TW201134549A - Preparation of zirconia-ceria-supported nano-palladium catalysts and its application in destruction of volatile organic compounds in air - Google Patents

Abstract

This invention declares the preparation of zirconium-cerium dioxide-supported nano-palladium catalysts and the process of destruction of volatile organic compounds in air stream to remove volatile organic compounds using zirconium-cerium dioxide-supported nano palladium catalysts. The palladium particle size is between 2 and 6 nm and supported on mixed oxide ZrO2-CeO2. Zr/Ce molar ratios are between 1/9 and 5/5. Destruction of volatile organic compounds in air stream over these catalysts is carried out in a fixed bed reactor to remove volatile organic compounds.

Description

201134549 No representative representative figure 5. If there is chemical scale in this case, please reveal the most age (4) w% Pd/ Cei-xZrx〇2 is the catalyst prepared by the invention, w ^ ^ ·

Cei-XZrx02) is the percentage of total catalyst weight, 'χ二° $ = 赖耳' one: 1, catalyst ==

CnHm + m/2 〇2 + n C02 + (10) η2〇 〇

The above is the chemical reaction type of this meal, and the composition of the towel Cniim rider exhaust. VI. Description of the Invention: [Technical Field to Which the Invention Is Applicable] The present invention discloses a method for preparing a catalyst supported by oxidizing and cerium oxide, and a species in which the cerium is oxidized to make cerium oxide. A method in which organic waste gas reacts with oxygen in the air to remove organic waste gas; wherein the wrong and the decorative system are mixed according to different molar ratios, and the wrong/钸 molar ratio is between 1/9 and 5/5, and the (four) particle diameter is Between 2 and 6 nm; the present invention contains the organic waste gas at the age of the organic waste gas in the presence of the oxidized oxidized _dioxane medium, and the organic gas is removed. x [Prior Art] In recent years, due to the rapid development of industrial development, the economic growth has also caused environmental pollution. _ is the volatile organic matter in the silk carving industry (VolatUe 0rganic c〇mp〇unds, v〇Cs) Scattered in the air, the accompanying pollution is inaudible to the industry. Jobs refer to volatile substances containing aza (10) = A 2 201134549 alkane hydrocarbons, such as benzene, toluene, nitrogen-containing amines, etc. Under normal conditions, the boiling point is below 25 (TC). VOCs are mostly harmful. Air pollutants, long-term exposure to VOCs in the human body, even at low concentrations, can cause mid-mother or carcinogenic tumors. In addition, the v〇Cs in the atmosphere are highly photochemically active [from the outside Light irradiation produces high oxidizing pollutants such as ozone, PAN (per〇xy acethy 1 trate), PM Cpemxy benzene nitrate, etc.

Exciting and harmful, so how to reduce the harm of these pollutants to the environment and the human body is the goal that researchers must work hard. The treatment methods of VOCs can be roughly divided into the following two types: one is destruction (destnictiQn) 'it includes high temperature and catalytic reduction, and the biological trampoline method' converts organic pollution into carbon dioxide and water in this mechanism. One is for recycling (constant y), Che Wei, _ condensation and thinner materials method, the pollutants are transferred or recovered from the exhaust gas to make it a clean gas. In the early stage, it was treated with the south temperature combustion method and was sufficient in oxygen, temperature and reaction time. Any hydrocarbon can be oxidized into carbon dioxide and water through the combustion process, and the malodorous gas can be burned to become odorless. Harmless gas, and discharged into the atmosphere, the machine volatile gas surface, each __ the same, so the temperature of the furnace to achieve the organic volatile gas in the burning side is also different, 対 a variety of Mixing 'm temperature and conditions are more complicated' - the direct burning furnace = the gas of Qi Qiu Jiu Baidu or even higher to remove most of the L but heating also consumes a lot of energy (electric heating, diesel), Therefore, the increase is caused. Therefore, at present, the advantages of the catalyzed combustion method are that the V0Cs are removed, and the advantages of the direct combustion method are: (1) low temperature treatment of organic pollutants (2) high energy efficiency (3) no pollution to the environment (product is carbon dioxide) And water). Catalysts for handling organic pollutants are mainly classified into (1) low-activity but inexpensive metal oxides (Cr03,

CuO) and (2) high activity, but expensive metals

(Pt, Rh, Pd, Ag, Au), the choice of the butterfly in this report is compared with other precious metals (Pt, Ag, Au, Rh), free from catalyst (1) lower price (7) good oxidation activity (3) high temperature Durability, riding heavy metal, atomic order 46, Zhousi Shang and Ming, nickel family, with money, Lang Li 'ant-species transition metal, gray white, excellent ductility' easy to weep, its (four) gamma, but _ green shoot other The elements are more susceptible to acid stagnation, and the point is up to 18 degrees to withstand high temperatures. Industrially, it is generally used as a by-product of selected copper and _shishi (four). In addition, it can absorb hydrogen in its own volume. The study of the support _ is a very important subject of the touch-reflection, and the nature of the catalyst is changed by the surface of the support and the surface area of the touch component.

Quality, increase the activity and selectivity of the reaction, and the cost of preparation of a large structure of low precious metal catalyst. Toluene is a kind of clarified, colorless liquid with a scent of scent, and it is an aromatic hydrocarbon with benzene. In fact, it should be used as an organic solvent. Benzene is very similar, but unlike the stupid oxidation reaction, the oxidation reaction of toluene does not occur on the benzene ring but on the methyl group. Therefore, the oxidation product n of toluene is extremely small in the by-product of oxidation reaction of benzene (epoxy with strong carcinogenicity > wu [Catal Today, Vol. 63 (9), pp. 419-426], etc. Carbon as a platinum catalyst for the support, can fully oxidize 4 201134549 A low temperature below 200 ° C, wherein the activated carbon can be heated to 400 C or 800 C in a nitrogen stream, and cleaned with fluoric acid to remove surface impurities Or minerals.

Luo [Appl. Catal. B: Environ. Vol. 69 (2007) pp. 213-218] et al. prepared a palladium catalyst using CeCrY2〇 co-oxide as a support and coated the catalyst with water. Attached to the honeycomb ceramic, it was found to be 5 〇〇. The calcined catalyst can completely oxidize terpene at 21 ° C. The durability of the catalyst is also important in addition to its activity. The researchers repeatedly heat the catalyst between 200 and 240 ° C. Cooling Chuanyi a total of 8 times 'has found no significant change in the activity of the catalyst within 30 hours, showing its repeatability and stability. Hosseini [Catalysis Today, Vol. 122 (2007) pp. 391-396] and others used the sedimentation method and the impregnation method to carry the gold and the tributary on the high surface area titanium dioxide support with porous structure. The activity is 0.5% Pd-1% Au/TiO2> 1.5% Pd/TiO2> 0.5% Pd/Ti02>1% Au-0.5% Pd/Ti02 > 1% Au/Ti02 > Ti02, the best activity 〇.5% Pd-1% Au/Ti〇2 can completely oxidize toluene at 230 °C. Liu et al. [Journal of Hazardous Materials, Vol. 149 (2007), pp. 742-746] uses alumina as a mixed carrier of ceria and cerium oxide coprecipitates prepared by coprecipitation. The Pt^AlzCVCeojZi^Yo.iMniuOx catalyst with ruthenium and manganese as additives was proved to have higher activity at 216 by using the impregnation method to prepare the platinum catalyst. (: The conversion rate of complete oxidation of toluene can reach 90%. Zheng et al. [Catal. Comrmm. Vol. 9 (2008) pp. 990-994] use stainless steel as a support, prepare by anodizing procedure, and forge Boiled under (7) (8), it can obtain the best activity of the catalyst, and the total conversion temperature of the A 5 201134549 element is 21〇c. Qingba〇 et al. [Chin J Catal. Vol. 29 (2〇〇8), p. 373) 3 8 pages] Using ζΓ〇2 to easily exchange the tetragonal phase of oxygen atoms and the characteristics of wear resistance, high temperature resistance, corrosion resistance, etc., and to make a proper ratio with Ce〇2, the result is not Pd/Ceo.sZi ^CVsubstrate monolithic catalyst, calcination temperature is 400C, reaction temperature is 2l (97% conversion of toluene can be obtained under TC. Domestic patents, hydrogenation and hydrogenation in the full-charged part The application ' does not carry out the oxidation reaction of benzene in the air environment, and does not use the sulphur storage - cerium oxide mixed oxide as the support, and reacts at 25 〇. 国内The application patents are listed in Table 1. The foreign patents on saturated catalyst applications are listed in Table 2. In the patent, there is no method for utilizing nanometer to apply the oxidization and cerium oxide catalyst to the organic waste gas removal as disclosed in the present invention. 一 Table 1 Domestic Patent Search Bulletin Announcement Day ------- ----- Patent Name 1 200842125 2008/11/1 --~----- Method for Selective Hydrogenation of Conjugated Diene by Negative Ionic Liquid Nano-Palladium Catalyst 1 200304850 2003/10/16 ~~ ^—----- #机: Waste gas treatment method and 奘詈

6 201134549 Table 2 Foreign related patent search N 0. Patent No. --------- Date — Title 1 US6458741 2002/10/01 ~ — Catalysts for low-temperature destruction 2 5753583 of volatile organic compounds in air 1998/05/19 Supported palladium catalyst [Summary of the Invention] The present invention discloses a method for preparing a ruthenium catalyst supported on oxidized and oxidized bismuth and a method for carrying nano zirconia on zirconia and cerium oxide. The catalyst catalyzes the method of removing the organic waste gas by reacting the organic exhaust gas with oxygen; wherein the oxidation fault and the cerium oxide are mixed according to different molar ratios, and the oxidation/smoothing molar ratio is 1/9. Between 5/5, bear it! The bar particles are between 2 and 6 nm in diameter. This month, the 16/Oxygen-dioxo-transfer ship was used in Qian Weiyu to use a packed bed reactor to remove organic waste gas. [Embodiment] Embodiment.]: Ce(N03)3 · 6H2 〇 (cerium nitrate hexahydrate) and Zr0(N03)2 · D 2Η2〇 (Zirc〇nium oxynitrate dihydrate) are dissolved in deionized water according to different ratios. The metal salt solution is further filtered and washed with ammonia water (amm〇nias〇luti〇n) as an alkali solution, and then dried at any temperature between 70 and 100 t: 2 to 1 hour, and at 300 to 600 t: calcined at any temperature for 4 to 16 hours to obtain a CeuZrxOr coprecipitation catalyst. Example 1: 7 201134549 1. 9.3477 g of Ce(N〇3)3.6H2〇 and 0.6393 g of ZrO(N03)2 · 2H20 were dissolved in 400 ml of deionized water. 2. Measure 25 wt.% of ammonia 400. 3 • Quantitatively titrate the prepared metal salt solution and ammonia water in 丨〇 ml/min and stir. 4. The above yellow solution was filtered and washed with an air suction filter, and the filter cake was washed with deionized water to a water-washed filtrate of about ρ Η $8, and dried under vacuum at 70 rpm for 2 hours. Ο 5· The yellow powder was further heated to 500 at a heating rate of 10 ° C/min. (: calcination, for 8 hours) to obtain dgCe^Zro.A-coprecipitation catalyst. Example 2: 1. Take 8.3578g of Ce(N03)r6H20 and 1.3168g of Zr0(N03)2.2H20 In 400 ml of deionized water. 2. Measure 25 wt.% of ammonia water 400 ml. 3. Quantitatively titrate the prepared metal salt solution and ammonia water at 1 〇ml/min, and stir the mixture. The yellow solution was filtered and washed with a suction filter, and the filter cake was washed with deionized water to a water-washed filtrate of about PHS8 at 70. (: vacuum drying for 2 hours. 5. Re-slall yellow powder at ° C/min Heating rate, calcined to 5〇〇〇c, for 8 hours, can get 4gCea8Zr〇.2〇r common sedimentation method. 眚2 method The initial wetness method first measures the pore volume of the support, ie First measure the amount of water required. The amount of 201134549 can make the support reach the critical point of microwetting. To prepare the Cei_xZrxOr incipient wetness catalyst, firstly, take the appropriate amount of Ce〇2 to test the pore volume, and slowly drop the deionized water into the load. In the body and mix it, to ensure that the deionized water can be filled in the hole, when the support reaches a slightly wet, deionized water Void volume is the product of the carrier body is then appropriate amount of

After ZrO(N〇3)2 · 2H2〇 is dissolved in the previously measured amount of water, the metal salt solution is slowly dropped into the Ce〇2 catalyst to allow the solution to completely inhale into the pores, 7〇 to 1〇〇. The temperature between any of 〇 is dried for 2 to 10 hours' and at any temperature of 3 〇〇 to 6 ,, 煅 is calcined for 4 to 16 hours to obtain a Ce^xZrxCV incipient wetness impregnation catalyst. Example 3: 1. 2.7789 g of Ce〇2 was used to test the pore volume, and the deionized water was slowly dripped into the support and stirred to ensure that the deionized water could be filled in the pores. When the support reached a slightly wet condition, The volume of deionized water is the pore volume of the support. 2. After dissolving 0.4795 g of Zr〇(N〇3)2 · 2·0 in the previously measured amount of water, slowly slowly drop the metal salt solution into the Ce〇2 catalyst to allow the solution to completely inhale the gap. in. 3. Dry in C vacuum for 2 hours, then increase the temperature to 500 °C at 1 ° ° C / min, and then heat at 500 ° C for 8 hours to obtain 3 g of Cea9Zr () 1 〇 2 _ initial wet impregnation method Catalyst Example 4: L Take 2.5445 g of Ce〇2 to test the pore volume, slowly drop the deionized water into the support and mix it to ensure that the deionized water can be filled in the pores, when the support reaches the micro-wet The volume of deionized water is the pore volume of the support. 9 201134549 2. Take 0.9877 g of Zr0(N03)2. 2H20 dissolved in the previously measured amount of water. Slowly drop the metal salt solution into the Ce〇2 catalyst to allow the solution to completely absorb the gap. 3. Dry in vacuum at °C for 2 hours, then raise the temperature to 500 〇C at 1 °C/min, and then heat at 500 for 8 hours to obtain 3 g of Ce〇.8ZrG.2〇2-incipient wetness impregnation. Law catalyst. Embodiment 3 i First test the initial moisture content of the catalyst, and then dissolve the appropriate amount of Pd(N〇3)2 · 2H2 〇 in the measured water. Slowly, the metal salt solution is dropped into the appropriate amount of Cei- xZrx〇2-Common in the bath system to enable the solution to completely inhale into the hole; dry at any temperature between 7〇 and 1〇〇〇c for 2 to 1 hour, and at 3〇〇 to 6〇〇 The pd/Cei crystal-coprecipitation catalyst can be obtained by calcining at any temperature for 4 to 16 hours; the catalyst pd/CeniZnOr·coprecipitation method is used to place the catalyst in the packed reaction bed reactor. Inside, the reaction of completely oxidizing in the air is carried out, and the reactor is continuously tested in a continuous catalyst packed bed reactor; the flow rate is controlled, and the reaction is carried out at a fixed temperature. Example 5: 1. The initial moisture content of the catalyst was measured, and 〇〇518gpd(N〇3)2 · 2h2〇 was dissolved in the measured amount of water. 'The metal salt solution was slowly dropped into 2 g of Ce〇. .9Zr〇.1〇2_ total/child; in the Syrian catalyst, the solution can be completely inhaled into the hole; 2. Dry at 70 C for 2 h, then heat up to 5 °C at 1 °C/min. , maintained at 500 C for 8h, can get lwt%pd/Ce〇9Zr〇i〇2_ coprecipitation method 201134549 medium; 3. Catalyst lwt.%Pd/Cea9Zrai〇2-coprecipitation method, set The reaction of oxidizing toluene in air is carried out in a U-type catalyst packed reaction bed, and the experiment is carried out in a continuous catalyst packed bed reactor; 4. The flow rate is 10 〇ml per minute, and the reactor is introduced at room temperature. The inside and outside diameter of the pipe is 0.9 cm and 1.3 cm, the length is 21 cm, and there is a fused quartz sand of 〇5 cm in the middle to support the catalyst of the reaction, but it can be ventilated; Ο 5·Weighing catalyst weight 0.5 g Placed in a U-shaped quartz tube, the temperature of the sulphurizer in the water bath is controlled at 30 °C, the temperature of the catalyst is raised from room temperature to 300 °C, and the temperature is raised at a rate of 4 °C/min. After the minute, when the reaction temperature is reached, control the reaction at this temperature for '10 minutes. 6. The feed flow rate is controlled by a mass flow controller (MassFlow Controller, generally referred to as MFC), and the feed is first filled with a small amount of air. After the benzene cone bottle takes out the steam of the feed, the feed concentration is adjusted by another air dilution, and the reaction bed is filled by the U-type contact medium, and the reacted gas flows through the gas chromatograph and then by the flame. Free price analyzer analysis. The reaction results are as follows' and the conversion rate is shown in Fig. 4. The results of the reaction of the above embodiment are as follows; wherein the toluene conversion rate is defined as follows: Toluene conversion rate = (Important benzene concentration - outlet 笨 stupid concentration), mouth arbitrage. From these results, it was confirmed that the catalyst of the present invention can effectively remove organic exhaust gas (toluene) in the air. 11 201134549 Temperature 丨50丨70 (°C) 1 ..........h———”__ 90 110 130 ! 150| 170 1 190 210 230 250 270 Exit 曱; 1.8 I 1.6 Stupid 1 '(g/rn3) 1 -....................................... „,, ί ----- ---------- 1.4 1.2 0.9 0.6 0.3 1 1 0.05 0.01 0 0 0 Example 6: 〇i·Test the initial moisture content of the catalyst' and then add 0.0518g Pd(N03)2 · 2H20 Dissolve in the measured amount of water 'slowly drop the metal salt solution into 2g of Cea8Zr0.2〇2-coprecipitation catalyst to make the solution completely inhaled into the gap; 2. Dry at 70 C for 2 hours, then After heating to 5〇〇〇c at 1〇°c/min, it is maintained at 500. (: After calcination for 8 hours, lwt% Pd/Ce〇8Zr〇2〇2j precipitation catalyst can be obtained; 3. Will touch The medium iwt%Pd/Ce〇8Zr〇2〇2_ coprecipitation method is placed in the u-type catalyst filled 〇 〇 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' Experiment; 4. Control flow rate is just ascending every minute. Pass into the reactor at room temperature. The direct control inside and outside the tube is 〇·9 cm and U cm, the length is 21 cm, and there is 0.5 in the middle. The dissolved quartz sand is used to support the reaction catalyst, but it can be ventilated; 5. The weight of the catalyst is taken in the G.5S U-shaped quartz tube, and the temperature of the sulphurizer in the water is controlled to be 3G t The catalyst reaction temperature is 5G. (: The temperature is raised to 300 t, and the 乂4 C/min call rate is raised for 5 minutes. When the reaction temperature is reached, the reaction is controlled after the temperature of 12 201134549 ίο minutes. 6. The feed flow rate is passed. The mass flow controller (MassFlow Controller, generally referred to as MFC) controls 'first take a small amount of air through the conical flask containing the feed benzene to bring out the steam of the feed, and then adjust the feed concentration by another air dilution, ( The MFC ratio of toluene is controlled at 7/93), and the reaction bed is filled by U-type catalyst. The reacted gas (ie, the gas passing through the catalyst bed) flows through the gas chromatograph (GC) and is detected by flame free. (FID) analysis. The reaction results are as follows, and the conversion rate is shown in Figure 4. The reaction results of the above embodiment are as follows; wherein the conversion of toluene is defined as follows: conversion of toluene = (injected toluene concentration - outlet toluene concentration) + import Benzene concentration. From these results, it was confirmed that the catalyst of the present invention can Effectively removes organic waste gas (toluene) in the air. Temperature (°C) 50 70 90 110 130 150 170 190 210 230 250 270 Export 曱 | 1.8 Stupid concentration (g/m1 2 3) 1.7 1.6 ...... ......................... 1.4 1.2 0.9 0.6 0.4 0.3 0.01 V : 0 Example 7 : 13 1 Test the initial moisture content of the catalyst Then, 〇.〇518g pd(N〇3)2 · 2H2〇 is dissolved in the measured amount of water' Slowly, the metal salt solution is dropped into 2g of Ce0_9Zrai〇r incipient wetness impregnation catalyst to make the solution completely In the suction gap; 2 vacuum drying at 70 °C for 2 hours' and then heating to 500 °C at 1 ° ° C / min, 3 maintained at 500 ° C for 8 hours, you can get lwt.% Pd / Ce () 9Zr ( ) 1〇r initial 201134549 wet impregnation catalyst; 3. The catalyst lwt%Pd/Ce〇.9Zrai02-incipient wetness impregnation method is placed in a U-type catalyst packed reaction bed to carry out oxidation of benzene in air. The reaction was carried out in a continuous catalyst packed bed reactor; 4. The control flow rate was 10 〇ml per minute, and it was introduced into the reactor at room temperature. The inner and outer diameters of the tube were 0.9 cm and 1.3 cm, and the length was 21 cm. Has a 0.5 cm melting quartz sand to The catalyst for carrying the reaction, but it can be ventilated; Ο 5. The weight of the catalyst is 0.5 g and placed in a U-shaped quartz tube. The temperature of the sulphurizer in the water bath is controlled at 30 °C, and the temperature of the catalyst is 50 °. C is heated to 300 X:, after heating at a rate of 4 ° C / min for 5 minutes, when the reaction temperature is reached, the reaction test is carried out after 10 minutes at this temperature;

6. The feed flow rate is controlled by a mass flow controller (MassFlow Controller, generally referred to as MFC). First, a small amount of air is taken out of the feed vapor through a conical flask containing the feed benzene, and then diluted by another air. Adjust the feed concentration (the MFC enthalpy ratio of toluene is controlled at 7/93), fill the reaction bed with a U-type catalyst, and the reacted gas (ie, the gas passing through the catalyst bed) flows through the gas chromatograph (GC). 'After the flame free detector (FID) analysis. The reaction results are as follows, and the conversion rate is shown in Fig. 4. The reaction results of the above embodiments are as follows; wherein the toluene conversion rate is defined as follows. Toluene conversion rate = (imported toluene concentration - exporting a stupid concentration of imported benzene and benzene is abundantly produced. From these results, it was confirmed that the catalyst of the present invention can effectively remove organic matter in the air. Exhaust gas (A stupid). , 14 201134549 Temperature 50 ; ; j 70 90 1 no ...........'....•μ,.....···. 130 150) 170 190 210 ................................................ .................................................. ............230 , 250 I 270 | 1 (°C) ! ! !丨ί 1Export 曱丨1.8 1.6 1.4 I 1.2 0.9 0.5 0.2 0.01 0 ο 1 〇丨ο I ; Benzene concentration II i (g/m3): ί 1 1 ; Example 8: Q h was tested for the initial wet moisture content of the catalyst, and then 0.0518 g of Pd(NO3) 2 · 2H20 was dissolved in the measured amount of water, slowly The metal salt solution was dropped into 2 g of Ce〇8Zr〇2〇r in the incipient wetness impregnation catalyst to allow the solution to completely absorb into the gap; 2. Dry at 70 C for 2 hours, then raise the temperature to 1 〇^/min. After 500 °C, it can be calcined at 500 °C for 8 hours to get lwt %pd/Ce() 8ZrG2 2_Incipient wetness impregnation catalyst; 3. Catalyst lwt.%Pd/Ce〇_8Zr〇.202-incipient wetness impregnation method, placed in U-type catalyst filled 〇 reaction bed 'to oxidize toluene in air The reaction was carried out in a continuous catalyst packed bed reactor; 4. The control flow rate was 1 〇〇ml per minute, and it was introduced into the reactor at room temperature. The inner and outer diameters of the tube were 9.9 cm and 1.3 cm, and the length was 21 cm, with 〇5 cm of molten quartz sand in the middle to support the catalyst of the reaction, but it can be ventilated; 5. Weighing the weight of the catalyst G.5g placed in the u-type quartz f, the saturator of the toluene The temperature in the water bath is controlled at 30, and the temperature of the catalyst is raised from 50 °C to 300. (:, after heating at a rate of 4 C/min for 5 minutes, the reaction temperature is controlled at this temperature 15 201134549 degrees for 10 minutes after reaching the reaction temperature; 6. The feed flow rate is passed through a mass flow controller (MassFlow Controller, generally referred to as MFC) ) control, first take a small amount of air through the cone containing the feed benzene to bring out the steam of the feed, and then adjust the feed concentration by another air dilution (the MFC ratio of benzene is controlled at 7/93) The reaction bed is filled by a U-type catalyst, and the reacted gas (ie, the gas passing through the catalyst bed) flows through a gas chromatograph (GC) and is analyzed by a flame free detector (FID). The reaction results are as follows. And the conversion rate is shown in Figure 4. The reaction results of the above embodiments are as follows; wherein the conversion of toluene is defined as follows: 曱 stupid conversion rate = (imported benzene concentration - export benzene concentration) + imported benzene concentration. The catalyst of the invention can effectively remove organic waste gas (nonylbenzene) in the air. Temperature (c) | benzene concentration Oi (g/m3) 50 export armor 1.8 70 90 | ........i 110 130 150 170 ............................. 190 210 230 250 270 1.6 1.4 1.3 1.2 1.1 0.9 0. 4 0.1 0.01 0 0 [Simple description of the diagram] Figure 1 XRD pattern of each catalyst powder BET surface area and elemental analysis results of each catalyst Figure 2 TEM image of the powder catalyst of lwto/oPd/Ceo.gZriniVlw Conversion rate of T-benzene oxidation by the medium Figure 5 Endurance test of complete oxidation of each pair of toluene 16 201134549 [Explanation of main component symbols] No main component symbol description

Claims (1)

201134549 VII. Scope of application for patents: 1. A method for the production of secret oxygen and oxygen dioxide and oxygen-catalyzed catalysts, which includes: an oxidized and oxidized mixed oxide prepared by impregnation, mixed with bromine The molar ratio is between 1/9 and 5/5, and between 5% and 2% by weight of the bar. It is characterized by the preparation of the oxidized oxidized composite oxide '70 by the incipient wetness method. It is dried for 2 to 1 hour, and between 4 and 16 hours in the sub-period-temperature zone, and then the infusion of the salt and its oxide in the water, followed by 7 to qing. Dry between c (8) to 10 hours, slowly heat up to _ after 'turning to the final temperature satin for 4 to 16 hours. A method for producing a mixed catalyst of oxidized and cerium oxide mixed oxide, wherein the molar ratio of the wrong mixed material is between 1/9 and 5/5, and the weight percentage is 〇·5 to 2 wt·%. Between the characteristics of the composite oxide is prepared by the common sinking method, 70 to 峨 dry 2 to 1 () hours, and at ~ to 60 (rc at any temperature for 4 to Between 16 hours, the read and its oxides are placed in water by impregnation, then dried at 7G to (10).c for 2 to 10 hours. After slowly heating up to _ °C, the calcination is maintained at the final temperature. Up to 16 hours. 3:: When the time is gone, it contains the benzene benzene method, which contains the catalyst of Natto supported on cerium oxide and cerium oxide mixed oxide, in air, between 5 〇 and 300 ° C. The reaction is carried out at any temperature to completely oxidize the toluene. The method of the third aspect of the patent application, wherein the oxidization error prepared by the time immersion method and 18 201134549 - a gas-reducing compound, the material of the wrong age is as a product The method of the third item, the h is between the sag and the sulphate, and the smear of the smear is ι/9 = oxygen: . The method of the invention comprises the nanometer prepared by the impregnation method, wherein the calcining temperature of the catalyst is maintained between 3 Torr and 600 ° C. The method of claim 3, wherein the nano palladium is contained in the oxidation fault. And the catalyst of cerium oxide, wherein the weight percentage of palladium is between 2% and 2%. 19