CN1181028A

CN1181028A - Cleaning ambient air by moving a vehicle having a pollutant treating surface through the atmosphere

Info

Publication number: CN1181028A
Application number: CN 96191519
Authority: CN
Inventors: J·B·霍克; J·R·诺瓦克; J·J·斯迪格; T·C·泼里斯; L·M·魁克; R·M·赫克; Z·胡; F·M·阿兰; P·W·比罗瑟; M·德巴
Original assignee: Engelhard Corp
Current assignee: BASF Catalysts LLC
Priority date: 1995-01-20
Filing date: 1996-01-19
Publication date: 1998-05-06
Also published as: JP4065022B2; WO1996022148A3; WO1996022148A2; JPH10512805A; MX9705527A; CN1174519A

Abstract

A method and apparatus for treating the atmosphere comprising moving a vehicle through the atmosphere, the vehicle having at least one atmosphere contacting surface and a pollutant treating composition located on said surface. A specific embodiment comprises coating a motor vehicle radiator with pollutant treating catalyst.

Description

By moving the method that the vehicle with pollutant treating surface passes through the atmosphere cleaning ambient air

The application's book is the part continuation application of the U.S. Patent application No.08/537206 of submission on September 29 nineteen ninety-five, the latter is the part continuation application of the U.S. Patent application No.08/410445 of submission on March 24 nineteen ninety-five, the latter is the part continuation application of the U.S. Patent application book No.08/376332 of submission on January 20 nineteen ninety-five, and the present invention is all incorporated in above-mentioned here all applications as a reference into.

The present invention relates to a kind of equipment that purifies atmosphere; More particularly, the present invention relates to have at least a kind of vehicle of the surface that contacts with atmosphere, the pollutant treatment compositions is arranged on its surface.

The literature survey of one piece of relevant prevention and cure of pollution proposes, and method in common is that reaction purifies the waste stream that enters atmosphere.If there is too much one or another kind of pollutant to be detected or to be discharged, so target tightening in the source of pollutant, the cause of pollutant or contain the waste stream of pollutant.Most of gas stream enter before the atmosphere processed with the minimizing pollutant.

Disclose and handled the atmospheric air that is imported in the space of determining removing the wherein method of undesirable pollutant.But, seldom attempt to handle the pollutant that is present in the environment; But allow environment itself as purification systems.

Existing many lists of references disclose the initiatively content of environment purification.US 3738088 discloses a kind of motor vehicles that use and has been used for air filtration complete set of equipments from the surrounding air purifying contaminated as portable cleaning equipment.When motor vehicles travelled in environment, disclosed various elements combined with motor vehicles and are used for cleaning ambient air.Particularly, the speed and the conduit of air being delivered to different filter apparatus that is used for controlling air stream is disclosed.Filter is established and can be comprised various filters and electric cleaner.Disclose rearmounted catalytic filter and be used to handle non-particulate or aerocolloidal pollutant, as carbon monoxide, unburned hydro carbons, nitrogen oxide and/or oxysulfide etc.DE4318738C1 also discloses a kind of physical cleaning of outdoor air and the method for chemical cleaning method.Motor vehicle is as the delivery vehicle of conventional filtration device and/or catalyst, and filter and catalyst do not constitute the functional unit of motor vehicles, and directly is used for purifying atmosphere.

Other method is disclosed among the US5147429.A kind of movably atmospheric air purifying station is disclosed.Particularly, the feature of this patent is the dirigible that a collection air is arranged.Various types of air cleaning facilities are arranged in the dirigible.Disclosed air cleaning facility comprises wet gas scrubbing appts, filter and cyclone type spraying scrubber.

Disclosed equipment is that for the difficulty that initiatively purifies atmospheric air they need new and equipment that add.Even disclosed improvement motor vehicles also need conduit and filter in US 3,738 088, may comprise catalytic filter.

License to DE 400 7965C of Klaus Hager ₂Disclose and be useful on various cupric oxide and a kind of catalyst that is used for the mixture that contains various cupric oxide and various manganese oxide of carbon monoxide conversion that ozone transforms a kind of containing.Catalyst can be used as coating and is coated on self-heating radiator, oil cooler or the charge air cooler.Catalyst coat contains the also heat-resistant adhesive of permeable gas.Show that various cupric oxide and manganese oxide are widely used in Antigas mask filter, but it there is the shortcoming of being poisoned by water vapour.But in operation process, the heating of car surface makes water vapor.Use this method, the long-term use of catalyst is possible, does not therefore need drier.

Known various manganese oxide can make catalytic ozonation become oxygen.Disclose commercially available manganese compound and the composition of containing of the many kinds that comprise alpha-oxidation manganese, be used for the reaction that catalysis ozone generates oxygen.Particularly, known use potassium manganese ore type alpha-oxidation manganese comes catalysis ozone to generate the reaction of oxygen.

Alpha-oxidation manganese is disclosed in some lists of references, " having the hydro-thermal of the manganese oxide of pore passage structure to synthesize; the modern analytical technique of petroleum analysis " as O ' Young, in zeolite and the discussion of layer post carclazyte works progress, deliver, petrochemistry branch of American Chemical Society, New York City Meeting, August 25-30,1991, the 348 pages of beginnings.Such material is also open in granting the US5340562 of O ' Young etc.In addition, various α-MnO ₂In " sodium manganite, potassium manganese ore and some other the oxide of manganese and hydroxide synthetic " of McKenzie, the mineralogy magazine, in December, 1971, the 38th volume is described among the 493-502.For the present invention, α-MnO ₂Be defined as and comprise hollandite (BaMn ₈O ₁₆XH ₂O), potassium manganese ore (KMn ₈O ₁₆XH ₂O), manjiroite (NaMn ₈O ₁₆XH ₂O) and coronadite (PbMn ₈O ₁₆XH ₂O).O ' Young discloses these materials three-dimensional framework pore passage structure (US 5340562 and O ' Young " having the hydro-thermal of the manganese oxide of pore passage structure to synthesize " incorporates the present invention here as a reference into).For the present invention, α-MnO ₂Be considered to 2 * 2 pore passage structures, it comprises hollandite, potassium manganese ore, manjiroite and coronadite.

The present invention relates to handle equipment, method and the composition of atmosphere.For purpose of the present invention, atmosphere is defined as circumterrestrial air main body.

The present invention relates to handle the equipment and the correlation technique of atmosphere, comprising vehicle and the device such as the engine that this vehicle are transferred to another place by the somewhere by atmosphere.This vehicle comprises at least one surface of vehicle that contacts with atmosphere and the pollutant treatment compositions that is positioned on this surface.The atmosphere contact surface is the surface of the vehicle component that directly contacts with atmosphere.Preferably comprise assembly surface under bodywork surface, deep bead surface, vehicle body radiator grille surface, the reflective mirror back of the body and the hood with the atmosphere contact surface that is suitable for.Preferred atmosphere contact surface is positioned at motor-driven vehicle body, general close engine is the cabin.These surfaces are preferably the cooling device surface, and comprising liquid or the gas flow channel by the cooling agent that sealed by wall, these airtight containers are just like pipe or which is provided with the hood and the outer surface of the fin that is used to promote heat exchange.Preferred atmosphere contact surface comprises the outer surface that fin is housed and is selected from the surface of radiator outer surface, air-conditioning condenser, radiator fan, oil cooler, transmission oil cooler, power-assisted steering liquid cooler and the charge air cooler that is considered intercooler or aftercooler equally.Most preferred atmosphere contact surface is the outer surface of air-conditioning condenser and radiator, and its reason is that its surface area is big and Ambient Operating Temperature is higher, about 40-135 ℃, typically up to 110 ℃

The invention has the advantages that and be applicable to that it can be the surface that has vehicle assembly now that the atmosphere contact surface that pollutes composition is handled in carrying.Need not to use the device of additional filter or carrying pollutant treatment compositions.Therefore, apparatus and method for of the present invention can be set at the existing assembly of new car or be retrofitted on used car, and renovation improves the suitable pollutant treatment compositions of coating on the existing surface of vehicle that contacts with atmospheric air in the time of can being included in vehicle by atmosphere.

The present invention relates to handle various compositions, method and the goods of airborne pollutant.Such pollutant contains 0～400, more generally 1～300 usually, 1～200PPb ozone more generally; 0～30,1～20PPm carbon monoxide more generally; And undersaturated hydrocarbon compound of 2～3000ppb such as C ₂To about C ₂₀Alkene and part oxygen-containing hydrocarbon class are as alcohol, aldehyde, ester, ether, ketone etc.Accessible typical hydro carbons includes but not limited to the hydrocarbon gas and the steam of propylene, butylene, formaldehyde and other air carrying bands.Other pollutants that exist comprise nitrogen oxide and oxysulfide.National Ambient Air Quality Standards (NAAQS) to ozone is 120ppb, and carbon monoxide is 9ppm.

The pollutant treatment compositions comprises and is used for the carbon monoxide-olefin polymeric that pollutant that the catalyzed conversion atmosphere exists becomes harmless material.On the other hand, adsorbent composition can be used as the pollutant treatment compositions, and destructible pollutant when adsorbing to be adsorbed on is perhaps stored pollutant, further handles after being equipped with.

Can use the carbon monoxide-olefin polymeric that helps pollutant is changed into the compound of innoxious compound or less harm.What be suitable for comprises that with preferred catalyst compositions catalysis ozone generates the reaction of oxygen, the catalysis carbon monoxide generates the reaction of carbon dioxide and/or the reacted composition that the catalysis hydro carbons generates water and carbon dioxide.Concrete and the preferred catalyst of catalysis hydrocarbon reaction is applicable to that catalysis contains 2～20 carbon atoms and the low-molecular-weight unsaturated hydrocarbons that has two keys at least, as C ₂To about C ₈The reaction of alkene.Such low molecular weight hydrocarbons has sufficiently high reactivity to producing smog.The specific alkene that can react comprises propylene and butylene.But the reaction of catalyst catalysis ozone that be suitable for and preferred and the reaction of carbon monoxide; But reaction, the reaction of carbon monoxide and the reaction of hydro carbons of preferred catalysis ozone.

Ozone

In order to handle ozone, suitable comprise containing with preferred catalyst compositions comprise oxide such as Mn ₂O ₃And MnO ₂At the composition of interior manganese compound, preferably contain α-MnO ₂Composition; The potassium manganese ore is most preferred.What other were suitable for comprises MnO with preferred compositions ₂Mixture with CuO.Concrete and preferred compositions are hopcalite, and it contains CuO and MnO ₂Carulite more preferably ^, it contains MnO ₂, CuO and Al ₂O ₃, sell by Carus chemical company.The composition that substitutes contains the refractory metal oxide carrier, and the palladium component of the effective quantity of catalysis is dispersed on this carrier, preferably also contains the manganese component.On the carrier of the zirconia of co-precipitation and manganese oxide, there is the catalyst of the preferred platinum component of noble metal component also to be suitable for.Find that it is effective especially that the use of this co-precipitation carrier is used to handle ozone for the platinum component.Another composition that can make ozone change into oxygen contains charcoal, be loaded in palladium on the charcoal or platinum, manganese dioxide, Carulite ^And/or hopcalite (a kind of catalyst, the oxide mixture of manganese, copper, cobalt, silver is used for the gas breathing mask).Find that also the manganese that is loaded on refractory oxide such as the aluminium oxide also is suitable for.

Carbon monoxide

In order to handle carbon monoxide, suitable comprises a kind of like this composition that contains the refractory metal oxide carrier with preferred catalyst compositions, and the preferred platinum component of the platinum of the effective quantity of catalysis or palladium component is dispersed on this carrier.In order to handle carbon monoxide, most preferred carbon monoxide-olefin polymeric contains the reduction platinum-group component that is loaded on refractory metal oxide, the preferred titanium oxide.The catalysis material that is suitable for contains the noble metal component that comprises platinum-group component, and this component comprises metal and compound thereof.Such metal can be selected from platinum, palladium, rhodium and ruthenium, gold and/or silver components.Platinum also promotes the catalytic reaction of ozone.The catalyst that contains the zirconia that is loaded in co-precipitation and the noble metal component on the manganese dioxide carrier, preferred platinum component also is suitable for.This catalyst preferably reduces.Other suitable compositions that can make carbon monoxide change into carbon dioxide comprise the platinum component on the carrier that is loaded in charcoal or contains manganese dioxide.The preferred catalyst of handling such pollutant is the catalyst of reduction.Be applicable to that another composition of handling carbon monoxide contains platinum group metal component (preferred platinum component), refractory oxide carrier (preferred aluminium oxide and titanium oxide) and at least a metal component (preferably being the metal oxide form) that is selected from tungsten component and rhenium component.

Hydro carbons

Comprise C for processing ₂To about C ₂₀Alkene is generally C ₂-C ₈What monoolefine such as propylene were suitable in interior unsaturated hydrocarbons and part oxygen-containing hydrocarbon class belongs to same type with preferred catalyst compositions and the catalyst for reaction composition of being mentioned that is used for the catalysis carbon monoxide, and the preferred composition that is used for unsaturated hydro carbons contains the refractory metal oxide carrier of the platinum component and the platinum component of reduction.Preferred refractory metal oxide carrier is a titanium oxide.Convertible hydrocarbons becomes another suitable compositions of carbon dioxide and water to comprise platinum component on the carrier that is loaded in charcoal or contains manganese dioxide.The preferred catalyst of handling such pollutant is the catalyst of reduction.Be applicable to that another composition that transforms hydro carbons contains platinum group metal component (preferred platinum component), refractory oxide carrier (preferred aluminium oxide and titanium oxide) and at least a metal component (preferable alloy oxide form) that is selected from tungsten component and rhenium component.

Ozone and carbon monoxide

Can handle simultaneously ozone and carbon monoxide be suitable for and preferred catalyst contain a kind of like this carrier, as the refractory metal oxide carrier, noble metal component is dispersed on this carrier.The refractory oxide carrier can contain the carrier component that is selected from cerium oxide, aluminium oxide, silica, titanium oxide, zirconia and composition thereof.The coprecipitate of zirconia and manganese oxide also is suitable for the carrier of making the noble metal catalyst component.Most preferably, this carrier uses with the platinum component and catalyst is in the reduction form.Find that this single catalyst can be handled ozone and carbon monoxide effectively simultaneously.Noble metal component that other are suitable for and preferred is the noble metal component that is selected from palladium and platinum component, and platinum is preferred.The combination of cerium oxide carrier and palladium component obtains a kind of effective catalyst of handling ozone and carbon monoxide simultaneously.For handling ozone and carbon monoxide simultaneously, catalyst that other are suitable for and preferred comprises platinum-group component, preferred platinum component or palladium component, more preferably platinum component, be loaded on the titanium oxide or the composition of zirconia and silica on.Can transform ozone simultaneously becomes oxygen to become other suitable compositions of carbon dioxide to comprise with carbon monoxide to be loaded on the charcoal or contains platinum component on the carrier of manganese dioxide.Preferred catalyst is the catalyst of reduction.

Ozone, carbon monoxide and hydro carbons

Can handle simultaneously ozone, carbon monoxide and hydro carbons be suitable for and preferred catalyst contain a kind of carrier, preferred refractory metal oxide carrier, noble metal component is dispersed on this carrier, hydro carbons is low molecular weight olefins (C normally ₂To about C ₂₀, be generally C ₂-C ₈Monoolefine) and the oxygen containing hydro carbons of above-mentioned part, the refractory metal oxide carrier can contain the carrier component that is selected from cerium oxide, aluminium oxide, titanium oxide, zirconia and composition thereof, and titanium oxide is most preferred.Noble metal component that be suitable for and preferred is the noble metal component that is selected from the platinum-group component that comprises palladium and platinum component, and platinum is most preferred.Find that the effective catalyst of ozone, carbon monoxide and low-molecular-weight gaseous olefin component is handled in the combination of titanium dioxide carrier and platinum component simultaneously.It is preferred making the platinum-group component reduction with the reducing agent that is fit to.Can transform the platinum component on the carrier of carrier that ozone becomes oxygen, carbon monoxide to become carbon dioxide to become other compositions that are suitable for of carbon dioxide to comprise with hydro carbons to be loaded in charcoal, to contain manganese dioxide or manganese oxide and zirconic coprecipitate simultaneously.Preferred catalyst is the catalyst of reduction.

Available cladding process is coated to above-mentioned composition at least one atmosphere contact delivery vehicle surface.Particularly preferred composition is catalysis ozone, carbon monoxide and/or unsaturated low molecular weight olefins conversion of compounds under environmental condition or environmental operations condition.Environmental condition is the condition in the atmosphere.So-called environmental operations condition refers to that in the delivery vehicle course of normal operation do not using additional-energy to come under the condition of heat contaminants treatment compositions, the condition of atmosphere contact surface is as temperature.Some atmosphere contact surface such as grid or deep bead can be in temperature identical with atmosphere or similar temperature.Find that the preferred catalyst of catalysis ozone reaction can be in the reaction that is low to moderate catalysis ozone under 5～30 ℃ the environmental condition.

Because the operating characteristic of atmosphere contact surface lower member, the temperature of atmosphere contact surface can be higher than the ambient air temperature.For example, because its high surface, the surface of air-conditioning condenser and radiator is preferred atmosphere contact surface.When vehicle uses charge air cooler and since its high surface with environment temperature-250 °F down operation form and be preferred kind.Usually, under the environmental operations condition, the surface of these parts is higher than the temperature of environment temperature owing to operating characteristic rises to.After waiting the engine prewarming of the instrument that delivers, these parts are generally at about 130 ℃, generally at 40～110 ℃.The temperature range of these atmosphere contact surfaces helps to improve the conversion rate that is carried on this surperficial ozone, carbon monoxide and hydrocarbon catalyst.Charge air cooler up to about 130 ℃, be generally 60-130 ℃ of down operation.

Various carbon monoxide-olefin polymerics are capable of being combined, and with the combination catalyst-coated to the atmosphere contact surface.On the other hand, the different piece of different surface or similar face can apply with different carbon monoxide-olefin polymerics.

Pollutant designs method and apparatus of the present invention like this, so that can be handled under ambient atmospheric conditions or under the environmental operations condition of delivery vehicle atmosphere contact surface.The present invention be specially adapted to by be generally at least 0 ℃, preferred 0-105 ℃ with being applicable under environmental condition in the delivery vehicle surface temperature, more preferably 40-100 ℃ of suitable catalyst-coated motor vehicle atmosphere contact surface that transforms ozone down handled ozone.Preferably under 40-105 ℃ atmosphere contact surface temperature, handle CO, typically the low molecular weight hydrocarbon such as the C of at least one unsaturated bond arranged ₂～about C ₂₀Alkene and typical C _2-8Monoolefine.The percentage conversion ratio of ozone, CO and/or hydrocarbon and the temperature of atmospheric air and the temperature of the air speed of catalyst surface and atmosphere contact surface is relevant relatively.

Therefore, in the most preferred embodiment of the present invention, it makes the ozone, carbon monoxide and/or the hydrocarbon content that exist in the atmosphere descend at least, and don't needs to give existing vehicle, particularly motor vehicle to increase any mechanical property or the energy.In addition, carry out under the home operating condition that catalytic reaction is run on these automotive component surfaces, so that need not the structure or the method for operating of motor vehicle are done any change.

Because present device and method relate generally to the processing atmosphere,, the laudable practice is applicable to the equipment variant of handling the volume of air in the confined space so being design.For example, can use air in motor vehicle processing plant, mine and the tunnel of atmosphere contact surface with carrying pollutant treatment compositions.This equipment can comprise the vehicle that is used for this environment.

Though the preferred embodiment of the invention is intended to conversion pollutant under the Ambient Operating Temperature of atmosphere contact surface, handles the pollutant that the catalytic reaction temperature is higher than the Ambient Operating Temperature of environment temperature or atmosphere contact surface and also wish.Such pollutant comprises hydro carbons and nitrogen oxide and any by-passing or the carbon monoxide of not handling on the atmosphere contact surface.These pollutants can be handled under higher temperature, usually at least 100 to 450 ℃.This point for example can realize by the catalytic surface that uses auxiliary heating.With the surface of auxiliary heating, just meaning has additional equipment to come the area of heating surface.The preferred auxiliary area of heating surface is the surface of electrically heated integer catalyzer, as the known cellular thing of electrically heated catalytic metal of those skilled in the art.Can be by base part power supply such as generator in the motor vehicle or battery.Carbon monoxide-olefin polymeric can be any oxidation that everybody is familiar with and/or reducing catalyst, preferably contains the three-element purifying catalyst (TWC) of the noble metal that is loaded on the refractory oxide carrier such as platinum, palladium, rhodium etc.The catalytic surface of auxiliary heating can be with delivery vehicle atmosphere contact surface and is preferably combined with this downstream, surface, is used for further handling pollutant.

As above-mentioned, adsorbent composition also can be used to adsorb pollutant such as hydro carbons and/or particle, so that with rear oxidation or remove.Adsorbent composition that be suitable for and preferred comprises zeolite, other molecular sieves, charcoal and IIA family alkaline earth oxide, as calcium oxide.Hydro carbons and particle can carry out desorption, catalytic reaction or incineration process subsequently 0～110 ℃ of absorption.

The preferred coating when motor vehicle is exposed to the surface of vehicle that high surface area is arranged under the atmospheric air high flow rate during by environment.For the terrestrial applications motor vehicle, particularly preferred atmosphere contact surface comprises radiator, fan blade, air-conditioning condenser or heat exchanger, inflation condenser, oil cooler, transmission oil cooler and is used for the truck frame sails deep bead on the ceiling of chamber.

Most preferred atmosphere contact surface is a spreader surface.In order to increase the cooling to the internal combustion engine fluid coolant, radiator has big surface area.By with catalyst-coated to the surface of radiator, can utilize huge cellular surface area, the cooling effect of radiator is not exerted an influence usually hardly or fully.High cellular surface area can make catalyst contact to greatest extent with the air of radiator by cellular design.In addition, thus the radiator in many automobiles all is in air-conditioning condenser below is subjected to the air-conditioning condenser protection.

The present invention includes the pollutant treatment compositions is coated to method on the atmosphere contact surface of motor vehicle.Particularly, the present invention includes carbon monoxide-olefin polymeric is coated to method on gelled element such as radiator, air-conditioning condenser, the charge air cooler.

Result of calculation shows in the automobile traffic congested areas, exists the motor vehicle of enough numbers that the pollutant that the present invention handles is produced tangible percussion.For example, at Nan Jialifu Nene south coast AQMD, 800 ten thousand cars of having an appointment.Have found that if each car travels 20 miles every day, all air in 100 feet this areas below the height can circulate a week by radiator.

Fig. 1 is the side view of truck, expresses grid, air-conditioning condenser, electrical heating catalyst, charge air cooler, radiator, fan and engine and the deep bead on the driver's cabin ceiling;

Fig. 2 is the partial view of motor vehicle, expresses grid, aerial condenser, radiator and fan;

Fig. 3 is the front view of radiator;

Fig. 4 is the front view of air-conditioning condenser;

Fig. 5 is the front view of type deep bead shown in Figure 1;

Fig. 6 is the front view of truck among Fig. 1;

Fig. 7 is the partial cross section schematic diagram of coated flange-cooled cooling-part;

Fig. 8 is the photo of coated radiator in embodiment 1 and 2;

Fig. 9-14 and 16-17 be for adopting embodiment 4,9-12, and during different catalysts, CO is with respect to the inversion cuver of temperature in 14 and 15;

Figure 15 is based on the propylene of embodiment 14 inversion cuver with respect to temperature;

Figure 18 is for to add the inversion cuver of the ozone of round parentheses 17 with respect to temperature based on embodiment;

Figure 19 is the infrared light IR spectrogram of potassium manganese ore.

Figure 20 is an X-ray diffraction XRD figure of measuring the potassium manganese ore that the relation of the counting represented and Bragg angle 2 θ represents with square root.

The present invention relates to add round parentheses makes vehicle pass through the apparatus and method for of vehicle cleaning atmosphere of the device of atmosphere by having. When vehicle passed through atmosphere, at least one contained the atmosphere contact surface that pollutes treatment compositions (for example catalyst or adsorbent) and contacts with atmospheric air. When atmospheric air runs into when polluting treatment compositions, catalytic reaction occurs or is adsorbed owing to being in pollution treatment compositions on the atmosphere contact surface in the airborne various pollutants that comprise particulate matter and/or gas pollutant.

Those skilled in the art should be appreciated that this vehicle can be any suitable mobile device with propelled vehicles such as wheel, sail, conveyer belt, cover the vehicle of band etc. This device can drive with any suitable power set, comprising the engine that uses fossil fuel such as gasoline or diesel oil, ethanol, methanol-driving, usefulness fuel such as the gas-powered gas burning engine of methane, wind-force such as sail or wind-power propeller, solar energy or electric energy such as battery power automobile. Vehicle comprises automobile, truck, bus, train, canoe, large ship, aircraft, airship, balloon etc.

The atmosphere contact surface can be any suitable surface of meeting and contacting with air during by atmosphere at vehicle. Preferably in motor vehicle, take automobile, truck and open automobile as good, contact device is to be located at the surface of front part of vehicle and can to contact with empty chlorine when vehicle advances. Applicable contact surface should have larger surface area. Preferred contact surface is sealed in the vehicle at least in part. Preferred atmosphere contact surface is in the hood below and is positioned within the motor-driven vehicle body, is the cabin near engine typically. These surfaces are preferably the outer surface of cooling device, comprise liquid or gas flow supercooling agent wall seal such as pipe or outer cover and have the passage of the outer surface of the fin that promotes heat exchange. Applicable contact surface comprises the outer surface of fluid cooling device, comprising be used for vehicle such as air-conditioning condenser, radiator, charge air cooler, oil cooler, lube oil cooler, power-assisted guiding liquid cooler, fan guide card circle, all be in the radiator fan that is loaded in vehicle hood in liquid and/or air. Applicable vehicle outer contacting surface can be to be usually located at and to be loaded in the grid of hood front portion or generally be stated from deep bead on the large-scale truck cab ceiling. Contact surface is preferably surface, dead ahead, side surface or vehicle end face or bottom surface. The dead ahead surface is facing to vehicle front, and the surface such as radiator fin and condenser parts is facing to vehicular sideview, end face and bottom surface. Even towards with rightabout surface, sharp side with also can be the rear surface of atmosphere contact surface such as fan blade towards the surface with the vehicle rear of contact with air. Can apply surface such as wing, the propeller of aircraft engine and comprise turbine rotor and/or the jet-engine parts of stator.

Atmosphere contact surface in the preferred motor vehicle is arranged on engine cool parts such as vehicle radiator, air-conditioning condenser, charge air cooler (also being known as intercooler or aftercooler) oil cooler and lube oil cooler. These parts generally have larger surface texture thereby have improved heat-transfer effect. High surface area is applicable to make atmospheric air to contact with the pollution treatment compositions to greatest extent. All these parts all belong to the known content of automotive field. Referring to the Bosch automotive handbook, second edition, 301-303,320 and 349-351 pages, Rokert Bosch GmbH published in 1986, quoted at this for reference. This documents has been described the truck Diesel engine with radiator, intercooler and fan. This base part can be coated with pollution treatment surface of the present invention. Radiator and intercooler generally operate being higher than under the temperature of atmospheric air. Another list of references is the The Intermal Combustion Engine in Theory and Practice of Taylon, Vol.1:Thermo Dynamics, Fluid Flow, Performance, second edition, Rev.The MIT Press, 304-306 page or leaf in 1985, radiator and heat sink design; The 392nd page, aftercooler. It is for reference that the document is incorporated this paper into.

All right reference papers collection Vehide Themal Management Systems Conference Proceedings, SAE P:263 is published 1993 by Society of automotive engineers. Following document can be for reference. SAE paper No.931088 begins from the 157th page of Calculation and Design of Cooling Systems, Eichlseder and Raab of Steyr Damler Puchag and Charge Air Cooler for Passenger Cars, Collette of Valeo Thermique Moteur; SAE paper No.931092 exercise question is State of the Art and Future Developments of Aluminum Radiators for Cars and Trucks, the 187th page of Kern and Eitel of Behr GmbH and Co.; SAE paper 931112 exercise questions are Air Mix vs.Coolant Flow to Control Discharge Air Temperature and Vehicle Heating Air Conditioning Systems, Rolling and Cummings of Behr of America, Inc. and Schweizer of Behr GmbH ﹠ Co. Above-mentioned paper comprises the description to radiator, air-conditioning and the charge air cooler structure that is used for motor vehicle. Other incorporate into this paper for reference for SAE paper 931115 from the Engine Cooling of the 379th page of beginning Module Development Using Air Flow Management Techniques, E1-Bourini and Chen, Calsonic technique center. Interesting is has described the typical heat sink that is applicable to motor vehicle and the appendix 1 and 2 of condenser structure. Documents also comprises incorporates this paper SAE paper 931125 for reference into, exercise question is Durability Concerns of Aluminum Air to Air Charged Coolers by Smith, and Valeo Engine Cooling Inc. has wherein described the inflation condenser.

With reference to the accompanying drawings 1～7, those skilled in the art will understand the present invention.

Fig. 1 illustrates and comprises many trucies 10 that the vehicle part of atmosphere contact surface is arranged. These surfaces comprise the surface of grid 12, air-conditioning condenser 14, charge air cooler 25, radiator 16 and radiator fan 18. Also illustrate front surface 22 the deep bead 20 that keeps out the wind is arranged on this truck. It should be understood that various parts have different relative positions at different vehicles.

With reference to figure 1～4, preferred contact surface comprises front 17 and side 19, the respective surfaces of charge air cooler 25 and front 21 and the back side 23 of radiator fan 18 of the front 13 of air-conditioning condenser 14 and side 15, radiator 16. These surfaces are all in truck shell 24. They are the truck engine cover between truck positive 26 and engine 28 24 times usually. Air-conditioning condenser, charge air cooler, radiator and radiator fan can directly or indirectly be supported with the framework (not shown) in shell 24 or the shell.

Fig. 2 generally represents the diagram of automobile complete set of equipments. Corresponding parts have identical numbering in Fig. 1 and 2. Automobile has shell 30. The motor vehicles front 32 that grid 12 is arranged that the front that is supported on shell 30 is arranged. Air-conditioning condenser 14, radiator 16 and radiator fan 18 can be in shells 30.

With reference to the embodiment among the figure 1,2 and 6, at least one front and side in grid 12, air-conditioning condenser 14, charge air cooler 25 and radiator 16; Can scribble the pollutant treatment compositions on the contact surface in the front of the front and back of radiator fan 18 and deep bead 20. Grid 12 can have the design of suitable lattice grid type, and when truck 12 travels by atmosphere, thereby grid 12 has the perforate 36 that suitable lattice grid type design provides air to pass through. Perforate is limited by grid grizzly bar 38. Grid grizzly bar 38 has positive grid surface 40 and side grid surface 42. Grid grizzly bar positive 40 and side 42 can be used as the atmosphere contact surface, and the pollutant treatment compositions is arranged on it.

With reference to figure 1 and 4, air-conditioning condenser 14 has many air-conditioning condenser fin 44. In addition, an air-conditioning fluid conduit systems 46 is arranged, it crosses condenser 14 with the air-conditioning fluid flow guiding. The front of heat sink of air conditioner 44 and side, and the front of air conditioning duct 46 can be the atmosphere contact surface, and the pollutant treatment compositions is arranged on it. As described, front 21 and the back side 23 of radiator fan 18 can be the atmosphere contact surface, and the pollutant treatment compositions is arranged on it.

Most preferred atmosphere contact surface is on radiator 16, as shown in Figure 3. Typical radiator 16 has radiator positive 17 and many radiator corrugated platings or fin 50 (in corresponding heat sink) or fin channels 52 (it is by radiator 16). It is preferred applying front 17 and the side of heat-radiator plate 50 and the surface of passage 52. Radiator is most preferred, because it is in

shell

24 and 30, and positively is subject at least protection of grid 12 and preferred air-conditioning condenser 14. When motor vehicles travelled by atmosphere, deacration entered outside the hood 34, and radiator fan 18 also makes air pass through passage 52. So radiator 16 is subjected to the protection of grid 12, air-conditioning condenser 19 and is in the front of radiator fan 18. In addition, as above-mentioned, radiator has large surface area in order to conduct heat. According to the present invention, pollute treatment compositions and can effectively be placed in and utilize large like this surface area and can not produce to the heat transmission function of radiator obvious adverse effect.

The above-mentioned application that is particularly related to and illustrates atmospheric treatment surface on equipment such as radiator 16 and air-conditioning condenser 14. As described, the atmosphere contact surface can be on the suitable equipment of some other cooled engine fluid, comprise the equipment that everybody is familiar with, such as above-mentioned charge air cooler 25 and engine oil cooler, speed change oil cooler and power steering gear cooler. The common ground of all these cooling devices is shell and the conduits that have fluid to pass through. Shell has the outer surface that contacts with atmosphere common and in the carriage frame with the inner wall surface of fluid contact, usually in enging cabin. In order in these distinct devices, effectively to conduct heat from fluid, there are fin or plate to stretch out from shell or the catheter outer surface of cooling.

Fig. 7 has described the applicable and preferred embodiment of each above-mentioned cooling device. Fig. 7 is the schematic cross-section of the coated cooling-part that fin is housed 60. These parts comprise hood or the conduit that is limited by hood or catheter wall 62. Be in being fluid such as oil or cooling fluid or containing passage or the chamber 64 of liquia air by wherein among the conduit. This fluid be numbered 66. Enclosure walls comprises inner surface 68 and outer surface 70. Plate or fin 72 are arranged on or are connected on the outer surface. According to the present invention, pollutant treatment compositions 74 can be positioned on outer surface 70 and fin or the plate 72. Operating period, thus the air logistics contacts with the pollutant treatment compositions and makes various pollutants obtain processing.

The applicant here incorporates common issued patents application No.08/537208 (attorney docket number 3794/3810) " pollutant treatment facility and manufacture method thereof " into as a reference. In addition, any embodiment of present device and using method thereof depend on the needs and also can comprise such as alternative pollutant treatment facility disclosed herein.

The pollutant treatment compositions also can be on the outer surface of vehicle. As described, in the truck situation shown in Fig. 1 and 6, such composition can be on grid 12, also can be on deep bead surface, the front of deep bead 20 22. In addition, the pollutant treatment compositions can be on positive and any various front face surface of visor 54.

Charge air cooler 25 has the especially effectively atmosphere contact surface of carryover contamination treatment compositions. Operating temperature can be up to 250 °F. Under this temperature, carbon monoxide-olefin polymeric of the present invention can more effectively be processed ozone, hydrocarbon and carbon monoxide pollution thing. Particularly suitable be the composition that contains precious metal such as platinum, palladium, gold or silver components. In addition, catalyst can also comprise manganese compound such as MnO₂With the copper compound that comprises cupric oxide such as Carulite or hopcalite.

During normal operating, when vehicle 10 advanced, its front portion 26 contacted with atmospheric air at the beginning. Usually, jet plane is to pass through air up to the speed of about 1000 miles per hours. Water, the land vehicles are generally with up to 300 miles per hours, more typically move with the speed up to 200 miles per hours, and vehicle running speed is up to 100 miles per hours and be generally the 5-75 miles per hour. The ocean delivery vehicle as ship to pass through the waters up to 30 miles per hours and the speed that is generally the 2-20 miles per hour. According to the inventive method, the relative velocity of atmosphere contact surface and atmosphere (or face velocity) at vehicle, be generally automobile or based on the vehicle on land during by atmosphere, be the 0-100 miles per hour, be generally the 2-75 miles per hour, be generally 5～60 miles per hours for automobile, face velocity is the speed with respect to the air that pollutes treatment surface.

Motor vehicle such as the truck 10 with radiator fan 18 in, when motor vehicle when the atmosphere, pass through the following parts except air is arranged, fan also can aspirate air by grid 12, air-conditioning condenser 14, charge air cooler 25 and/or radiator 16. When motor vehicle dallied, the opposite face speed that is sucked the air that enters radiator was generally about 5-15 miles per hour (MPh). Radiator fan is regulated air by the flow velocity of radiator when motor vehicle passes through atmosphere. When general automobile passed through atmosphere with the speed of about 70mph, the inlet face speed of air was about 25mph. According to the design of the motor vehicle that uses radiator fan, when during spinning using fan, the face velocity of automobile is low to moderate corresponding to about 100% of the face velocity of motor vehicle speed. Yet generally speaking, air equals idle speed+0.1～1.0 with respect to the face velocity of atmosphere contact surface, more typically 0.2～0.8 times of car speed.

According to the present invention, when delivery vehicle passes through atmosphere, can under lower temperature, process a large amount of air. The high surface parts of vehicle comprise that radiator, air-conditioning condenser and charge air cooler have the large front face surface that contacts with the air logistics long-pending usually. But these equipment are quite narrow, and usually about 3/4 is thick up to about 2 o'clock, be generally 3/4 to

The time thick. The linear speed of the atmospheric air of the positive contact of these equipment reaches at the most 20, more generally 5～15 miles per hours usually. When air when the vehicle part of catalyst is arranged, the quantitative index of processed air is commonly referred to as air speed, more precisely body hourly space velocity (VHSV). It is by per hour measuring by the volume of air (corresponding to the volume of catalysis element) of unit catalyst article volume. It is divided by the cubic feet catalyst substrate by the cubic feet per hour air. The volume of catalyst substrate is thickness or the axial length that front face area multiply by airflow direction. On the other hand, the body hourly space velocity is by the caltalyst product of catalyst article stereometer to be processed per hour. Because it is thinner that the present invention contains the elements relative of catalyst, so air speed is quite high. The body hourly space velocity of the air that can process by the present invention can be up to 1,000,000 hours^-1Or higher. Air to the face speed of one of these elements under 5 miles per hours available air speed up to 300000 hours^-1 According to the present invention, the design catalyst in air speed up to 250000～750000, generally at 300000～600000 hours^-1In the scope, process the pollutant in atmosphere. This point in addition under the lower environment temperature and containing pollutant treatment compositions of the present invention vehicle component than the low environment operating temperature under finish.

Whether the Ambient Operating Temperature of atmosphere contact surface can be positioned near the vehicle endogenous pyrogen or noly belonged to the parts surface of cooling vehicle part effect and change according to it. Yet, contact surface such as grid 12, deep bead 20 is under the environmental condition, in the general operation process, cooling device operates being higher than under the ambient air temperature, contact surface such as air-conditioning condenser 14, radiator 16 and inflation condenser 25 can be up to 130 ℃, generally typically be 10-105 ℃ and more typically for 100 ℃ of 40-up to 105 ℃, can be 10-75 ℃. Charge air cooler 25 is generally 75-130 ℃ of lower operation. The contact surface size can change, and air-conditioning condenser, radiator and charge air cooler are generally the 20-2000 square feet, and fan blade 18 is generally 0.2～about 40 square feet, comprising front surface and rear surface.

The pollutant treatment compositions is carbon monoxide-olefin polymeric or adsorbent composition preferably. Applicable and preferred carbon monoxide-olefin polymeric is under the air speed of the air with Surface Contact the time, and under the temperature on contact point surface, but the composition of the reaction of catalysis target contaminant. Usually, these catalytic reactions are 0～130 ℃, 20～105 ℃ especially typically, more typically carry out under about 40～100 ℃ in the temperature range of atmosphere contact surface. To the efficient of reaction without limits, as long as these reactions occur. Preferably, at least 1% conversion ratio is arranged, high as far as possible transformation efficiency should be arranged. Applicable transformation efficiency is preferably at least about 5%, more preferably at least about 10%. Preferred conversion ratio depends on specific pollutant and pollutant treatment compositions. When ozone is processed with the carbon monoxide-olefin polymeric on the atmosphere contact surface, preferably transformation efficiency greater than about 30 to 40%, more preferably greater than 50%, more preferably greater than 70%. The preferred conversion ratio of carbon monoxide greater than 30%, be preferably greater than 50%. The preferred transformation efficiency of hydro carbons and the oxygen containing hydro carbons of part is at least 10%, preferably at least 15%, most preferably at least 25%. Particularly preferred when the atmosphere contact surface is in up to about 110 ℃ environmental operations condition these conversion ratios of lower time. These temperature are to comprise during the normal operating of delivery vehicle atmosphere contact surface on radiator and air-conditioning condenser surface the usually surface temperature of experience. Have at the atmosphere contact surface under the occasion of supplementary heating, as with electrically heated integer catalyzer, grid, screen cloth, net etc., preferred transformation efficiency is greater than 90%, more preferably greater than 95%. Transformation efficiency is based on the mole percent that there is specific pollutants reaction in the lower air in carbon monoxide-olefin polymeric.

The ozone treatment carbon monoxide-olefin polymeric contains the manganese compound that contains that comprises manganese dioxide, comprises that non-stoichiometric manganese dioxide is (such as MnO_(1.5～2.0)) and/or Mn₂O ₃ Be commonly referred to MnO₂Preferred manganese dioxide such chemical formula is arranged, wherein the mol ratio of manganese and oxygen is about 1.5 to 2.0, such as Mn₈O ₁₆ Until the manganese dioxide MnO of 100% (weight)₂Can be used for processing the carbon monoxide-olefin polymeric of ozone. Available alternate sets compound contains manganese dioxide and some other compound, such as independent cupric oxide or cupric oxide and aluminium oxide.

The mol ratio that applicable and preferred manganese dioxide class is common manganese and oxygen is 1～2 α-manganese dioxide class. Applicable α-manganese dioxide is open in granting the US 5340562 of O ' Young etc.; " Hydrothermal Synthesis that the manganese oxide class of pore passage structure is arranged " that also develops in zeolite and the discussion of layer post carclazyte works progress at O ' Young, petrochemistry branch of American Chemical Society, New York City Meeting, August 25-30,1991, since the 342nd page, and at Mckenzie, " sodium manganite, potassium manganese ore and some other the oxide of manganese and hydroxide synthetic ", the mineralogy magazine, in December, 1971, the 38th volume, the 493rd～502 page. For the present invention, preferred α-manganese dioxide is 2 * 2 pore passage structure things, can be hollandite (BaMn₈O ₁₆·XH ₂O), potassium manganese ore (KMn₈O ₁₆·XH ₂O), manjiroite (NaMn₈O ₁₆·XH ₂O) and coronadite (PbMn₈O ₁₆·XH ₂O)。

The surface area that is applicable to manganese dioxide class of the present invention is preferably greater than 150 meters²/ gram, more preferably greater than 200 meters²/ gram, more preferably greater than 250 meters²/ gram, most preferably greater than 275 meters²/ gram. The surface area upper limit of these materials can be up to 300 meters²/ gram, 325 meters²/ gram, even 350 meters²/ gram. The surface area of preferred material is at 200～350 meters²In/gram the scope, preferred 250～325 meters²/ gram, most preferably 275～300 meters²/ gram. Composition preferably contains the adhesive of following type, and preferred adhesive is polymer adhesive. Composition also can contain noble metal component, and preferred noble metal component is the oxide of noble metal, the oxide of preferred platinum group metal, and most preferably the oxide of palladium or platinum is also referred to as palladium black or platinum black. Press the weighing scale of manganese component and noble metal component, the quantity of palladium black or platinum black can be in 0～25% scope, and applicable quantity is about 1 to 25 and 5～15% (weight).

Have now found that using the composition (also containing polymer adhesive) contain potassium manganese ore class alpha-oxidation manganese is under 0～400ppb at ozone concentration, at air stream take air speed as 300000～650000 o'clock^-1During by radiator, can obtain greater than 50%, be preferably greater than 60%, most preferably 75～85% ozone conversion ratio. A part of potassium manganese ore by at the most 25%, under the occasion that replaces of preferred 15～25% (weight) palladium black (PdO), when using under these conditions the powdered reaction device, the conversion ratio of ozone is 95～100%.

The crystal size of preferred potassium manganese ore manganese dioxide is 2～10, preferably less than 5 nanometers. It can be at 250～550 ℃, preferred below 500 ℃ and under greater than 300 ℃, and roasting at least 1.5 hours, preferably at least 2 hours until about 6 hours.

Preferred potassium manganese ore can be standby according to list of references and the patent system of above-mentioned O ' Young and McKenzie. The potassium manganese ore can be selected from MnCl by comprising₂、Mn(NO ₃) ₂、MnSO ₄And Mn (CH₃COO) ₂Salt react to prepare at interior manganese salt and permanganate compounds. The potassium manganese ore prepares with potassium permanganate; Hollandite prepares with barium permanganate; Coronadite prepares with permanganic acid lead; And manjiroite prepares with sodium permanganate. Have recognized that being applicable to alpha-oxidation manganese of the present invention can contain one or more hollandites, potassium manganese ore, manjiroite or coronadite compound. Even when preparation potassium manganese ore, other metal ions such as sodium can exist on a small quantity. The usability methods of preparation α-manganese dioxide is described in the above referred-to references, incorporates as a reference the present invention here into.

Preferred α-manganese that the present invention uses is the potassium manganese ore.Preferred potassium manganese ore is " pure " or be substantially free of inorganic anion, particularly from the teeth outwards.Such anion can comprise chlorion, sulfate radical and nitrate anion, and they are to introduce in the process of preparation potassium manganese ore.The other method for preparing pure potassium manganese ore is preferred manganese acetate of manganese carboxylate and potassium permanganate reaction.Find that the material of roasting is pure.The use that contains the material of inorganic anion can make ozone change into the conversion ratio of oxygen up to about 60%.There is the use of potassium manganese ore on " pure " surface can obtain conversion ratio up to about 80%.

We think that carboxylate radical is burnt in roasting process.But, both having made in roasting process, inorganic anion is still stayed on the surface.Inorganic anion such as sulfate radical available water solution or acid slightly aqueous solution flush away.Preferably, α manganese dioxide is " pure " α-manganese dioxide.The potassium manganese ore can be washed about 1.5 hours down at about 60 to 100 ℃, so that remove the sulfate anion of remarkable quantity.The also available similar method of nitrate anion is removed.The feature of " pure " α-manganese dioxide is that IR spectrogram shown in Figure 19 and XRD figure shown in Figure 20 are arranged.The surface area of such potassium manganese ore is preferably greater than 200 meters ²/ gram, more preferably greater than 250 meters ²/ gram.The feature of the IR spectrogram of most preferred potassium manganese ore shown in Figure 19 is not belong to the spectrum peak of carbonate, sulfate radical and nitrate anion.The carbonate spectrum peak of expection appears in 1320～1520 wave-number ranges; And sulfate radical spectrum peak appears at 950～1250 wave-number ranges.Figure 20 is the x-ray diffractogram of powder of the high surface potassium manganese ore of preparation among the embodiment 23.The feature that is applicable to the X-ray diffractogram of potassium manganese ore of the present invention is to obtain broad peak by little crystal grain (about 5 to 10 nanometers).Use the CuK alpha ray, in the approximate peak position (± 0.15 ° of 2 θ) and the approximate relative intensity (± 5) of the potassium manganese ore shown in Figure 20 be: 2 θ/relative intensity-12.1/9; 18/9; 28.3/10; 37.5/100; 41.8/32; 49.7/16; 53.8/5; 60.1/13; 55.7/38 and 68.0/23.

Preparation is applicable to that the method for optimizing of potassium manganese ore of the present invention comprises that the aqueous solution of acid manganese salt mixes with liquor potassic permanganate.The pH value of acid manganese salt solution is preferably 0.5～3.0, and the preferred acetate of available any acid commonly used produces acidity, and preferred concentration is 0.5～5.0N, the more preferably acetate of 1.0～2.0N.Mixture is made slurries, and it is stirred under 50～110 ℃.Filter slurries, with filtrate at 75～200 ℃ of scope inner dryings.The surface area of the potassium manganese ore crystal that generates is generally 200～350 meters ²/ gram.

Other compositions that are suitable for contain manganese dioxide and optional cupric oxide and aluminium oxide; And at least a noble metal component is as being loaded in the platinum group metal on the manganese dioxide, under the occasion that has cupric oxide and aluminium oxide.The composition that is suitable for contains until 100,40～80, preferred 50～70% (weight) manganese dioxide and 10～60, common 30～50% (weight) cupric oxide.The composition that is suitable for comprises the hopcalite of about 60% manganese dioxide and about 40% cupric oxide; And Carulite ^200 (being sold by Carus chemical company) it is reported and contain 60～75% (weight) manganese dioxide, 11～14% cupric oxide and 15～16% aluminium oxide.It is reported Carulite ^Surface area be about 180 meters ²/ gram.Make Carulite 450 ℃ of following roastings ^Surface area descend approximately 50%, and can obviously not influence its activity.300～500, more preferably 350～450 ℃ of following roasting manganese compounds are preferred.550 ℃ of following roastings surface area and ozone treatment activity are descended greatly.With the acetate ball milling and after being coated on the base material, roasting Carulite ^Can improve the adhesiveness of coating and base material.

Other compositions of handling ozone can contain manganese dioxide component and noble metal component, as platinum group metal component.Though two kinds of components all have catalytic activity, manganese dioxide also can play the carried noble metal component.Platinum group metal component is palladium component and/or platinum component preferably.The quantity of platinum group metal compounds be preferably composition about 0.1 to about 10% (weight) (by the weight of platinum group metal).Under the occasion that platinum exists, its quantity is preferably 0.1～5% (weight); And by the stereometer of support materials, pollutant handle on the catalyst volume be suitable for and preferred quantity be about 0.5 to about 70 gram/Foot ³The quantity of palladium component be preferably composition about 2 to about 10% (weight), and pollutant handle on the catalyst volume be suitable for and preferred quantity be about 10 to about 250 gram/Foot ³

Various suitable and preferred pollutant processing carbon monoxide-olefin polymerics, particularly those contain catalytic active component as the precious metal catalyst component, can contain suitable carrier material, as the refractory oxide carrier.The preferred optional autoxidation silicon of refractory oxide, aluminium oxide, titanium oxide, cerium oxide, zirconia and chromium oxide, and mixture.More preferably, carrier is at least a high surface compound that is selected from the activation of aluminium oxide, silica, titanium oxide, silica-alumina, silica-zirconia, aluminium oxide-silicate, aluminium oxide-zirconium oxide, aluminium oxide-chromium oxide and aluminium oxide-cerium oxide.Refractory oxide can be made into suitable form, comprises that granularity is about 0.1 to about 100, preferred 1～10 micron loose particles form, and perhaps granularity is about 1 to about 50, preferred about 1 solation to about 10 nanometers.It is about 1 to titanium oxide about 10, that be generally about 2 to 5 nanometers that preferred titanium oxide sol carrier contains granularity.

Manganese oxide and zirconic coprecipitate also are carriers that be suitable for and preferred.Said composition can be incorporated the present invention here into as a reference by disclosed preparation among the US 5,283 041.Briefly, the carrier material of this co-precipitation by weight the weight ratio of manganese and zirconium be 5: 95 to 95: 5, preferred 10: 90 to 75: 25 more preferably 10: 90 to 50: 50, most preferably 15: 85 to 50: 50.That be suitable for and Mn embodiment preferred: the Zr weight ratio is 20: 80.US 5283041 discloses a kind of method for optimizing for preparing the coprecipitate of manganese oxide component and zirconia component.As disclosed among the US5283041, zirconia and manganese oxide material can prepare by following steps: with the aqueous solution such as nitric acid oxidation zirconium, zirconium acetate, basic zirconium chloride or sulfated zirconia and suitable manganese oxide precursor such as manganese nitrate, manganese acetate, manganous chloride or the manganese dibromide mixing of suitable zirconium oxide precursor; Add the alkali such as the ammonium hydroxide of sufficient amount, make the pH value reach 8～9; Filter the precipitation that generates; Wash with water; Dry down at 450～500 ℃ then.

The suitable carrier of handling the catalyst of ozone is selected from a kind of refractory oxide carrier, preferred aluminium oxide and silica-alumina, preferred carrier is to contain the 1 silica-alumina carrier to about 10% (weight) silica and 90～99% (weight) aluminium oxide of having an appointment.

For the catalyst of the platinum group metal of handling carbon monoxide, the refractory oxide carrier that is suitable for is selected from aluminium oxide, titanium oxide, silica-zirconia and manganese-zirconia.For the carbon monoxide-olefin polymeric of handling carbon monoxide, preferred carrier is the aluminium oxide as disclosed manganese-silica support and high surface among disclosed zirconia-silica support, the US 5283041 among the US5145825.For the catalyst of handling carbon monoxide, most preferred carrier is a titanium oxide.There is the reducing catalyst of titanium dioxide carrier higher carbon monoxide conversion ratio to be arranged than corresponding raw catalyst.

For the catalyst of handle hydrocarbon such as low molecular weight hydrocarbons, particularly low molecular weight olefins (have 2 to about 20 carbon atoms, common 2 to about 8 carbon atoms) and the oxygen containing hydro carbons of part, carrier is preferably selected from the refractory metal oxide that comprises aluminium oxide and titanium oxide.The same with the catalyst of handling carbon monoxide, the catalyst of reduction has higher hydrocarbon conversion rate.Particularly preferably be titanium dioxide carrier, found that it can obtain the carbon monoxide-olefin polymeric of high ozone conversion ratio and significant carbon monoxide conversion ratio and low molecular weight olefins conversion ratio.The refractory oxide of high surface macropore also is suitable for, preferred such aluminium oxide and titanium oxide, and its surface area is greater than 150 meters ²/ gram, preferred about 150 to 350, preferred 200～300, more preferably 225～275 meters ²/ gram; Porosity greater than 0.5 milliliter/gram, common 0.5～4.0, preferred about 1 to 2 milliliter/gram (based on mercury porosity method); And granularity is 0.1～10 micron.The material that is suitable for is the VersalGL aluminium oxide, and its surface area is about 260 meters ²/ gram, porosity are 1.4～1.5 milliliters/gram, are provided by LaRoche industrial group.

For handling carbon monoxide and/or hydro carbons, the preferred high-temperature resistant carrier that is used for platinum is a titanium dioxide.Titanium oxide can the loose powder form or is used with the form of TiO 2 sol.This carbon monoxide-olefin polymeric can be by with the platinum group metal in the liquid medium, preferably be added in the titanium oxide sol with the form of solution such as platinum nitrate solution and prepare, and this colloidal sol is most preferred.The slurries that make can be coated on the suitable base material then, surperficial as atmospheric treatment as radiator, metal integral base material or ceramic base material.Preferred platinum group metal is a platinum compounds.The platinum oxidation titanium colloidal sol catalyst that is made by above-mentioned steps has high activity to carbon monoxide and/or hydrocarbon oxidation under Ambient Operating Temperature.The metal component except that platinum-group component that can combine with titanium oxide sol comprises gold, palladium, rhodium and silver components.For handle hydrocarbon alkene particularly, also find to be that the reduction platinum-group component on the preferred titanium catalyst, preferred platinum component are that be suitable for and preferred to handling carbon monoxide.

It is about 1 to about 10, the titanium oxide of about 2 to 5 nanometers usually that preferred titanium oxide sol carrier contains granularity.

The surface area of preferred loose titanium oxide be about 25 to 120, preferred 50～100 meters ²/ gram; Granularity is about 0.1 to 10 micron.A kind of surface area concrete and preferred loose titanium dioxide carrier is 45～50 meters ²/ gram, granularity are about 1 micron, are sold as P-25 by DeGussa company.

Preferred silica-Zirconia carrier contains 1～10% silica and 90～99% zirconias.Preferred carrier granular has high surface area, as 100～500 meters ²/ gram, preferred 150～450 meters ²/ gram, more preferably 200～400 meters ²/ gram is to improve the decentralization of catalytic metal component on carrier.Preferred refractory metal oxide carrier also has high porosity (hole up to about 145 nano-radius is arranged), 0.75 to 1.5 milliliter according to appointment/gram, preferred about 0.9 to 1.2 milliliter/gram, is provided by the hole of radius for 5～100 nanometers at least about 50% porosity.

The ozone treatment catalyst that is suitable for contains at least a noble metal component, preferably is dispersed in the palladium component that is fit on carrier such as the refractory oxide carrier.By the weight of noble metal (metal rather than oxide) and carrier, composition contains 0.1～20.0 on carrier such as refractory oxide carrier, preferred 0.5～15% (weight) noble metal.The preferred consumption of palladium is 2～15, more preferably 5～15, more preferably 8～12% (weight).The preferred consumption of platinum is 0.1～10, more preferably 0.1～5.0, more preferably 2～5% (weight).Palladium most preferably is used for the reaction that catalysis ozone generates oxygen.Carrier material can be selected from above-mentioned carrier material.In preferred embodiments,, above-mentioned loose manganese component can be arranged also, or be dispersed in the manganese component on the identical or different refractory oxide carriers as noble metal, preferred palladium component.In the pollutant treatment compositions, by the weight of palladium and manganese metal, can have at the most 80, preferred 50, more preferably 1～40, more preferably 5～35% (weight) manganese component at the most.On the other hand, 2 to 30, more preferably 2～10% (weight) manganese component of preferably having an appointment.The catalyst loading of every cube of Foot catalyst volume is 20～250 grams, preferred about 50 to 250 gram palladiums.Catalyst volume is the cumulative volume of finished catalyst composition, so the air-conditioning condenser in the space that is provided by gas channel or the cumulative volume of radiator are provided.Usually, the carrying capacity of palladium is high more, and the conversion ratio of ozone is high more, and promptly the percentage that ozone decomposes in processed air stream is big more.

Under about 40 to 50 ℃, be loaded in conversion ratio that ozone that the carbon monoxide-olefin polymeric on the aluminium oxide reaches generates oxygen 50% (mole) of having an appointment with palladium/manganese, condition is that ozone concentration is 0.1～0.4ppm, face speed is about 10 miles per hours.Use platinum/aluminium oxide catalyst to obtain lower conversion ratio.

The special use that meaningfully contains the carrier of above-mentioned manganese oxide and zirconic coprecipitated product, it is used for carried noble metal, preferred platinum and palladium, platinum most preferably.Platinum is significant especially, because find, when platinum was used on this co-precipitation carrier, it was effective especially.By metal platinum and co-precipitation carrier, the quantity of platinum can be 0.1～6, preferred 0.5～4, more preferably 1～4, most preferably 2～4% (weight).Find that to be used to handle ozone be effective especially to platinum on this carrier.In addition, as what discuss below, this catalyst also is applicable to the processing carbon monoxide.Preferably, noble metal is a platinum, and catalyst is the catalyst through reduction.

Other catalyst that are applicable to that ozone catalytic changes into oxygen are open in US 4343776 and 4405507, and here both incorporate the present invention as a reference into.A kind of suitable United States Patent (USP) of submitting on February 25th, 1994 with most preferred composition of granting jointly 08/202397 now be to disclose among the US5422331 " aircraft with light-duty low pressure drop ozone decomposition catalyst ", incorporates the present invention here as a reference into.Other compositions that can make ozone change into oxygen contain charcoal and are loaded in palladium on the charcoal or platinum, manganese dioxide, Carulite ^And/or hollandite.Find that also the manganese that is loaded on refractory oxide such as the above-mentioned oxide also is suitable for.

Carbon monoxide is handled catalyst and is preferably contained at least a noble metal component, preferred platinum and palladium component, and the platinum component is most preferred.Composition contains 0.01～20% (weight), preferred 0.5～15% (weight) noble metal component on carrier that is fit to such as refractory oxide carrier, the quantity of noble metal is based on the weight of noble metal (metal and be not metal component) and carrier.Platinum is most preferred, and its preferable amount is 0.01～10, more preferably 0.1～5, most preferably 1.0～5.0% (weight).The consumption of palladium is 2～15, preferred 5～15, more preferably 8～12% (weight).Preferred carrier is a titanium oxide, and titanium oxide sol is most preferred as mentioned above.In being loaded in overall structure thing such as radiator, or when being downloaded on other atmosphere contact surfaces, catalyst loading is preferably about 1 to 150, more preferably 10～100 gram platinum/Foot ³Catalyst volume and/or 20～250, preferred 50～250 gram palladium/Foot ³Catalyst volume.Preferred catalyst is the catalyst through reduction.Concentration at carbon monoxide is 15～25ppm, and air speed is 300000～500000 hours ^-1Occasion under, under 25～90 ℃, use the core product that are coated with obtain by the automobile radiators that 1～6% (weight) platinum (by metal)/titanium oxide composition is arranged to cause 5～80% (mole) carbon monoxide to change into carbon dioxide.Equally, the concentration at carbon monoxide is that about 15ppm, air speed are about 300000 hours ^-1Occasion under, at the most under about 95 ℃, cause 5～65% (mole) carbon monoxide to change into carbon dioxide with 1.5～4.0% (weight) platinum/alumina support composition.Use palladium/cerium oxide carrier to obtain lower conversion ratio.

A kind of handle carbon monoxide substitute contain the noble metal component that is loaded on above-mentioned manganese oxide and the zirconic coprecipitate with preferred catalyst compositions.Coprecipitate makes by above-mentioned.Manganese and zirconic preferred proportion are 5: 95 to 95: 5,10: 90 to 75: 25,10: 90 to 50: 50 and 15: 85 to 25: 75, and the manganese oxide of preferred coprecipitate is 20: 80 with the zirconia ratio.By platinum, the percentage that is loaded in the platinum on the coprecipitate is 0.1～6, preferred 0.5～4, more preferably 1～4, most preferably 2～4% (weight).Catalyst is the catalyst through reducing preferably.Catalyst can form of powder reduction or be coated to the load base material after restore.Other suitable compositions that carbon monoxide can be changed into carbon dioxide comprise and are loaded on the charcoal or contain platinum component on the carrier of manganese dioxide.

The catalyst of handle hydrocarbon contains at least a noble metal component, be preferably selected from platinum and palladium, platinum is most preferred, and hydro carbons is generally the unsaturated hydrocarbons that relates to above, the 2 unsaturated monoolefines to about 20 carbon atoms, especially 2～8 carbon atoms are more typically arranged, and the oxygen containing hydro carbons of part.The carbon monoxide-olefin polymeric that is suitable for comprises that those are used to handle the composition of carbon monoxide.The composition of handle hydrocarbon contains and is loaded in 0.01～20 on suitable carrier such as the refractory oxide carrier, preferred 0.5～15% (weight) noble metal component, and the quantity of noble metal is based on the weight of noble metal, (not being metal component) and carrier.Platinum is most preferred, and its preferable amount is 0.01～10, more preferably 0.1～5, most preferably 1.0～5% (weight).When on the radiator that is downloaded to overall structure thing such as motor vehicle or other atmosphere contact surfaces, the carrying capacity of catalyst is preferably about 1 to 150, more preferably 10～100 gram platinum/Foot ³Catalyst volume.Preferred refractory oxide carrier is the refractory metal oxide, and they are preferably selected from cerium oxide, silica, zirconia, aluminium oxide, titanium oxide and composition thereof, and aluminium oxide and titanium oxide are most preferred.The feature of preferred titanium oxide such as above-mentioned, titanium oxide sol is most preferred.Preferred catalyst is the catalyst through reduction.The test of the automobile radiators that applies draws, and is that about 10ppm, air speed are about 320000 hours at density of propylene ^-1Occasion under, use 1.5～4% (weight) platinum/aluminium oxide or titanium dioxide carriers, the conversion ratio that low-molecular-weight monoolefine such as propylene generate water and carbon dioxide is 15～25%.These catalyst are unreduced.The reduction of catalyst can improve conversion ratio.

The catalyst that is applicable to carbon monoxide and hydro carbons oxidation generally includes above-mentioned those and is applicable to the catalyst of handling carbon monoxide or hydro carbons.Having found has the most preferred catalyst of excellent activity to contain the platinum component that is loaded on the preferred titanium dioxide carrier to handling carbon monoxide and hydro carbons such as unsaturated olefin.Composition preferably contains adhesive, and can be coated on the suitable carrier structure thing, and its quantity is 0.8～1.0 gram/inch ³The concentration of the platinum on titanium dioxide carrier is 2～6, preferred 3～5% (weight).The cell density with preferred substrate that is suitable for equals about 300 to 400 abscess/inch ²Catalyst preferably reduces with the reducing agent that is fit to powder type or on the goods that apply.Catalyst preferably contain 7% hydrogen of having an appointment, all the other are in the air-flow of nitrogen, 200～500 ℃ of reduction 1～12 hour down.Most preferred reduction or preparation temperature are 400 ℃ in 2-6 hour.Find that this catalyst still keeps high activity under 100 ℃ intensification after air and the medium-term and long-term exposure of humid air.

The suitable catalyst that can handle ozone and carbon monoxide contains at least a noble metal component, and most preferred noble metal is selected from palladium, platinum and composition thereof, and it is loaded on the suitable carrier, on the refractory oxide carrier.The refractory oxide that is suitable for is cerium oxide, zirconia, aluminium oxide, titanium oxide, silica and composition thereof, comprises the above-mentioned zirconia and the mixture of silica.Carrier that be suitable for and preferred also has above-mentioned manganese oxide and zirconic coprecipitate.By the weight of noble metal and carrier, composition contains 0.1～20.0 on carrier, preferred 0.5～15, more preferably 1～10% (weight) noble metal component.The consumption of palladium is preferably 2～15, more preferably 3～8% (weight).The consumption of platinum is preferably 0.1～6, more preferably 2～5% (weight).Preferred compositions is a kind of like this composition, and wherein high temperature resistant component is a cerium oxide, and noble metal component is a palladium.Said composition has quite high ozone and carbon monoxide conversion ratio.More particularly, contain the 16ppm carbon monoxide in the air stream on 95 ℃ of surfaces of contact, the face velocity of gas is under the condition of 5 miles per hours, and it is 21% that the test that is coated to the said composition on the radiator is caused the carbon monoxide conversion ratio.Containing 0.25ppm ozone, treatment surface temperature at air-flow is that 25 ℃, air draught face velocity are under the occasion of 10 miles per hours, and identical catalyst obtains 55% ozone conversion ratio.Equally, preferred compositions contains noble metal and above-mentioned manganese oxide and zirconic coprecipitate, the noble metal preferred platinum group metal, more preferably is selected from platinum and palladium component, most preferably platinum component.This catalyst that contains above-mentioned noble metal that is the coating on catalyst fines or the suitable base material is a reduction form catalyst.Preferred reducing condition comprises those above-mentioned conditions, and most preferred condition is under 250～350 ℃, reductase 12～4 hour in the reducing gas that contains 7% hydrogen and 93% nitrogen.Found that this catalyst is specially adapted to handle simultaneously carbon monoxide and ozone.Other are applicable to that ozone changes into the composition that oxygen and carbon monoxide change into carbon dioxide and contains the platinum component that is loaded on charcoal, manganese dioxide or the refractory oxide carrier, and optionally contain other manganese component.

Can handle simultaneously ozone, carbon monoxide and hydro carbons and part oxygen-containing hydrocarbon class be suitable for and preferred catalyst contain noble metal component, preferred platinum component, be loaded on the suitable carrier, on the refractory oxide carrier.The refractory oxide carrier that is suitable for comprises cerium oxide, zirconia, aluminium oxide, titanium oxide, silica and composition thereof, comprises the above-mentioned zirconia and the mixture of silica.Above-mentioned manganese oxide and zirconic coprecipitate carrier also are suitable for.By the weight of noble metal and carrier, composition contains 0.1～20 on high-temperature resistant carrier, preferred 0.5～1 5, more preferably 1～10% (weight) noble metal component.Attempting hydrocarbon component is changed under the occasion of carbon dioxide and water, platinum is most preferred catalyst, and its preferable amount is 0.1～5, more preferably 2～5% (weight).In specific embodiment, a kind of like this composition of catalyst can be arranged, it comprises above-mentioned catalyst and a kind of catalyst that is particularly preferred for handling ozone, as contains the catalyst of manganese component.The manganese component can be chosen wantonly with the platinum component and combine.Manganese can be on identical or different carriers with platinum.By the weight of noble metal and manganese, in the pollutant treatment compositions, can have at the most 80, preferred 50, more preferably 1～40, more preferably 10～35% (weight) manganese component at the most.Catalyst loading is identical with above-mentioned relevant ozone reforming catalyst.Preferred compositions is a kind of like this composition, and wherein high temperature resistant component is aluminium oxide or titanium dioxide carrier, and noble metal component is the platinum component.When contacting with 95 ℃ of surfaces, the face velocity of air-flow is that (air speed is 320000 o'clock to about 10 miles per hours ^-1), when air dew point was 35 °F, the test that is coated in the composition on the radiator obtained, the conversion ratio of carbon monoxide is 68～72%, the conversion ratio of ozone be 8～15% and propylene conversion be 17-18%.Usually, the air speed or the face velocity that flow through the pollutant contact surface along with decline of contact surface temperature and atmospheric air increase, and the percentage conversion ratio descends.

Activity of such catalysts, the activity of particularly handling carbon monoxide and hydro carbons can further improve by reducing catalyst in as the forming gas of hydrogen, carbon monoxide, methane or hydro carbons+nitrogen.On the other hand, reducing agent can be liquid form, as hydrazine, formic acid and formates, as sodium formate solution.Catalyst reduces after can be used as powder or being coated to base material.Reduction can be carried out under 150～500 ℃, preferred 200～400 ℃ in gas 1～12 hour, preferred 2-8 hour.In a preferred process, the goods of coating or powder can be in the nitrogen that contains 7% hydrogen, 275～350 ℃ of following reductase 12～4 hour.

The alternate sets compound that is applicable to the inventive method and equipment contains catalytically-active materials that is selected from noble metal component (comprising platinum group metal component, golden component and silver components) and the metal component that is selected from tungsten component and rhenium component.By the weight of metal, the relative populations of catalytically-active materials and tungsten component and/or rhenium component is 1: 25 to 15: 1.

The tungsten and/or the rhenium that contain the preferred oxycompound form of composition of tungsten component and/or rhenium component.Oxide can be by at first making composition with tungsten salt or rhenium salt, and the roasting composition method that obtains tungsten oxide and/or rheium oxide prepares subsequently.Composition also can contain other components, as carrier, comprises refractory oxide carrier, manganese component, charcoal and manganese oxide and zirconic coprecipitate.The refractory metal oxide that is suitable for comprises aluminium oxide, silica, titanium oxide, cerium oxide, zirconia, chromium oxide and composition thereof.Composition also can contain adhesive material, as comprises the metal-sol of alumina sol or titanium oxide sol, the polymer adhesive that perhaps can polygalacto viscose binder form be provided.

In preferred compositions, have 0.5～15, preferred 1～10, most preferably 3～5% (weight) catalytically-active materials.Preferred catalytically-active materials is the platinum group metal, and platinum and palladium are preferred, and platinum is most preferred.By metal, the quantity of tungsten and/or rhenium component is 1～25, preferred 2～15, most preferably 3～10% (weight).The quantity of adhesive can be 0～20, preferred 0.5～20, more preferably 2～10, most preferably 2～5% (weight) changes.Decide on carrier material, adhesive can be not necessarily in said composition.Preferred compositions contains 60～98.5% (weight) refractory oxide carrier, 0.5～15% (weight) catalytically-active materials, 1～25% (weight) tungsten and/or rhenium component and 0～10% (weight) adhesive.

Contain roasting under the condition that the composition of tungsten component and rhenium component can mention in the above.On the other hand, composition can be reduced.But, show that as following examples composition need not reduce, and the existence of tungsten and/or rhenium component can make the carbon monoxide and the hydrocarbon conversion and contain through the composition of the platinum group metal of reduction suitable.

Pollutant treatment compositions of the present invention preferably contains adhesive, and it makes composition bonding, and the atmosphere contact surface is produced adhesiveness.Find that preferred adhesive is a polymer adhesive, its consumption is counted 0.5～20, more preferably 2～10, most preferably 2～5% (weight) by the weight of composition.Preferably, but adhesive is polymer adhesive thermosetting or thermoplastic.Polymer adhesive can have known suitable stabilizing agent and the antiaging agent of polymer specialty.Polymer can be thermoplastic polymer or elastomeric polymer.Most preferably be incorporated into thermoset elastomeric polymeric thing in the carbon monoxide-olefin polymeric slurries preferred water slurries as latex.When composition applied and heat, the adhesive material crosslinkable provided suitable support, and it increases the globality of coating, to the adhesiveness increase of atmosphere contact surface, and kept structural stability under the vibration that produces in motor vehicle.The application of preferred polymer adhesive can adhere on the atmosphere contact surface pollutant treatment compositions, and does not need prime coat.Adhesive can contain water-fast additive, to improve resistance to water and adhesiveness.Such additive comprises fluorine carbon emulsion and pertroleum wax emulsion.

The polymeric compositions that is suitable for comprises polyethylene, polypropylene, polyolefin copolymer, polyisoprene, polybutadiene, polybutadiene copolymer, chlorinated rubber, acrylonitrile-butadiene rubber, polychlorobutadiene, the ethylene-propylene diene elastomer, polystyrene, polyacrylate, polymethacrylates, polyacrylonitrile, poly-(vinyl esters), poly-(vinyl halide), polyamide, cellulosic polymer, polyimides, acrylic resin, vinylacrylic acid resinoid and styrene-acrylonitrile copolymer acid resin, polyvinyl alcohol, thermoplastic polyester, thermosetting polyester, polyphenylene oxide, polyphenylene sulfide, polymer of fluoridizing such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride, polyvinyl fluoride and chlorine/fluo-copolymer such as ethene one chlorotrifluoroethylcopolymer copolymer, polyamide, phenolic resins and epoxy resin, polyurethane and silicone polymer.Most preferred polymeric material is a disclosed acrylic polymer latex in attached embodiment.

Particularly preferred polymer and copolymer are vinylacrylic acid base polymer and EVAc.Preferred vinylacrylic acid base polymer is the cross-linked polymer that NationalStarch and Chemical Company sells with Xlink 2833.It is called the vinylacrylic acid base polymer, and its Tg is-15 ℃, solid content 45%, pH value 4.5 and viscosity 300 centipoises.Particularly, be expressed as vinyl-acetic ester CASNo.108-05-4, its concentration range is less than 0.5%.Be indicated as vinyl acetate copolymer.Other preferred vinyl acetate copolymers of being sold by National Starch and Chemical Company comprise Dur-O-Set E-623 and Dur-O-SetE-646.Dur-O-Set E-623 is a vinyl-vinyl acetate copolymer, and its Tg is 0 ℃, solid content 52%, pH value 5.5 and viscosity 200 centipoises.Dur-O-Set E-646 is a vinyl-vinyl acetate copolymer, its Tg-12 ℃, solid content 52%, pH value 5.5 and viscosity 300 centipoises.

Jointing material that substitute and that be suitable for is to use zirconium compounds.Zirconyl acetate is the preferred zirconium compounds that uses.It is believed that zirconia as high-temperature stabiliser, promote catalytic activity and improve the adhesiveness of catalyst.When roasting, zirconium compounds such as zirconyl acetate change into ZrO ₂It is believed that it is a jointing material.Various suitable zirconium compounds comprise acetate, hydroxide, nitrate etc., are used for generating ZrO at catalyst ₂Under with the situation of zirconyl acetate, only after the radiator coating is by roasting, just generate ZrO as the adhesive of catalyst of the present invention ₂Because be issued to good adhesiveness in " roasting " temperature of 120 ℃ only, thus think the undecomposed one-tenth zirconia of zirconyl acetate, but handle material such as Carulite with pollutant ^Particle and the acetate that is generated by usefulness acetate ball milling form cross-linked network.Therefore, in catalyst of the present invention, any use that contains the compound of zirconium all is not limited only to zirconia.In addition, zirconium compounds can use with other adhesive such as above-mentioned polymer adhesive.

A kind of alternative pollutant is handled carbon monoxide-olefin polymeric can contain activated carbon composite.Charcoal composition contains active carbon, adhesive such as polymer adhesive and optional conventional additives such as defoamer etc.The activated carbon composite that is suitable for contains 75～85% (weight) active carbon, as " cocoanut shell " charcoal or timber charcoal, and adhesive such as acrylic ester adhesive and defoamer.The slurries that are suitable for contain 10～50% (weight) solid.But the active carbon catalysis ozone is reduced into oxygen, and the pollutant that adsorbs other.

Pollutant of the present invention is handled carbon monoxide-olefin polymeric and can be prepared with any suitable method.A kind of preferable methods is open in US 4134860, incorporates the present invention here as a reference into.According to this method, refractory oxide carrier such as activated alumina, titanium oxide or active oxidation silicon-aluminium oxide are through jet grinding, with the preferred precious metal salt solution dipping of the metal salt solution of catalytic activity, then at the roasting temperature about 0.5 that is fit to about 12 hours, about 300 to about 600 ℃ usually, preferred about 350 to about 550 ℃, more preferably from about 400 to about 500 ℃.Palladium salt is preferably palladium nitrate or palladium amine, as acid chloride tetramine or palladium dydroxide tetramine.Platinum salt is preferably included in the platinic hydroxide of solubilising in the amine.In concrete and embodiment preferred, through the catalyst of roasting by above-mentioned reduction.

In the ozone treatment composition, manganese salt such as manganese nitrate then can be in the presence of deionized water mix with the palladium of the alumina load of drying and roasting.The water yield that adds should be such quantity, up to reaching the beginning wetting point.Relate to the method for in the above-mentioned US4134860 that quotes and incorporate into, commenting.The beginning wetting point is more like this, and the amount of liquid that adds under this point is that mixture of powders is still sufficiently dry, so that absorbs the least concentration of all liquid basically.Use this method, can be with manganese salt in the water soluble such as Mn (NO ₃) ₂Be added in the catalytic precious metal of the load of roasting.With the mixture drying and at the roasting temperature that is fit to, preferred 400～500 ℃ of following roastings about 0.5 were to about 12 hours then.

On the other hand, the catalyst fines of load (promptly being loaded in the palladium on the aluminium oxide) can mix with the liquid preferred water, makes slurries, with manganese salt such as Mn (NO ₃) ₂Solution is added in the slurries.Preferably, the manganese component and be loaded in high-temperature resistant carrier such as activated alumina, more preferably the palladium on active silica-aluminium oxide mixes with the water of suitable quantity, obtains 15～40, the slurries of preferred 20～35% (weight) solid.The mixture that merges can be coated on carrier such as the radiator; In air, following dry 1～12 hour as 50～150 ℃ then in the condition that is fit to.The base material of load coating then can be in stove, under the condition that is fit to (being generally 300～550 ℃, preferred 350～500 ℃, more preferably 350～450 ℃, most preferably 400～500 ℃), in oxygen containing atmosphere, preferred air, heated about 0.5 to about 12 hours, each component of roasting helps coating to be fixed on the atmosphere contact surface of base material.Also contain at composition under the occasion of noble metal component, preferably after roasting, reduce.

Method of the present invention comprises making and contains the catalytically-active materials that is selected from least a platinum group metal component, golden component, silver components, manganese component and the mixture of water.Catalytically-active materials can be loaded on the suitable carrier, preferred refractory oxide carrier.Mixture can grinding, roasting and the reduction that depends on the needs.Calcination steps can carry out in the past at the adding polymer adhesive.The reduction catalysts active material also is preferred before the adding polymer adhesive.Slurries contain carboxylic acid compound or contain the polymer of carboxylic acid, and the pH value that its amount makes slurries is for about 3 to 7, common 3～6, and by the weight of catalyst reactive material and acetate, preferably contain 0.5～15% (weight) glacial acetic acid.Can add suitable quantity of water, to obtain the slurries of required viscosity.The percentage solid content is generally 20～50, preferred 30～40% (weight).Preferred medium is deionized water (D.I.).When the mixture of the catalytically-active materials of making roasting and water, can add acetate.On the other hand, acetate can add with polymer adhesive.The preferred composition that uses manganese dioxide to make the processing ozone of catalyst can restrain acetate with about 1500 gram manganese dioxide and 2250 gram deionized waters and 75 be mixed and make.Mixture mixes in 1 gallon of ball mill, and about 8 hours of ball milling, until about 90% particle is less than till 8 microns.From ball mill, take out, add 150 gram polymer adhesives.Then in roller mill with mixture blend 30 minutes.The mixture that generates is ready to be coated on the suitable base material, on automobile radiators according to following method.

The pollutant treatment compositions can be coated on the atmosphere contact surface with any suitable method, for example spraying, powder coating, brushing or with surperficial dip-coating in catalyst slurry.

The atmosphere contact surface preferably through cleaning, is removed and may be made the surperficial dust of pollutant treatment compositions to the adhesiveness variation on surface, particularly oil.If possible, preferred heated substrate is under the sufficiently high temperature substrate surface, makes the vaporization of surperficial detritus and oils or burns.

But there is the base material of atmosphere contact surface to make under the occasion of (as aluminium radiator) by exotic material thereon, substrate surface can be handled with such method, so that improve to carbon monoxide-olefin polymeric, the adhesiveness of preferred ozone, carbon monoxide and/or hydro carbons carbon monoxide-olefin polymeric.A kind of method is in air aluminium base such as radiators heat to be arrived sufficiently high temperature, heats the sufficiently long time, the feasible thin layer that forms aluminium oxide from the teeth outwards.Helping like this may be to the oils clean surface of adhesiveness illeffects by removing.In addition, if the surface is an aluminium, found that enough thick alumina layer can make by the following method: in air, 350～500, preferred 400～500, more preferably add under 425～475 ℃ heat radiator 0.5～24, preferred 8～24, more preferably 12～20 hours.In some cases, in air, be heated under 16 hours the occasion at 450 ℃, under the condition of not using prime coat, just can reach sufficiently high adhesiveness at aluminium radiator.When in motor vehicle as original equipment or as changing when being coated to coating on new surface such as radiator or the air-conditioning condenser surface before the device assembles, this method is a particularly suitable.

By improving adhesiveness to base material coating prime coat or precoated shet.The refractory oxide carrier that prime coat that is suitable for or precoated shet comprise the above-mentioned type, aluminium oxide is preferred.Open in the US 5422331 that grants jointly for the adhering preferred prime coat that improves between atmosphere contact surface and the ozone catalytic agent composition top coat, incorporate the present invention here as a reference into.Prime coat is the mixture that contains fine grained refractory metal oxide and be selected from a kind of colloidal sol of silica, aluminium oxide, zirconia and titanium oxide sol.The method according to this invention, when base material such as radiator, radiator fan or air-conditioning condenser were positioned on the vehicle, the surface of existing vehicle can apply.Carbon monoxide-olefin polymeric can directly be coated on the surface.Increase under the adhering occasion available as mentioned above prime coat layer in hope.

Separating with vehicle at radiator is under the occasion of practicality, carrier material such as activated alumina, silica-alumina, loose titanium oxide, titanium colloidal sol, silica zirconia, manganese zirconia and described other carriers can be made into slurries and are coated on the base material, preferably use Ludox so that improve adhesiveness.Apply through the available subsequently solubility precious metal salt of the base material of precoated shet such as platinum and/or palladium salt, optionally apply with manganese nitrate.Base material through applying in stove, heats the sufficiently long time (heating 0.5～12 hour down at 350～550 ℃) then in air, make palladium and the roasting of manganese component, forms its oxide.

The present invention can comprise the adsorbent composition that is loaded on the atmosphere contact surface.Adsorbent composition can be used to adsorbed gas pollutant such as hydro carbons and sulfur dioxide, and particle such as particle hydro carbons, cigarette ash, pollen, bacterium and microorganism.The composition of the load that is suitable for can comprise the zeolite of adsorbent such as adsorbs hydrocarbons.The WO 94/27709 that the zeolite compositions that is suitable for was announced on December 8th, 1994, title are open in " decompose nitrogen oxides catalyst ", incorporate the present invention here as a reference into.Particularly preferred zeolite is the y-type zeolite of β zeolite and dealuminzation.

Charcoal, preferred active carbon can be made into the carbon adsorbent composition, and they contain active carbon and adhesive, polymer as known in the profession.The carbon adsorbent composition can be coated on the atmosphere contact surface.The adsorbable hydro carbons of active carbon, volatile organic constituents, bacterium, pollen etc.Another adsorbent composition can contain absorption SO ₃Component.The SO of particularly suitable ₃Adsorbent is a calcium oxide.Calcium oxide is converted to calcium sulfate.The calcium oxide adsorbent composition also can contain vanadium or platinum catalyst, and they can be used to Sulphur Dioxide is become sulfur trioxide, is attracted to then in the calcium oxide, generates calcium sulfate.

Contain the atmospheric air of pollutant except handling under environmental condition or under the environmental operations condition, the present invention also attempts to come catalytic oxidation and/or reduction hydro carbons, nitrogen oxide and residual carbon monoxide with the known conventional three-element purifying catalyst that is loaded on the electrically heated catalyst of this specialty.Electrically heated catalyst can place on the electric heating integer catalyzer 56 shown in Figure 1.Such electrically heated catalyst material is known and open in list of references such as US 5308591 and 5317869 in this specialty, and here both incorporate the present invention as a reference into.For the present invention, electrically heated catalyst is a kind of streamwise setting and the honeycomb metal thing that suitable thickness (preferred 1/8 inch to 12 inch, more preferably 0.5～3 inch) is arranged.Must be located at when electrically heated catalyst under the situation of narrow space, its thickness can be the 0.25-1.5 inch.Preferred carrier is to have many inner faces from carrier to extend to the integral carriers of the tiny parallel airflow passage of outside, so that passage is towards 26 that enter and along towards the direction of the fan 20 air stream by overall structure 56 from the front.Preferably, passage is straight line basically from its import to outlet, and is determined as the wall that wash coat applies by catalyst, so that the gas that flows through passage contacts with catalyst material.The gas channel of integral carriers is the thin-walled duct, they can have any suitable shape of cross section and size, as trapezoidal, rectangle, square, sinusoidal, hexagon, ellipse, circle, perhaps make with flat metal assembly, as known in this specialty by corrugated.Every square of inch cross section of such works can have an appointment 60 to 600 or more gas feed hole (" abscess ").Monolith is made by any suitable material, preferably can use current flow heats.The catalyst that is suitable for is aforesaid three-element purifying catalyst (TWC), and it can improve the oxidation of hydro carbons and carbon monoxide and the reduction of nitrogen oxide.The TWC catalyst that is suitable for is open in US 4714694,4738947,5010051,5057483 and 5139992.

The present invention further specifies with following embodiment, does not plan to limit the scope of the invention with these embodiment.

Embodiment 1

With 1993 Nissan Altima radiator cores (Nissan part number 21460-1E400), 450 ℃ of following heat treated 16 hours in air, so that make cleaning surfaces and oxidation; Use following step then, (dry measure is 0.23 gram/inch with high surperficial silica-alumina priming coat ³) apply part surface: pour monox-alumina containning aqueous slurry into the radiator duct; Blow out excessive slurries with air cannon; At room temperature use the fan drying; Then 450 ℃ of roastings.By the SRS-II aluminium oxide (Davison) of high surface roasting is prepared silica-alumina slurries to 90% granularity less than 4 microns method with acetate (counting 0.5% by aluminium oxide) and water (total solid content is about 20%) ball milling.Through the material of ball milling then with Nalco Ludox (#91SJ06S-28% solid) in 25%/75% ratio blend.The feature of SRS-II aluminium oxide is that structural formula is xSiO ₂YAl ₂O ₃ZH ₂O has 92-95% (weight) Al after the activation ₂O ₃With 4～7% (weight) SiO ₂BET surface area minimum is 260 meters after the roasting ²/ gram.

Prepare Pd/Mn/Al by aqueous solution dipping high surface SRS-II aluminium oxide (Davison) to the beginning wetting point with the acid chloride tetramine that contains sufficient amount ₂O ₃Catalyst slurry (common 10% (weight) Pd/Al ₂O ₃).The dry powder that generates is then 450 ℃ of following roastings 1 hour.Subsequently under high shear with powder and manganese nitrate aqueous solution (in an amount equivalent to 5.5% (weight) MnO ₂/ Al ₂O ₃Powder) and the dilution water of q.s mix, make the slurries of 32-34% solid.Apply radiator, in air, use the fan drying with this slurries, roasting 16 hours in 450 ℃, air then.This ozone decomposition catalyst contains palladium and (does carrying capacity 263 gram/Foot on high surface SRS-II aluminium oxide ³The radiator volume) and manganese dioxide (do carrying capacity 142 gram/Foot ³).Radiator and coolant tank that part applies fit together, and are also referred to as header box, as shown in Figure 8.

Ozone decomposability with following step measurements coated catalysts: the air logistics that will contain finite concentration ozone is blown over the radiator duct with the face velocity of common actuating speed; Measure the radiator back side then and discharge the ozone concentration of gas.Used air is in about 20 ℃, and its dew point is about 35 °F.Coolant fluid circulates by radiator under about 50 ℃.Ozone concentration is 0.1～0.4ppm.The ozone conversion ratio that equals to measure under 12.5 miles per hours at air linear speed (face velocity) is 43%; Be 33% under 25 miles per hours; Be 30% under 37.5 miles per hours, and be 24% under 49 miles per hours.

Embodiment 2 (Comparative Examples)

Do not carry out the evaluation (being the contrast experiment) of similar ozone decomposability with the part of used identical radiator among the embodiment 1 of catalyst-coated.It is unconverted to observe ozone.

Embodiment 3

450 ℃ of following heat treatments are after 60 hours in air, and Lincoln Town Car radiator core (parts #FIVY-8005-A) uses various ozone decomposition catalyst composition (being different catalyst, catalytic amount, adhesive formula and heat treatment) to apply 6 inch * 6 inch square sub-district subsequently.Several radiators sub-district is with high surface area alumina or silica-alumina precoating, and before coated catalysts 450 ℃ of following roastings.The actual following step of coating similar embodiment 1 usefulness is finished: the aqueous slurry that will contain concrete catalyst formulation is poured into and is passed through the radiator duct; Blow away excessive slurries with air cannon; At room temperature use the fan drying then.Then with radiator core 120 ℃ of dryings, perhaps 120 ℃ of dryings, then 400～450 ℃ of roastings.And then radiator core is contained on its plastic box, and under the spreader surface temperature is about 40～50 ℃, face velocity 10 miles per hours, measure the ozone decomposability of various catalyst, as described in example 1 above.

Table I has gathered the various catalyst that are coated on the radiator.The details of catalyst slurry preparation provide below.

With the H that is dissolved in the 520 gram water by solubilising in amine ₂Pt (OH) ₆The 114 gram platinum salting liquids (17.9%Pt) that obtain are impregnated into 1000 gram Condea SBA-150 high surfaces (for about 150 meters ²/ gram) prepares Pt/Al on the alumina powder ₂O ₃Catalyst (is generally 2% (weight) Pt/Al ₂O ₃).Add 49.5 gram acetate subsequently.Then powder was descended dry 1 hour at 110 ℃, 550 ℃ of following roastings 2 hours.Then by in ball mill, 875 gram powder being added in 1069 gram water and the 44.6 gram acetate, and mixture being ground to 90% granularity and making catalyst slurry (sub-district 1 and 4) less than 10 microns.

The Pd/carbon catalyst slurries are by Grant industrial group (Elmwood Park, NJ) a kind of prescription of Gou Maiing (29% solid).Charcoal is made by cocoanut shell.Contain acrylic ester adhesive and defoamer (sub-district 8 and 12).

Carulite

^200 catalyst (CuO/MnO ₂) by at first restraining Carulite with 1000 ^200 (bought by Carus chemical company, Chicago IL) is ground to 90% granularity less than 6 microns with 1500 gram water polo.Carulite ^200 contain 60～75% (weight) MnO ₂, 11～14%CuO and 15～16%Al ₂O ₃The slurries that generate are diluted to about 28% solid then, mix then or with 3% (by solid) Nalco#1056 Ludox or 2% (by solid) National Starch#x4260 acrylic copolymer.(sub-district 5,9 and 10).

The Pd/Mn/Al for preparing by embodiment 1 description ₂O ₃Catalyst slurry (is generally 10% (weight) Pd/Al ₂O ₃) (sub-district 2,3 and 6).

Prepare I.W. (beginning wetting) Pd/Mn/Al by at first high surface SRS-II aluminium oxide (Davison) being impregnated into the beginning wetting point equally with the aqueous solution that contains the acid chloride tetramine ₂O ₃Catalyst (is generally 8%Pd+5.5%MnO ₂/ Al ₂O ₃).With powder for drying and 450 ℃ of following roastings after 2 hours, powder is dipped into the beginning wetting point with the aqueous solution stain that contains manganese nitrate once more.In addition, dry and 450 ℃ of following roastings after 2 hours, powder is mixed with acetate (3% (weight) of catalyst fines) and enough water in ball mill, obtain the slurries of 35% solid.Then mixture is ground, until 90% granularity is less than till 8 microns.(sub-district 7 and 11).

Press the preparation SiO that embodiment 1 describes ₂/ Al ₂O ₃Precoated shet slurries (sub-district 3 and 11).

By high surface Condea SBA-150 aluminium oxide and acetate (are pressed Al ₂O ₃Count 5% (weight)) and water (total solid content is about 44%) together the granularity of ball milling to 90% prepare Al less than 10 microns ₂O ₃The precoated shet slurries.(sub-district 9 and 12).

The results are summarized in Table I.Under the embodiment 1 described condition, sub-district 4 has also been measured the conversion ratio of carbon monoxide behind 5000 miles of the running cars.Being 50 ℃ at radiator temperature is not observe conversion under 10 miles per hours with linear speed.

The Table I catalyst gathers

The sub-district	Catalyst	Ozone conversion ratio (%)
The sub-district	Catalyst	Ozone conversion ratio (%)	??1	??????????Pt/Al ₂O ₃0.67 gram/inch ³(23 gram/Foot ³Pt) no precoated shet does not fuse (only 120 ℃)	?????12
??2	?????????Pt/Mn/Al ₂O ₃0.97 gram/inch ³(171 gram/Foot ³Pd)	?????25	??1		?????12

	450 ℃ of roastings of no precoated shet
	450 ℃ of roastings of no precoated shet		??3	???????????Pd/Mn/Al ₂O ₃1.19 gram/inch ³(209 gram/Foot ³Pd) ???SiO ₂/Al ₂O ₃Precoated shet (0.16 gram/inch ³) 450 ℃ of roastings	???24
??4	????????????Pt/Al ₂O ₃0.79 gram/inch ³(27 gram/Foot ³Pt) 450 ℃ of roastings of no precoated shet	???8	??3		???24
??4		???8	??5	Carulite 200 0.49g gram/inch ³????3％SiO ₂/Al ₂O ₃Adhesive does not have 400 ℃ of roastings of precoated shet	???50
??6	??????????Pd/Mn/Al ₂O ₃0.39 gram/inch ³(70 gram/Foot ³Pd) 450 ℃ of roastings of no precoated shet	???28	??5		???50
??6		???28	??7	????????I.W.Pd/Mn/Al ₂O ₃0.69 gram/inch ³(95 gram/Foot ³Pd) not roasting of no precoated shet (only 120 ℃)	???50
??8	Carbon 0.80 gram/inch ³Not roasting of no precoated shet (only 120 ℃)	???22	??7		???50
??8		???22	??9	Carulite 200 0.65 gram/inch ³??????3％SiO ₂/Al ₂O ₃Adhesive A l ₂O ₃Precoated shet (0.25 gram/inch ³) 450 ℃ of roastings	???38
??10	Carulite 200 0.70 gram/inch ³2% latex adhesive does not have not roasting of precoated shet (only 120 ℃)	???42	??9		???38
??10		???42	??11	????????I.W.Pd/Mn/Al ₂O ₃0.59 gram/inch ³(82 gram/Foot ³Pd) ????SiO ₂/Al ₂O ₃Precoated shet (0.59 gram/inch ³) not roasting of two coatings (only 120 ℃)	???46

??12

Charcoal 1.07 gram/inch ³?Al ₂O ₃Precoated shet (0.52 gram/inch ³) 450 ℃ of not roastings of roasting top coat (only 120 ℃)

???17

Embodiment 4

In air, 400 ℃ of following heat treated 16 hours, a part used Condea high surface SBA-150 alumina coated (to do carrying capacity 0.86 gram/inch according to the following steps then with 1993 Nissan Altima radiator cores (Nissan part number 21460-1E400) ³): the aqueous slurry that will contain aluminium oxide is toppled over and by the radiator duct; Blow away excessive slurries with air cannon; At room temperature use the fan drying; Then 400 ℃ of following roastings.Press the preparation aluminium oxide precoated shet slurries that embodiment 3 describes.Apply radiator (Table II) with seven kinds of different CO reforming catalysts by 2 inch * 2 inch square sub-district then.Apply each coating with following step: the aqueous slurry that will contain the special catalyst prescription is toppled over and by the radiator duct; Blow away excessive slurries with air cannon; At room temperature use the fan drying.

The step of describing by embodiment 3 prepares Carulite ^And 2%Pt/Al ₂O ₃Catalyst (being respectively sub-district 4 and 6).At first at 500 ℃ of following roasting 510 gram zirconia/silica material (95% ZrO ₂/ 5% SiO ₂-Magnesium ElektronXZ0678/01) made 3%Pt/ZrO in 1 hour ₂/ SiO ₂Catalyst (sub-district 3).Restrain by H by powder, the 42 gram glacial acetic acid and 79.2 that 468 grams are generated then with the amine solubilising ₂Pt (OH) ₆The platinum salting liquid (18.2%Pt) that obtains is added in the 480 gram deionized waters and makes catalyst slurry.The mixture that generates was ground on ball mill 8 hours, make 90% granularity less than 3 microns.

By in the blending machine of routine, restraining TiO with 500 ₂(Degussa P25), 500 gram deionized waters, the 12 dense ammonium hydroxide of gram and 82 grams are by the H with the amine solubilising ₂Pt (OH) ₆The mixed 3%Pt/TiO that gets of the platinum salting liquid (18.2%Pt) that makes ₂Catalyst (sub-district 7).Blending made 90% granularity less than after 5 microns in 5 minutes, added 32.7 gram Nalco1056 Ludox and capacity deionized waters, made solid content drop to about 22%.With the mixture blending on ball mill that generates, all components is mixed.

Restrain by H by manganese/zirconia material (Magnesium ElektronXZO719/01), 100 gram deionized waters, the 3.5 gram acetate and 11.7 that 70 grams contained 20% (weight) manganese and 80% (weight) zirconia (by metal weight) with the amine solubilising ₂Pt (OH) ₆The platinum salting liquid (18.2%Pt) that obtains mixes in ball mill and prepares 3%Pt/Mn/ZrO ₂Catalyst slurry (sub-district 5).The mixture that generates was ground 16 hours, make 90% granularity less than 10 microns.

By using H by the amine solubilising ₂Pt (OH) ₆Be dissolved in 54.9 gram platinum salting liquids (18.2%Pt) dippings, 490 grams that deionized water (155 milliliters of cumulative volumes) obtains aluminium oxide (Rhone Poulenc) and make 2%Pt/CeO with the high surface ceria stabilized ₂Catalyst (sub-district 1).Powder was descended dry 6 hours at 100 ℃, then 400 ℃ of following roastings 2 hours.By in ball mill, 491 gram powder being added in the 593 gram deionized waters, then mixture was ground 2 hours then, make 90% granularity make catalyst slurry less than 4 microns.Prepare 4.6%Pd/CeO by beginning wetting dipping equally with 209.5 gram (180 milliliters) acid chloride tetramine solution ₂Catalyst (sub-district 2).

After all 7 kinds of catalyst-coated, with radiator about 16 hours of 400 ℃ of following roastings.After installing to radiator core in the plastic box, with the carbon monoxide conversion performance of the various catalyst of following step measurements: the air logistics that will contain CO (about 16ppm) is with 5 miles per hour line face speed (air speeds 315000 hours ^-1) blow over the radiator duct; Measure the radiator back side then and discharge the CO concentration of gas.The temperature of radiator is about 95 ℃, and the dew point of air stream is about 35 °F.The results are summarized in Table II.

Press that embodiment 1 describes, 25 ℃, 0.25ppm ozone, line face speed 10 miles per hours, 135.2 liters/minute of flows and air speed 640000 hours ^-1Measure the decomposability of ozone down.The dew point of used air is 35 °F.The results are summarized in Table II.Fig. 4 illustrates the CO conversion ratio of sub-district 3,6 and 7 and the relation of temperature.

Also by online speed 5 miles per hours, 68.2 liters/minute of flows and air speed 320000 hours ^-1Make the air stream that contains propylene (about 10ppm) blow over the radiator duct down, the method for measuring the density of propylene of radiator back side effluent gases is then come the propylene conversion capability of detecting catalyst.The temperature of radiator is about 95 ℃, and the dew point of air stream is about 35 °F.The results are summarized in Table II.

Table II CO/ hydro carbons/ozone conversion ratio gathers

The sub-district	Catalyst	CO conversion ratio (%) ¹	Ozone conversion ratio (%) ²	Propylene conversion (%) ³
The sub-district	Catalyst	CO conversion ratio (%) ¹	Ozone conversion ratio (%) ²	Propylene conversion (%) ³	??1	?????2％Pt/CeO ₂0.7 gram/inch ³(24 gram/Foot ³Pt)	????2	???14	????0
??2	????4.6％Pd/CeO ₂0.5 gram/inch ³(40 gram/Foot ³Pd)	???21	???55	????0	??1	?????2％Pt/CeO ₂0.7 gram/inch ³(24 gram/Foot ³Pt)	????2	???14	????0
??2	????4.6％Pd/CeO ₂0.5 gram/inch ³(40 gram/Foot ³Pd)	???21	???55	????0	??3	????3％Pt/ZrO ₂/SiO ₂0.5 gram/inch ³(26 gram/Foot ³Pt)	???67	???14	????2
??4	Carulite 200 0.5 gram/inch ³???3％SiO ₂/Al ₂O ₃Adhesive	????5	???56	????0	??3	????3％Pt/ZrO ₂/SiO ₂0.5 gram/inch ³(26 gram/Foot ³Pt)	???67	???14	????2
??4	Carulite 200 0.5 gram/inch ³???3％SiO ₂/Al ₂O ₃Adhesive	????5	???56	????0	??5	????3％Pt/Mn/ZrO ₂0.7 gram/inch ³(36 gram/Foot ³Pt)	????7	???41	????0
??6	????2％Pt/Al ₂O ₃0.5 gram/inch ³(17 gram/Foot ³Pt)	???72	????8	????17	??5	????3％Pt/Mn/ZrO ₂0.7 gram/inch ³(36 gram/Foot ³Pt)	????7	???41	????0
??6	????2％Pt/Al ₂O ₃0.5 gram/inch ³(17 gram/Foot ³Pt)	???72	????8	????17	??7	????3％Pt/TiO ₂0.7 gram/inch ³(36 gram/Foot ³Pt) ?3％SiO ₂/Al ₂O ₃Adhesive	???68	???15	????18
¹Experimental condition: 16ppmCO; 95 ℃; 5 miles per hour face velocities; 68.2 rise/minute; LHSV=320000 hour ^-1 Air dew point=35 ²Experimental condition: 0.25ppm O ₃ 25 ℃; 10 miles per hour face velocities; 135.2 rise/minute; LHSV=640000 hour ¹ Air dew point=35 ³Experimental condition: 10ppm propylene; 95 ℃; 5 miles per hour face velocities; 68.2 rise/minute; LHSV=320000 hour ^-1 Air dew point=35					??7		???68	???15	????18

Embodiment 5

This embodiment has gathered the technical result of the motor vehicles test of travelling on the highway that carries out in Los Angeles in February nineteen ninety-five and March.The purpose of test is to measure the ozone catalytic decomposing efficiency of the radiator of band catalyst under the actual travel condition.Selecting area, Los Angeles (LA) is can measure at its ozone content of duration of test in March as optimal experimental field chief reason.In addition, the concrete travel route of determining area, Los Angeles have peak in the typical morning, afternoon the peak and non-peak travel.Two kinds of different carbon monoxide-olefin polymerics are estimated: 1) Carulite ^200 (CuO/MnO ₂/ Al ₂O ₃, buy by Carus chemical company); With 2) Pd/Mn/Al ₂O ₃(77 gram/Foot ³Pd presses the preparation that embodiment 3 describes).Two kinds of catalyst are coated on the up-to-date model Cadillac V-6 engine aluminum radiator with the form of sub-district.Copper-brass OEM radiator on the aluminium radiator replaced C hevrolet Caprice test vehicle.This car is equipped with 1/4 inch Teflon ^The PTFE sampling line is directly every kind of back, catalyst sub-district with in the back of the uncoated part of radiator (contrast sub-district).Sampling line measurement environment by being in the radiator front (entering catalyst) ozone content.Measure ozone concentration with two Dasibi Model, the 1003 AH ozone monitoring devices that are installed in the rear seat for vehicle.Temperature probe (using epoxy resin) is directly installed in a few inch distances of each radiator experimental plot sampling line.Single air velocity probe is installed in the centre of two sub-districts, radiator front.Collect and be recorded on the floppy disc with the personal computer that is installed in the luggage case from the data that ozone analyzer, temperature probe, air velocity probe and vehicle speed measuring instrument obtain.

The whole Table III that the results are summarized in down that obtains by test.For every kind of catalyst (Carulite ^And Pd/Mn/Al ₂O ₃), provided the result who travels on cold idling, intensification idling and the highway.The data of February nineteen ninety-five and March twice independent Los Angeles trip have been collected.First road performance test has only just stopped after several days owing to the environment ozone content is low.Though the environment ozone content is slightly higher in the second road performance test process in March, the environment ozone content 40ppb that still on average only has an appointment.Run into the highest ozone content last 3 days (on March 17 to 20) of test.Peak value content is about 100ppb.Usually, do not observe the variation tendency of conversion ratio and ozone concentration.

Except cold idling result, those results that list in Table III are the mean value (actual range of numerical value is in bracket) of at least 11 different tests.Include only corresponding to the data of import ozone concentration more than or equal to 30ppb.The data that do not comprise highway are because environment content drops to 20ppb or lower.For cold idle running test, only carry out twice test.So-called cold idling refers in the idling process behind the vehicle launch, opens and the coolant fluid of heat is pumped into the radiator data of collection immediately in the past at constant temperature.Generally speaking, two kinds of catalyst all have good ozone conversion ratio, obtain the highest numerical value in hot idling process.This point can be given the credit to higher temperature relevant with idling and lower side speed.Because the environment temperature of spreader surface is lower, cold idling obtains minimum conversion ratio.The result that travels is between hot idling result and cold idling result.Though radiator is hot, with comparing of running under the hot idling condition, temperature is lower, and face velocity is higher.Usually, use Carulite ^The ozone conversion ratio of measuring is greater than using Pd/Mn/Al ₂O ₃When travelling (as 78.1% and 63.0%) measured.But, for hot idling and travel Carulite ^The mean temperature of catalyst is usually than Pd/Mn/Al ₂O ₃Catalyst is high 40 °F, and usually low 1 miles per hour of radiator centre plane speed.

Generally speaking, the result shows, under common driving conditions, and may be with high conversion rate ozone decomposition.

Scope is in bracket.</entry></row></tbody></tgroup></table></tables>

Usually, the result of engine test is consistent with the former fresh activity of measuring in the laboratory of radiator is installed.Under room temperature (～25 ℃), 20% relative humidity (0.7% water vapour absolute value) and 10 miles per hour equivalent face velocities, Pd/Mn/Al ₂O ₃And Carulite ^Laboratory ozone conversion ratio be respectively 55 and 69%.Be increased to 70% (2.3% water vapour absolute value) in room temperature (about 25 ℃) relative humidity, conversion ratio drops to 38 and 52% respectively.Because the conversion ratio under the cold idling of measuring under the 9 miles per hour face velocities (70) is respectively 48 and 67%, obviously the humidity that runs in process of the test is low.

The face velocity that enters the air of radiator is low.Be about (being generally the area travels) under 20 miles per hours at average overall travel speed, the face velocity of radiator only is about 13 miles per hours.Even surpass under 60 miles per hours in the speed of highway, the face velocity of radiator is also about only 25 miles per hours.Fan is given birth to tangible adverse effect to control by the air miscarriage of radiator.When idling, fan makes face velocity reach about 8 miles per hours usually.

Embodiment 6

8% (weight) Pd/Carulite ^Catalyst prepares in order to the below method: the aqueous solution that contains acid chloride tetramine (12.6%Pd) with 69.0 grams is with 100 gram Carulite ^200 powder (pulverizing in the blending machine) are impregnated into the beginning wetting point.With powder 90 ℃ of following dried overnight, then 450 ℃ or 550 ℃ of following roastings 2 hours.The catalyst through roasting that in ball mill 92 grams is generated then mixes with 171 gram deionized waters, obtains the slurries of 35% solid.Grind made 90% granularity be less than or equal to 9 microns in 30 minutes after, add 3.1 gram National Starch * 4260 acrylic based emulsion adhesives (50% solid), the mixture that generates was ground 30 minutes again, adhesive is disperseed.Same preparation contains 2,4 and 6% (weight) Pd/Carulite ^The composition of catalyst, and estimate.

300cpsi (hole count/inch with the coating of washcoat coating ²) the ceramic honeycomb thing, room temperature and 630000 hours ^-1The ozone decomposability of evaluate catalysts under the air speed.Catalyst sample is by above-mentioned preparation.The results are summarized in Table IV.As what be easy to find out, at 4 and 8%Pd/Carulite of 450 ℃ of following roastings ^Catalyst obtains suitable first ozone conversion ratio and 45 minutes ozone conversion ratios (being respectively about 62 and 60%).These results with under identical experimental condition, only contain Carulite ^The result suitable.2 and 4%Pd catalyst 550 ℃ of following roastings obtained obviously low conversion ratio (47%) after 45 minutes.This is because under higher sintering temperature, and surface area descends causes.6% activity of such catalysts 550 ℃ of roastings does not have big decline like that yet.

The result of Table IV ozone (the cellular thing of 300cpsi, air speed 630000 hours ^-1)
				Catalyst	Carrying capacity (gram/inch ³)	First conversion ratio (%)	45 minutes conversion ratios (%)
	??????Pd/Carulite?200			Catalyst	Carrying capacity (gram/inch ³)	First conversion ratio (%)	45 minutes conversion ratios (%)
	??????Pd/Carulite?200			4%Pd/Carulite (450 ℃ of roastings)	???1.8	????64	????59
8%Pd/Carulite (450 ℃ of roastings)	???2.0	????61	????60	4%Pd/Carulite (450 ℃ of roastings)	???1.8	????64	????59
8%Pd/Carulite (450 ℃ of roastings)	???2.0	????61	????60	2%Pd/Carulite (550 ℃ of roastings)	???2.1	????57	????48
4%Pd/Carulite (550 ℃ of roastings)	???1.9	????57	????46	2%Pd/Carulite (550 ℃ of roastings)	???2.1	????57	????48
4%Pd/Carulite (550 ℃ of roastings)	???1.9	????57	????46	6%Pd/Carulite (550 ℃ of roastings)	???2.3	????59	????53

Embodiment 7

Carry out a series of tests, estimated the various carbon monoxide-olefin polymerics that contain the palladium component of handling the air that contains 0.25ppm ozone.Air is under the environmental condition (23 ℃; 0.6% water).Composition is coated on the cellular thing of pottery (cordierite) circulation of 300 abscess/inch the about 2 gram washcoat coating of the carrying capacity of every cube of inch base material.The whole block material through applying that will contain various load type palladium catalysts is packed in the stainless steel tube of 1 inch diameter, with air stream with air speed 630000 hours ^-1Pass through with direction perpendicular to the opening surface of cellular thing.The ozone concentration that catalyst is imported and exported is measured.A kind of alumina support that uses is SRS-II γ-Al ₂O ₃(being bought by Davison company), its feature is as (about 300 meters of surface area as described in the embodiment 1 ²/ gram).Also used a kind of low surface area θ-Al ₂O ₂, it is characterized in that surface area is about 58 meters ²/ gram and average pore radius are about 80 dusts.The E-160 aluminium oxide is a kind of γ-Al ₂O ₃, it is characterized in that surface area is about 180 meters ²/ gram, average pore radius is about 47 dusts.The surface area of used cerium oxide is about 120 meters ²/ gram, average pore radius be about 28 dusts, also use the β zeolite of dealuminzation, its silica alumina ratio is about 250/1, and surface area is about 430 meters ²/ gram, a kind of surface area is about 850 meters ²The micropore charcoal of/gram is also as carrier.At last, the titanium oxide of being bought by Rhone-Poulenc company (DT51 brand) is used as carrier, it is characterized in that surface area is about 110 meters ²/ gram.The results are summarized in the Table V, it comprises relative weight percentage, the carrying capacity on cellular thing of various catalytic components, first conversion ratio and 45 minutes conversion ratios of ozone of ozone.Table V ozone conversion results (the cellular thing of 300cpsi, air speed 630000 hours ^-1, water 0.6%, the about 0.25ppm of ozone)

Catalyst	Carrying capacity (gram/inch ³)	First conversion ratio (%)	45 minutes conversion ratios (%)
Catalyst	Carrying capacity (gram/inch ³)	First conversion ratio (%)	45 minutes conversion ratios (%)	I.W.8％Pd/5％Mn/Al ₂O ₃	????1.8	????60	????55
I.W.8%Pd/5%Mn/ bottom surface area Al ₂O ₃	????1.9	????64	????60	I.W.8％Pd/5％Mn/Al ₂O ₃	????1.8	????60	????55
I.W.8%Pd/5%Mn/ bottom surface area Al ₂O ₃	????1.9	????64	????60	8%Pd/ low surface area Al ₂O ₃	????1.9	????56	????44
??8％Pd/E-160?Al ₂O ₃	????2.2	????61	????57	8%Pd/ low surface area Al ₂O ₃	????1.9	????56	????44
??8％Pd/E-160?Al ₂O ₃	????2.2	????61	????57	????4.6％Pd/CeO ₂	????1.99	????59	????58
8%Pd/ β (dealuminzation) zeolite	????1.9	????38	????32	????4.6％Pd/CeO ₂	????1.99	????59	????58
8%Pd/ β (dealuminzation) zeolite	????1.9	????38	????32	????5％Pd/C	????0.5	????63	????61
??8％Pd/DT-51?TiO ₂	????1.8	????39	????20	????5％Pd/C	????0.5	????63	????61

Embodiment 8

Below be the Carulite that preparation contains the vinyl acetate emulsion binder ^Slurries are used to apply radiator, and the adhesiveness of fabulous catalyst to aluminium radiator arranged.

With 1000

gram Carulite

^200,1500 gram deionized waters and 50 gram acetate (are pressed Carulite ^Meter 5%) in 1 gallon of ball mill, mixes, and ground 4 hours, make 90% granularity≤7 micron.After from ball mill, taking out the slurries that generate, add the 104 gram crosslinked EVA copolymers of (5% solid) NationalStarch Dur-O-Set E-646 (48% solid).By on the grinder under the condition that does not add abrasive media roll extrusion slurries a few hours make the abundant blending of adhesive.This slurries are coated on a slice aluminium base (as radiator), after under 30 ℃ dry 30 minutes, obtain fabulous adhesiveness (being that coating can not peeled off).If necessary, can use higher solidification temperature (until 150 ℃).

Embodiment 9

By various titania oxide supported platinum compositions are coated to the conversion ratio of testing carbon monoxide on the ceramic honeycomb thing described in the embodiment 6.The carrying capacity of catalyst is about 2 gram/inch ³, test was air speed 315000 hours ^-1Carry out with the air stream (35 of dew points) that the 16ppm carbon monoxide is arranged down.At the carbon monoxide-olefin polymeric on the cellular thing under 300 ℃, with containing 7%H ₂And 93%N ₂Synthesis gas reduction 3 hours.Contain TiO ₂Composition be included in 2 and 3% (weight) platinum component arranged on the P25 titanium oxide; And 2 and 3% (weight) platinum component arranged on DT51 brand titanium oxide.DT51 brand titanium oxide is bought by Rhone-Poulenc company, and its surface area is about 110 meters ²/ gram.DT52 brand titanium oxide is a kind of titanium oxide of the tungstenic that is obtained by Rhone-Poulenc, and its surface area also is about 210 meters ²/ gram.P25 brand titanium oxide is bought by Degussa company, it is characterized in that granularity is about 1 micron, and surface area is about 45～50 meters ²/ gram.The result illustrates in Figure 10.

Embodiment 10

Embodiment 10 relates to the evaluation of the CO conversion of the composition that contains aluminium oxide, cerium oxide and zeolite.Carrier is as explanation among the embodiment 7.The composition of being estimated comprises 2% (weight) platinum/low surface area θ-Al ₂O ₃2% (weight) platinum/cerium oxide; 2% (weight) platinum/SRS-II γ-Al ₂O ₃With 2% (weight) platinum/β zeolite.The result illustrates in Figure 11.

Embodiment 11

Measured the CO conversion ratio of following composition and the relation of temperature, composition contains 2% (weight) Pt/SRS-II γ-Al ₂O ₃With 2% (weight) Pt/ZSM-5 zeolite; Press shown in the embodiment 4, composition is coated on the 1993 Nissan Alfima radiators, and presses the same steps as test CO that uses among the embodiment 4.The result illustrates in Fig. 9.

Embodiment 12

The 0.659 platinic hydroxide solution that restrains the amine solubilising that contains 17.75% (weight) platinum (by metal platinum) slowly is added to 20 of glass beaker to be restrained in the aqueous slurry of 11.7% (weight) titanium oxide sols.There is the bulk metal core sample of the long 1 inch abscess of 400 diameter 1 inch to immerse in the slurries every square of inch.On the bulk metal that applies, blow air to clean the duct, then under 110 ℃ with dry 3 hours of bulk metal.Subsequently bulk metal is immersed in the slurries once more, repeat with air purge duct and dry down at 110 ℃.With the bulk metal of twice coating 300 ℃ of following roastings 2 hours.Uncoated bulk metal weighs 12.36 grams.After the dip-coating for the first time, weight is 14.06 grams, and dry for the first time back weight is 12.6 grams, and weight is 14.38 grams after the dip-coating for the second time, and weight is 13.05 grams after the roasting, illustrates that net gain is 0.69 gram.By metal, the bulk metal through applying has 72 gram/Foot ³Platinum is called 72pt/Ti.Catalyst is estimated in containing the air stream of 20ppm carbon monoxide, and its gas flow rate is 36.6 liters/minute.After this was just estimated, the catalyst core was under 300 ℃, and reduction is 12 hours in the gaseous mixture that contains 7% hydrogen and 93% nitrogen, and the result who repeats processing is contained the air stream of 20ppm carbon monoxide estimates.The bulk metal of the coating through reducing is called 72Pt/Ti/R.Use a kind of like this 400 hole/inch that have then ²(cpsi) the core product that bulk ceramics makes are estimated above-mentioned slurries; This core is with 40 gram/Foot ³Weight ratio is 5: 1 Pt/Rh and 2 gram/inch ³ES-160 (aluminium oxide) precoating, core have a hole, 11 hole * 10 * 0.75 inch long whole, are called 33Pt/7Rh/Al; The core of precoating is immersed in the above-mentioned slurries, and blow air and make the duct cleaning.This bulk ceramics was descended dry 3 hours at 110 ℃, then 300 ℃ of following roastings 2 hours.The catalyst substrate that contains first platinum and rhodium layer weighs 2.19 grams.Weight is 3.40 grams after the dip-coating for the first time, is 2.38 grams after the roasting, illustrates that net gain is 0.19 gram, and it is equivalent to 0.90 gram/cube inch platinum/titanium oxide slurries.By platinum, the ceramic core of dip-coating contains 74 gram platinum/cube Foot, is called 74Pt/Ti//Pt/Rh.The result illustrates in Figure 12.

Embodiment 13

Described in above-mentioned embodiment 12, platinum/titanium catalyst is used for containing the air stream of 4ppm propane and 4ppm propylene, and air speed is 650000 hours ^-1By used integer catalyzer and base material, platinum and titanium catalyst have 72 gram platinum/cube Foot.Mention as embodiment 13, on the ceramic honeycomb thing, estimate.65 ℃ of following propylene conversion is 16.7%; Be 19% under 70 ℃; Be 23.8% under 75 ℃; Be 28.6% under 80 ℃; Be 35.7% under 85 ℃; Be to be 47.6% under 40.5% and 105 ℃ under 95 ℃.

Embodiment 14

Embodiment 14 is illustrative examples of platinum component/titanium dioxide carrier.The platinum that this embodiment explanation is loaded on the titanium oxide has advantages of high activity to the oxidation of carbon monoxide and hydro carbons.Making the catalyst that the composition that contains 5.0% (weight) platinum component (by the weight of platinum and titanium oxide) makes with the colloid titanium oxide sol estimates.The form of platinum with the platinic hydroxide solution of amine solubilising added in the titanium oxide.Be added to it in the titanium oxide slurries of colloid or be added in the titanium dioxide powder, make the slurries of platiniferous and titanium oxide.Slurries are coated on the bulk ceramics that contains 400 abscesses/square Foot (cpsi).The coated weight of sample is at 0.8～1.0 gram/inch ³Bulk ceramics through applying is under 300 ℃, and roasting is 2 hours in air, then reduction.Under 300 ℃, reduction is 12 hours in the gas that contains 7% hydrogen and 93% nitrogen.The titanium oxide slurries of colloid contain 10% (weight) titanium oxide in aqueous medium.The nominal particle size of titanium oxide is 2～5 nanometers.

The conversion ratio of measure CO in containing the air stream of 20ppm CO.Between room temperature to 110 ℃, between air speed 300000 to 650000VHSH, change in the flow velocity different experiments of carbon monoxide.Used air makes air heat by water-bath for from the purifying air of air bottle.Under the occasion of research temperature, the relative humidity under the room temperature (25 ℃) changes between 0～100% humidity.The air stream that will contain carbon monoxide was with air speed 650000 hours ^-1By the bulk ceramics that applies with catalytic component.

Figure 13 has represented a result of study with the relation of the conversion ratio of the air measurement carbon monoxide that contains the 20ppm carbon monoxide and temperature, and it has compared at 300 ℃ down with 12 hours the above-mentioned platinum/titanium oxide (Pt/Ti-R) of reducing gas reduction and unreduced platinum/titanium oxide catalyst (Pt/Ti) coating that contain 7% hydrogen and 93% nitrogen.Figure 13 explanation has tangible advantage when using the catalyst of reduction.

Figure 14 has illustrated through the comparison of the catalyst of the palladium/titanium oxide of reduction and different carriers, has comprised platinum/tin oxide (Pt/Sn), platinum/zinc oxide (Pt/Zn) and platinum/cerium oxide (Pt/Ce).All samples are reduction under these conditions all.The flow velocity that contains the air of carbon monoxide is 650000shsv.As what can find out, than the platinum on various other carrier materials much higher conversion results is arranged at the reduction platinum on the colloid titanium oxide.

Measured the oxidation of hydro carbons with 6ppm propylene/air mixture.Propylene/air stream passes through integer catalyzer with air speed 300000vhsv under room temperature to 110 ℃.Measured the density of propylene of catalyst front and back with flame ionization gas detector.The result is compiled in Figure 15.Used carrier is 5% (weight), by metal platinum and yittrium oxide Y ₂O ₃Meter.Between reducing catalyst and raw catalyst, compare.As shown in Figure 15, the reduction of catalyst has significantly propylene conversion increases.

Above-mentioned platinum/titanium oxide catalyst is under 500 ℃, and reduction is 1 hour in the mist that contains 7% hydrogen and 93% nitrogen.Assessed the conversion ratio of carbon monoxide in the air that be 0% in relative humidity, flow velocity is 500000vhsv.Whether the evaluation of carrying out is reversible with the reduction of determining catalyst.At first evaluate catalysts is 22 ℃ of abilities that transform carbon monoxide down.As shown in Figure 16, the initial carbon monoxide conversion ratio of catalyst is about 53%, drops to 30% after about 200 minutes.In the time of 200 minutes, air and carbon monoxide are heated to 50 ℃, the conversion ratio of carbon monoxide is increased to 65%.Again catalyst is heated to 100 ℃ in air and carbon monoxide, and kept 1 hour down, then cool to room temperature (about 25 ℃) in air at 100 ℃.At first, during about 225～400 minutes, conversion ratio drops to about 30%.Continue to estimate 1200 minutes under 100 ℃, the conversion ratio of Ce Lianging is about 40% at this moment.Under 50 ℃, carried out parallel study.In the time of about 225 minutes, conversion ratio is about 65%.After 1200 minutes, in fact conversion ratio is raised to about 75%.This embodiment shows that the reduction of catalyst makes the permanent raising of activity of such catalysts.

Embodiment 15

Embodiment 15 is used for illustrating the platinum and/or the conversion of ozone at room temperature of palladium component of manganese oxide/zirconia co-precipitation load.This embodiment illustrates that also the platinum catalyst that catalysis ozone changes into oxygen also makes simultaneously carbon monoxide and hydrocarbon oxidation.Make by manganese and zirconium metal manganese oxide/zirconia mixed oxide in respect of 1: 1 and 1: 4 weight ratio.Make co-precipitation by above-mentioned list of references US 5283041 disclosed steps.Make 3% and 6%Pt/ manganese/zirconia catalyst (weight ratio of manganese and zirconium 1: 4) by embodiment 4 is described.With SBA-150 γ-Al ₂O ₃(weight by mixed oxide powder counts 10%) as adhesive, adds with the form (5% (weight) alumina powder) of 40% aqueous slurry that contains acetate, and is ground to 90% granularity less than 10 microns.Prepare 6% (weight) Pd catalyst with the aqueous solution dipping manganese/zirconia material (weight ratio of manganese and zirconium is 1: 1) that contains the acid chloride tetramine to the method that begins wetting point., after 2 hours catalyst is mixed with the Nalco#1056 Ludox (10% (weight) of catalyst fines) and the water of capacity in ball mill with powder for drying with 450 ℃ of following roastings, obtain the slurries of about 35% solid.Milled mixtures then is until 90% granularity is less than 10 microns.Each sample was reduced 3 hours under 300 ℃ with the mixture that contains 7% hydrogen and 93% nitrogen.Carry out various evaluations, to determine the conversion ratio of ozone on the little core of coating radiator of 1993Altima radiator, about 1/2 inch of this radiator * 7/8 inch * 1 inch is thick.Estimate and carry out under the following conditions; Room temperature is used 1 inch diameter stainless steel tube shown in embodiment 7,630000 hours ^-1The room air of air speed (air that the laboratory provides), the inlet concentration of ozone is 0.25ppm.The result lists Table VI in.Table VI ozone initial activity result (39Cpsi Nissan Altima core, 630000 hours ^-1

Air speed; 25 ℃; 0.25ppm O ₃Room air-Yue 0.6% water) the first conversion ratio of core catalyst loading is 45 minutes

(gram/inch ³) (%) conversion ratio (%) 1 3%Pt/MnO ₂/ ZrO ₂(1: 4) is 450 0.7 70.7 65.8

℃ following roasting 2 3%Pt/MnO ₂/ ZrO ₂(1: 4) is 450 0.7 70.5 63.7

℃ following roasting; Reduction 3 6%Pt/MnO under 300 ℃ ₂/ ZrO ₂(1: 4) is 450 0.68 68.2 62.3

℃ following roasting; 4 6%Pt/MnO ₂/ ZrO ₂(1: 4) is 450 0.66 66 55.8

℃ following roasting; Reduction 5 6%Pt/MnO under 300 ℃ ₂/ ZrO ₂(1: 1) 10% 0.39 38.3 21.1

(weight) Nalco 10566 MnO ₂/ ZrO ₂(1: 1) 10% (weight) 0.41 58.3 44.9

Nalco 10567 MnO ₂/ ZrO ₂(1: 1) 10% (weight) 0.37 55.8 41.2

Nalco 10568 3%Pt/ZrO ₂/ SiO ₂At 450 ℃ following 0.79 27.4 10

Roasting; 9 3%Pt/ZrO ₂/ SiO ₂At 450 ℃ following 0.76 54.2 30.1

Roasting; 300 ℃ of reduction down

As from Table VI can, only have the core 1 and 2 of 3%Pt to have fabulous initial ozone conversion ratio, after 45 minutes, reducing catalyst and unreduced catalyst all have fabulous ozone conversion ratio.Have the core 3 and 4 of 6%Pt content that fabulous result is also arranged, but the result who is not so good as 3%Pt is good.Core 5～7 explanation makes that ozone transforms various other carrier materials.Core 5 has the palladium that is loaded in manganese oxide/zirconia co-precipitation, obtain lower than what estimate, but still significant ozone conversion ratio.Core 6 and 7 uses co-precipitation but does not contain noble metal, and they also have tangible ozone conversion ratio.But it is good like that platinum also of no use is made catalyst.Core 8 is platinum/zirconia/silica support, and they are reduction through roasting but, and core 9 is platinum/zirconia/silica support, and they are reduced.Core 8 and 9 obtains identical conversion ratio, but still the conversion ratio that obtains not as platinum/co-precipitation is good like that.

In addition, on the little core of 39cpsi radiator, as mentioned above to 3% and 6%Pt/ manganese/Zirconia carrier estimated the conversion of carbon monoxide.Reduction and unreduced sample have been estimated.In order to illustrate, also list reduction with unreduced platinum/zirconia/silica and platinum/Carulite ^As can be seen from Figure 12, when comparing with other embodiment, the result of 3% reduction platinum/manganese/Zirconia carrier is best.

Embodiment 16 (Comparative Examples)

Under room temperature and 80 ℃, measured the conversion ratio of ozone on 1995 uncoated FordContour radiators with following step: in 10 miles per hour linear speeds (air speed 630000 hours ^-1) the air stream that will contain down ozone (0.25ppm) blows over the radiator duct; Measure the radiator back side then and discharge the ozone concentration of gas.The dew point of air stream is about 35 °F.Cooling agent through heating does not circulate by radiator, but if necessary, air stream is heated with the heating tape, to reach required radiator temperature.As described in example 7 above, in 1 inch stainless steel tube, finish another test with uncoated 0.75 inch (length) * 0.5 inch (wide) * 1.0 inch (thick) Ford Taurus radiator " little core ".With the heating of air stream, reach required radiator temperature with the heating tape.For these two tests, all do not observe ozone up to 120 ℃ and decompose.

Embodiment 17

Under different temperatures,, measured the 3%Pt/TiO of reduction in the presence of the 15ppmCO and do not contain under the 15ppm CO ₂The ozone conversion ratio of catalyst.Degussa P25 brand titanium oxide is as carrier, and it is characterized by granularity is about 1 micron, and surface area is about 45～50 meters ²/ gram.Catalyst-coated is arrived on the cellular thing of 300cpsi pottery (cordierite), and reduced 3 hours down at 300 ℃ with the gaseous mixture that contains 7% hydrogen and 93% nitrogen.Test is by the carrying out of describing in the foregoing description 7.With the heating tape air stream (35 of dew points) is heated to required temperature.As can be seen from Figure 18, observe the ozone conversion ratio from 25 ℃ to 80 ℃ and have a net increase of about 5%.The existence of CO increases the ozone conversion ratio.

Embodiment 18

About 28 gram platinum amine hydroxide (Pt (A) salt) are diluted in the 100 gram Versal GL aluminium oxide that the 80 gram solution impregnation that obtain in the water are obtained by LaRoche industrial group.Add 5 gram acetate, Pt is fixed on the alumina surface.After mixing half an hour, by adding water, the catalyst that will soak Pt is made the slurries of about 40% solid.With slurries ball milling 2 hours.The granularity of measuring 90% is less than 10 microns.On diameter 1.5 inch, long 1.0 inch 400cpsi ceramic base materials, obtaining dry back wash coat carrying capacity is about 0.65 gram/inch with catalyst-coated ³Catalyst then 100 ℃ down dry, 550 ℃ of following roastings 2 hours.Press that embodiment 21 describes, under 60～100 ℃, the C of detecting catalyst in dry air ₃H ₆Oxidation susceptibility.

An above-mentioned part is through the Pt/Al of roasting ₂O ₃Sample is also at 7%H ₂/ N ₂In, reduced 1 hour down at 400 ℃.By at H ₂/ N ₂Gas flow rate is under 500 ml/min, the temperature of catalyst is risen to 400 ℃ from 25 ℃ reduce.Programming rate is about 5 ℃/minute.Catalyst is cooled to room temperature, presses then that embodiment 21 describes, the C of detecting catalyst ₃H ₆Oxidation susceptibility.

Embodiment 19

6.8 gram ammonium tungstates are dissolved in 30 ml waters, and the pH value is adjusted to 10, with solution impregnation to 50 gram VersalGL aluminium oxide (LaRoche industrial group).This material is dry under 100 ℃, and 550 ℃ of following roastings 2 hours.With about 10% (weight metal) W/Al ₂O ₃Cool to room temperature, and with 13.7 the gram platinum amine hydroxide (18.3Pt) dipping.Add 2.5 gram acetate and fully mixing.Catalyst is made the slurries that contain 35% solid by adding water then.Then slurries are coated on the ceramic base material of 400cpsi 1.5 inch * 1.0 inch diameters, the wash coat carrying capacity of dry rear catalyst is 0.79 gram/inch ³The dry then catalyst that applies, and 550 ℃ of following roastings 2 hours.Through the catalyst of roasting at C ₃H ₆In dry air, 60～100 ℃ of tests down.

Embodiment 20

6.8 gram perrhenic acid (36%Re solution) further are diluted in the water, make 10% perrhenic acid solution.On this solution impregnation to 25 gram VersalGL aluminium oxide.With the dipping the aluminium oxide drying, and under 550 ℃ with powder roasting 2 hours.Then further with 6.85 gram platinum amine hydroxide solution (it is 18.3% that GOLD FROM PLATING SOLUTION belongs to Pt) dippings 10% (weight) Re/Al through dipping ₂O ₃Powder.Add 5 gram acetate, mix half an hour.By adding the slurries that water obtains 28% solid.With slurries ball milling 2 hours, be coated to then on the 400cpsi ceramic base material of diameter 1.5 inch * length 1.0 inch, dry rear catalyst wash coat carrying capacity is 0.51 gram/inch ³The base material that scribbles catalyst is dry under 100 ℃, 550 ℃ of following roastings 2 hours.The catalyst of calcined form is under 60～100 ℃, with containing 60ppmC ₃H ₆Dry air test.

Embodiment 21

Embodiment

18,19 and 20 catalyst are tested in microreactor.The catalyst sample size is diameter 0.5 inch and length 0.4 inch.Charging is by 60ppm C ₃H ₆Form 25～100 ℃ of temperature with dry air.Under 60,70,80,90 and 100 ℃, under limit, measure C ₃H ₆Content.The result is compiled in the Table VII.

Table VII C ₃H ₆Conversion results

Catalyst	Pt/Al ₂O ₃Roasting (embodiment 18)	Pt/Al ₂O ₃Roasting and reduction (embodiment 18)	Pt/10％W/ Al ₂O ₃Roasting (embodiment 19)	Pt/10％Re/ Al ₂O ₃Roasting (embodiment 20)
Catalyst	Pt/Al ₂O ₃Roasting (embodiment 18)	Pt/Al ₂O ₃Roasting and reduction (embodiment 18)	Pt/10％W/ Al ₂O ₃Roasting (embodiment 19)	Pt/10％Re/ Al ₂O ₃Roasting (embodiment 20)	C ₃H ₆Conversion ratio, %@
??60℃	?????0	????10	????9	????11	C ₃H ₆Conversion ratio, %@
??60℃	?????0	????10	????9	????11	??70℃	?????7	????22	???17	????27
??80℃	?????20	????50	???39	????45	??70℃	?????7	????22	???17	????27
??80℃	?????20	????50	???39	????45	??90℃	?????38	????70	???65	????64
??100℃	?????60	????83	???82	????83	??90℃	?????38	????70	???65	????64

Can know from last table and to find out that the adding of the oxide of W or Re makes the Pt/Al of calcined form ₂O ₃Activity increase.When catalyst at 400 ℃ of down reduction after 1 hour, the Pt/Al of roasting ₂O ₃C ₃H ₆Conversion ratio significantly improves.The calcined catalyst that adds the oxide of W or Re also observes active increasing.

Embodiment 22

This is to use MnSO ₄The example of preparation high surface cryptomelane.

KMnO ₄: MnSO ₄: the mol ratio of acetate is 1: 1.43: 5.72.Mn molar concentration in solution is before mixing:

0.44M????KMnO ₄

0.50M????MnSO ₄

FW KMnO ₄=158.04 gram/moles

FW MnSO ₄H ₂O=169.01 gram/mole

FW C ₂H ₄O=60.0 gram/mole

Carry out following steps:

1. make 3.50 moles of (553 gram) KMnO ₄Solution in 8.05 liters of deionized waters, and be heated to 68 ℃.

2. restrain glacial acetic acid and be diluted to 10.5 liters with 1260 and make 10.5 liters of 2N second vinegar with deionized water.The density of this solution is 1.01 grams per milliliters.

3. 5.00 moles of weighings (846 gram) manganese sulfate hydrate (MnSO ₄H ₂O), and be dissolved in the above-mentioned 10115 gram 2N acetic acid solutions, and be heated to 40 ℃.

4. under constantly stirring, in 15 minutes, solution 3 is added in the solution 1.After adding, by following rate of heat addition heating slurries

Afternoon, 1:06 was 69.4 ℃

Afternoon, 1:07 was 71.2 ℃

Afternoon, 1:11 was 74.5 ℃

Afternoon, 1:15 was 77.3 ℃

Afternoon, 1:18 was 80.2 ℃

Afternoon, 1:23 was 83.9 ℃

Afternoon, 1:25 was 86.7 ℃

Afternoon, 1:28 was 88.9 ℃

5. 1:28 in the afternoon takes out about 100 milliliters of slurries from container, and filters on Buchner funnel rapidly, with 2 liters of deionized waters washings, then in stove 100 ℃ dry down.The BET Multi-Point surface area of working sample is 259 meters ²/ gram.

Embodiment 23

This is with Mn (CH ₃COO) ₂An example of preparation high surface cryptomelane.KMnO ₄: Mn (CH ₃COO) ₂: the mol ratio of acetate is 1: 1.43: 5.72FW KMnO ₄=158.04 gram/mole Aldrich Lot#08824MGFW Mn (CH ₃COO) ₂H ₂O=245.09 gram/mole Aldrich Lot#08722HGFW C ₂H ₄O ₂=60.0 gram/moles

1. make 2.0 moles of (316 gram) KMnO ₄Solution in 4.6 liters of deionized waters, and on heating plate, be heated to 60 ℃.

2.720 the gram glacial acetic acid is diluted to 6.0 liters with deionized water and makes 6.0 liters of 2N acetate.The density of this solution is 1.01 grams per milliliters.

3. take by weighing 2.86 moles of (700 gram) manganese acetate (II) tetrahydrate [Mn (CH ₃COO) ₂` ₄H ₂O], and be dissolved in the above-mentioned 5780 gram 2N acetic acid solutions (in reactor).And in reactor, be heated to 60 ℃.4. under 62～63 ℃, under constantly stirring, solution 1 is added in the solution 3.After adding, by the following slurries that heat gradually:

Afternoon, 3:58 was 82.0 ℃

Afternoon, 4:02 was 86.5 ℃

Afternoon, 4:06 was 87.0 ℃

Afternoon, 4:08 was 87.1 ℃

After stopping heating, 10 liters of deionized waters are pumped into make the slurries chilling in the container.4:13 in the afternoon, slurries are cooled to 58 ℃.

Slurries filter on Buchner funnel.With the filter cake that generates once more pulp in 12 liters of deionized waters, stir in 5 GPBs with mechanical agitator and to spend the night.Filter product morning once more through washing, dry down at 100 ℃ in stove then.The BET Multi-Point surface area of working sample is 296 meters ²/ gram.The cryptomelane that generates characterizes with the XRD spectra of Figure 20.Estimate that its IR spectrogram is similar to shown in Figure 19.

Embodiment 24

It below is the explanation that this embodiment is used to measure the ozone test method of ozone percentage resolution ratio.Testing equipment comprises that ozone generator, gas flow rate control appliance, drum bubble are counted, Cold Mirrors is showed a hygrometer and ozone detector, measures the ozone percentage that the catalyst sample decomposes with it.Ozone is to utilize ozone generator to produce on the spot in the air-flow of being made up of air and water vapour.Measure the concentration of ozone with ozone detector, and measure water content with cold-spot hygrometer.Be that the inlet concentration of ozone in about 1.5 liters of/minute air-flows of 15～17 ℃ is that the sample of 4.5～7ppm is tested at dew point under 25 ℃.-25/+45 order particle is contained in internal diameter 1/4 inch Pyrex ^Test between the glass wool plug in the glass tube.The sample of test is contained in 1 centimetre of part in the glass tube.

The sample of test need reach the conversion stable state in 2～16 hours usually.When on-test, the common conversion ratio of sample slowly drops to the conversion ratio of " flattening " then near 100%, and (48 hours) keep stable between longer-term.After reaching stable state, calculate conversion ratio in order to following equation: ozone conversion ratio %=[(1-(by the ozone concentration behind the catalyst)/(by the ozone concentration before the catalyst)] * 100.

The conversion ratio that carries out the ozone decomposition run on the sample of embodiment 22 is 58%.

The conversion ratio that carries out the ozone decomposition run on the sample of embodiment 23 is 85%.

Embodiment 25

This embodiment attempts to illustrate that the method for embodiment 10 makes the high surface potassium manganese ore of " cleaning ", and its ozone decomposability can not further improve by roasting and washing.Shown in the embodiment 23 20 gram sample 200 ℃ of following roastings 1 hour, is cooled to room temperature in air, washing in 30 minutes by slurries are stirred in 200 ml deionized water under 100 ℃ then.Filter the product that generates, dry in stove under 100 ℃.The BET multiple spot surface area of working sample is 265 meters ²/ gram.The ozone decomposition run conversion ratio of sample is 85%.Compare explanation with the test of embodiment 23 samples, the washing of the sample of embodiment 23 and roasting transform ozone does not have any benefit.

Embodiment 26

Obtain high surface potassium manganese ore sample by the commercial supplier place, and through roasting and/or washing modification.The ozone decomposability of the powder of buying by the test of the method for embodiment 24 and the powder of modification, and measure sign with X-ray powder diffraction, infrared spectrum and nitrogen adsorption method BET surface area.

Embodiment 26a

(Baltimore MD) in deionized water, 60 ℃ of washings 30 minutes down, filters, and cleans also dry in 100 ℃ of following stoves for Chemetals, Inc. with the high surface potassium manganese ore sample of commercial offers.The ozone conversion ratio of buying sample is 64%, and by contrast, the ozone conversion ratio of washing sample is 79%.Washing can not change (223 meters of the surface area of sample or crystal structures ²/ gram cryptomelane), as using nitrogen adsorption method and x-ray powder diffraction to measure respectively.But The results of FT-IR shows that the peak of 1220 and 1320 wave numbers disappears in the spectrogram of the sample through washing.Illustrate that sulfate anion is removed.

Embodiment 26b

(Baltimore is MD) 300 ℃ of following roastings 4 hours with 400 ℃ of following roastings 8 hours for Chemetals, Inc. with the high surface potassium manganese ore sample of commercial offers.The ozone conversion ratio of buying sample is 44%, by contrast, is 71% at the ozone conversion ratio of the sample of 300 ℃ of following roastings, and is 75% at the ozone conversion ratio of the sample of 400 ℃ of roastings.Roasting can obviously not change (334 meters of the surface area of 300 ℃ or 400 ℃ samples or crystal structures ²/ gram potassium manganese ore).In 400 ℃ of samples, detect micro-MnO ₂Roasting makes sample generation deshydroxyization.The results of FT-IR shows that the band intensity that belongs to 2700～3700 wave numbers of surface hydroxyl descends.

Embodiment 27

Found Pd black (containing metal palladium and oxide) is added in the high surface potassium manganese ore and can significantly improve the ozone decomposability.Preparation contains the sample that the potassium manganese ore (samples of 300 ℃ of roastings describing among the embodiment 26b) buied with powder (1) commerce and (2) are synthetic in embodiment 23, deceive powder at the Pd of 1 hour high surface potassium manganese ore physical mixed of 200 ℃ of following roastings.By under drying regime, black the mixing by weight 1: 4 with the potassium manganese ore of Pd being prepared sample.With the drying composite vibration, till color evenly.In beaker, the deionized water of some is added in the mixture, make the suspension of 20～30% solid contents.With the aggregate in the stirring rod Mechanical Crushing suspension.With suspension at Bransonic ^Ultrasonic processing is 10 minutes in the 5210 type ultrasonic cleaners, and in stove, 120～140 ℃ following dry about 8 hours then.

The ozone conversion ratio of the potassium manganese ore of buying in the commerce of 300 ℃ of following roastings is 71%, as (the embodiment 26b) that measures on the powdered reaction device.With the ozone conversion ratio of black this product sample that mixes of 20% (weight) Pd is 88%.

The ozone conversion ratio of the potassium manganese ore sample of preparation in embodiment 23 200 ℃ of following roastings is 85%.Add the black back of 20% (weight) Pd ozone conversion ratio and bring up to 97%.

Claims

1. method of handling atmosphere, comprising making the vehicle that has at least one atmosphere contact surface and pollute treatment compositions by atmosphere, composition contains and is selected from active material and the polymer adhesive that is in described lip-deep carbon monoxide-olefin polymeric and adsorbing composition.

2. a method of handling atmosphere is passed through atmosphere comprising making to have at least one atmosphere contact surface and be used to handle the vehicle that contains the pollution treatment compositions on the described surface of being in of hydrocarbon pollutant.

3. method of handling atmosphere, comprising making the vehicle that has at least one atmosphere contact surface and pollute treatment compositions pass through atmosphere, composition contains and is selected from the active material that is in described lip-deep carbon monoxide-olefin polymeric and adsorbing composition, this pollution treatment compositions is on the described surface, and wherein carbon monoxide-olefin polymeric contains the catalytically-active materials that is selected from least a platinum group metal component, golden component and silver components.

4. according to the method for claim 1,2 or 3, wherein vehicle is a motor vehicle.

5. according to the method for claim 4, wherein vehicle is selected from automobile, truck, train, aircraft, canoe, big ship, motorcycle.

6. according to the method for claim 5, wherein vehicle also comprises hood and the engine that is stated from the hood.

7. according to the method for claim 6, wherein vehicle also comprises the cooling device of engine.

8. according to the method for claim 7, wherein the cooling device of engine is the cooling system that is selected from liquid-cooling system and atmospheric air cooling system.

9. according to the method for claim 8, wherein cooling system is to comprise that a plurality of and engine is the atmospheric air cooling system of the atmosphere contact heat spreader of heat exchanging relation.

10. according to the method for claim 9, wherein the atmosphere contact heat spreader comprises having the atmosphere contact surface that pollutes treatment compositions.

11. according to the method for claim 8, wherein cooling system is the liquid-cooling system with radiator of the atmosphere contact surface that is stated from the hood and has subsidiary pollution treatment compositions.

12. according to the method for claim 8, wherein cooling system is a liquid-cooling system, it has the subsidiary fan that pollutes the atmosphere contact surface of treatment compositions.

13. according to the method for claim 12, the fan pollution treatment compositions that comprises flabellum and have on it wherein.

14. according to the process of claim 1 wherein that polluting treatment compositions is at least a composition that is selected from carbon monoxide-olefin polymeric and adsorbing composition.

15., wherein also comprise polymeric binder is added to the step of polluting treatment compositions according to the method for claim 14.

16., wherein also comprise polymeric binder is added to the step of polluting treatment compositions according to the method for claim 2.

17., wherein also comprise polymeric latex binder is added to the step of polluting treatment compositions according to the method for claim 1,15 or 16.

18. according to the method for claim 17, wherein polymeric binder comprises the polymeric compositions that contains the polymer that is selected from thermoplasticity and thermosetting polymer.

19. according to the method for claim 17, wherein polymeric binder comprises and contains the polymeric compositions that is selected from following polymers: polyethylene, polypropylene, polyolefin copolymer, polyisoprene, polybutadiene, polybutadiene copolymer, chlorinated rubber, acrylonitrile-butadiene rubber, polychlorobutadiene, ethylene-propylene-diene elastomer, polystyrene, polyacrylate, polymethacrylates, polyacrylonitrile, poly-(vinyl esters), poly-(vinyl halide), polyamide, cellulosic polymer, polyimides, acrylic resin, the styrene-acrylonitrile copolymer acid resin, polyvinyl alcohol, thermoplastic polyester, thermosetting polyester, polyphenylene oxide, polyphenylene sulfide, the polymer of fluoridizing, polyamide, phenolic resins and epoxy resin, polyurethane, silicone polymer and EVAc.

20. method according to claim 14, wherein carbon monoxide-olefin polymeric comprises the carrier material that is selected from refractory oxide carrier, manganese component, charcoal and manganese oxide and zirconic coprecipitate, at least a catalytically-active materials that is selected from least a platinum group metal component, golden component, silver components, manganese component.

21. method according to claim 2, wherein carbon monoxide-olefin polymeric comprises the carrier material that is selected from refractory oxide carrier, manganese component, charcoal and manganese oxide and zirconic coprecipitate, at least a catalytically-active materials that is selected from least a platinum group metal component, golden component, silver components, manganese component.

22. according to the method for claim 3,20 or 21, wherein catalytically-active materials is selected from least a platinum group metal component, golden component, silver components, this method also comprises the step of reducing catalyst composition.

23., wherein pollute treatment compositions and also comprise carrier according to the method for claim 3.

24. according to the method for claim 20,21 or 23, wherein carrier comprises manganese oxide and zirconia.

25. according to the method for claim 24, wherein catalytically-active materials is selected from palladium and platinum component.

26. according to the method for claim 25, wherein catalytically-active materials is the platinum component.

27., wherein also comprise the step of reducing catalyst composition according to the method for claim 26.

28. according to the method for claim 1,3 or 14, wherein carbon monoxide-olefin polymeric comprises refractory oxide carrier, at least a platinum group metal of platinum and palladium and the manganese component that optionally exists of being selected from.

29. according to the method for claim 28, wherein carbon monoxide-olefin polymeric comprises polymer adhesive.

30. according to the method for claim 29, wherein carbon monoxide-olefin polymeric comprises 65-99% (weight) refractory oxide carrier, is at least a platinum group metal of benchmark 0.5-15% (weight) and 0.5-20% (weight) polymer adhesive in the weight metal.

31。According to the method for claim 28, wherein refractory oxide is selected from aluminium oxide, silica, titanium dioxide, ceria, zirconia, chromium oxide and composition thereof.

32. according to the method for claim 31, wherein refractory oxide is a TiO 2 sol.

33., wherein also comprise the step of calcined catalyst composition according to the method for claim 1,3 or 14.

34. according to the method for claim 1,3 or 14, wherein carbon monoxide-olefin polymeric comprises active carbon.

35. according to the method for claim 1,3 or 14, wherein carbon monoxide-olefin polymeric comprises the manganese component.

36. according to the method for claim 35, wherein carbon monoxide-olefin polymeric comprises manganese dioxide and cupric oxide.

37., wherein also comprise the step of calcined catalyst composition according to the method for claim 36.

38., wherein also be included in the step of the catalytic reaction of finishing ozone in the atmosphere according to the method for claim 3 or 14.

39., wherein also be included in CO and have the step that down ozone is reacted according to the method for claim 38.

40., wherein also be included in the step of the catalytic reaction of finishing CO in the atmosphere according to the method for claim 3 or 14.

41., wherein also comprise the step that makes hydrocarbon and/or partial oxidation of hydrocarbons generation catalytic reaction according to the method for claim 1,3 or 14.

42. according to the method for claim 41, wherein hydrocarbon is a unsaturated hydrocarbons.

43. according to the method for claim 42, wherein unsaturated hydrocarbons is selected from unsaturated olefinic compound.

44. according to the method for claim 43, wherein the olefin(e) compound contains 2-8 carbon atom.

45. according to the method for claim 44, wherein unsaturated olefinic compound is selected from propylene and butylene.

46. according to claim 1,3 or 14 method, comprising the step of using carbon monoxide-olefin polymeric catalysis CO and ozone to react, carbon monoxide-olefin polymeric contains the carrier that is selected from ceria, alundum (Al, titanium dioxide, zirconia, manganese oxide and zirconic coprecipitate and composition thereof; The platinum group metal comprises the metal component that is selected from palladium, platinum and composition thereof.

47., wherein also comprise the surface being maintained at about 20-105 ℃ step according to the method for claim 1,3 or 14.

48. according to the method for claim 1,3 or 14, wherein the atmosphere contact surface directly contacts with atmosphere when vehicle passes through atmosphere.

49. according to the method for claim 1,3 or 14, wherein at the relative velocity of vehicle atmosphere contact surface and atmosphere when the atmosphere up to 100 miles per hours.

50. according to the method for claim 49, wherein at the relative velocity of vehicle atmosphere contact surface and atmosphere when the atmosphere up to the 5-60 miles per hour.

51., comprise also that wherein heating atmosphere contact surface with make CO in atmosphere the step of catalytic reaction takes place according to the method for claim 3 or 14.

52., wherein also comprise heating atmosphere contact surface and the step that in atmosphere, makes hydrocarbon generation catalytic reaction according to the method for claim 1,3 or 14.

53., wherein also comprise heating atmosphere contact surface and the step that makes the nitrogen oxide generation catalytic reaction in the atmosphere according to the method for claim 1,3 or 14.

54., wherein also comprise the step that is selected from the pollutant of hydrocarbon, sulfur oxide, particulate matter and CO in the absorption atmosphere according to the method for claim 1,3 or 14.

55. according to the method for claim 6, wherein engine is a genemotor.

56., wherein also comprise energy heating atmosphere contact surface and the step that is positioned at this lip-deep pollution treatment compositions by electro-motor according to the method for claim 55.

57. according to the method for claim 1,3 or 14, wherein the atmosphere contact surface is selected from the outer surface of air-conditioning condenser, radiator, radiator fan, charge air cooler and deep bead.

58. according to the method for claim 1,3 or 14, wherein vehicle comprises the fluid cooling device that has the atmosphere contact surface, this method comprises makes atmosphere contact with the atmosphere contact surface.

59. according to the method for claim 58, wherein cooling device is selected from air-conditioning condenser, radiator, charge air cooler, oil cooler, speed changer cooler and power-assisted steering liquid cooler.

60. equipment of handling atmosphere, comprising vehicle, this vehicle comprises mobile device, at least one atmosphere contact surface of vehicle and is positioned at this lip-deep pollution treatment compositions, and this pollution treatment compositions comprises and is selected from active material and the polymeric binder that is positioned at this lip-deep carbon monoxide-olefin polymeric and adsorbing composition.

61. an equipment of handling atmosphere, comprising vehicle, this vehicle comprises mobile device, at least one atmosphere contact surface of vehicle and is used to handle the pollution treatment compositions that contains hydrocarbon pollutant that this pollution treatment compositions is positioned on the described surface.

62. equipment of handling atmosphere, comprising vehicle, this vehicle comprises mobile device, at least one atmosphere contact surface of vehicle and pollutes treatment compositions, composition contains the active material that is selected from carbon monoxide-olefin polymeric and adsorbing composition, this pollution treatment compositions is on the described surface, and wherein carbon monoxide-olefin polymeric contains the catalytically-active materials that is selected from least a platinum group metal component, golden component and silver components.

63. according to the equipment of claim 60,61 or 62, wherein vehicle is a motor vehicle.

64. according to the equipment of claim 63, wherein vehicle is selected from automobile, truck, bus, train, aircraft, canoe, big ship, motorcycle.

65., wherein also comprise hood and the engine that is stated from the hood according to the equipment of claim 64.

66. according to the equipment of claim 65, wherein vehicle also comprises the cooling device of engine.

67. according to the equipment of claim 66, wherein the cooling device of engine is the cooling system that is selected from liquid-cooling system and atmospheric air cooling system.

68. according to the equipment of claim 67, wherein cooling system is to comprise that a plurality of and engine is the atmospheric air cooling system of the atmosphere contact heat spreader of heat exchanging relation.

69. according to the equipment of claim 68, wherein the atmosphere contact heat spreader comprises having the atmosphere contact surface that pollutes treatment compositions.

70. according to the equipment of claim 67, wherein cooling system is the liquid-cooling system with the radiator that attaches the atmosphere contact surface that pollutes treatment compositions.

71. according to the equipment of claim 67, wherein cooling system is a liquid-cooling system, it has the subsidiary fan that pollutes the atmosphere contact surface of treatment compositions.

72. according to the equipment of claim 71, the fan pollution treatment compositions that comprises flabellum and have on it wherein.

73. according to the equipment of claim 67, wherein vehicle comprises the fluid cooling device that has the atmosphere contact surface.

74. according to the equipment of claim 73, wherein cooling device is selected from air-conditioning condenser, radiator, charge air cooler, oil cooler, transmission oil cooler and power-assisted steering cooler.

75. according to the equipment of claim 61, wherein polluting treatment compositions is at least a composition that is selected from carbon monoxide-olefin polymeric and adsorbing composition.

76., wherein pollute treatment compositions and also comprise polymeric binder according to the equipment of claim 75.

77., wherein pollute treatment compositions and comprise that also polymeric binder pollutes the step of treatment compositions according to the equipment of claim 62.

78., wherein pollute treatment compositions and also comprise polymeric binder according to the equipment of claim 60,76 or 77.

79. according to the equipment of claim 78, wherein polymeric binder comprises the polymeric compositions that contains the polymer that is selected from thermoplasticity and thermosetting polymer.

80. according to the method for claim 78, wherein polymeric binder comprises and contains the polymeric compositions that is selected from following polymers: polyethylene, polypropylene, polyolefin copolymer, polyisoprene, polybutadiene, polybutadiene copolymer, chlorinated rubber, acrylonitrile-butadiene rubber, polychlorobutadiene, ethylene-propylene-diene elastomer, polystyrene, polyacrylate, polymethacrylates, polyacrylonitrile, poly-(vinyl esters), poly-(vinyl halide), polyamide, cellulosic polymer, polyimides, acrylic resin, the styrene-acrylonitrile copolymer acid resin, polyvinyl alcohol, thermoplastic polyester, thermosetting polyester, polyphenylene oxide, polyphenylene sulfide, the polymer of fluoridizing, polyamide, phenolic resins and epoxy resin, polyurethane, silicone polymer and EVAc.

81. want 60 equipment according to right, wherein carbon monoxide-olefin polymeric comprises the carrier material that is selected from refractory oxide carrier, manganese component, charcoal and manganese oxide and zirconic coprecipitate, at least a catalytically-active materials that is selected from least a platinum group metal, golden component, silver components, manganese component.

82. equipment according to claim 75, wherein carbon monoxide-olefin polymeric comprises the carrier material that is selected from refractory oxide carrier, manganese component, charcoal and manganese oxide and zirconic coprecipitate, at least a catalytically-active materials that is selected from least a platinum group metal, golden component, silver components, manganese component.

83. according to the equipment of claim 62,81 or 82, wherein catalytically-active materials is selected from least a platinum group metal component, golden component, silver components, this catalytic active component is reduced.

84., wherein pollute treatment compositions and also comprise carrier according to the equipment of claim 62.

85. according to the equipment of claim 81,82 or 84, wherein carrier comprises manganese oxide and zirconia.

86. according to the equipment of claim 85, wherein catalytically-active materials is selected from palladium and platinum component.

87. according to the equipment of claim 86, wherein catalytically-active materials is the platinum component.

88. according to the equipment of claim 86, wherein carbon monoxide-olefin polymeric is reduced.

89. according to the equipment of claim 60,62 or 75, wherein carbon monoxide-olefin polymeric comprises refractory oxide carrier, at least a platinum group metal of platinum and palladium and the manganese component that optionally exists of being selected from.

90. according to the equipment of claim 89, wherein carbon monoxide-olefin polymeric comprises polymer adhesive.

91. according to the equipment of claim 90, wherein carbon monoxide-olefin polymeric comprises 65-99% (weight) refractory oxide carrier.In the weight metal is at least a platinum group metal of benchmark 0.5-15% (weight) and 0.5-20% (weight) polymer adhesive.

92. according to the equipment of claim 89, wherein refractory oxide is selected from aluminium oxide, silica, titanium dioxide, ceria, zirconia, chromium oxide and composition thereof.

93. according to the equipment of claim 92, wherein refractory oxide is a TiO 2 sol.

94. according to the equipment of claim 92, wherein carbon monoxide-olefin polymeric is reduced.

95. according to the equipment of claim 92, wherein carbon monoxide-olefin polymeric comprises active carbon.

96. according to the equipment of claim 89, wherein carbon monoxide-olefin polymeric comprises the manganese component.

97. according to the equipment of claim 90, wherein carbon monoxide-olefin polymeric comprises manganese dioxide and cupric oxide.

98. according to the equipment of claim 60,62 or 75, wherein carbon monoxide-olefin polymeric is calcined.

99. according to the equipment of claim 60,62 or 75, wherein adsorbing composition comprises the component of at least a CaO of being selected from, charcoal, zeolite and non-zeolite molecular sieve.

100. according to the equipment of claim 63, wherein engine is a genemotor.

101., wherein also comprise energy heating atmosphere contact surface and the device that is positioned at this lip-deep pollution treatment compositions by electro-motor according to the equipment of claim 100.

102. according to the equipment of claim 63, wherein the atmosphere contact surface is selected from least a in air-conditioning condenser, radiator, radiator fan, charge air cooler and the deep bead outer surface.

103. an equipment of handling atmosphere, comprising:

A kind of vehicle, this vehicle comprises:

A kind of mobile device,

A kind of have the radiator of atmosphere contact surface and be positioned at this lip-deep pollution treatment compositions, and this pollution treatment surface is selected from:

Contain the active material that is selected from carbon monoxide-olefin polymeric and adsorbing composition and the composition of polymeric binder;

Be used to handle the composition that contains hydrocarbon pollutant;

The composition that contains the active material that is selected from carbon monoxide-olefin polymeric and adsorbing composition, wherein carbon monoxide-olefin polymeric contains the catalytically-active materials that is selected from least a platinum group metal component, golden component and silver group.

104. an equipment of handling atmosphere, comprising:

Be used to handle the composition that contains hydrocarbon pollutant;

105. an equipment of handling atmosphere, comprising:

A kind of have the air-conditioning condenser of atmosphere contact surface and be positioned at this lip-deep pollution treatment compositions, and this pollution treatment surface is selected from:

Be used to handle the composition that contains hydrocarbon pollutant;

106. an equipment of handling atmosphere, comprising:

A kind of have the charge air cooler of atmosphere contact surface and be positioned at this lip-deep pollution treatment compositions, and this pollution treatment surface is selected from:

Be used to handle the composition that contains hydrocarbon pollutant;

107. an equipment of handling atmosphere, comprising:

A kind of pollution treatment compositions that is selected from the cooling device of oil cooler, transmission oil cooler and power-assisted steering liquid cooler and is positioned at this surface, this pollution treatment surface is selected from:

Be used to handle the composition that contains hydrocarbon pollutant;

108. according to claim 103,104,105,106 or 107 equipment wherein pollutes treatment compositions and also contains the refractory oxide carrier.

109. according to claim 103,104,105,106 or 107 equipment wherein pollutes treatment compositions and also contains the refractory oxide carrier, platinum-group component and the manganese component that optionally exists.

110. according to the equipment of claim 109, wherein platinum-group component is selected from platinum combination branch and palladium component.

111., wherein pollute process element and comprise and contain manganese oxide and zirconic carrier that platinum-group component is selected from platinum and palladium according to the equipment of claim 109.

112. according to the equipment of claim 109, wherein catalyst is reduced.

113., wherein pollute treatment compositions and contain refractory oxide carrier and platinum component according to the equipment of claim 112.

114. according to the equipment of claim 113, wherein the refractory oxide carrier is a titanium dioxide.

115. according to claim 103,104,105,106 or 107 equipment wherein pollutes treatment compositions and also contains the refractory oxide carrier.

116. according to the equipment of claim 115, wherein dirty noble metal is a palladium.

117. according to claim 103,104,105,106 or 107 equipment, wherein pollute treatment compositions and contain the refractory oxide carrier that is selected from cerium oxide, aluminium oxide, titanium oxide, zirconia, manganese oxide and zirconic coprecipitate and composition thereof, be selected from the platinum group metal component of palladium, platinum and composition thereof.

118., wherein pollute treatment compositions and contain cerium oxide carrier and palladium component according to the equipment of claim 117.

119. a method, comprising:

With polluting the automotive surfaces that the treatment compositions coating is selected from spreader surface, air-conditioning condenser surface and charge air cooler surface, wherein this pollution treatment compositions is selected from:

Be used to handle the composition that contains hydrocarbon pollutant;

120., wherein also be included in coating and pollute before the treatment compositions step that adhesion promotion priming paint is coated on this surperficial at least a portion according to the method for claim 119.

121. according to the method for claim 119, wherein at least a portion of radiator is made of aluminum and comprise that radiator outer surface, this method also are included in coating and pollute oxidation at least a portion outer surface before the treatment compositions.

122. a method, comprising the following step:

Prepare a kind of mixture that contains the solution of the platinum group metal that is carried on the catalyst carrier and soluble manganese component, this mixture drying must be enough to absorb complete soln basically,

Dry this mixture,

Calcine this mixture,

Make the slurry that contains this mixture and liquid,

With this slurry coating machine motor-car atmosphere contact surface.

123. according to the method for claim 122, wherein carrier is selected from the coprecipitate of refractory oxide carrier and manganese oxide and zirconium dioxide.

124., wherein also comprise the step of the solution that adds reducing composition according to the method for claim 123.

125. the manganese compound that forms in about 300-500 ℃ calcining.

126. according to the manganese compound of claim 125, wherein its ignition temperature is 350-450 ℃.

127. a composition that contains magnesium compound wherein heats in oxygen-containing atmosphere so that the calcining said composition at about 300-550 ℃.

128. according to the composition of claim 127, wherein said composition is heated to about 350-450 ℃, lasts at least about 0.5 hour.

129. according to the composition of claim 127, wherein said composition also contains noble metal component.

130. according to the composition of claim 128, wherein said composition is reduced after calcining.

131. one kind contains the noble metal component that is on the catalyst carrier, the composition that obtains reducing.

132. according to the composition of claim 133, wherein refractory oxide is selected from refractory oxide carrier and manganese oxide and zirconic coprecipitate.

133. according to the composition of claim 132, wherein said composition was calcined before reduction.

134. according to the composition of claim 133, wherein catalyst carrier is selected from titanium dioxide and manganese oxide and zirconic coprecipitate.

135. according to the composition of claim 135, wherein noble metal component comprises the platinum component.

136. a composition wherein contains the catalysis material that is selected from manganese oxide; Be selected from refractory oxide carrier and manganese oxide and zirconic carrier; And adhesive.

137., wherein also comprise the waterproof work that is selected from wax and fluorocarbon and add agent according to the composition of claim 127,131 or 136.

138., wherein also comprise at least a catalyst material that is selected from manganese oxide, platinum component and palladium component according to the composition of claim 136.

139. according to the composition of claim 138, wherein carrier is selected from titanium dioxide, silica-zirconium dioxide and manganese oxide and zirconic coprecipitate.

140. according to the composition of claim 136, wherein adhesive is the polymeric binder that is selected from vinyl acetate polymer and copolymer.

141. according to the composition of claim 136, wherein adhesive is a zirconium compounds.

142. according to the composition of claim 136, wherein catalyst material is positioned on the carrier and the catalyst material of carrying obtains calcining.

143., wherein handle through the reduction that obtained by the bearing catalyst material of calcining according to the composition of claim 142.

144. according to the composition of claim 136, wherein adhesive comprises and contains the polymeric compositions that is selected from following polymers: polyethylene, polypropylene, polyolefin copolymer, polyisoprene, polybutadiene, polybutadiene copolymer, chlorinated rubber, acrylonitrile-butadiene rubber, polychlorobutadiene, ethylene-propylene-diene elastomer, polystyrene, polyacrylate, polymethacrylates, polyacrylonitrile, poly-(vinyl esters), poly-(vinyl halide), polyamide, cellulosic polymer, polyimides, acrylic resin, the styrene-acrylonitrile copolymer acid resin, polyvinyl alcohol, thermoplastic polyester, thermosetting polyester, polyphenylene oxide, polyphenylene sulfide, the polymer of fluoridizing, polyamide, phenolic resins and epoxy resin, polyurethane, silicone polymer and EVAc.

145. a method contains the composition of catalyst material of the manganese component that is selected from noble metal component and optionally exists and the reduction step through the composition of calcining comprising calcining.

146., wherein also be included in calcining and before composition be coated in suprabasil step according to the method for claim 145.

147., wherein also be included in calcining and afterwards composition be coated in suprabasil step according to the method for claim 145.

148., wherein also be included in reduction and afterwards composition be coated in suprabasil step according to the method for claim 145.

149. according to the method for claim 146,147 or 148, wherein substrate is the motor vehicle contact surface.

150. a method of handling atmosphere, comprising making vehicle pass through atmosphere, this vehicle has at least one atmosphere contact surface and contains α-MnO ₂The pollution treatment compositions.

151., wherein pollute treatment compositions and also contain polymeric binder according to the method for claim 150.

152., wherein pollute treatment compositions and also contain platinum-group component according to the method for claim 151.

153. according to the method for claim 152, wherein platinum-group component is selected from platinum and palladium component.

154., wherein pollute treatment compositions and contain the platinum component according to the method for claim 153.

155., wherein pollute treatment compositions and contain the palladium component according to the method for claim 153.

156., wherein also comprise and reduce the step of platinum-group component according to the method for claim 152.

157., wherein pollute treatment compositions and also contain high-temperature resistant carrier according to the method for claim 152.

158., wherein also comprise the step of calcining pollution treatment compositions according to the method for claim 150.

159., wherein also comprise the step of the potassium manganese ore of washing in liquid, aqueous according to the method for claim 150.

160. according to the method for claim 150, wherein α-MnO ₂Be selected from potassium manganese ore, alkali acid manganese ore, coronadite and manjiroite.

161., wherein also comprise by making acid manganese salt solution and liquor potassic permanganate be mixed into potassium manganese ore slurry according to the method for claim 159, stir slurry down at about 50-110 ℃, filter, be about 200-350m in about 75-200 ℃ drying so that form surface area ²The potassium manganese ore crystal of/g.

162. according to the method for claim 160, wherein manganese salt is selected from MnCl ₂, Mn (NO ₃) ₂, MnSO ₄And Mn (CH ₃COO) ₂

163. according to the method for claim 161, wherein manganese salt is Mn (CH ₃COO) ₂

164., wherein also comprise washing potassium manganese according to the method for claim 160.

165., wherein also comprise removing α-MnO according to the method for claim 150,152 or 162 ₂In the step of sulfate ion, chlorion and/or nitrate anion.

166., wherein also comprise the step of calcined catalyst composition according to the method for claim 150,152 or 161.

167. an equipment of handling atmosphere, comprising vehicle, this vehicle contains a kind of transfer device, at least a atmosphere contact surface of vehicle and is in this surface contamination treatment compositions, and this pollution treatment compositions contains α-MnO ₂

168., wherein pollute treatment compositions and also contain polymeric binder according to the equipment of claim 167.

169., wherein pollute treatment compositions and also contain platinum-group component according to the equipment of claim 167.

170. according to the equipment of claim 169, wherein platinum-group component is selected from platinum and palladium component.

171., wherein pollute treatment compositions and contain the platinum component according to the equipment of claim 170.

172., wherein pollute treatment compositions and contain the palladium component according to the equipment of claim 170.

173. according to the equipment of claim 169, wherein platinum-group component is reduced.

174., wherein pollute treatment compositions and also contain high-temperature resistant carrier according to the equipment of claim 169.

175., wherein pollute treatment compositions and calcined according to the equipment of claim 167.

176. according to the equipment of claim 167, wherein α-MnO ₂In liquid, aqueous, be washed.

177. according to the equipment of claim 167, wherein α-MnO ₂Be selected from potassium manganese ore, hollandite, coronadite and manjiroite.

178. according to the equipment of claim 166, wherein α-MnO ₂For surface area is about 200-350m ²The potassium manganese ore of/g.

179. according to claim 167,168,169,173,174,175,176,177 or 178 equipment, wherein α-MnO ₂Feature in Figure 19 infrared spectrum and the X-ray diffractogram among Figure 20 in obtain the expression.

180. method of handling atmosphere, comprising making vehicle pass through atmosphere, this vehicle has at least one atmosphere contact surface and the pollution treatment compositions that is on this surface, pollutes treatment compositions and comprises catalytically-active materials that is selected from least one platinum group metal component, golden component and silver components and the metal component that is selected from tungsten component and rhenium component.

181. according to the method for claim 180, wherein metal component is selected from tungsten oxide and rheium oxide.

182. according to the method for claim 180, wherein polluting treatment compositions is at least a composition that is selected from carbon monoxide-olefin polymeric and adsorbing composition.

183., wherein also comprise adhesive is added to the step of polluting treatment compositions according to the method for claim 182.

184., wherein also comprise polymeric binder is added to the step of polluting treatment compositions according to the method for claim 183.

185., wherein also comprise the polymeric latex adhesive is added to the step of polluting treatment compositions according to the method for claim 184.

186., wherein pollute treatment compositions and also contain carrier according to the method for claim 180.

187. according to the method for claim 186, wherein carbon monoxide-olefin polymeric contains the carrier material that is selected from refractory oxide carrier, manganese component, charcoal and manganese oxide and zirconic coprecipitate.

188. according to the method for claim 186, wherein carbon monoxide-olefin polymeric comprises the catalytically-active materials of at least a manganese component that is selected from least a platinum group metal component, golden component, silver components and optionally exists.

189. according to the method for claim 180 or 186, wherein catalytically-active materials is selected from least a platinum group metal component, golden component, silver components, this method also comprises the step of reducing catalyst composition.

190. according to the method for claim 186, wherein catalytically-active materials is selected from palladium and platinum component.

191. according to the method for claim 190, wherein catalytically-active materials is the platinum component.

192. according to the method for claim 186, wherein carbon monoxide-olefin polymeric comprises 60-98.5% (weight) refractory oxide carrier, is at least a platinum group metal of benchmark 0.5-15% (weight) and 1～25% (weight) metal component in the weight metal.

193。According to the method for claim 189, wherein refractory oxide is selected from aluminium oxide, silica, titanium dioxide, ceria, zirconia, chromium oxide and composition thereof.

194. according to the method for claim 193, wherein refractory oxide is a TiO 2 sol.

195., wherein also comprise calcined catalyst composition step according to the method for claim 180 or 186.

196., wherein also be included in the step that makes CO generation catalytic reaction in the atmosphere according to the method for claim 180.

197., wherein also be included in the step that makes hydrocarbon and/or partial oxidation of hydrocarbons generation catalytic reaction in the atmosphere according to the method for claim 180.

198. according to the method for claim 197, wherein hydrocarbon is a unsaturated hydrocarbons.

199. according to the method for claim 198, wherein unsaturated olefinic compound is selected from propylene and butylene.

200., wherein also comprise the surface being maintained at about 20-105 ℃ step according to the method for claim 180.

201. according to the method for claim 180, wherein the atmosphere contact surface directly contacts with atmosphere when vehicle passes through atmosphere.

202. according to the method for claim 201, wherein at the relative velocity of vehicle atmosphere contact surface and atmosphere when the atmosphere up to 100 miles per hours.

203., wherein also comprise the step of heating atmosphere contact surface according to the method for claim 180.

204. according to the method for claim 180, wherein the atmosphere contact surface is selected from the outer surface of air-conditioning condenser, radiator, radiator fan, charge air cooler and deep bead.

205. according to the method for claim 204, wherein vehicle comprises the fluid cooling device that has the atmosphere contact surface, this method comprises makes atmosphere contact with the atmosphere contact surface.

206. according to the method for claim 205, wherein cooling device is selected from air-conditioning condenser, radiator, charge air cooler, oil cooler, transmission oil cooler and power-assisted steering liquid cooler.

207. equipment of handling atmosphere, comprising vehicle, this vehicle comprises mobile device, at least one atmosphere contact surface of vehicle and is positioned at this lip-deep pollution treatment compositions that this pollution treatment compositions comprises catalyst reactive material that is selected from least a platinum group metal component, golden component, golden component and silver components and the metal component that is selected from tungsten component and rhenium component.

208. according to the equipment of claim 207, wherein metal component is selected from tungsten oxide and rheium oxide.

209. according to the equipment of claim 207, wherein the pollutant treatment compositions is at least a composition that is selected from carbon monoxide-olefin polymeric and adsorbing composition.

210., wherein pollute treatment compositions and also contain adhesive according to the equipment of claim 209.

211., wherein pollute treatment compositions and also contain polymeric binder according to the equipment of claim 207.

212., wherein pollute treatment compositions and be added into the form of polymeric latex adhesive according to the equipment of claim 211.

213., wherein pollute treatment compositions and also contain carrier according to the equipment of claim 207.

214. according to the equipment of claim 213, wherein carbon monoxide-olefin polymeric contains the carrier material that is selected from refractory oxide carrier manganese component, charcoal and manganese oxide and zirconic coprecipitate.

215. according to the equipment of claim 213, wherein carbon monoxide-olefin polymeric contains at least a catalytically-active materials that also contains the manganese component.

216. according to the equipment of claim 207 or 213, wherein catalytically-active materials is reduced.

217. according to the equipment of claim 213, wherein catalytically-active materials is selected from palladium and platinum component.

218. according to the equipment of claim 217, wherein catalytically-active materials is the platinum component.

219. according to the equipment of claim 213, wherein carbon monoxide-olefin polymeric comprises 60-98.5% (weight) refractory oxide carrier, is at least a platinum group metal of benchmark 0.5-15% (weight) and 1～25% (weight) metal component in the weight metal.

220. according to the equipment of claim 216, wherein refractory oxide is selected from aluminium oxide, silica, titanium dioxide, ceria, zirconia, chromium oxide and composition thereof.

221. according to the equipment of claim 220, wherein refractory oxide is a titanium oxide sol.

222. according to the equipment of claim 207 or 213, wherein carbon monoxide-olefin polymeric is sintered.

223. according to the equipment of claim 207, wherein the atmosphere contact surface is selected from the outer surface of air-conditioning condenser, radiator, radiator fan, charge air cooler and deep bead.

224. according to the method for claim 223, wherein vehicle comprises the fluid cooling device that has the atmosphere contact surface, this method comprises makes atmosphere contact with the atmosphere contact surface.

225. according to the method for claim 224, wherein cooling device is selected from air-conditioning condenser, radiator, charge air cooler, oil cooler, transmission oil cooler and power-assisted steering liquid cooler.

226. one kind is polluted treatment compositions, wherein contains the catalytically-active materials that is selected from least a platinum group metal component, gold and silver components, is selected from the metal component of tungsten component and rhenium component.

227. according to the composition of claim 226, wherein metal component is selected from tungsten oxide and rheium oxide.

228. according to the composition of claim 226, wherein the pollutant treatment compositions is at least a composition that is selected from carbon monoxide-olefin polymeric and adsorbing composition.

229., wherein also contain polymeric binder according to the composition of claim 228.

230., wherein also contain polymeric binder according to the composition of claim 226.

231. according to the composition of claim 230, wherein polymeric binder is added into the form of polymeric latex adhesive.

232., wherein pollute treatment compositions and also contain carrier according to the composition of claim 226.

233. according to the composition of claim 232, wherein carbon monoxide-olefin polymeric contains the carrier material that is selected from refractory oxide carrier, manganese component, charcoal and manganese oxide and zirconic coprecipitate.

234. according to the composition of claim 232, wherein catalyst composition contains at least a catalytically-active materials that also contains the manganese component.

235. according to the composition of claim 226 or 232, wherein catalytically-active materials is reduced.

236. according to the composition of claim 232, wherein catalytically-active materials is selected from palladium and platinum component.

237. according to the composition of claim 236, wherein catalytically-active materials is the palladium component.

238. according to the equipment of claim 29, wherein carbon monoxide-olefin polymeric comprises 60-98.5% (weight) refractory oxide carrier.In the weight metal is at least a platinum group metal of benchmark 0.5-15% (weight) and 1～25% (weight) metal component.

239。According to the composition of claim 235, wherein refractory oxide is selected from aluminium oxide, silica, titanium dioxide, ceria, zirconia, chromium oxide and composition thereof.

240. according to the composition of claim 239, wherein refractory oxide is a TiO 2 sol.

241., wherein also comprise the step of calcined catalyst composition according to the composition of claim 226 or 232.

242. a method, comprising the following step:

Mix following component: the catalytically-active materials that is selected from least a platinum group metal component, golden component, silver components and manganese component; Water;

Mixing this mixture;

In this mixture, add polymeric binder;

Mix this mixture;

In mixture, add in the mixture forming process and/or during the interpolation polymeric binder and contain carboxylic acid compound.

243. the method according to claim 242 wherein also comprises the following steps:

Preparation comprises the slurry of this mixture and liquid;

With this slurry coating machine motor-car atmosphere contact surface.

244. according to the method for claim 242, wherein catalytically-active materials

Also contain carrier.

245., wherein also be included in the step of calcining catalytically-active materials before the adding polymeric binder according to the method for claim 244.

246., wherein also comprise the step of reduction catalysts active material according to the method for claim 242.