room temperature one of claim 1-3 Suo Shu, It is characterized in that: using activation ball shaped nano attapulgite as catalyst carrier.
6. the nano rare earth catalytic ozonation method of volatile organic matter is cleared up according to the room temperature one of claim 1-3 Suo Shu, It is characterized in that: described nano rare earth element is in nano level lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium or erbium One.
7. the nano rare earth catalytic ozonation method of volatile organic matter is cleared up according to the room temperature one of claim 1-3 Suo Shu, It is characterized in that: the preprocessing process of the described volatile organic compounds in step (2) is: led to from the bottom of spray column by waste gas Entering spray column, waste gas enters in spray column, up by inner-tower filling material layer in tower, fully connects with spray liquid on packing layer surface Touching, make the acidity in waste gas and alkaline gas fully be neutralized, dust contained in waste gas and granule are then caught by descending drop Catch removing, it is achieved pretreatment and the preliminary purification to waste gas.
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