CN113101920A - Catalytic ozonation catalyst, preparation and application in catalytic ozonation of VOCs - Google Patents
Catalytic ozonation catalyst, preparation and application in catalytic ozonation of VOCs Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 43
- 238000006385 ozonation reaction Methods 0.000 title claims abstract description 34
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011572 manganese Substances 0.000 claims abstract description 46
- 238000010438 heat treatment Methods 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 36
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 26
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000003607 modifier Substances 0.000 claims abstract description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 8
- 238000007598 dipping method Methods 0.000 claims abstract description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 8
- 238000012986 modification Methods 0.000 claims abstract description 7
- 230000004048 modification Effects 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 238000010791 quenching Methods 0.000 claims abstract description 5
- 230000000171 quenching effect Effects 0.000 claims abstract description 5
- 239000002912 waste gas Substances 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 80
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 238000003303 reheating Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- 239000001569 carbon dioxide Substances 0.000 description 9
- 239000000084 colloidal system Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 8
- 230000033558 biomineral tissue development Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- -1 polyethylene Polymers 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000000593 degrading effect Effects 0.000 description 4
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 4
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B01J37/02—Impregnation, coating or precipitation
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- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
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Abstract
The invention belongs to the technical field of waste gas treatment, and discloses a catalytic ozonation catalyst, a preparation method thereof and application thereof in catalytic ozonation of VOCs. The method comprises the following steps: 1) adopts modifier to react on gamma-Al in a magnetic field2O3Carrying out modification treatment and heat treatment to obtain modified gamma-Al2O3A primary carrier; improvement ofThe sex agent is more than one of water, citric acid aqueous solution or polyethylene glycol aqueous solution; 2) preparing manganese-containing compound into impregnating solution, and modifying gamma-Al2O3Dipping the primary carrier in a dipping solution, and carrying out heat treatment to obtain a co-carrier loaded with an active component; 3) roasting and quenching the co-carrier by adopting a programmed heating method to obtain the catalytic ozonation catalyst. The method is simple, and the prepared catalyst has good activity, stability and selectivity. The catalyst of the invention is applied to catalyzing ozone to oxidize VOCs, in particular to the application of low-concentration VOCs under the dynamic low-temperature condition of catalyzing ozone oxidation.
Description
Technical Field
The invention belongs to the technical field of waste gas treatment, and particularly relates to a catalytic ozonation catalyst, a preparation method thereof and application of the catalytic ozonation catalyst in catalytic ozonation decomposition of low-concentration VOCs under a dynamic low-temperature condition.
Background
Volatile Organic Compounds (VOCs) are important precursors causing dust haze, photochemical smog and other air quality pollution, and the current VOCs end treatment is divided into separation technology and destruction technology. The common separation technologies include adsorption, absorption, condensation and membrane separation technologies. However, the separation technology only separates or phase-transfers the VOCs, and does not thoroughly destroy the VOCs, thereby not fundamentally solving the practical problems. The general principle of the destruction technology of VOCs is to perform oxidative degradation on VOCs and convert the VOCs into non-toxic and harmless inorganic substances such as carbon dioxide, water and the like. From the temperature perspective, the catalytic oxidation technology can be divided into thermal catalysis and non-thermal catalysis, and the thermal catalysis requires certain temperature requirement and can consume certain energy; the non-thermal catalysis method comprises a plasma method, a biological catalysis method, an ozone catalytic oxidation method and the like. The plasma method has low efficiency, the biocatalysis method needs mild environmental conditions and has high environmental requirements, and the ozone catalytic oxidation method shows the advantages of the method due to the strong oxidation characteristic of ozone.
The strong oxidizing property of ozone can greatly reduce the reaction temperature, so that the performance of the catalyst and the synergistic effect of the catalyst and the ozone play a crucial role in the reaction of degrading VOCs by ozone oxidation. The Chinese patent with the publication number of CN108126686B discloses a Chinese patent medicineThe hematite is a core-shell type catalytic ozonation catalyst with an inner core, and the surface of the core-shell type catalytic ozonation catalyst is coated with a plurality of metal oxides such as lanthanum, copper, titanium, manganese, iron, cerium and the like, and is used for catalytically degrading sodium oxalate in a water body. The catalyst prepared by the method has certain solubility in water, so that the loss of the catalyst can be caused, and the service life of the catalyst is shortened. The Chinese patent application with publication number CN111659376A discloses a method for degrading COD in waste water by using activated carbon as carrier and oxides of zinc and cerium with different valence states as active components, wherein the highest degradation rate of COD in waste water can reach 72.3%. The method has the advantages that the roasting temperature is high in the preparation process, and the catalyst is consumed to a certain extent in the test process. The Chinese patent application with the publication number of CN111375424A discloses a method for preparing gamma-Al2O3The carrier is manganese, copper and cerium are used as active components to catalyze the ozone oxidation catalyst, and the catalyst is used for degrading COD in the wastewater. The catalyst in the invention has more complex components and higher roasting temperature in the preparation process, and has certain limitation in practical application.
For catalyzing ozone to oxidize volatile organic compounds, the volatile organic compounds are difficult to treat and reach the standard, and particularly low-concentration methylbenzene is difficult to treat and is discharged after reaching the standard. When the catalyst is used for catalyzing and oxidizing organic matters, most of the objects treated by the catalyst are volatile organic matters such as methanol, cyclohexane and the like which have simple structures and are easy to remove, and the catalyst is applied to the field of water treatment; even if toluene is the object of treatment, the catalyst is generally difficult to achieve stability and high efficiency; and even if the catalyst has higher pollutant removal rate, the mineralization rate of the catalyst is lower, and more other byproducts and other secondary pollution are generated.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the present invention aims to provide a catalytic ozonation catalyst and a preparation method thereof. The catalyst of the invention has the characteristics of high performance, simple preparation operation, low cost and the like. The catalyst has high activity, strong stability and good selectivity, and can efficiently purify VOCs with low concentration.
Another object of the present invention is to provide the use of the above catalytic ozonation catalyst. The catalytic ozonation catalyst is used for catalyzing ozone to oxidize and decompose VOCs, particularly volatile organic compounds in waste gas. The catalytic ozonation catalyst shows good catalyst performance under the low-temperature condition, and can efficiently remove low-concentration toluene.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a catalytic ozonation catalyst comprises the following steps:
1) adopts modifier to react on gamma-Al in a magnetic field2O3Modified treatment is carried out, and then heat treatment is carried out at 100-200 ℃ to obtain modified gamma-Al2O3A primary carrier; the modifier is more than one of water, citric acid aqueous solution or polyethylene glycol aqueous solution;
2) preparing manganese-containing compound into impregnating solution, and modifying gamma-Al2O3Dipping the primary carrier in a dipping solution, and then carrying out heat treatment at 100-300 ℃ to obtain a co-carrier loaded with an active component;
3) roasting and quenching the co-carrier loaded with the active component by adopting a programmed heating method to obtain a catalytic ozonation catalyst; the temperature programming refers to firstly heating to 150-300 ℃ for 1-2 h, and then heating to 350-450 ℃ for 2-5 h.
The conditions of the modification treatment in the step 1) are that the temperature is 50-100 ℃, the magnetic field intensity is 0.1T-1T, and the time of the modification treatment is 3-8 h.
The heat treatment time in the step 1) is 10-20 h; the atmosphere of the heat treatment is protective gas atmosphere or vacuum state; the heat treatment is preferably carried out in the absence of oxygen.
The heating rate of the heat treatment is 2-10 ℃/min.
The concentration of the citric acid solution is 5 wt% -20 wt%.
The concentration of the polyethylene glycol solution is 5 wt% -20 wt%.
The modifier is mixed with gamma-Al2O3When treated, the modifier reacts with gamma-Al2O3Volume to mass ratio (10 to 30) mL: 1g of the total weight of the composition.
The gamma is-Al2O3Selecting active alumina balls with the grain diameter of 3-5mm, and grinding and screening the active alumina balls.
Modified gamma-Al in step 2)2O3gamma-Al in primary carrier2O3And the mass ratio of Mn in the manganese-containing compound is (0.5-2): 1.
the manganese-containing compound in the step 2) is a water-soluble manganese-containing compound; the water-soluble manganese-containing compound is manganese acetate, manganese nitrate or manganese chloride, and preferably manganese acetate (namely manganese acetate tetrahydrate).
The impregnation liquid is prepared from a manganese-containing compound and water.
The concentration of the impregnation liquid is (0.5-1.5) g/mL.
The heat treatment time in the step 2) is 10-20 h; the atmosphere of the heat treatment is protective gas atmosphere or vacuum state; the heat treatment is preferably carried out in the absence of oxygen.
The heating rate of the heat treatment is 2-10 ℃/min.
The impregnation refers to the modification of gamma-Al2O3The primary carrier is stirred and dipped into the dipping solution to be colloidal.
The heating rate of the heating and reheating in the step 3) is 3 ℃/min to 10 ℃/min;
the roasting atmosphere in the step 3) is protective gas atmosphere or in a vacuum state; the calcination is preferably carried out in the absence of oxygen for heat treatment.
The quenching treatment is to place the roasted product in cold air at 20-40 ℃ for cooling; the cooling time is 10-30 min.
The catalytic ozonation catalyst of the invention is gamma-Al2O3The manganese is used as a primary carrier to modify the manganese, and is added as a co-carrier of the catalyst, and the manganese is simultaneously used as an active component of the catalyst.
The catalytic ozonation catalyst disclosed by the invention is applied to catalytic ozonation of Volatile Organic Compounds (VOCs), and particularly applied to catalytic ozonation of toluene.
The catalytic ozonation catalyst has a good catalytic effect on treating low-concentration toluene under a dynamic low-temperature condition.
The application specifically comprises the following steps: introducing the waste gas containing volatile organic compounds and ozone into a reaction device filled with the catalyst for reaction, and oxidizing the volatile organic compounds by ozone in a reaction system.
The reaction is carried out under the condition of dynamic temperature change; the dynamic temperature change means that the temperature is increased from 30 ℃ to 130 ℃ at a certain temperature increasing rate, then is reduced from 130 ℃ to 30 ℃ at a certain temperature reducing rate, and the temperature is maintained for 2-4 hours at 10 ℃ per liter or 10 ℃ per liter in the temperature increasing or reducing process. The heating rate is 1-10 ℃/min; the cooling rate is 1-10 ℃/min.
The concentration of volatile organic compounds (such as toluene) is 25-35 ppm, and the concentration of ozone is 200-400 ppm.
0.1g of catalyst is required for treating volatile organic compounds with a concentration of 25 to 35 ppm.
Compared with the prior art, the invention has the following advantages:
(1) for the preparation of the catalyst, the invention uses modified gamma-Al2O3Mn is used as a co-carrier, wherein Mn is used as a carrier and an active component, has higher activity, stronger stability and selectivity, and solves the problems of complicated preparation, high cost, sintering and agglomeration of noble metal in a reaction system and the like of the existing catalyst; the method is simple, and the prepared catalyst has high activity, strong stability and good selectivity, and can efficiently purify the low-concentration VOCs.
(2) For the application of the catalyst, the catalyst has good catalytic performance on low-concentration toluene which is difficult to treat under dynamic low-temperature conditions.
Drawings
FIG. 1 is a graph of toluene removal rate over time and temperature in a dynamic low temperature environment;
FIG. 2 is a graph of selectivity for carbon dioxide over time and temperature under dynamic low temperature ambient conditions;
FIG. 3 is a graph of mineralization rate as a function of time and temperature under dynamic low temperature environmental conditions.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
(1) Preparation of a primary carrier: grinding 6g of 3-5mm active alumina pellets into powder, screening 60-mesh particles, adding 100mL of deionized water, stirring for 4h at 80 ℃ in a magnetic field of 0.3T-0.8T, placing the modified primary carrier solid-liquid mixture in a muffle furnace (air in the muffle furnace cannot be completely removed in actual operation, so a small amount of air is contained in the muffle furnace), and treating for 12h at 200 ℃ by adopting a temperature programming method to obtain the modified gamma-Al2O3A primary carrier;
(2) preparation of the co-carrier-active component: adding 14.10g of manganese acetate tetrahydrate into 17.75mL of deionized water, placing the primary carrier obtained in the step (1) into the deionized water, stirring the mixture into a colloid state, placing the colloid state in a muffle furnace containing a small amount of air, and treating the colloid state for 12 hours at 200 ℃ by adopting a temperature programming method to obtain a co-carrier loaded with an active component;
(3) aging of the catalyst: and (3) placing the co-carrier catalyst impregnated with the active component obtained in the step (2) into a muffle furnace containing a small amount of air for roasting, and raising the temperature through a program: raising the temperature to 200 ℃ at the room temperature at the speed of 5 ℃/min for 1h, raising the temperature to 400 ℃ at the same rate for 3h, and cooling in cold air at the temperature of 30 ℃ for a short time (the cooling time is 20min) to obtain the blank-Mn catalyst.
Example 2
(1) Preparation of a primary carrier: grinding active alumina pellets of 693-5mm into powder, screening 60-mesh particles, adding the powder into 100mL of 10 wt% citric acid solution, placing the active alumina powder in the solution, stirring for 4h at 80 ℃ and in a magnetic field of 0.3T-0.8T, placing the modified primary carrier solid-liquid mixture in a muffle furnace containing a small amount of air, and treating for 12h at 200 ℃ by adopting a temperature programming method to obtain the modified gamma-Al2O3A primary carrier;
(2) preparation of the co-carrier-active component: adding 14.10g of manganese acetate tetrahydrate into 17.75mL of deionized water, placing the primary carrier obtained in the step (1) into the deionized water, stirring the mixture into a colloid state, placing the colloid state in a muffle furnace containing a small amount of air, and treating the colloid state for 12 hours at 200 ℃ by adopting a temperature programming method to obtain a co-carrier loaded with an active component;
(3) aging of the catalyst: and (3) placing the co-carrier catalyst impregnated with the active component obtained in the step (2) into a muffle furnace containing a small amount of air for roasting, and raising the temperature through a program: raising the temperature to 200 ℃ at the room temperature at the speed of 5 ℃/min for 1h, raising the temperature to 400 ℃ at the same rate for 3h, and cooling in cold air at the temperature of 30 ℃ for a short time (the cooling time is 20min) to obtain the citric acid-Mn catalyst.
Example 3
(1) Preparation of a primary carrier: grinding 6g of 3-5mm active alumina pellets, screening 60-mesh particles, adding the particles into 100mL of 10 wt% polyethylene glycol solution (the molecular weight of the polyethylene glycol in the embodiment is 192g/mol, and the molecular weight of the polyethylene glycol can be 100-300 g/mol), placing the active alumina powder in the solution, stirring the solution for 4 hours at 80 ℃ in a magnetic field of 0.3T-0.8T, placing the modified primary carrier solid-liquid mixture in a muffle furnace containing a small amount of air, and treating the mixture for 12 hours at 200 ℃ by adopting a temperature programming method to obtain the modified gamma-Al2O3A primary carrier;
(2) preparation of the co-carrier-active component: adding 14.10g of manganese acetate tetrahydrate into 17.75mL of deionized water, placing the primary carrier obtained in the step (1) into the deionized water, stirring the mixture into a colloid state, placing the colloid state in a muffle furnace containing a small amount of air, and treating the colloid state for 12 hours at 200 ℃ by adopting a temperature programming method to obtain a co-carrier loaded with an active component;
(3) aging of the catalyst: and (3) placing the co-carrier catalyst impregnated with the active component obtained in the step (2) into a muffle furnace containing a small amount of air for roasting, and raising the temperature through a program: raising the temperature to 200 ℃ at the room temperature at the speed of 5 ℃/min for 1h, raising the temperature to 400 ℃ at the same rate for 3h, and cooling in cold air at the temperature of 30 ℃ for a short time (the cooling time is 20min) to obtain the polyethylene glycol-Mn catalyst.
Example 4
The three ozone catalytic oxidation materials prepared in examples 1, 2 and 3, namely blank-Mn, citric acid-Mn and polyethylene glycol-Mn, are used for decomposing low-concentration toluene by simulating the actual dynamic low-temperature environment condition, and the specific activity evaluation steps are as follows:
a fixed flow bed reactor was used to simulate low concentration toluene under actual dynamic low temperature environmental conditions, the toluene was generated using a nitrogen bubbling method with a toluene bubbling nitrogen flow of 0.1mL/min, yielding 30ppm toluene. Ozone is generated by discharging oxygen through an ultraviolet lamp tube, the concentration of the ozone is controlled by oxygen and nitrogen together, an ozone detector is used for detecting the concentration of the ozone, the flow rate of the generated ozone is 38mL/min, the flow rate of the nitrogen for controlling the concentration of the ozone is 62mL/min, and 300ppm of ozone is generated. Adopting a programmed temperature control method, firstly, raising the temperature through a program: increasing the temperature from 30 deg.C to 40 deg.C within 10min for 170min, and increasing the temperature from 40 deg.C to 50 deg.C within 10min for 170min until 130 deg.C; and (5) cooling in a process sequence: reducing the temperature from 130 ℃ to 120 ℃ within 10min and keeping the temperature for 170min, and reducing the temperature from 120 ℃ to 110 ℃ within 10min and keeping the temperature for 170min until reaching 30 ℃. And (4) introducing the gas discharged after the reaction into a gas chromatograph, and analyzing and detecting the content of carbon monoxide, carbon dioxide and toluene in the gas. The gas outlet end of the reactor is opened all the time, and the programmed temperature rise and the programmed temperature drop are circularly carried out in the whole reaction process. The catalyst of the invention selects dynamic low temperature when processing toluene, on one hand, the low temperature can reduce energy consumption and is beneficial to economy; on the other hand, this reaction condition is selected in consideration of the fact that the temperature of the RTO off-gas is low and is constantly changing in practical use.
The test results are shown in FIGS. 1 to 3. FIG. 1 is a graph of toluene removal rate over time and temperature in a dynamic low temperature environment; FIG. 2 is a graph of selectivity for carbon dioxide over time and temperature under dynamic low temperature ambient conditions; FIG. 3 is a graph of mineralization rate as a function of time and temperature under dynamic low temperature environmental conditions.
After 63h activity evaluation, the removal rate of toluene in the three catalytic ozonation catalysts (0.1g) prepared in examples 1, 2 and 3 in a dynamic low-temperature environment is shown in fig. 1, the removal rate of toluene in the whole reaction process shows a tendency of descending and then ascending, the removal rate is blank-Mn > citric acid-Mn > polyethylene glycol-Mn, when the reaction is carried out for 25h, the change of the removal rate of toluene is small, in the range, the removal rate of toluene is blank-Mn > citric acid-Mn > polyethylene glycol-Mn, the stability of toluene decomposition is blank-Mn > citric acid-Mn > polyethylene glycol-Mn, the toluene is basically stabilized at more than 99%, and the lowest removal rate of toluene also reaches 95%. The selectivity for carbon dioxide in a dynamic low-temperature environment is shown in fig. 2, the selectivity for carbon dioxide is citric acid-Mn > polyethylene glycol-Mn > blank-Mn during the first 25h of the whole reaction, the blank-Mn > citric acid-Mn > polyethylene glycol-Mn during the last 25h of the whole reaction, and the selectivity for carbon dioxide is greater than 86% and can be as high as close to 100% in the whole reaction process. The mineralization rate under the dynamic low-temperature environment is shown in figure 3, the mineralization rates of the three catalysts in the whole reaction process are not greatly different, and the citric acid-Mn is approximately equal to polyethylene glycol-Mn and is larger than blank-Mn in terms of the stability of the mineralization rate.
The catalytic ozonation catalyst provided by the invention has high activity, stability and selectivity, is simple in preparation method and low in cost, and shows good catalytic activity on low-concentration toluene under a dynamic low-temperature condition.
Comparative example 1
The differences from the embodiments 1 to 3 are as follows: there is no magnetic field.
Under the condition of no magnetic field, the catalyst citric acid-Mn with the best catalytic performance has the toluene removal rate: 42 to 51 percent; carbon dioxide selectivity: 75 to 85 percent; mineralization rate: 33 to 42 percent.
Comparative example 2
The differences from the embodiments 1-3 are as follows: raising the temperature to 400 ℃ at the room temperature at the speed of 5 ℃/min and preserving the heat for 4 h.
Under the condition of non-temperature programming, the catalyst citric acid-Mn with the best catalytic performance has the toluene removal rate: 33% -45%; carbon dioxide selectivity: 62 to 71 percent; mineralization rate: 26 to 35 percent.
Claims (10)
1. A preparation method of a catalytic ozonation catalyst is characterized by comprising the following steps: the method comprises the following steps:
1) using modifiers in a magnetic fieldFor gamma-Al2O3Modified treatment is carried out, and then heat treatment is carried out at 100-200 ℃ to obtain modified gamma-Al2O3A primary carrier; the modifier is more than one of water, citric acid aqueous solution or polyethylene glycol aqueous solution;
2) preparing manganese-containing compound into impregnating solution, and modifying gamma-Al2O3Dipping the primary carrier in a dipping solution, and then carrying out heat treatment at 100-300 ℃ to obtain a co-carrier loaded with an active component;
3) roasting and quenching the co-carrier loaded with the active component by adopting a programmed heating method to obtain a catalytic ozonation catalyst; the temperature programming refers to firstly heating to 150-300 ℃ for 1-2 h, and then heating to 350-450 ℃ for 2-5 h;
the conditions of the modification treatment in the step 1) are that the temperature is 50-100 ℃, the magnetic field intensity is 0.1T-1T, and the time of the modification treatment is 3-8 h.
2. The method of preparing a catalytic ozonation catalyst according to claim 1, wherein: modified gamma-Al in step 2)2O3gamma-Al in primary carrier2O3The mass ratio of Mn to Mn in the manganese-containing compound is (0.5-2) to 1;
the concentration of the citric acid solution in the step 1) is 5-20 wt%; the concentration of the polyethylene glycol solution is 5 wt% -20 wt%;
the modifier is mixed with gamma-Al in the step 1)2O3When treated, the modifier reacts with gamma-Al2O3The volume-to-mass ratio of (10-30) mL to 1 g.
3. The method of preparing a catalytic ozonation catalyst according to claim 1, wherein: the manganese-containing compound in the step 2) is a water-soluble manganese-containing compound; the impregnation liquid is prepared from a manganese-containing compound and water;
the heat treatment time in the step 1) is 10-20 h; the heat treatment is carried out under the condition of no oxygen;
the heating rate of the heat treatment in the step 1) is 2-10 ℃/min;
the heating rate of the heating and reheating in the step 3) is 3 ℃/min to 10 ℃/min;
and 3) carrying out heat treatment under the condition of no oxygen during roasting.
4. The method of preparing a catalytic ozonation catalyst according to claim 3, wherein: the water-soluble manganese-containing compound in the step 2) is manganese acetate, manganese nitrate or manganese chloride;
the atmosphere of the heat treatment in the step 1) is protective gas atmosphere or vacuum state;
the roasting atmosphere in the step 3) is protective gas atmosphere or vacuum state.
5. The method of preparing a catalytic ozonation catalyst according to claim 1, wherein: the quenching treatment in the step 3) is to place the roasted product in cold air at the temperature of 20-40 ℃ for cooling; the time for cooling the electrode is 10-30 min;
the heat treatment time in the step 2) is 10-20 h; the heat treatment is carried out under the condition of no oxygen;
the heating rate of the heat treatment in the step 2) is 2-10 ℃/min;
the gamma-Al in the step 1)2O3Selecting active alumina balls with the grain diameter of 3-5mm, and grinding and screening the active alumina balls;
the concentration of the impregnation liquid in the step 2) is (0.5-1.5) g/mL;
the impregnation in the step 2) refers to modification of gamma-Al2O3The primary carrier is stirred and dipped into the dipping solution to be colloidal.
6. A catalytic ozonation catalyst obtained by the preparation method according to any one of claims 1 to 5.
7. The catalytic ozonation catalyst according to claim 6, wherein the catalytic ozonation catalyst is used for catalyzing ozone to oxidize volatile organic compounds.
8. Use according to claim 7, characterized in that: the volatile organic compound is toluene.
9. Use according to claim 7, characterized in that: the method comprises the following steps: introducing waste gas containing volatile organic compounds and ozone into a reaction device filled with a catalyst for reaction, and oxidizing the volatile organic compounds by the ozone in a reaction system; the catalyst is as defined in claim 6.
10. Use according to claim 9, characterized in that: the reaction is carried out under the condition of dynamic temperature change; the dynamic temperature change refers to that the temperature is increased from 30 ℃ to 130 ℃ at a certain temperature increasing rate, then is reduced from 130 ℃ to 30 ℃ at a certain temperature reducing rate, and the temperature is maintained for 2-4 hours at 10 ℃ per liter or 10 ℃ per liter in the temperature increasing or reducing process; the heating rate is 1-10 ℃/min; the cooling rate is 1-10 ℃/min;
the concentration of the volatile organic compounds is 25-35 ppm, and the concentration of the ozone is 200-400 ppm.
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