GB1584998A - Treatment of exhaust gases from internal combustion engines - Google Patents
Treatment of exhaust gases from internal combustion engines Download PDFInfo
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- GB1584998A GB1584998A GB41055/77A GB4105577A GB1584998A GB 1584998 A GB1584998 A GB 1584998A GB 41055/77 A GB41055/77 A GB 41055/77A GB 4105577 A GB4105577 A GB 4105577A GB 1584998 A GB1584998 A GB 1584998A
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- catalyst
- zone
- catalyst body
- flow passages
- gas flow
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Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
- F01N3/22—Control of additional air supply only, e.g. using by-passes or variable air pump drives
- F01N3/222—Control of additional air supply only, e.g. using by-passes or variable air pump drives using electric valves only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
- F01N13/009—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
- F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
- F01N3/22—Control of additional air supply only, e.g. using by-passes or variable air pump drives
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
- F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
- F01N3/2825—Ceramics
- F01N3/2828—Ceramic multi-channel monoliths, e.g. honeycombs
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
- F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
- F01N3/2832—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support granular, e.g. pellets
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2330/00—Structure of catalyst support or particle filter
- F01N2330/06—Ceramic, e.g. monoliths
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2330/00—Structure of catalyst support or particle filter
- F01N2330/08—Granular material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Toxicology (AREA)
- Ceramic Engineering (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Exhaust Gas After Treatment (AREA)
- Catalysts (AREA)
Description
(54) TREATMENT OF EXHAUST GASES FROM INTERNAL COMBUSTION
ENGINES
-(71) We, ENGELHARD MINERALS & CHEMICALS CORPORATION, of 70
Wood Avenue South, Metro Park Plaza,
Iselin, New Jersey, United States of America, a corporation organized under the laws of the State of Delaware, one of the United
States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following state ment :- This invention relates to catalytic processes and apparatus suitable for purifying exhaust gases from internal combustion engines in order to decrease pollution of the atmosphere, and the invention is especially concerned with overcoming problems of purifying exhaust gases from two-stroke, also known as two-cycle, internal combustion engines emitting relatively high concentrations of hydrocarbon and carbon monoxide.
In catalytically treating exhaust gases from internal combustion engines, problems may exist in that excessively high catalyst temperatures may be reached due to the high temperatures of the exhaust gases being treated and the presence of exothermic reactions, and the high temperatures may be deleterious to the catalyst. These problems are accentuated when the exhaust gases contain relatively high concentrations of carbon monoxide and hydrocarbon along with molecular oxygen.
Gases of various sorts are discharged or exhausted by internal combustion engines.
and frequently these gases contain undesirable materials which. if released to the atmosphere. would be pollutants. The problem of minimizing the release of such pollutants to the atmosphere has been under consideration for many years, and it is becoming increasingly important that means for abating emissions of pollutants be devised. Certain modes of engine operation which result in relatively large amounts of hydrocarbon and carbon monoxide being discharged from an internal combustion engine are particularly troublesome with respect to effectively abating emissions of these atmospheric pollutants. Exemplary of internal combustion engines which typically discharge such large amounts of hydrocarbon and carbon monoxide are the twostroke combustion engines which are frequently employed as power sources for motorcycles, outboard boats. snow mobiles.
chain saws and small electrical generators.
It is estimated that emissions from motorcycles account for about 0.9 percent of the total mobile source of hydrocarbons and 0.6 percent of the total mobile source of carbon monoxide emissions annually in the United
States. However, because of the seasonal use of motorcycles and the higher concentration of motorcycles in large cities, the effect of the emissions from motorcycles on air quality in certain regions during certain periods during the year may be substantially more significant. For example. the raw emissions from a two-stroke motorcycle engine may frequently range from about 10 to 18 grams of hydrocarbon per mile and about 12 to 28 grams of carbon monoxide per mile, and the hydrocarbon and carbon monoxide emissions produced by such motorcycles may even be as great as ten to twenty passenger cars employing catalytic exhaust treating units. A typical exhaust from a two-stroke motorcycle engine operating at an air-to-fuel ratio of 12.8 may contain on a volume basis approximately 5 percent carbon monoxide, 1.7 percent hydrogen (estimated to be 1/3 of the amount of carbon monoxide in the exhaust gases), 3 percent oxygen, and 2,000 ppm hydrocarbon and may have a temperature of over 1000 F. While general technology exists for the treatment of undesirable components in exhaust streams, the application of such general technology to the treatment of emissions from two-stroke engines is faced with significant obstacles. Moreover, the exhaust gases from two-stroke engines also generally contain smoke which may comprise black carbon particles, white aerosol, and oil ash since lubricating oil is consumed with the fuel. The white aerosol (white smoke) could coat the catalyst and, in combination with black carbon particles, clog the catalyst. Oil ash could clog the catalyst as well as contribute to catalyst poisoning. The tendency of two-stroke engines to leave deposits can often be observed on examination of exhaust pipes after periods of use. Not only would clogging in the exhaust system be adverse to the performance of the engine and catalyst, but, also, the resultant back pressure may foster an increase in production of the pollutants in the engine.
The presence of relatively large amounts of carbon monoxide and hydrocarbon in typical exhausts from two-stroke engines may produce a significant thermal load on oxidative exhaust purification systems. For instance, the adiabatic temperature rise during catalytic combustion of 1 volume percent carbon monoxide in combustion gases is often about 85" to 90"C. The carbon monoxide concentration in exhaust gases from two-stroke engines may be as high as about 10 or more volume percent carbon monoxide. Two-stroke engines are often operated under fuel-rich conditions, and hence, their exhausts generally tend to contain increased amounts of hydrocarbon, say up to about 1 or more volume percent.
Moreover, two-stroke engines can misfire, in which case substantial amounts of hyrocarbon and oxygen are emitted from the engine, and the hydrocarbon concentration in the exhaust gases may be as high as about 2 percent or more during a misfire. Hydrocarbons and oxygen are also present in the exhaust due to the normal scavenging process within the cylinder, during which a portion of the air, fuel and lubricating oil mixture passes from the inlet port to the exhaust port without significant combustion. The adiabatic temperature rise during catalytic combustion of 1000 ppm hydrocarbon in the exhaust gases is approximately 100"C. Also, during periods of high fuel consumption, e.g., operations under heavy load conditions and/or high speeds, the volume of exhaust gases to be treated may result in an increase in catalystic temperature, for instance, due to the limited inherent cooling capacity of the catalyst. Thus, the thermal load on catalysts used to treat exhausts from two-stroke engines can be severe, particularly during periods of high fuel consumption and complete or partial misfiring, and theoretically exceed the upper temperature limit for efficient catalyst operation and even cause melting of the catalyst support.
The exhaust from a cylinder of an internal combustion engine is in a pulsating mode with exhaust being emitted during the exhaust phase of operation. Two-stroke engines usually employ a separate exhaust system for each cylinder of the engine.
Thus, the pulsating flow environment is generally more pronounced than in combined exhaust streams from, e.g., multicylindered automobile engines. This pulsating flow can adversely affect the mounting system for an exhaust catalyst as well as provide strains on the catalyst structure itself. Moreover, it has also been found that, in general, two-stroke engines may tend to temporarily reverse the direction of the exhaust flow. Thus, catalytically combusted exhaust effluent may be drawn back into the catalyst, thereby accentuating the pulsating effect and increasing the thermal load on the catalyst.
Houdry in U. S. Patent No. 2,664,340 discloses a catalytic apparatus and method for treating exhaust gases employing a plurality of catalytic elements arranged in series. Each grouping of downstream catalytic elements is more catalytically-active than the preceding grouping of catalytic elements, and cooling zones are provided between each grouping of catalytic elements. Saufferer in U. S. Patent No.
3,440,817 discloses a catalytic treatment system for exhaust gases wherein a smaller catalyst is placed closely adjacent to the engine and a larger catalyst is positioned downstream from the smaller catalyst. An adjustable diverter is provided upstream from the smaller catalyst to by-pass a sufficient portion of the exhaust gases around the smaller catalyst to avoid its achieving deleteriously high temperatures.
Keith, et al., in U. S. Patent No. 3,896,616 describe a process and apparatus for treating exhaust gases containing carbon monoxide, hydrocarbon and nitrogen oxides comprising a first and second catalytic convertor. The first catalytic convertor is operated during start-up under oxidizing conditions to heat the second catalytic convertor. Then the first catalytic convertor is operated under reducing conditions by the addition of fuel to the exhaust gases entering the first catalytic convertor to reduce nitrogen oxides and the second catalytic convertor oxidizes combustible materials contained in the exhaust gases. These patents serve to illustrate representative systems for catalytically treating exhaust gases in two or more catalyst beds.
According to the presetit invention, there is provided a process for catalytically treating an exhaust gas emanating from an internal combustion engine and comprising carbon monoxide, hydrocarbons and free oxygen, which process comprises (a) contacting the gas with a first catalyst body to partially oxidize the gas and to provide a first catalyst combustion effluent containing combustible values and (b) contacting the exhaust gas treated in the first catalyst body with a second catalyst body positioned sequentially downstream with respect to the first catalyst body for receiving the exhaust gas combusted in the first catalyst body and providing a combustion effluent, the temperatures in the first and second catalyst bodies being insufficient to be deleterious to the catalysts, the first catalyst body having a plurality of gas flow passages with inlet openings and outlet openings for. receiving and emitting the exhaust gas, the second catalyst body having a plurality of gas flow passages having inlet and outlet openings for receiving and emitting an effluent gas, and the number of individual gas flow passages per unit of cross-sectional area of the first catalyst body being less than the number of individual gas flow passages per unit of cross-sectional area of the second catalyst body whereby the open crosssectional area of individual gas flow passages of the first catalyst body is greater than the open cross-sectional area of individual gas flow passages of the second catalyst body to avoid plugging of the gas flow passages of the said bodies. The present invention also provides an apparatus suitable for catalytically treating an exhaust gas emanating from an internal combustion engine and comprising carbon monoxide, hydrocarbons and free oxygen. which apparatus comprises a first catalyst body for partially combusting the gas to provide a catalytic combustion effluent containing residual combustible values, a second catalyst body positioned sequentially downstream with respect to the first catalyst body and for further combusting the same to provide a combustion gas effluent, the catalyst bodies being such that the temperatures produced in the catalyst bodies are insufficient to be deleterious to the catalyst bodies, and the first catalyst body having a plurality of gas flow passages with inlet openings and outlet openings for passing the gas therethrough, the second catalyst body having a plurality of gas flow passages with inlet and outlet openings for passing the gas therethrough, the open cross-sectional area of individual gas flow passages of the first catalyst body being greater than the open cross-sectional area of individual gas flow passages of the second catalyst body.
By the present invention there are provided catalytic processes and apparatus for treating exhaust gases from two-stroke internal combustion engines, which gases contain relatively high amounts of carbon monoxide and hydrocarbon, along with free or molecular oxygen. High carbon monoxide and hydrocarbon-content exhaust gases are catalytically processed using a suitable oxidation catalyst for treating exhaust gases from internal combustion engines without reaching unduly high temperatures which may adversely affect the catalyst, and these undesirable components of exhaust gases can be abated by oxidation over wide ranges of throughput volumes and engine Qperar tion conditions. The catalytic processes of this invention provide for rapid achievement of temperatures suitable for activation of the catalyst after startrup and rapid adjustment to changes in operating conditions of internal combustion engines. Moreover, this invention provides for the abatement of undesirable components in such exhaust gases without undue adverse effect on the operation of the internal combustion engine, e.g., by causing an unduly high back pressure. The processes of this invention are particularly suitable for use in treating exhaust gases from two-stroke engines where pulsing flows of exhaust gases exist; the exhaust gases may contain black carbon particles, white aerosol, oil ash, and the like; and engine misfiring as well as cylinder scavenging may occur producing exhaust gases containing large amounts of uncombusted fuel and oxygen values.
In accordance with the processes of this invention for oxidizing constituents from two-stroke internal combustion engine exhaust, gases having relatively high carbon monoxide and hydrocarbon contents, the exhaust gases from the engine containing carbon monoxide, hydrocarbon. and free oxygen are passed without significant addition of additional free oxygen, to a first catalyst zone containing an oxidation catalyst wherein insufficient oxidation occurs to increase the temperature of the exhaust gases, but insufficient to produce temperatures within the catalyst which are deleterious to the catalyst. The gases exiting the first catalyst contain combustible values, e.g., carbon monoxide and hydrocarbon, and are cooled and then passed to at least one downstream catalyst zone containing an oxidation catalyst wherein further oxidation of remaining combustible values takes
place. Frequently, only a first catalyst zone
and a second catalyst zone need be em
ployed; however, expecially in treating ex
haust gases having higher carbon monoxide
and hydrocarbon content, additional
catalyst zones may be employed to avoid
excessively high temperatures in the second
catalyst zone while still obtaining an adequ
ate decrease in the amount of undesirable
components in the exhaust gases. The gases
passing between each downstream catalyst
zone, if more than one is employed, are
preferably cooled before being passed to
each immediately following catalyst zone.
Sufficient heat is lost during cooling of the
exhaust gases from a preceeding catalyst
zone that the combustion taking place in the
subsequent catalyst zone will not provide
temperatures which are unduly deleterious
to the catalyst; however, the decrease in
temperature should not be so great that
gases containing significant combustible
values are cooled below the temperature
required for activation of the catalyst for
promotion of the oxidation of combustible
values in the gases in the following catalyst
zone.
In- another aspect of this invention ex h ust gases from two-stroke internal com
bustion engines are catalytically processed in a catalyst zone having'suitable oxidation
catalyst therein wherein the catalyst is in the
form of at least two sequentially adjacent
unitary bodies. Each of the unitary bodies
has a plurality of passages, or channels,
through a single piece of the carrier wherein
the passages are open to fluid flow and thus are not blocked or sealed against flow from
an inlet to a separate outlet. The first
catalyst body in the direction of exhaust
flow has passages sufficiently large in cross
section to facilitate entry of black carbon
particles, white smoke aerosol, and the like,
into the passages without undue deposition
of these materials onthe walls of the catalyst
which may tend to restrict the flow of gases
and even cause blockage of the passages.
Combustion occurring in the first catalyst
body tends to heat the gases passing there
through and thus reduce the tendency of
black carbon particles, white smoke aerosol,
and the like, to form deposits on the catalyst
walls. The heated gases pass from the first
catalyst body to a sequentially adjacent
second catalyst body having a greater num
ber of flowthrough passages per unit of
cross-section than the first catalyst body in
order to provide additional active surface
area to enhance catalytic combustion of
combustible values in the exhaust gases.
Additional sequentially adjacent catalyst
bodies can be employed having essentially
the same or a greater number of flow
through passages per unit of cross-section
than the second catalyst body. The greater active surface area in the second, and, if employed, subsequent, catalyst bodies enhances the degree of conversion per unit volume. Thus, a smaller volume of catalyst can be employed as compared to the volume required if the flowthrough passages were the same size as those in the first catalyst body, and the back pressure provided by the catalyst is reduced since undue formation of deposits is abated. Also, when the catalyst is cold, the first catalyst body can be relatively quickly heated to temperatures at which catalytic oxidation is promoted by the gases contacting it since the first catalyst body can contain a lesser volume of solid structure which is to be heated than that of an equivalent total volume catalyst body having a greater number of flowthrough passages. The first catalyst body which may be quickly heated to catalytically-active temperatures thus serves to increase the temperature of the gases passing to the second catalyst body and hasten reaching temperatures at which catalytic oxidation is promoted in the second catalyst body. During operation, generally the coolest portion of the catalyst is the initial portion of''the catalyst where the cooler gases to be treated first contact the catalyst. Since the second catalyst body has more catalytically-active surface area per unit volume, the temperatures reached therein due to the exothermic combustion reaction are sufficiently high that heat is radiated to the first catalyst body to enhance catalytic combustion therein.
The catalyst of this aspect of the invention may be employed in the process of this invention wherein at least two catalyst zones are employed or in any suitable catalytic process for treating exhaust gases from two-stroke engines.
The processes and apparatus of this invention are particularly suited for treating two-stroke engine exhaust gases containing, say, at least about 2 volume percent carbon monoxide and at least about 0.05 volume percent hydrocarbon (calculated on the bases of C6 hydrocarbon). The gases also contain free oxygen, hydrogen, and inert diluents, e.g., nitrogen, and final products of combustion such as carbon dioxide and water. Free oxygen is generally present in the exhaust gases from the engine due to one or more of misfiring or other incomplete combustion of fuel in the engine, the normal cylinder scavenging process and the use of fuel lean combustible mixtures, the use of a stoichiometric excess of air in the fuel-air combustion mixture. Often, the exhaust gases from two-stroke internal combustion engines contain on an average basis about 2 to 8 percent carbon monoxide, about 1 to 2.7 volume percent hydrogen, about 0.05 to 0.8 volume percent hydrocarbon, and about 0.5 to 5 volume percent free oxygen during normal operating conditions.
During a misfire or during periods of startup or high loads, the amounts of combustible components in the gases may be significantly higher. For instance, the exhaust gases from a misfire may contain as much as about 2 or more volume percent hydrocarbon.
In accordance with this invention, oxidation reactions which occur within a given catalyst zone, whether it be the first catalyst zone or a subsequent, downstream catalyst zone, are insufficient to result in temperatures which would be deleterious to the catalyst. The temperatures achieved in a catalyst zone will, at least in part, be determined by the temperature of the gases entering the catalyst zone and the temperature increase due to the combustion reactions occurring therein. Factors which influence the combustion rections and the temperature increase resulting therefrom include the amount of combustible components in the gases, the amount of free oxygen available for the combustion, the space velocity of the gases through the catalyst, and the level of catalytic activity per unit area of the catalyst.
By way of example, the factors which .influence the amount of combustion in a catalyst zone are illustrated with respect to the first catalyst zone; however it should be
appreciated that subsequent catalyst zones may operate in essentially the same manner in accordance with this invention. For inst
ance, one engine operating condition which
may occur is idling in which a relatively
small volume of exhaust gases is produced.
The relatively slow volume flow rate may permit substantial cooling of the exhaust
gases prior to impinging on the catalyst in
the first catalyst zone, but the cooling is not
sufficient to reduce the catalyst tempera
tures to below those which activate the
catalyst to promote oxidation. Due to the
reduced space velocity through the catalyst,
a high portion of the combustible components in the exhaust gases can be reacted; however, since the amount of gases being
treated is relatively small and heat loss from
the catalyst is significant, the temperature
increase is insufficient to provide tempera
tures which are deleterious to the catalyst.
Under high speed engine operating condi
tions, the volume flow rate of exhaust gases
is much higher than the volume flow rate at
idling conditions and the temperature drop
between the engine and the first catalyst
zone is generally less. The space velocity
through the catalyst is also much greater,
and, therefore, the catalyst is not able to
effect a proportionately larger amount of
combustion, i.e., the amount of catalyst
employed is insufficient to effect complete
combustion of the combustible materials passing therethrough. Moreover, the additional gases passing through the catalyst which do not enter into the combustion reactions in the catalyst zone serve as a heat sink for heat provided by the oxidation in the catalyst zone. Accordingly, the temperature in the first catalyst zone remains below those which are deleterious to the catalyst.
Under conditions of misfire and scavenging larger concentrations of combustible materials, especially hydrocarbon, with oxygen passed to the catalyst zone; however, due to the lower temperature of the gases passing to the catalyst zone and an insufficient amount of catalyst to effect complete conversion of the combustible materials, the temperatures reached in the catalyst zone are not deleterious to the catalyst.
Often, two-stroke internal combustion engines are operated under stoichiometric air-fuel ratios for theoretically complete combustion of the fuel to carbon dioxide and water or to the fuel-rich side of the stoichiometric ratio. The lack of sufficient free oxygen for complete combustion of the combustible materials in the exhaust gases may additionally assist in maintaining suitable temperature increases in the catalyst zone. In order to enhance the combustion of carbon monoxide and hydrocarbons in the exhaust gases, oxygen-containing gases may be added to the exhaust gases treatment system after the first catalyst zone. Generally, sufficient free oxygen will be available during the treatment of exhaust gases in accordance with this invention for substantially complete combustion on a stoichiometric basis of carbon monoxide and hydrocarbon contained therein to carbon dioxide and water, and desirably, at least about 0.6 volume percent, generally about 0.6 to 3 volume percent, free oxygen in excess of that required on a stoichiometric basis for complete combustion of carbon monoxide and hydrocarbon components is provided.
Since significant cooling of the exhaust gases from the engine, especially during start-up when the engine is cold, may occur, the first catalyst is preferably positioned relatively close to the internal combustion engine such that the combustion exhaust gases have sufficiently high temperatures when they impinge on the first catalyst,that, when cold, the catalyst is rapidly heated to catalytically-active temperatures. Generally, the first catalyst zone is positioned such that the gases contacting the catalyst are at temperatures in excess of about 250"C., preferably about 300 to 600"C, under operating conditions expected to be encountered during operation of the engine. Additional means for reaching temperatures sufficient for the catalyst in the first zone to achieve suitable catalytic activity such as electrical heating, ignition and thermal combustion of supplemental fuel upstream from the first catalyst zone, and the like, may be employed but are generally not used due to the complexity which they would add to the exhaust gases treatment system. Upon reaching temperatures sufficient to provide catalytic activity, the catalyst in the first catalyst zone promotes oxidation of carbon monoxide and hydrocarbon components in the exhaust gases to carbon dioxide and water.
The amount of oxidation occurring in the first catalyst zone is insufficient, under a wide range of operating conditions which may occur, to produce temperatures therein which are deleterious to the catalyst. Generally, the first catalyst zone serves to promote combustion of about 5 to 75, preferably about 15 to 50, volume percent of the cumbustible materials, i.e., carbon monoxide, hydrogen, hydrocarbons, and the like, in the exhaust gases.
The increase in temperature of the gases in the first catalyst zone due to the oxidation therein is often at least about 50 C. but is insufficient to provide temperatures in the first catalyst zone which are deleterious to the catalyst. Frequently, the temperature increase is less than about 500"C., and often ranges, say, from about 50 to 3000C.
Generally, the maximum temperature of the exhaust gases exiting the first catalyst zone is less than about 800"C., e.g., ranges from about 400" to 800"C., preferably about 450" to 650"C. The maximum peak temperatures in the first catalyst zone are below temperatures which may be deleterious to the catalyst due to the use of an insufficient amount of catalyst in the first catalyst zone to promote complete combustion of the combustible values in the exhaust gases and, optionally, providing insufficient oxygen for complete combustion of the combustible values in the exhaust gases. Advantageously, the catalyst in the first catalyst zone is relatively small in volume, thereby facilitating its warming to active temperatures during start-up.
During operation, the temperature of the catalyst in the first catalyst zone is preferably maintained sufficiently high that the formation of deposits on the catalyst, if occurring at all, is negligible. In treating exhaust gases from two-stroke engines which contain black carbon particles and white aerosol, the temperature of the catalyst during use should be above about 300, preferably above about 500"C., to minimize the formation of deposits. In the operation of two-stroke engines, the exhaust gases may contact the catalyst in a pulsing manner, and hot catalytic combus tidn gases may even be drawn back into the first catalytic zone. Desirable temperatures can be maintained in the catalyst zone between the intermittent pulses of exhaust gases by further catalytic combustion of combustible values remaining in the hot combustion gases which may be drawn back into the catalyst.
The gases exiting the first catalyst zone contain combustible values, i.e., uncombusted carbon monoxide and hydrocarbon, under at least most engine operating conditions. Generally, the relative amount of uncombusted material in the effluent from the first catalyst zone is dependent upon the volume flow rate of the gases. For instance, over a range of operating conditions, the exhaust gases from the first catalyst zone will contain carbon monoxide and most usually hydrocarbon, e.g., at least abdut 0.1, often about 1 to 4, volume percent carbon monoxide and at least about 0.02, often about 0.02 to 0.8, volume percent hydrocarbon. The gases exiting the first catalyst zone are, e.g., by being passed through a cooling zone which interconnects the first catalyst zone and a second catalyst zone. The cooling serves to reduce the temperature of the exhaust gases such that further combustion can take place in the second catalyst zone without unduly high temperatures being obtained which may be deleterious to the catalyst th
In an aspect of this invention where the gases are exhausted from the system after the second catalyst zone, the second catalyst is advantageously of sufficient surface area and activity to provide the desired level of reduction of carbon monoxide and hydrocarbons in the exhaust gases over most of the expected range of operating conditions of the internal combustion engine. Generally, sufficient combustion of carbon monoxide and hydrocarbons will occur in the first catalyst zone and the gases emitted therefrom sufficiently cooled, that the combustion occurring in the second catayst zone will not reach temperatures which are deleterious to the catalyst therein even under conditions when the engine misfires. Under conditions of low throughput, there may be a lesser volume combustible values in the effluent from the first catalyst zone than under conditions of high exhaust throughput. Thus, the increase in temperature of the gases passing through the second catalyst zone may vary widely under varying engine operating conditions. Generally, the increase in temperature of the gases passing 'through the second catalyst zone is at least
about 25"C., preferably at least about 50"C., and often ranges between about 25 to 250"C., preferably about 50 to 2000C. The maximum temperatures of the gases obtained in the second catalyst zone are generally less than about 900"C., and often
are in the range of about 400 to 900"C. The catalyst in the second catalyst zone is prefer
ably maintained at a temperature of at least about 450"C., preferably at least about 550"C., in order to minimize deposition of undesired components on the catalyst surface and to effect catalytic combustion.
In an aspect of this invention when more than one sequentially subsequent catalyst zone is employed, the second catalyst zone generally has insufficient catalyst to prom
ote such large amounts of oxidation that high temperatures which may be deleterious
to the catalyst can be reached. In other respects such as maximum temperature of the gases in the second catalyst zone, the operation is similar to the aspect of the invention wherein the gases are exhausted from the system after the second catalyst zone. This second catalyst zone is preferably followed by a cooling zone through which the gases are cooled prior to impinging on the catalyst in a subsequent catalyst zone.
The cooling may be effected in essentially
the same manner as with the cooling zone
between the first and second catalyst zones;
however, the amount of cooling may often
be somewhat less, for instance, about 100 to 300"C., to facilitate maintaining the temper
ature of the subsequent catalyst sufficiently
high under the wide range of engine operat
ing conditions which may be encountered so as to minimize the formation of deposits on the catalyst surface and to maintain the catalyst at or near catalytically-effective temperatures.
In a further aspect of this invention, the catalytic treatment of the exhaust gases from the internal combustion engine may also serve to reduce the nitrogen oxides content therein. Exhaust gases containing nitrogen oxides and an insufficient amount of oxygen on a stoichiometric basis for complete combustion of the carbon monoxide and hydrocarbon may enhance any reduction of nitrogen oxides in the first catalyst zone. The catalyst, employed, especially in the first catalyst zone, may have catalytic activity for promoting oxidation as well as reduction of nitrogen oxides. The oxidation reactions can serve to provide heat for the reduction reactions. Generally, in the operation of two-stroke internal combustion engines under fuel-rich or near stoichiometric fuel-air ratio conditions, the production of nitrogen oxides during combustion in the internal combustion engine is relatively minor. For instance, the exhaust gases from two-stroke engines may produce about 0.0 to 0.08 gram per mile of nitrogen oxides.
The gases, after being treated by .the processes of this invention often contain less than about 0.02, preferably less than about 0.005, volume percent carbon monoxide and less than about 0.002, preferably less than about 0.001, volume percent hydrocarbon.
Catalysts which are suitable for treating exhaust gases from internal combustion engines include macrosized catalysts. The catalysts have one or more metal components, especially a platinum group metal component, as a catalytic promoter combined with a high surface area, refractory oxide support. Depending upon the catalytically-active, promoting metal components in the catalysts and the conditions of their use, the catalysts may serve to promote both oxidation and reduction reactions simultaneously. The catalysts may thus serve to enhance the oxidation of hydrocarbons or carbon monoxide, while promoting the reduction of nitrogen oxides, to less noxious materials such as carbon dioxide, nitrogen, and water.
The catalytically-active promoting metal component of the catalysts which may be employed may comprise one or more metals which may be in elemental or combined form as in the case of alloys, salts, oxides and the like. The metals are generally the heavy or transition metals of Groups III to
VIII having an atomic weight of at least about 45. The metals include, for instance, the iron group metals such as nickel and cobalt; the metals of Groups VB and VIB, e.g., vanadium, chromium, molybdenum and tungsten; copper; manganese; rhenium; and combinations of such metals. The previous metals may also be in the catalysts as catalytically-active components, and it is quite preferred that one or more metals from the platinum group be present. The useful platinum group metals include, for instance, platinum, ruthenium, palladium, and rhodium, and mixtures or alloys of such metals, e.g., platinum-palladium, platinumrhodium, may serve in the platinum group metal component of the catalysts.
The amount of promoting metal is generally a minor portion of the catalytic composite based on the weight of the total promoting metal and the high surface area refractory oxide support, and the amount is sufficient to provide a desired catalyticallypromoting effect during the use of the catalyst. Such amounts may depend on the choice of metal and the intended use of catalyst, and the amounts, are generally at least about 0.01 weight % based on the total promoting metal and high area base. These amounts may be up to about 30 or 40% or more, and preferably, the amounts are about 1 to 20%. In the case of the base or non-precious metals the amounts are frequently at least about 2%. In the case of platinum group metals, the amounts do not materially exceed about 5 weight percent based on the promoting metal component and the high area support. For instance, the amount may be about 0.01 to 4% and is preferably about 0.05 to 2%. Frequently, when the catalyst is in the form of pellets, the amount of platinum group metal is about 0.02 to 2 or more weight percent and is most often up to about 0.2 weight percent based on the total catalyst. When the platinum group metal component of the catalysts contains more than one of such metals, this component may, for instance, be composed of a major amount of platinum and a minor amount of one or more of the other platinum group metals, e.g., palladium, rhodium or ruthenium. For example, this component of the catalyst may have about 55 to 95 weight % platinum and about 5 to 45 weight % palladium or rhodium based on the total of these metals. The amounts of the catalytically-promoting.met- als, whether they be base or precious metals, are stated herein on the basis of the metals regardless of their form.
Catalysts which may be particularly useful in systems in which it is desired to conduct both oxidation and reduction simultaneously, for instance, to reduce nitrogen oxides while oxidizing carbon monoxide and hydrocarbons which may be present in the reaction system comprise a platinum group metal and one or more base metal components which may be selected from those described above, and may particularly contain an iron group metal such as nickel, for instance, in the form of metal oxides, e.g., nickel oxide. The amounts of the platinum group metal present may be as indicated above, e.g., about 0.01 to 4%, preferably about 0.5 to 1.5 or 2%, while the base metal is often present in an amount greater than the platinum group metal, say at least about 2% and up to about 20%. These amounts are again based on the total weight of the promoting metal and the high area support.
The macrosize catalysts have alumina applied to their surfaces to provide protection against the poisoning effects of various materials such as lead, zinc, other metals, sulfur, phosphorus and the like. Often the surface-applied alumina (Al203 basis) comprises a minor amount, say, about 10 to 100%, of the total weight of the catalytic promoting metal and the high area support, and preferably this amount is about 20 to 75 percent, and does not unduly adversely affect, if at all, the catalyst. The surfaceapplied alumina contains catalytically-active alumina or a hydrous alumina precursor thereof, as an essential component. This active alumina component is of the high surface area-type, e.g., having a surface area 6f at least about 25, preferably at least about 100, square meters per gram as determined, by the BET method, and is generally referred to as being catalyticallyactive. The active aluniinas include the members of the gamma or activated alumina family, such as gamma and eta aluminas, as distinguished from relatively inactive, low surface area alpha-alumina. The surfaceapplied materials .may be calcined or activated alumina or a hydrous alumina which can be converted to active alumina by calcination, or use, at high temperatures, for instance, amorphous hydrous alumina, alumina monohydrate, alumina trihydrate or their mixtures. These alumina materials may contain minor amounts of other components such as rare earth oxides, e.g., ceria, silica and the like. The alumina is preferably a major amount of the surfaceapplied material on a solids basis. Most desirably, the amount of alumina is at least about 75% of the total weight of the solids.
If other ingredients are added to the catalyst after the surface-applied alumina component, it is preferred that they be essentially free of catalytically-active, promoting metal components, e.g., platinum group metals, or other promoters, of substantially greater catalytic activity than the surface-applied alumina component.
The high area support with which the catalytically-active, promoting metal component is combined in the catalysts of this invention, is comprised of one or more refractory oxides. These oxides include, for example, silica and metal oxides such as alumina, including mixed oxide forms such as silica-alumina, aluminosilicates which may be amorphous or crystalline, aluminazirconia, alumina-chromia, alumina-ceria and the like. Preferably, the support is composed to a major extent of alumina which especially includes the members of the gamma or activated alumina family, such as' gamma and eta aluminas. The support materials which are in admixture with the catalytically-active, promoting metal component in the catalysts of this invention are often referred to as being in catalytically-active form, but such activity is of a low order compared with that of the catalytically-active, promoting metal components. The high surface area supports comprise a major amount based on the combined weight of the support and catalytically-active, promoting metal, and the surface area of the support is usually at least ab'out 25 square meters per gram as determined' by the BET method, preferably at least about 100 square meters per gram.
The catalysts of this invention are in macrosize form as are the catalytic compositions to which the 'alumina is applied to impart the desired resistance to the effect of materials which would otherwise poison the catalysts to a greater extent. Generally, macrosize catalysts have minimum dimensions of at least 1/16 inch, and often at least one or all dimensions are at least 1/8 inch.
The catalyst's may be in particle form such as spheres, cubes, elongated pellets or the like, but preferably are in the form of monolithic or unitary structures having a plurality of gas flow paths through a single piece of catalyst.
The catalysts of the invention may have a carrier component which is relatively catalytically-inert compared with the high surface area support, and the carrier is generally of considerably lower total surface area than the support which is applied thereto. Thus, the carrier may have a total surface area of less than about 5 or 10 square meters per gram, more often less than about 1 square meter per gram, as determined by the BET method. The carrier may be in macrosize particle form and preferably is in monolithic form, e.g.. a honeycpmb configuration. The high area support material is generally distributed as a coating over most. if not all, of the surface of the carrier. and usually the high surface area support material is present in the catalysts in a minor amount based on the weight of the relatively inert carrier. say about 5 to 25. preferably about 10 to 20.
weight percent.
The relatively inert carriers of the catalysts of this invention may be made of one or more of a variety of materials. but preferably are composed primarily of one or more refractory oxides or other ceramics or metals. The preferred carriers are comprised of cordierite, cordierite-alpha alumina, silicon nitride, zircon mullite, spodumene, alumina-silica-magnesia or zirconium silicate. Examples of other refractory ceramic materials utilizable in place of the preferred materials as a carrier are sillimanite, magnesium silicates, zircon, petalite, alphaalumina and aluminosilicates. Although the carrier may be a glass ceramic, it is preferably unglazed and may be essentially entirely crystalline in form and marked by the absence of any significant amount of glassy or amorphous matrices, for instance, of the type found in porcelain materials. Further; the structure may have considerable accessible porosity as distinguished from the substantially non-porous porcelain utilized in electrical applications, for instance in spark plugs, characterized by having relatively little accessible porosity. Thus, the carrier structure may have a water pore volume of at least about 10 weight percent. Such carriers are described, for example, in U. S.
Patent No. 3,565,830, herein incorporated by reference.
The monolithic carriers of the catalysts of this invention are of the type that have a plurality of passages through a single piece of the carrier. The passages are open to fluid flow and thus are not blocked or sealed against flow from an inlet to a separate outlet, and, accordingly, the passages are not merely surface pores. The passages are generally rather large compared with the size of the surface pores in order that the fluids going through the passages are not subject to excessive pressure drop. The monolithic catalyst carriers have a unitary, skeletal structure of macrosize with a minimum cross-sectional dimension generally perpendicular to the direction of fluid flow therethrough of. for instance. at least about 2 centimeters. e.g., in honeycomb form. and have flow path lengths of at least about 10 millimeters. preferably at least about 20 millimeters.
The flow passages of the monolithic darrier may be thin-walled channels providing a relatively large amount of superficial surface area. The channels can be one or more of a variety of cross-sectional shapes and sizes.
The channels can be of the cross-sectional shape of. for example. a triangle. trapezoid, rectangle. polygon or more than four sides.
square. sinusoid. oval or circle. so that cross-sections of the carrier represent a repeating pattern that can be described as a honeycomb, corrugated or lattice structure.
The walls of the cellular channels are generally of a thickness necessarv to provide a sufficiently strong unitary body. and the thickness will often fall in the range of about 2 to 25 mils. With this wall thickness, the structures may contain from about 50 to
2500 or more gas inlet openings for the flow
channels per square inch of cross-section
and a corresponding number of the gas flow
channels, preferably about 60 to 500 gas
inlets and flow channels per square inch.
The open area of the cross-section may be in excess of about 60% of the total area. The size and dimensions of the unitary refractory .skeletal support of this invention can be varied. The support is unitary or monolithic
in the sense that a significant portion, preferably a major portion or even essen
tially all, of its cross-section is composed of
one interconnected skeletal structure or
unit. Generally, such a unit may have a
cross-sectional area of at least about 1.5
square inches, preferably at least about 2
square inches.
In an aspect of this invention, the catalyst
in the first zone has about 50 to 300,
preferably about 60 to 300, gas flow chan
nels per square inch of surface area of the
face of the catalyst. Desirably, the first
catalyst has large flow through openings,
i.e., less gas flow channels per square inch,
in order than minimal back pressure be
provided and any formation of deposits on
the catalyst surface would not rapidly cause
plugging of the catalyst. The catalyst in the
second and subsequent, if employed,
catalyst zones may also employ large open
ings.
In the aspect of this invention wherein the
catalyst in a catalyst zone is comprised of a
plurility of sequentially adjacent catalyst
bodies, the first catalyst body generally may
have less than about 100, frequently about
50 to 100, gas flow channels per square inch
of cross section. The second and additional
downstream catalyst bodies, if employed,
generally may have at least about 150, often
at least about 200, gas flow channels per
square inche of cross-section. The catalyst
bodies are sequentially adjacent, i.e., they
may be integral or in contact, or they may
be separated, but not by such distances that
significant cooling of the gases occurs and
are arranged such that the gases pass
through the preceding catalyst body prior to
passing the following catalyst body. The
ratio of volume of the first catalyst body to
the overall catalyst body may vary widely
and frequently the first catalyst body comi prises about 10 to 90 volume percent of the
total catalyst. When employed in the pro
cess of this invention for treating exhaust
gases for two-stroke engines, the sequential
adjacent catalyst bodies are employed at
least in the first catalyst zone.
The invention is further described with
reference to the drawings in which
Figure I is a schematic diagram of an
apparatus of this invention having two
catalyst zones, and
Figure 2 is a schematic diagram of an apparatus of this invention having two catalyst zones and supplemental air supplied between the first and second catalyst zones.
With reference to the drawings, the numeral 10 generally designates an exhaust port of an exhaust manifold from a two-stroke internal combustion engine. The exhaust gases from the internal combustion engine pass from the exhaust port to first catalyst interconnect line 12 to first catalyst zone 14.
The first catalyst zone 14 contains catalyst 16 mounted therein. The gases exit first catalyst zone 14 and pass through cooling zone or line 18 whereat the gases are cooled and transported to second catalyst zone 20 having catalyst 22 mounted therein. The gases exit the second catalyst -zone 20 vialine 24 and may be exhausted to the atmosphere, transported to a muffler, or the like.
With reference to Figure 2, air line 26 is provided to supply air to the gases in cooling zone 18 flowing to the second catalyst zone 20. The rate of flow of air to the cooling zone 18 is controlled by control means 28 which may be a valve, volume flow adjustable pump, or the like, which is in turn controlled by sensing means 30 which is in communication there-with. Sensing means 30 may be in communication with at least one of the carburetors of the engine to respond to fuel-rich or fuel-lean conditions, to the ignition system or drive mechanism of the engine to respond to engine speed and thus the rate of flow of the exhaust gases, to a temperature sensor before or after the first catalyst zone 14, to a carbon monoxide and/or hydrocarbon sensor before or after the first catalyst zone 14, or to an oxygen sensor before or after the catalyst zone 14.
The supplemental air may thus be supplied to the exhaust gases in amounts suitable for operation of the engine exhaust treatment system to provide sufficient oxygen for combustion of the combustible impurities in the exhaust gases and/or to provide sufficient cooling of the gases prior to passing to a catalyst zone.
The invention is further illustrated by the following Example. All parts and percentages are by volume unless otherwise designated. The works "Yamaha" and "Clayton" are registered Trade Marks.
Example
A Yamaha motorcycle having a two cylinder, 350 cubic centimeter, two-stroke engine is provided with an exhaust treatment device similar to that depicted in
Figure 2. The air supply is manually controlled to provide 1.5 cubic feet per minute of air at motorcycle speeds of less than about 30 miles per hour and 4.0 cubic feet per minute of air at motorcycle speeds of greater than 30 miles per hour. The air is injected into the exhaust immediately downstream of the rear face of the first catalyst.
The first catalyst is positioned 15 inches downstream from the exhaust manifold port and contains two sequentially-abutting pieces of unitary catalyst providing a total catalyst volume of 181 cubic centimeters and cross-sectional area of 17.8 square centimeters. The upstream catalyst piece has a length of 1 inch and has 64 openings or gas flow passages per square inch and the adjacent downstream catalyst piece has a length of 3 inches and has 260 openings per square inch. The catalyst in the second catalyst zone is essentially identical to that in the first catalyst zone. The first and second catalysts are separated by 10.5 inches, and conventional metal exhaust tubing interconnects the catalyst zones. The effluent from the second catalyst zone passes to a conventional muffler for the motorcycle. The fuel employed in this example for the motorcycle is a conventional combination of commercial two-stroke lubricating oil injected into gasoline having a 91 research octane number, about 0.02 to 0.025 gram of lead per gallon, an average of about 300 parts per million of sulfur, and less than about one part per million of phosphorous.
The use of the process of this invention on the two-stroke motorcycle described above is demonstrated using a motorcycle dual-roll chassis dynomometer (Clayton Model) with an inertia weight of 480 pounds. The motorcycle is cooled during testing with two 29 inch fans, one on each side of the front tire and angled toward the engine. The cooling air flow is approximately equivalent to the air flow at motorcycle speeds of 25 miles per hour.
The effluent gases from the exhaust system are analyzed essentially in accordance with the EPA Light Duty Vehicle Emission
Test Procedure (1975-FTP). The duration of the test is about 31 minutes with about 14 minutes of operation under stop and go conditions ranging from idle to about 35 miles per hours, and about 10 percent of the test is conducted at a motorcycle speed of about 50 miles per hour. During the emissions test, the emissions are determined to be 5.2 grams of hydrocarbon per mile, 10.4 grams of carbon monoxide per mile and 0.03 gram of nitrogen oxides per mile. Without employing the process of this invention, the emissions are determined to be about 18.4 grams of hydrocarbon per mile, 22.6 grams of carbon monoxide per mile, and 0.03 gram of nitrogen oxides per mile. The maximum temperature profiles of the exhaust treatment system are determined for engine operations at 56 miles per hour and under stop and go driving conditions at less than about 35 miles per hour. At about 56 miles per hour, the exhaust gases impinging on the first catalyst are about 710 F., and the effluent from the first catalyst is about 1410"F. The gases impinging on the second catalyst are about 13700F., and the effluent from the second catalyst is about 1640 F.
Under stop and go conditions, the exhaust gases impinging on the first catalyst are about 588"F., and the effluent from the first catalyst is about 1050"F. The gases impinging on the second catalyst are about 685"F., and the effluent from the second catalyst is about 1090"F.
WHAT WE CLAIM IS:
1. A process for catalytically treating an exhaust gas emanating from an internal combustion engine and comprising carbon monoxide, hydrocarbons and free oxygen, which process comprises (a) contacting the gas with a first catalyst body to partially oxidize the gas and to provide a first catalyst combustion effluent containing combustible values and (b) contacting the exhaust gas treated in the first catalyst body with a second catalyst body positioned sequentially downstream with respect to the first catalyst body for receiving the exhaust gas combusted in the first catalyst body and providing a combustion effluent, the temperatures in the first and second catalyst bodies being insufficient to be deleterious to the catalysts, the first catalyst body having a plurality of gas flow passages with inlet openings and outlet openings for receiving and emitting the exhaust gas, the second catalyst body having a plurality of gas flow passages having inlet and outlet openings for receiving and emitting an effluent gas, and the number of individual gas flow passages per unit of cross-sectional area of the first catalyst body being lesst than the number of individual gas flow passages per unit of cross-sectional area of the second catalyst body whereby the open crosssectional area of individual gas flow passages of the first catalyst body is greater than the open cross-sectional area of individual gas flow passages of the second catalyst body to avoid plugging of the gas flow passages of the said bodies.
2. A process according to claim 1, wherein the open cross-sectional area of each of the catalyst bodies is at least 60 per cent of its total cross-sectional area.
3. A process according to claim 1 or 2, wherein the first catalyst body has less than 100 gas flow passages per square inch of cross-sectional area and the second catalyst body has at least 150 gas flow passages per square inch of cross-sectional area.
4. A process according to any of claims 1 to 3, wherein the first catalyst body has from 50 to 100 gas flow passages per square inch of cross-sectional area.
5. A process according to any of claims
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (30)
1. A process for catalytically treating an exhaust gas emanating from an internal combustion engine and comprising carbon monoxide, hydrocarbons and free oxygen, which process comprises (a) contacting the gas with a first catalyst body to partially oxidize the gas and to provide a first catalyst combustion effluent containing combustible values and (b) contacting the exhaust gas treated in the first catalyst body with a second catalyst body positioned sequentially downstream with respect to the first catalyst body for receiving the exhaust gas combusted in the first catalyst body and providing a combustion effluent, the temperatures in the first and second catalyst bodies being insufficient to be deleterious to the catalysts, the first catalyst body having a plurality of gas flow passages with inlet openings and outlet openings for receiving and emitting the exhaust gas, the second catalyst body having a plurality of gas flow passages having inlet and outlet openings for receiving and emitting an effluent gas, and the number of individual gas flow passages per unit of cross-sectional area of the first catalyst body being lesst than the number of individual gas flow passages per unit of cross-sectional area of the second catalyst body whereby the open crosssectional area of individual gas flow passages of the first catalyst body is greater than the open cross-sectional area of individual gas flow passages of the second catalyst body to avoid plugging of the gas flow passages of the said bodies.
2. A process according to claim 1, wherein the open cross-sectional area of each of the catalyst bodies is at least 60 per cent of its total cross-sectional area.
3. A process according to claim 1 or 2, wherein the first catalyst body has less than 100 gas flow passages per square inch of cross-sectional area and the second catalyst body has at least 150 gas flow passages per square inch of cross-sectional area.
4. A process according to any of claims 1 to 3, wherein the first catalyst body has from 50 to 100 gas flow passages per square inch of cross-sectional area.
5. A process according to any of claims
1 to 4, wherein the second catalyst body has at least 200 passages per square inch of cross-sectional area.
6. A process according to any of claims 1 to 5, wherein the first catalyst body is sequentially adjacent to, and in the same exhaust gas treating zone as, the second catalyst body.
7. A process according to any of claims 1 to 6, wherein the gas flow passages in the catalyst bodies are formed by walls of from 2 to 25 mils in thickness.
8. A process according to any of claims 1 to 7, wherein the exhaust gas emanates from a two-stroke internal combustion engine and comprises at least 2 volume per cent of carbon monoxide and at least 0.05 volume per cent of hydrocarbon; wherein the exhaust gas is passed to a first catalyst zone having the first and second catalyst bodies to provide a first catalyst zone cumbustion effluent containing combustible values, the first catalyst zone having an insufficient amount of oxidation catalyst to promote complete combustion of the carbon monoxide and hydrocarbon in the exhaust gas or to produce temperatures in the first catalyst zone which are deleterious to the catalyst, and the temperature of the first catalyst zone combustion effluent being from 50 to 500"C higher than the temperature of the exhaust gas passed to the first catalyst zone; and wherein the first catalyst zone combustion effluent is cooled by at least 50"C and is passed to a second catalyst zone containing an oxidation catalyst .to provide a second catalyst zone combustion effluent the temperature of which is at least 50"C higher than the temperature of the cooled first catalyst zone combustion effluent but is insufficient to produce temperatures in the second catalyst zone which are deleterious to the catalyst.
9. A process according to claim 8.
wherein the maximum temperature of the first catalvst combustion zone effluent is from 400 to 800"C.
10. A process according to claim 8 or 9.
wherein the first catalyst zone combustion effluent is cooled by 50 to 400 C prior to being passed to the second catalyst zone.
11. A process according to any of claims 8 to 10. wherein supplemental air is admixed with the first catalyst zone combustion effluent, prior to the latter being passed to the second catalyst zone. in an amount sufficient to provide an excess of free oxygen on a stoichiometric basis for combustion of the combustible values in the first catalyst zone combustion effluent.
12. A process according to any of claims 8 to 11. wherein the exhaust gas from the engine contains an insufficient amount of free oxygen on a stoichiometric basis for complete combustion of the carbon monox
ide and hydrocarbon contained therein.
13. A process according to any of claims
8 to 12, wherein the maximum temperature
of the second catalyst zone combustion
effluent is from 400 to 900 C.
14. A process according to any of claims
8 to 13, wherein from 15 to 50 volume per
cent of combustible materials in the exhaust
gas is combusted in the first catalyst zone.
15. A process according to any of claims
8 to 14, wherein the oxidation catalyst of the
second catalyst zone comprises a minor
amount of at least one metal component
having catalytic activity on a high surface
area, refractory oxide support.
16. A process according to any of claims
1 to 15, wherein the first and second catalyst
bodies each comprise a minor amount of at
least one metal component having catalytic
activity on a high surface area. refractory
oxide support.
17. A process according to claim 15 or
16, wherein said at least one metal compo
nent comprises platinum group metal.
18. A process. according to claim 16,
wherein the said at least one metal compo .nent comprises platinum group metal and
iron group metal.
19. A process according to any of claims
1 to 18. wherein the exhaust gas is passed
into contact with the first catalyst body
without significant addition of free oxygen.
20. A process according to claim 1,
substantially as hereinbefore described with
reference to either of Figures 1 and 2 of the
accompanying drawings.
21. An apparatus suitable for catalytic ally treating an exhaust gas emanating from
an internal combustion engine and compris
ing carbon monoxide. hydrocarbons and
free oxygen. which apparatus comprises a
first catalyst body for partially combusting
the gas to provide a catalytic combustion
effluent containing residual combustible
values. a second catalyst body positioned
sequentially downstream with respect to the
first catalyst body for receiving gas com
busted in the first catalyst body and for
further combusting the same to provide a
combustion gas effluent. the catalyst bodies
being such that temperatures. produced in
the catalyst bodies. and the first catalyst
body having a plurality of gas flow passages
with inlet openings and outlet openings for
passing the gas therethrough. the second
catalyst body having a plurality of gas flow
passages with inlet and outlet openings for
passing the gas therethrough. the open
cross-sectional area of individual gas flow
passages of the first catalyst body being
greater than the open cross-sectionai area of
individual gas flow passages of the second
catalyst body.
22. An apparatus according to claim 21.
wherein the open cross-sectional area of each of the catalyst bodies is at least 60 per cent of its total cross-sectional area.
23. An apparatus according to claim 21 or 22, wherein the first catalyst body has less than 100 gas flow passages per square inch of cross-sectional area and the second catalyst body has at least 150 gas flow passages per square inch of cross-sectional area.
24. An apparatus according to any of claims 21 to 23, wherein the first catalyst body has from 50 to 100 gas flow passages per square inch of cross-sectional area.
25. An apparatus according to any of claims 21 to 24, wherein the second catalyst body has at least 200 passages per square inch of cross-sectional area.
26. An apparatus according to any of claims 21 to 25, wherein the first catalyst body is sequentially adjacent to, and in the same exhaust gas treating zone as, the second catalyst body.
27. An apparatus according to any of claims 21 to 25, wherein the gas flow passages in the catalyst bodies are formed by walls of from 2 to 25 mils in thickness.
28. An apparatus according to any of claims 21 to 27, wherein there is positioned, downstream of the catalyst bodies, another catalyst body having a plurality of gas flow passages therethrough, and wherein gas cooling means are positioned therebetween.
29. An apparatus according to claim 28, wherein the cooling means comprises means for introducing an oxygen-containing gas into a passage means for the gas.
30. An apparatus according to claim 21, substantially as hereinbefore described with reference to either of Figures 1 and 2 of the accompanying drawings.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US73047176A | 1976-10-07 | 1976-10-07 |
Publications (1)
Publication Number | Publication Date |
---|---|
GB1584998A true GB1584998A (en) | 1981-02-18 |
Family
ID=24935501
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB41055/77A Expired GB1584998A (en) | 1976-10-07 | 1977-10-03 | Treatment of exhaust gases from internal combustion engines |
Country Status (13)
Country | Link |
---|---|
JP (1) | JPS5346515A (en) |
AR (1) | AR212664A1 (en) |
AU (1) | AU518302B2 (en) |
BE (1) | BE859454A (en) |
BR (1) | BR7706619A (en) |
CA (1) | CA1101638A (en) |
DD (1) | DD133058A5 (en) |
DE (1) | DE2745013A1 (en) |
ES (2) | ES462971A1 (en) |
FR (1) | FR2367188A1 (en) |
GB (1) | GB1584998A (en) |
PL (1) | PL201333A1 (en) |
SE (1) | SE7711247L (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4373452A (en) | 1980-07-28 | 1983-02-15 | Corning Glass Works | Wood burning stove |
USRE33077E (en) * | 1980-07-28 | 1989-10-03 | Corning Glass Works | Wood burning stove |
AU628474B2 (en) * | 1989-02-06 | 1992-09-17 | Nippon Shokubai Kagaku Kogyo Co. Ltd. | Catalyst for purification of exhaust gas from diesel engine |
US5894068A (en) * | 1992-12-14 | 1999-04-13 | Kharas; Karl C. C. | Reduction of NOx in the exhaust gases from internal combustion engines containing excess oxygen |
US6365118B1 (en) | 1992-12-14 | 2002-04-02 | Delphi Technologies, Inc. | Reduction of NOx in the exhaust from leanOx internal combustion engines |
FR2827908A1 (en) * | 2001-07-26 | 2003-01-31 | Peugeot Motocycles Sa | Exhaust gas purification system for two-stroke engine comprises two separate catalytic purifiers in series in exhaust pipe and device for injecting air between the purifiers |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2460709A1 (en) * | 1979-07-09 | 1981-01-30 | Renault | Protective device for catalytic purifier in vehicle exhaust system - comprises small auxiliary catalytic reactor installed upstream of purifier |
JPS5890452A (en) * | 1981-11-18 | 1983-05-30 | Nippon Seiko Kk | Grinding method and grinder using whetstone wheel |
DE3904550A1 (en) * | 1989-02-15 | 1990-08-16 | Siemens Ag | Catalyst shaped body for a flowing liquid or gaseous medium |
JP2904431B2 (en) * | 1993-03-26 | 1999-06-14 | 日本碍子株式会社 | Exhaust gas purification equipment |
DE19904314A1 (en) * | 1999-01-28 | 2000-08-17 | Porsche Ag | Exhaust gas purifying device has a catalyst arrangement consisting of a main catalyst and several pre-catalysts arranged relatively near to the cylinder head |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE497441A (en) * | 1949-08-09 | |||
DE1542112A1 (en) * | 1963-02-07 | 1972-02-24 | Engelhard Ind Inc | Process for the catalytic conversion of gaseous reactants |
DE1235666B (en) * | 1963-04-03 | 1967-03-02 | Auto Union Gmbh | Device for cleaning exhaust gases from internal combustion engines |
FR1438944A (en) * | 1965-07-07 | 1966-05-13 | Method and apparatus for the suppression of the toxicity of the exhaust gases of internal combustion engines and the removal of the foul-smelling components contained therein | |
DE1476627A1 (en) * | 1966-06-10 | 1970-04-09 | Veit Dr Ing Theodor | Method and device for cleaning gases and sound insulation, in particular for exhaust gases from internal combustion engines |
US3599427A (en) * | 1969-09-22 | 1971-08-17 | Ford Motor Co | Exhaust gas purification |
JPS4832764A (en) * | 1971-08-30 | 1973-05-02 | ||
US3791143A (en) * | 1971-11-10 | 1974-02-12 | Engelhard Min & Chem | Process and apparatus |
US3896616A (en) * | 1972-04-21 | 1975-07-29 | Engelhard Min & Chem | Process and apparatus |
IN141845B (en) * | 1973-09-26 | 1977-04-23 | Engelhard Min & Chem | |
JPS5073022A (en) * | 1973-11-02 | 1975-06-17 |
-
1977
- 1977-10-03 GB GB41055/77A patent/GB1584998A/en not_active Expired
- 1977-10-04 BR BR7706619A patent/BR7706619A/en unknown
- 1977-10-05 CA CA288,201A patent/CA1101638A/en not_active Expired
- 1977-10-05 FR FR7729957A patent/FR2367188A1/en not_active Withdrawn
- 1977-10-05 ES ES462971A patent/ES462971A1/en not_active Expired
- 1977-10-05 DD DD7700201374A patent/DD133058A5/en unknown
- 1977-10-06 JP JP11955477A patent/JPS5346515A/en active Pending
- 1977-10-06 AU AU29420/77A patent/AU518302B2/en not_active Expired
- 1977-10-06 SE SE7711247A patent/SE7711247L/en not_active Application Discontinuation
- 1977-10-06 PL PL20133377A patent/PL201333A1/en unknown
- 1977-10-06 BE BE181518A patent/BE859454A/en unknown
- 1977-10-06 DE DE19772745013 patent/DE2745013A1/en not_active Withdrawn
- 1977-10-07 AR AR269506A patent/AR212664A1/en active
-
1978
- 1978-08-23 ES ES472787A patent/ES472787A1/en not_active Expired
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4373452A (en) | 1980-07-28 | 1983-02-15 | Corning Glass Works | Wood burning stove |
USRE33077E (en) * | 1980-07-28 | 1989-10-03 | Corning Glass Works | Wood burning stove |
AU628474B2 (en) * | 1989-02-06 | 1992-09-17 | Nippon Shokubai Kagaku Kogyo Co. Ltd. | Catalyst for purification of exhaust gas from diesel engine |
US5894068A (en) * | 1992-12-14 | 1999-04-13 | Kharas; Karl C. C. | Reduction of NOx in the exhaust gases from internal combustion engines containing excess oxygen |
US6365118B1 (en) | 1992-12-14 | 2002-04-02 | Delphi Technologies, Inc. | Reduction of NOx in the exhaust from leanOx internal combustion engines |
FR2827908A1 (en) * | 2001-07-26 | 2003-01-31 | Peugeot Motocycles Sa | Exhaust gas purification system for two-stroke engine comprises two separate catalytic purifiers in series in exhaust pipe and device for injecting air between the purifiers |
Also Published As
Publication number | Publication date |
---|---|
AR212664A1 (en) | 1978-08-31 |
SE7711247L (en) | 1978-04-08 |
BE859454A (en) | 1978-04-06 |
AU2942077A (en) | 1979-04-12 |
BR7706619A (en) | 1978-07-18 |
FR2367188A1 (en) | 1978-05-05 |
ES472787A1 (en) | 1979-02-16 |
AU518302B2 (en) | 1981-09-24 |
PL201333A1 (en) | 1978-04-24 |
DE2745013A1 (en) | 1978-04-13 |
JPS5346515A (en) | 1978-04-26 |
DD133058A5 (en) | 1978-11-29 |
ES462971A1 (en) | 1978-12-16 |
CA1101638A (en) | 1981-05-26 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PS | Patent sealed | ||
732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
PCNP | Patent ceased through non-payment of renewal fee |