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US3094394A - Catalytic muffler - Google Patents

Catalytic muffler Download PDF

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US3094394A
US3094394A US4467460A US3094394A US 3094394 A US3094394 A US 3094394A US 4467460 A US4467460 A US 4467460A US 3094394 A US3094394 A US 3094394A
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Prior art keywords
end
catalyst
tube
exhaust
housing
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William B Innes
Mordach Walter
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Wyeth Holdings Corp
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Wyeth Holdings Corp
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10Exhaust 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
    • F01N3/24Exhaust 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
    • F01N3/30Arrangements for supply of additional air
    • F01N3/34Arrangements for supply of additional air using air conduits or jet air pumps, e.g. near the engine exhaust port
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10Exhaust 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
    • F01N3/18Exhaust 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
    • F01N3/20Exhaust 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
    • F01N3/2053By-passing catalytic reactors, e.g. to prevent overheating
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10Exhaust 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
    • F01N3/18Exhaust 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
    • F01N3/22Control of additional air supply only, e.g. using by-passes or variable air pump drives
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10Exhaust 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
    • F01N3/24Exhaust 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
    • F01N3/28Construction of catalytic reactors
    • F01N3/2839Arrangements for mounting catalyst support in housing, e.g. with means for compensating thermal expansion or vibration
    • F01N3/2846Arrangements for mounting catalyst support in housing, e.g. with means for compensating thermal expansion or vibration specially adapted for granular supports, e.g. pellets
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2290/00Movable parts or members in exhaust systems for other than for control purposes
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2330/00Structure of catalyst support or particle filter
    • F01N2330/08Granular material
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2350/00Arrangements for fitting catalyst support or particle filter element in the housing
    • F01N2350/08Arrangements for fitting catalyst support or particle filter element in the housing with means for compressing granular material
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2410/00By-passing, at least partially, exhaust from inlet to outlet of apparatus, to atmosphere or to other device
    • F01N2410/02By-passing, at least partially, exhaust from inlet to outlet of apparatus, to atmosphere or to other device in case of high temperature, e.g. overheating of catalytic reactor
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2450/00Methods or apparatus for fitting, inserting or repairing different elements
    • F01N2450/04Filling or emptying a chamber with granular material
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2470/00Structure or shape of gas passages, pipes or tubes
    • F01N2470/02Tubes being perforated
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02TCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00Road transport of goods or passengers
    • Y02T10/10Internal combustion engine [ICE] based vehicles
    • Y02T10/20Exhaust after-treatment
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S55/00Gas separation
    • Y10S55/30Exhaust treatment

Description

June 18, 1963 w. B. INNES ETAL CATALYTIC MUFFLER Filed July 22, 1960 IN V EN TORS W ILL/AM B. lN/VES WA L 7'5 M ORDACH ATTORNEY United States Patent @fiice 3,094,394 Patented June 18, 1963 3,0?4,394 CATALYTIC MUFFLER William B. Innes and Walter Mordach, Stamford, Conn, assignors to American Cyanamid Company, New York, N.Y., a corporation of Maine Filed July 22, 1960, Ser. No. 44,674 3 Claims. (C1. 23-28S) This invention relates to catalytic apparatus of the type employable with an internal combustion engine for oxidizing the toxic and obnoxious components of hydrocarbon combustion exhaust gases.

More particularly, the present invention relates to a catalytic converter and more preferably, a catalytic converter which is capable of being readily inserted into the exhaust system of an internal combustion engine as, for example, in lieu of a muflier therein. Suitable converters may be inserted before or after the exhaust manifold or other convenient locations.

The exhaust gases from the combustion of hydrocarbon fuels such as gasoline, diesel fuel and the like in internal combustion engines, contain mixtures of carbon monoxide and various hydrocarbons, both saturated and unsatu rated, nitrogen and other constituents. These mixtures are both poisonous and obnoxious.

In addition to the known hazards resulting from the inhalation of combustion exhaust gases of hydrocarbon fuels, such gases have, of comparatively recent times, been identified with smog formation and, to a lesser extent, with various forms of cancer.

Thus, it is known that exhaust gases from automobiles, particularly olefin and nitrogen oxide components, have been demonstrated to be a primary cause of photochemical smog in heavily populated metropolitan centers of this country, such as Los Angeles, California. Smog, as the term is generally employed, is broadly understood to refer to a variety of phenomena which are related to the interaction of nitrogen oxides, hydrocarbons and sunlight. These include a fog-like haze, high oxidant concentration in the atmosphere (mostly ozone), eye irritation, plant damage and the like. In general, smog is defined more fully in an article by W. L. Faith, entitled Nature of Smog, in Chemical Engineering Progress, 53, 406 (1957).

The hazards and nuisance created by hydrocarbon combustion exhaust gases from internal combustion engines have, over the years, resulted in a number of processes, catalysts and apparatus whereby the reduction or the elimination of the harmful components of these gases has been the primary object.

A relatively common device employed for this purpose has been what is sometimes referred to as a catalytic mufller which normally refers to a device which is to be substituted into the exhaust line of an internal combustion engine in lieu of a mufiler. This has been a particularly preferred area of activity in View of the fact that the cost of such a device is reduced by the cost of a conventional muffler normally employed, and by other obvious advantages. Such devices are inserted into the exhaust line of an internal combustion engine and by the action of catalysts contained therein, oxidize the exhaust gases so that the exit gases from the muflier contain reduced amounts of the harmful and obnoxious constituents of the exhaust gases.

To our knowledge, none of these devices have in the past proved successful, probably because of a number of practical considerations. Among these might be included the development of significant back pressures, the size, weight and cost of such devices, the comparative short activity life of catalysts employed and the difiiculty of recharging the device with fresh catalysts, the inability of many of these devices to withstand the elevated temperatures obtained in the catalytic oxidation of exhaust gases, the difiiculty in achieving uniform conditions in such devices under operating conditions and the difficulty in maintaining the catalyst bed under a constant pressure so as to prevent the formation of voids therein whereby the catalyst is rapidly and prematurely attrited and whereby catalyst is prematurely deactivated through the development of hot spots in the catalyst bed.

The present invention has for its principal object the providing of a catalytic converter and, more preferably, a catalytic mufller whereby uniform conditions are maintained both in the operation of the internal combustion engine and in the muffler itself by virtue of its novel design.

It is a particular object of the present invention to provide such a catalytic muffler which is of simple construction, is easily adaptable to be positioned in the exhaust line of an internal combustion engine and may be readily recharged after deactivation of the catalyst contained therein.

It is a further and particular object of the present invention to provide a catalytic muffler so constructed that losses in catalysts due to attrition are readily and automatically compensated for and whereby the presence of voids otherwise formed in a catalyst bed are automatically eliminated, thus avoiding excessive attrition and deactivation.

It is a further and particular object of this invention to provide a catalytic muffler which, in the event that excessively high temperatures are achieved during its normal operation, automatic means for permitting the ready exit of the unoxidized exhaust gases is provided.

Further objects include providing a catalytic muffler which substantially eliminates pressure drop or results in a low pressure drop due to minimum back pressure, and to provide a muffler device which effects good noise elimination.

These and other objects, advantages and features of the present invention will become more'apparent from the detailed description thereof set forth, which description is particularly in reference to the accompanying drawing of which:

' FIGURE 1 is a longitudinal cross-sectional view of the catalytic converter contemplated by this invention;

FIGURE 2 is a sectional view along the line 22 of FIGURE 1; and

' FIGURE 3 is an end view of the converter of FIG- URE 1.

In accordance with the present invention, a catalytic converter is provided comprising a cylindrical housing having an inlet end and an outlet end, and having centrally positioned therein a longitudinally extending cylindrical tube, which is perforated intermediate its ends. A longitudinally extending perforated cylindrical sleeve having a cross-section greater than that of the aforesaid cylindrical tube but less than that of said housing is positioned intermediate the inlet and outlet ends of the cylindrical housing and the area between the said cylindrical sleeve and tube define the bed for hydrocarbon combustion exhaust catalyst. The area between the outside surface of said sleeve and said inside surface of said housing define a space for catalytically oxidized exhaust gases to be carried to the outlet end of the housing. The catalytic mufiier of this invention is of a symmetrical design whereby uniform operating conditions are maintained for both the internal combustion exhaust engine and in the catalytic muflier itself.

While caflalytic mufflers of this invention are described as being cylindrical and as being of symmetrical design, it should be noted that the term cylindrical as employed herein also contemplates catalytic converters having elipa tical configurations. In all of the converters of this invention the construction may further be described as being radial in that the catalyst bed extends outwardly from the center of the device where the exhaust gases enter. It is essentially this radial arrangement from which uniform operation conditions, faster warm up times, and maximum flexibility of construction are accomplished that comprise the essential elements of this invention.

At the inlet end of the catalytic muffler, means are provided for the addition of air to the combustion exhaust gases entering the catalytic mulfler. This may be accomplished by the construction of a venturi at the inlet end thereby avoiding the need for pumps and other complicated and expensive devices readily subject to mechanical failure.

Further, at the inlet end of the device, inside the cylindrical housing and surrounding the centrally disposed cylindrical tube through which the exhaust gases enter the catalytic chamber, a catalyst reservoir is provided which may contain, for example, between 2 and percent or more of the total volume of catalysts in the activity zone. Means are provided for maintaining a uniform and steady pressure on this catalyst reservoir as, for example, a spring which means preferably have an external or exposed element whereby pressure on the reservoir may be perio dically increased as the catalyst attrits. This aspect of the present invention is particularly desirable in that it permits, a user, by comparatively simple adjustment, to maintain the catalyst bed in this catalytic mufiler of uniform density and thereby prevents excessive attrition and premature deactivation of the catalyst.

At the exit end of the catalytic muffler, means areprovided for closing the catalyst bed as for example, a suitable plate-like member disposed about the central tube. In order to recharge the muffler, this plate-like member must be removed and so it may be connected to the outside end plate that this may be accomplished readily. Alternatively, such a plate-like member may be placed under pressure as for example by means of springs.

A further important aspect of this invention involves the employment of relief means whereby when the catalyst bed reaches a predetermined and undesirable intense heat, which if allowed to continue would result in the ready deactivation and possible destruction of the catalyst contained therein as well as the container; a cap or other closing means positioned at the exit end of the centrally positioned cylindrical tube is released, permitting the combustion exhaust gases to flow directly through the device without benefit of contact and oxidation by the catalyst bed. Such a means could involve a heat sensitive cap subject to melting at a predetermined temperature or, and preferably, a capping means maintained in the closed position by a heat fusible element which when a predetermined heat is reached becomes molten enabling the capping means to be opened merely by the force of unoxidized exhaust gases contacting the same.

Referring to the drawing, in which a specific illustrative embodiment of this invention will be described, it will be seen that a catalytic muffler A of a cylindrical configuration and a symmetrical design is shown comprising a cylindrical housing 1, preferably of a high grade heat resistant steel, though in general steels or metals, and preferably light weight metals able to resist temperatures of up to 750 C. may be employed. Said cylindrical housing 1 has an inlet end plate 2 and an outlet end plate 3 and having extending at right angles from end plates 2 and 3 centrally positioned inlet and outlet tubes 4 and 5 respectively. Tubes 4 and 5, in general, provide a convenient means for adapting the catalytic muffler of this invention into an exhaust system of an internal combustion engine and for purposes of this description are of substantially the same diameter. With respect to tube 4, it will be noted that this tube extends into the housing 1 in a centrally disposed longitudinal plane terminating a short distance from the inside surface 6 of exit end 3 and in the same plane as exit tube 5. This portion of tube 4 is comprised 'of a major perforated segment 7 which segment may be said to comprise a major and central portion of the internal segment of tube 4.

The entrance end of tube 4 is designed in the form of a venturi whereby the combustion exhaust gases are readily mixed with air or other oxidizing gas to insure their complete oxidation. The venturi is composed of a centrally disposed tapered cone 8, the narrowed inner end 9 of which is positioned between but spaced from the inside walls of a collar-like member 10, the end of which extends inward from narrowed end 9 but is spaced from the perforation 7 in the central portion of tube 4. An opening 1 1 in the upper surface of the external portion of tube 4 is the entrance for air which is drawn in by the raw combustion exhaust gases entering the external end of tube 4 from the exhaust line of the internal combustion engine.

Positioned about the longitudinally extending cylindrical tube 4 is a longitudinally extending perforated heat resistant metal sleeve 12 having a crosssection greater than that of said cylindrical tube 4 but less than that of the inside diameter of housing 1. In general, the diameter of sleeve 12 will be from about 1.5 to about 3 times the diameter of tube 4. In this illustrative embodiment it is about 2.5 times. The cylindrical sleeve 12 has perforations l3 and is of a length substantially equal to the length of the internally disposed portion tube 4. Sleeve 12 may be welded to the inside surface of inlet entrance plate 2 or otherwise supported therein by suitably positioned lugs or the like. Positioned between the outer surface of longitudinally extending tube 4- and longitudinally extending sleeve 12 is the catalyst bed 14 containing a suitable oxidizing catalyst 15. Such catalysts may be any of a number suitable for use for this purpose as, for example, an iron oxide-chromium oxide catalyst prepared from to 97 percent of E2 0 and 0.5 to about 15 percent of Cr O which is described in copending application Serial No. 786,973, filed January 15, 1959. Alternatively, such catalysts may be of the type described in U.S. Patent 2,912,300.

Exit pipe is preferably joined to end plate 3 as by a weld or other suitable means. Extending perpendicular from the inside surface 6 of plate 3 are arms 16 which in turn are connected to a circular plate 17 having a centrally disposed opening therein for receiving the exit end of longitudinally positioned tube 4. When assem bled, as will be seen in FIGURE 1, plate 17, positioned on arms 16, functions as a retaining member for the catalyst 15 in catalyst bed 14. Alternatively, springs 18 (only one of which is shown only on a lower arm 16) may be positioned over the arms 16, as a means of maintaining a force at the exit end of the mufiier to maintain the density of the catalyst bed. In such an arrangement it will be apparent that plate 17 is free for longitudinal movement.

The exit end plate 3 is mechanically joined to the cylindrical housing 1 in that the exit end of said housing contains an annular flange 19, said annular flange I9 and exit plate 3 having correspondingly positioned holes 25 in their peripheral edges for receiving a suitable number of bolts 21 which are secured in position by nuts 22. It will be seen that such an arrangement provides an easy method for removing deactivated catalyst from catalyst bed 14 and permits the ready and rapid refilling of said catalyst bed.

At the inlet end of the illustrative exhaust muffler, the catalyst bed is provided with a reservoir area 23 which may, depending upon the particular device, contain from between about 2 and about 10 percent or more of the total catalyst charged to a given catalyst bed. In eifect, this reservoir area 23, which area can be varied by the amount of compression placed on springs 24 normally does not include catalyst particles extending over the perforated portion of tube 4. Reservoir area 23 has positioned at its outside end a ring-like plate 25 which has a centrally disposed opening for receiving tube 4. Plate 25 is movably positioned between the outside surface of tube 4 and the inside surface of sleeve f2. Positioned between outside surface of plate 25 and the inside surface of the entrance end plate 2 is a second cylindrical plate 26 having a centrally disposed opening which also is free for longitudinal movement and positioned between said plate 26 and said plate 25 are a plurality of coil springs 24. Preferably, springs 24 are made of a highly heat resistant steel alloy and is preferably positioned in a refractory wool or other stabilized heat resisting media 25a.

Extending through thread retaining nuts 27 positioned in contact with inlet end plate 2 are a plurality of screws 28. The inside end of screws 28 are in contact with the outside surface of plate 26 and as will be apparent by turning the screw in the appropriate direction, the pres sure of springs 24 can be brought to bear on plate 25 and consequently the catalyst reservoir in the reservoir area. Such an arrangement enables the user to maintain a uniform density in the catalyst bed simply by tightening screw 28. In this connection it will be noted that a fully packed uniform density is important if excessive losses due to attrition is to be avoided. In addition, the action of the springs alone will compensate for some loss in bed density due to attrition.

The outlet or exit end of centrally disposed tube 4 has thereon a cap 29 which is connected to a wire 30 extending through the upper surface of tube 4 through the catalyst bed 14 and is looped 31 between the internal surface of cylindrical housing 1 and the outer surface of sleeve 12. Positioned about the loop 31 is a heat sensitive metallic ring 32. Wire 30 then extends through the upper surface of cylindrical housing 1 where it is coiled 33 and the end thereof afiixed to a mounting stud 34. This simple device insures that the catalyst bed will not be prematurely deactivated and the device overheated as, for example, as a result of the misfiring of a cylinder in an internal combustion engine, in that as the temperature of the oxidized combustion exhaust gases exceed a predetermined temperature as, for example, 800 C., loop 31 flows permitting the coiled 33 and loop 31 portion of the wire to be stretched under the force of the combustion exhaust gases against the inside surface of cap 29. This permits the direct exit of the raw exhaust gases through outlet pipe 5, whereby little or no oxidation is effected.

As will be apparent in the operation of the instant device, the hydrocarbon combustion exaust gases enter inlet pipe 4 and the force of their movement results in air entering the venturi arrangement at the entrance end through opening it. This mixture then enters the central perforated portion of tube 4 from Where it is distributed readily to the catalyst bed 12 through perforations 7 Where it is oxidized and enters into the conduit or channel-like area between the inside surface of housing 1 and the outside surface of sleeve 12 through perforations 13. The natural direction of flow is then to the outlet end of the device and the ultimate emission of the oxidizing gases through outlet pipe 5 directly into the atmosphere or into suitable conduit for emission into the atmosphere The employment of a device of the type illustrated in FIGURES 1-3 whereby the inlet gas enters at the center of the cylindrical mufiler device in addition to being capable of simple adaptation to the above described and illustrative combinations (means for maintaining catalyst bed density etc.) its construction lessens Warm-up time significantly in that the maximum amount of exhaust gas contacts the maximum amount of catalyst in the briefest time period. Thus mufflers of the type of this invention are in general characterized by more rapid warm-up than units with a centrally positioned catalyst bed, such as is described in US. Patent 2,909,415.

It will be evident from the present description that the catalytic niufiler device of this invention results in low catalytic attrition and fast warm-up in addition to being of easy and simple assembly and manufacture. It will be apparent that other numerous modifications and advantages of this invention will be obvious and, therefore, no limitations should be set thereon except insofar as they are set forth in the appended claims.

We claim:

1. A catalytic muffler for oxidizing hydrocarbon combustion exhaust gases comprising a cylindrical housing having an inlet end and an outlet end, a longitudinally extending cylindrical tube centrally positioned within said housing between said inlet end and said outlet end and extending from said inlet end, that portion of said tube within said housing being perforated, a capping element for said tube adjacent said outlet end, a longitudinally extending perforated cylindrical sleeve Within said housing and surrounding said tube, said sleeve having a crosssection greater than that of said tube but less than that of said housing, catalyst particles for oxidizing said hydrocarbon combustion exhaust gases disposed within the zone defined by said tube and said sleeve, a plate like retaining member transversely situated between said tube and said sleeve adjacent to said outlet end of said housing, the area between the outer surface of said sleeve and the inner surface of said housing defining a zone for catalytically oxidized exhaust gases to be carried to the outlet end of said housing, a moveable disk positioned within said housing and adjacent to the inlet end of said housing said disk being slideably fitted for longitudinal movement over said tube, the inner surface of said disk disposed to be in contact with catalyst particles in said catalyst zone and yieldable means contacting said slideably mounted disk whereby a force is created by said means against said catalyst particles so as to maintain said zone free of voids.

2. A catalytic muffler according to claim 1 in which a venturi is positioned Within said tube and adjacent said inlet end, that portion of said tube extending from said inlet end of said housing having an orifice for admitting air under the influence of the moving hydrocarbon combustion exhaust gases to be oxidized.

3. A catalytic mufiler according to claim 1 having means for retaining said capping element in a normally closed position and a heat sensitive element secured to said retaining means whereby when said heat sensitive element reaches a predetermined temperature, said retaining means is released thus permitting said capping element to open from a normally closed position thereby allowing hydrocarbon combustion exhaust gases to pass from said outlet end of said housing without significant oxidation.

References Cited in the file of this patent UNITED STATES PATENTS 1,465,904 'Herdle Aug. 21, 1923 1,605,484 Thompson et al. Nov. 2, 1926 1,794,276 Bowes Feb. 24, 1931 2,071,119 Harger Feb. 16, 1937 2,260,578 Murray Oct. 28, 1941 2,378,083 Hull June 12, 1945 2,937,490 Calvert May 24, 1960 2,956,865 Williams Oct. 18, 1960

Claims (1)

1. A CATALYTIC MUFFLER FOR OXIDIZING HYDROCARBON COMBUSTION EXHAUST GASES COMPRISING A CYLINDRICAL HOUSING HAVING AN INLET END AND AN OUTLET END, A LONGITUDINALLY EXTENDING CYLINDRICAL TUBE CENTRALLY POSITIONED WITHIN SAID HOUSING BETWEEN SAID INLET END AND SAID OUTLET END AND EXTENDING FROM SAID INLET END, THAT PORTION OF SAID TUBE WITHIN SAID HOUSING BEING PERFORATED, A CAPPING ELEMENT FOR SAID TUBE ADJACENT SAID OUTLET END, A LONGITUDINALLY EXTENDING PERFORATED CYLINDRICAL SLEEVE WITHIN SAID HOUSING AND SURROUNDING SAID TUBE, SAID SLEEVE HAVING A CROSSSECTION GREATER THAN THAT OF SAID TUBE BUT LESS THAN THAT OF SAID HOUSING, CATALYST PARTICLES FOR OXIDIZING SAID HYDROCARBON COMBUSTION EXHAUST GASES DISPOSED WITHIN THE ZONE DEFINED BY SAID TUBE AND SAID SLEEVE, A PLATE LIKE RETAINING MEMBER TRANSVERSELY SITUATED BETWEEN SAID TUBE AND SAID SLEEVE ADJACENT TO SAID OUTLET END OF SAID HOUSING, THE AREA BETWEEN THE OUTER SURFACE OF SAID SLEEVE AND THE INNER SURFACE OF SAID HOUSNG DEFINING A ZONE FOR CATALYTICALLY OXIDIZED EXHAUST GASES TO BE CARRIED TO THE OUTLET END OF SAID HOUSING, A MOVEABLE DISK POSITIONED WITHIN SAID HOUSING AND ADJACENT TO THE INLET END OF SAID HOUSING SAID DISK BEING SLIDEABLY FITTED FOR LONGITUDINAL MOVEMENT OVER SAID TUBE, AND INNER SURFACE OF SAID DISK DISPOSED TO BE IN CONTACT WITH CATALYST PARTICLES IN SAID CATALYST ZONE AND YIELDABLE MEANS CONTACTING SAID SLIDEABLY MOUNTED DISK WHEREBY A FORCE IS CREATED BY SAID MEANS AGAINST SAID CATALYST PARTICLES SO AS TO MAINTAIN SAID ZONE FREE OF VOIDS.
US3094394A 1960-07-22 1960-07-22 Catalytic muffler Expired - Lifetime US3094394A (en)

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US3094394A US3094394A (en) 1960-07-22 1960-07-22 Catalytic muffler
US3197287A US3197287A (en) 1961-04-03 1961-04-03 Catalytic converter

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NL267408A NL267408A (en) 1960-07-22
US3094394A US3094394A (en) 1960-07-22 1960-07-22 Catalytic muffler
GB2556061A GB919667A (en) 1960-07-22 1961-07-14 Improvements in exhaust gas catalytic purifiers and mufflers for internal combustionengines
FR868317A FR1299792A (en) 1960-07-22 1961-07-19 catalytic converter
BE606410A BE606410A (en) 1960-07-22 1961-07-20 catalytic converter

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Cited By (53)

* Cited by examiner, † Cited by third party
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US3167400A (en) * 1962-07-30 1965-01-26 Norris Thermador Corp Catalytic converter
US3172251A (en) * 1963-01-14 1965-03-09 Minnesota Mining & Mfg Afterburner system
US3180712A (en) * 1962-12-26 1965-04-27 Universal Oil Prod Co Two-stage converter-muffler
US3201207A (en) * 1961-09-15 1965-08-17 Walker Mfg Co Muffler
US3222140A (en) * 1962-10-29 1965-12-07 Universal Oil Prod Co Means and apparatus for catalytically oxidizing an exhaust gas stream
US3223491A (en) * 1962-09-27 1965-12-14 Firestone Tire & Rubber Co Muffler construction
US3236044A (en) * 1962-12-21 1966-02-22 Ruge Willi Heating system for motor vehicles
US3252767A (en) * 1963-01-21 1966-05-24 Walker Mfg Co Exhaust system
US3307920A (en) * 1962-07-10 1967-03-07 Llewellyn T Barnes Apparatus for purifying exhaust gases
DE1244477B (en) * 1964-09-22 1967-07-13 American Cyanamid Co Catalyst-silencer
US3338682A (en) * 1964-12-14 1967-08-29 Walker Mfg Co Muffler secondary air silencer
US3441382A (en) * 1963-02-07 1969-04-29 Engelhard Ind Inc Catalyst cartridge
US3445196A (en) * 1966-06-06 1969-05-20 Nelson Muffler Corp Exhaust muffler with removable catalytic unit
DE1301337B (en) * 1965-05-26 1969-08-21 Aerolyt Vertriebsgesellschaft An apparatus for detoxifying exhaust gases, particularly from internal combustion engines
US3751917A (en) * 1970-10-24 1973-08-14 Alfa Romeo Spa Exhaust chamber for a motor vehicle provided with an internal combustion engine
US3762163A (en) * 1972-06-08 1973-10-02 Tenneco Inc Bypass for catalytic reactor
US3824790A (en) * 1973-03-14 1974-07-23 Granlin Corp Catalytic exhaust purifier for diesel engines
US3838977A (en) * 1972-02-24 1974-10-01 Ethyl Corp Catalytic muffler
US3872821A (en) * 1972-12-20 1975-03-25 Nissan Motor Catalytic converter failure alarm device
US3889776A (en) * 1973-06-14 1975-06-17 Sherritt Gordon Mines Ltd Exhaust gas silencer
US3925026A (en) * 1974-08-20 1975-12-09 Gen Motors Corp Spring loaded catalytic converter with externally mounted spring
US3930805A (en) * 1973-08-27 1976-01-06 Hoechst Aktiengesellschaft Apparatus receiving catalysts for the decontamination of exhaust gas of internal combustion engines
US3945803A (en) * 1972-04-07 1976-03-23 Kali-Chemie Ag Elastic support for a ceramic monolithic catalyzer body
US3947252A (en) * 1972-04-07 1976-03-30 Kali-Chemie Ag Elastic suspension or support for a ceramic monolithic catalyzer body
US3954418A (en) * 1972-09-27 1976-05-04 Tenneco Inc. Catalytic converter with bypass
US3957445A (en) * 1974-06-12 1976-05-18 General Motors Corporation Engine exhaust system with monolithic catalyst element
US3969095A (en) * 1973-08-25 1976-07-13 Shigeru Kurahashi Air filter apparatus
US3989471A (en) * 1975-04-14 1976-11-02 Tenneco Inc. Radial flow catalytic converter having thermal expansion compensating means
US4004887A (en) * 1973-03-16 1977-01-25 Tenneco Inc. Catalytic converter having a resilient thermal-variation compensating monolith-mounting arrangement
US4224285A (en) * 1978-04-05 1980-09-23 Texaco Inc. Smoke filter for internal combustion engines
US4457895A (en) * 1981-10-13 1984-07-03 Institut Francais Du Petrole Catalytic muffler for purifying the exhaust gases of an internal combustion engine
US4489549A (en) * 1983-08-17 1984-12-25 The Garrett Corporation Gas generator with ratchet no-back and method
US4505105A (en) * 1983-08-17 1985-03-19 The Garrett Corporation No-back gas generator and method
US4554784A (en) * 1983-08-17 1985-11-26 The Garrett Corporation Emergency power unit and method
US4682470A (en) * 1984-04-17 1987-07-28 Echlin, Inc. Catalytic converter for exhaust gases
US4788819A (en) * 1986-10-15 1988-12-06 Man Nutzfahrzeuge Gmbh Apparatus for removing soot from the exhaust gases of an internal combustion engine, in particular a diesel engine
US5809776A (en) * 1996-07-29 1998-09-22 Outboard Marine Corporation Catalytic converter with radial outflow and by-pass valve
EP1003232A2 (en) * 1998-11-17 2000-05-24 DBB Fuel Cell Engines Gesellschaft mit beschränkter Haftung Device for the catalytic afterburning of anode exhaust gases from fuel cell systems
US6468333B2 (en) * 2001-01-22 2002-10-22 Aeronex, Inc. Gas purifier apparatus
US6946013B2 (en) 2002-10-28 2005-09-20 Geo2 Technologies, Inc. Ceramic exhaust filter
US7211232B1 (en) 2005-11-07 2007-05-01 Geo2 Technologies, Inc. Refractory exhaust filtering method and apparatus
US20070104620A1 (en) * 2005-11-07 2007-05-10 Bilal Zuberi Catalytic Exhaust Device
US20070104622A1 (en) * 2005-11-07 2007-05-10 Bilal Zuberi Device for Catalytically Reducing Exhaust
US20070207070A1 (en) * 2006-03-03 2007-09-06 Bilal Zuberi Catalytic exhaust filter device
US7444805B2 (en) 2005-12-30 2008-11-04 Geo2 Technologies, Inc. Substantially fibrous refractory device for cleaning a fluid
US7451849B1 (en) 2005-11-07 2008-11-18 Geo2 Technologies, Inc. Substantially fibrous exhaust screening system for motor vehicles
US20090071136A1 (en) * 2007-09-14 2009-03-19 Mack Trucks, Inc. Exhaust diffuser for an internal combustion engine
US7572311B2 (en) 2002-10-28 2009-08-11 Geo2 Technologies, Inc. Highly porous mullite particulate filter substrate
US7574796B2 (en) 2002-10-28 2009-08-18 Geo2 Technologies, Inc. Nonwoven composites and related products and methods
US7582270B2 (en) 2002-10-28 2009-09-01 Geo2 Technologies, Inc. Multi-functional substantially fibrous mullite filtration substrates and devices
US20100000187A1 (en) * 2007-01-03 2010-01-07 Kim Ki-Ho Assembly of ceramic filter and method of assembling the same
US7682577B2 (en) 2005-11-07 2010-03-23 Geo2 Technologies, Inc. Catalytic exhaust device for simplified installation or replacement
US7722828B2 (en) 2005-12-30 2010-05-25 Geo2 Technologies, Inc. Catalytic fibrous exhaust system and method for catalyzing an exhaust gas

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4318720A (en) * 1979-07-19 1982-03-09 Hoggatt Donald L Exhaust filter muffler
GB9520716D0 (en) * 1995-02-09 1995-12-13 Breitman Marcos Device for the control of the emission of internal combustion engine exhaust gases
US5921080A (en) * 1997-03-07 1999-07-13 The Lubrizol Corporation Oxidation catalytic converter system for small spark ignited engines
EP1676020B1 (en) * 2003-10-20 2008-07-09 Honeywell International, Inc. Adjustable valve, in particular a recirculation valve for a turbocharger

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US1465904A (en) * 1920-01-16 1923-08-21 Frederick J Herdle Muffler
US1605484A (en) * 1925-09-03 1926-11-02 Thompson Method of and apparatus for treating exhaust gases
US1794276A (en) * 1929-12-14 1931-02-24 John J Bowes Exhaust muffler
US2071119A (en) * 1932-05-12 1937-02-16 Harger John Process and apparatus for treating furnace gases and exhaust gases from internal combustion engines
US2260578A (en) * 1940-01-06 1941-10-28 Thomas E Murray Automobile construction
US2378083A (en) * 1943-11-02 1945-06-12 Cecil R Hull Vacuum exhaust muffler
US2937490A (en) * 1957-08-12 1960-05-24 Oxy Catalyst Inc Catalytic purification of exhaust gases
US2956865A (en) * 1958-02-03 1960-10-18 John E Morris Exhaust gas purifier

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Publication number Priority date Publication date Assignee Title
US1465904A (en) * 1920-01-16 1923-08-21 Frederick J Herdle Muffler
US1605484A (en) * 1925-09-03 1926-11-02 Thompson Method of and apparatus for treating exhaust gases
US1794276A (en) * 1929-12-14 1931-02-24 John J Bowes Exhaust muffler
US2071119A (en) * 1932-05-12 1937-02-16 Harger John Process and apparatus for treating furnace gases and exhaust gases from internal combustion engines
US2260578A (en) * 1940-01-06 1941-10-28 Thomas E Murray Automobile construction
US2378083A (en) * 1943-11-02 1945-06-12 Cecil R Hull Vacuum exhaust muffler
US2937490A (en) * 1957-08-12 1960-05-24 Oxy Catalyst Inc Catalytic purification of exhaust gases
US2956865A (en) * 1958-02-03 1960-10-18 John E Morris Exhaust gas purifier

Cited By (58)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3201207A (en) * 1961-09-15 1965-08-17 Walker Mfg Co Muffler
US3307920A (en) * 1962-07-10 1967-03-07 Llewellyn T Barnes Apparatus for purifying exhaust gases
US3167400A (en) * 1962-07-30 1965-01-26 Norris Thermador Corp Catalytic converter
US3223491A (en) * 1962-09-27 1965-12-14 Firestone Tire & Rubber Co Muffler construction
US3222140A (en) * 1962-10-29 1965-12-07 Universal Oil Prod Co Means and apparatus for catalytically oxidizing an exhaust gas stream
US3236044A (en) * 1962-12-21 1966-02-22 Ruge Willi Heating system for motor vehicles
US3180712A (en) * 1962-12-26 1965-04-27 Universal Oil Prod Co Two-stage converter-muffler
US3172251A (en) * 1963-01-14 1965-03-09 Minnesota Mining & Mfg Afterburner system
US3252767A (en) * 1963-01-21 1966-05-24 Walker Mfg Co Exhaust system
US3441382A (en) * 1963-02-07 1969-04-29 Engelhard Ind Inc Catalyst cartridge
US3449086A (en) * 1964-09-22 1969-06-10 American Cyanamid Co Catalytic muffler
DE1244477B (en) * 1964-09-22 1967-07-13 American Cyanamid Co Catalyst-silencer
US3338682A (en) * 1964-12-14 1967-08-29 Walker Mfg Co Muffler secondary air silencer
DE1301337B (en) * 1965-05-26 1969-08-21 Aerolyt Vertriebsgesellschaft An apparatus for detoxifying exhaust gases, particularly from internal combustion engines
US3503714A (en) * 1965-05-26 1970-03-31 Fitterer & Sohn Arno Apparatus for decontamination of exhaust gases of internal combustion engines
US3445196A (en) * 1966-06-06 1969-05-20 Nelson Muffler Corp Exhaust muffler with removable catalytic unit
US3751917A (en) * 1970-10-24 1973-08-14 Alfa Romeo Spa Exhaust chamber for a motor vehicle provided with an internal combustion engine
US3838977A (en) * 1972-02-24 1974-10-01 Ethyl Corp Catalytic muffler
US3945803A (en) * 1972-04-07 1976-03-23 Kali-Chemie Ag Elastic support for a ceramic monolithic catalyzer body
US3947252A (en) * 1972-04-07 1976-03-30 Kali-Chemie Ag Elastic suspension or support for a ceramic monolithic catalyzer body
US3762163A (en) * 1972-06-08 1973-10-02 Tenneco Inc Bypass for catalytic reactor
US3954418A (en) * 1972-09-27 1976-05-04 Tenneco Inc. Catalytic converter with bypass
US3872821A (en) * 1972-12-20 1975-03-25 Nissan Motor Catalytic converter failure alarm device
US3824790A (en) * 1973-03-14 1974-07-23 Granlin Corp Catalytic exhaust purifier for diesel engines
US4004887A (en) * 1973-03-16 1977-01-25 Tenneco Inc. Catalytic converter having a resilient thermal-variation compensating monolith-mounting arrangement
US3889776A (en) * 1973-06-14 1975-06-17 Sherritt Gordon Mines Ltd Exhaust gas silencer
US3969095A (en) * 1973-08-25 1976-07-13 Shigeru Kurahashi Air filter apparatus
US3930805A (en) * 1973-08-27 1976-01-06 Hoechst Aktiengesellschaft Apparatus receiving catalysts for the decontamination of exhaust gas of internal combustion engines
US3957445A (en) * 1974-06-12 1976-05-18 General Motors Corporation Engine exhaust system with monolithic catalyst element
US3925026A (en) * 1974-08-20 1975-12-09 Gen Motors Corp Spring loaded catalytic converter with externally mounted spring
US3989471A (en) * 1975-04-14 1976-11-02 Tenneco Inc. Radial flow catalytic converter having thermal expansion compensating means
US4224285A (en) * 1978-04-05 1980-09-23 Texaco Inc. Smoke filter for internal combustion engines
US4457895A (en) * 1981-10-13 1984-07-03 Institut Francais Du Petrole Catalytic muffler for purifying the exhaust gases of an internal combustion engine
US4489549A (en) * 1983-08-17 1984-12-25 The Garrett Corporation Gas generator with ratchet no-back and method
US4505105A (en) * 1983-08-17 1985-03-19 The Garrett Corporation No-back gas generator and method
US4554784A (en) * 1983-08-17 1985-11-26 The Garrett Corporation Emergency power unit and method
US4682470A (en) * 1984-04-17 1987-07-28 Echlin, Inc. Catalytic converter for exhaust gases
US4788819A (en) * 1986-10-15 1988-12-06 Man Nutzfahrzeuge Gmbh Apparatus for removing soot from the exhaust gases of an internal combustion engine, in particular a diesel engine
US5809776A (en) * 1996-07-29 1998-09-22 Outboard Marine Corporation Catalytic converter with radial outflow and by-pass valve
EP1003232A2 (en) * 1998-11-17 2000-05-24 DBB Fuel Cell Engines Gesellschaft mit beschränkter Haftung Device for the catalytic afterburning of anode exhaust gases from fuel cell systems
EP1003232A3 (en) * 1998-11-17 2000-08-02 DBB Fuel Cell Engines Gesellschaft mit beschränkter Haftung Device for the catalytic afterburning of anode exhaust gases from fuel cell systems
US6468333B2 (en) * 2001-01-22 2002-10-22 Aeronex, Inc. Gas purifier apparatus
US6946013B2 (en) 2002-10-28 2005-09-20 Geo2 Technologies, Inc. Ceramic exhaust filter
US7574796B2 (en) 2002-10-28 2009-08-18 Geo2 Technologies, Inc. Nonwoven composites and related products and methods
US7582270B2 (en) 2002-10-28 2009-09-01 Geo2 Technologies, Inc. Multi-functional substantially fibrous mullite filtration substrates and devices
US7572311B2 (en) 2002-10-28 2009-08-11 Geo2 Technologies, Inc. Highly porous mullite particulate filter substrate
US7682578B2 (en) 2005-11-07 2010-03-23 Geo2 Technologies, Inc. Device for catalytically reducing exhaust
US20070104622A1 (en) * 2005-11-07 2007-05-10 Bilal Zuberi Device for Catalytically Reducing Exhaust
US7451849B1 (en) 2005-11-07 2008-11-18 Geo2 Technologies, Inc. Substantially fibrous exhaust screening system for motor vehicles
US7682577B2 (en) 2005-11-07 2010-03-23 Geo2 Technologies, Inc. Catalytic exhaust device for simplified installation or replacement
US7211232B1 (en) 2005-11-07 2007-05-01 Geo2 Technologies, Inc. Refractory exhaust filtering method and apparatus
US20070104620A1 (en) * 2005-11-07 2007-05-10 Bilal Zuberi Catalytic Exhaust Device
US7444805B2 (en) 2005-12-30 2008-11-04 Geo2 Technologies, Inc. Substantially fibrous refractory device for cleaning a fluid
US7722828B2 (en) 2005-12-30 2010-05-25 Geo2 Technologies, Inc. Catalytic fibrous exhaust system and method for catalyzing an exhaust gas
US20070207070A1 (en) * 2006-03-03 2007-09-06 Bilal Zuberi Catalytic exhaust filter device
US7563415B2 (en) 2006-03-03 2009-07-21 Geo2 Technologies, Inc Catalytic exhaust filter device
US20100000187A1 (en) * 2007-01-03 2010-01-07 Kim Ki-Ho Assembly of ceramic filter and method of assembling the same
US20090071136A1 (en) * 2007-09-14 2009-03-19 Mack Trucks, Inc. Exhaust diffuser for an internal combustion engine

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Publication number Publication date Type
BE606410A1 (en) grant
BE606410A (en) 1962-01-22 grant
NL267408A (en) application
GB919667A (en) 1963-02-27 application

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