CN1112539C - Support structure for catalyst - Google Patents

Support structure for catalyst Download PDF

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Publication number
CN1112539C
CN1112539C CN 96180325 CN96180325A CN1112539C CN 1112539 C CN1112539 C CN 1112539C CN 96180325 CN96180325 CN 96180325 CN 96180325 A CN96180325 A CN 96180325A CN 1112539 C CN1112539 C CN 1112539C
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catalyst
globality
catalyst structure
open cell
cell mesh
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CN1228152A (en
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拉尔夫·A·达拉·贝塔
詹姆斯·C·施拉特
马丁·伯纳德·卡特隆
肯尼思·威斯顿·毕比
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Catalytica Inc
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Catalytica Inc
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Abstract

The present invention relates to a support structure (53) used for fixing a catalyst structure (52) in a reaction room. The catalyst structure (52) comprises a plurality of longitudinally arranged channels, and flowing gas mixtures pass through the channels; the support structure is composed of an integral opening grid type or a honeycomb structure which is abutted on one end of the catalyst structure, the integral opening grid type or the honeycomb structure is made of high temperature resistant metal or ceramic sheet bands or ribs, and the integral opening grid type or the honeycomb structure extends along the direction which is perpendicular to the longitudinal axis of the catalyst structure to basically cover the end surface (at the inlet end or the outlet end or both ends) of the catalyst structure so as to fix the periphery of the support structure to a reaction wall (54). The sheet bands or the ribbed plates used for producing the support structure are coiled together to form a single structure, and the grid type openings of the structure is at least as large as the openings of the channels of the catalyst structure. The grid type openings of the support structure are communicated with liquid in the channels of the catalyst structure, and thus, an air flow (50) which is basically unaltered from the catalyst structure through the support structure is supplied.

Description

The supporting structure that catalyst is used
Invention field
The present invention relates to be used for the monolithic catalyst structure that pyroreaction such as catalytic combustion use is fixed on improved supporting structure in reative cell or the reactor.In addition, the present invention is directed to the method for using this improved supporting structure in a kind of high-temperature catalytic method of the catalytic combustion at high-temperature catalytic method such as gas powered turbine station-service.
Background of invention
Known many kinds of high temperature process (process), they use the monolithic catalyst structure to promote desired reaction, for example the partial oxidation hydrocarbon and the complete oxidation hydrocarbon of usefulness controlled in toxic emission, catalyst muffler in the almost car toxic emission control, and for the further catalytic combustion of the fuel of use of gas turbine, stove and so on.The typical case of this kind catalysis system is the catalyst that uses in the hot burner of gas turbine, so that low toxic emission and high efficiency of combustion are provided.In order to obtain high turbine efficiency, need high gas temperature.This applies a high thermal stress for certainly the catalyst integral body of using, this catalyst integral body metal normally a kind of single-piece or combination or ceramic structure, make and have a plurality of passages that longitudinally are provided with, be used for by combustion gas mixt, at least a portion passage scribbles one deck combustion catalyst on the surface within it.
Except high thermal stress, high airflow rate as burner feature in the gas turbine applies a significant axial load or a power that promotes along airflow direction to catalyst structure, and this axial load is to produce owing to the resistance to the air-flow in the passage that longitudinally is provided with of catalyst structure promptly rubs.For example, if use as people such as Dalla Betta in U.S. Patent No. 5,183, the multistage monolithic catalyst structure of describing in 401 is as the catalyst of 20 inch diameters in the catalyst combustion reactor, wherein the flow rate of air/fuel mixture is reduced to 4psi by the pressure of this catalyst for about 50lbs/ second, so will be for about 1 to total axial load of this catalyst, 260lbs.
High temperature (as near and even surpass 1000 ℃ temperature, this moment, metal integral began lost strength) and above-mentioned big both combinations of axial load (getting) from high air velocity under, can produce significantly moving or being out of shape of catalyst supports part.In fact, under the situation of using a corrugated metal foil catalyst integral body, wherein this corrugated foils is wound on together to form a cylindrical helical structure with non-intussusception form, these metal formings are not bonded together in interior, high temperature and may make total along airflow direction generation intussusception from the big axially combination of load that high gas flow produces, especially when axial force above paper tinsel in this winding-structure during to the resistance to sliding of paper tinsel.Therefore, need provide a kind of supporting for catalyst structure, make it not along axially being moved and/or being out of shape of airflow direction so that utilize a supporting structure to fix this catalyst structure, this supporting structure will at high temperature provide necessary supporting and not disturb efficient and benefit as the motive catalytic combustion of gas turbine.
At the U.S. Patent application serial number No.08/165 of people such as Dalla Betta in the common pending trial of proposition on December 10th, 1993, among 966 (agents be equipped with examine document number No.P-1065), cold pillar or pole have been described in use in the exit of catalyst structure as the mechanism of supporting this catalyst.The advantage of this method is, these pillars are by air or the cooling of other heat transmission medium, even so these pillars under excessive temperature, also can have the high strength of opposing axial load.But the shortcoming of this method is, these pillars need a cooling air source and this can cause the combustion system design more complicated, perhaps requires to use pressure-air and this may not use in combustion gas turbine.An additional shortcoming is that air cooled pillar is than widely being placed on the surface of catalyst.This causes high local contact force or stress.In some part of Catalyst Design, these contact forces may surpass the yield strength of thin catalyst foil, cause the distortion of paper tinsel.This obviously is not the result who wishes, and impairs in high axial load is used and make air-cooled pillar.
A kind of possible solution of paper tinsel problem on deformation provides more cooling pole, so that reduce the contact stress in the catalyst outlet surface.But because air cooling pole is thicker, so use a large amount of poles can increase the obstruction of air-flow and the total pressure drop in the increase combustion system at the catalyst outlet place, this is undesirable.Simultaneously, the interval of air cooling pole must be very approaching, so that reduce the contact stress with catalyst foil.
Another kind of possible method is to use a kind of metal support that does not cool off.This will allow the cross section of pole much thin, and reduce total sectional area and final pressure falls.But this also has a conceptual issues, and usual exactly idea is that under the High Operating Temperature of these systems, the intensity of most of metals reduces greatly, does not use very thick material just can not support axial load, thereby causes serious block airflow.
Summary of the invention
Surprisingly, have been found that now, can be with the supporting structure that does not cool off that refractory metal or pottery are made as the superior mechanism that a monolithic catalyst structure is fixed in the reactor, this monolithic catalyst structure comprises a plurality of passages that longitudinally are provided with, so that by the flowing gas mixture, this reactor is designed for pyroreaction and high gas flow rate or flow, and this supporting structure can not produce unsuitable pressure and fall or otherwise disturb catalytic reaction.The efficient supporting structure of this uniqueness comprises a cellular or open cell mesh form supporting structure of globality, its grid type perforate is big as the passage in the catalyst structure at least, described grid type perforate exists fluid to be communicated with the passage of catalyst structure, and with refractory metal or the pottery strip or floor make, they combine, form an individual construction, near the whole exit end face of catalyst structure and extension in the above, the periphery of supporting structure is fixed on the reactor wall like this, makes any axial force that is applied on the open cell mesh form supporting structure to be passed on the reactor wall.
No matter the profile of its perforate grid how, cellular or open cell mesh form (honeybee slot type) supporting structure of globality of the present invention has enough intensity when being fixed in reactor wall, can bear the catalyst structure of under high temperature and high gas flow rate, operating and impose on the axial load or the power of supporting structure, thus reduced catalyst structure as far as possible anyly move axially or be out of shape.Secondly, the inherent strength of this open cell mesh format structure makes it possible to use thin metal or ceramic strip or floor in this structural framing, this point combines as the big perforate grid of catalytic reactor channel aperture at least with use, supporting structure of the present invention can be advantageously used in remain and avoid in the high gas flow rate purposes that the pressure by supporting structure falls, as the catalytic combustion of the fuel/air mixture that is used for gas turbine subsequently.At last, of the present inventionly provide a plurality of near the whole end face of catalyst structure or the supporting strap or the floor in cross section with the cellular of bearing structure or open cell mesh form characteristic, therefore, the axial load of catalyst structure more is evenly dispersed on the whole globality supporting structure, and has avoided the local deformation in the catalyst structure.
Though globality open cell mesh form supporting structure of the present invention is suitable for being placed in the port of export or the outlet side of catalyst structure most, so that the fixed catalyst structure prevents moving axially along the airflow direction by this catalyst structure, but they are extremely low to the resistance of the air-flow by supporting structure, this makes them also be applicable to very much the entrance side of supporting catalyst structure, moves backward to prevent that appearance is any under unexpected air-flow reversing situation.Secondly, in the U.S. Patent No. of using as people such as above-mentioned Dalla Betta 5,183, in 401 under the situation of disclosed multistage antigravity system, supporting structure of the present invention can be placed in the outlet end place of one or more catalyst grades, and thereby works to discharge the intergrade supporting of axial force on the follow-up catalyst grade.
Therefore, one aspect of the present invention is fixed on supporting structure in the reative cell at a kind of being used for a catalyst structure, this catalyst structure is made the passage that longitudinally is provided with a plurality of tape entries and outlet end, these passages are used for the admixture of gas by flowing, described supporting structure is made up of a kind of globality open cell mesh format structure, wherein the wall of grid is made with the band of resistant to elevated temperatures metal or ceramic material, so that the grid type perforate to be provided, its size passage as catalyst structure at least is big in the perforate that its place, entrance and exit end forms, described globality open cell mesh format structure:
(a) be placed in the place, inlet end of the outlet end place of catalyst structure or catalyst structure or the inlet end and outlet end two places of catalyst structure;
(b) locate and be configured near an end of catalyst structure and along direction extension perpendicular to the catalyst structure longitudinal axis, to cover the end face of catalyst structure basically, the grid type perforate of this globality open cell mesh format structure exists fluid to be communicated with the passage of catalyst structure; And
(c) be fixed on the reaction chamber wall with its periphery, make the axial load that is applied on this globality open cell mesh format structure be passed on this reaction chamber wall, limit described catalyst structure thus and be parallel to moving axially of its longitudinal axis.
Another aspect of the present invention is devoted to a kind of improved method that supplies catalytic combustion or a kind of fuel of partial combustion to use, this fuel is specially adapted to the gas turbine purposes, wherein uses globality open cell mesh form supporting structure of the present invention and this combustion catalyst structure is fixed in burner or the reative cell.This method comprises the following steps:
(a) form a kind of fuel mixture that has oxygen-containing gas; With
(b) make this oxygen-containing gas and fuel mixture flow through the monolithic catalyst structure that is arranged in reative cell as air flow, described catalyst structure is made has a plurality of passages that longitudinally are provided with, be used for by described air flow, described catalyst structure utilizes a globality open cell mesh format structure to come stable in described reative cell, the wall of grid is made with resistant to elevated temperatures metal or ceramic material band in this structure, so that the grid type perforate to be provided, this perforate passage as catalyst structure at least is big in the perforate that its place, entrance and exit end forms, described globality open cell mesh format structure:
(i) be placed in the place, inlet end of the outlet end place of catalyst structure or catalyst structure or the inlet end and outlet end two places of catalyst structure;
(ii) locate and be configured near an end of catalyst structure and along direction and extend perpendicular to the catalyst structure longitudinal axis, to cover the end face of catalyst structure basically, the grid type perforate of this globality open cell mesh format structure exists fluid to be communicated with the passage of catalyst structure; And
(iii) be fixed on the reaction chamber wall, limit described catalyst structure thus and be parallel to moving axially of its longitudinal axis with its periphery.
Others of the present invention comprise a kind ofly utilizes globality open cell mesh format structure of the present invention that the monolithic catalyst structure is fixed on method in the reative cell, and as the intergrade of using for the multistage catalysis process that uses monolithic catalyst support according to supporting structure of the present invention.
The accompanying drawing summary
Fig. 1 is the side view of the catalytic combustion reactor in a kind of gas turbine combustor.
Fig. 2 A and 2B represent a kind of manufacturing of monolithic catalyst structure, and it can utilize globality supporting structure of the present invention to be fixed in the reactor effectively.
Fig. 3 A and 3B represent building block and a part of cross section of supporting structure of the present invention.
Fig. 4 A to 4E represents the end-view of the various configurations of catalyst support of the present invention.
Fig. 5,6,7, the 8th, the schematic diagram of catalyst according to the invention reactor.
Fig. 9 A and 9B schematically illustrate since the axial load that the high gas flow by catalyst structure produces to the influence of supporting structure of the present invention.
Detailed Description Of The Invention
The present invention includes a supporting structure that does not cool off, be used for fixed-site with a monolithic catalyst structure in reative cell or reactor, catalyst structure is subjected to because high temperature that the high velocity air by catalyst produces and big axial load there.In addition, the invention still further relates to a kind of method that this supporting member is applied to catalytic combustion method.More particularly, the present invention is directed to a kind of like this supporting structure, it can limit moving axially of the interior a kind of quite flexible monolithic catalyst structure of combustion reactor.Except the moving axially of limiting catalyst structure, this supporting structure increases the intensity of force that the antagonism of catalyst is applied by the air-flow by catalyst.
Fig. 1 illustrates a kind of typical catalytic combustion reactor.As shown in this Fig, a kind of catalyst structure (10) is placed in the downstream of pre-burners (4) in the combustion reactor (1), and perpendicular to oxygen flow (being generally air and fuel mixture), this fuel is introduced the monolithic catalyst structure through fuel injector (5).Catalyst structure is provided with in this manner, so that obtain the uniform air/fuel mixture stream by catalyst, and allows this mixture to flow through the passage that longitudinally passes catalyst structure.For catalyst structure is remained in combustion reactor in the stable position, must use certain type supporting device or structure that catalyst structure is fixed on the combustion reactor, comprise the supporting structure of (as a kind of possibility) a kind of outlet side (9) near catalyst structure.As used herein, " outlet side " (9) of catalyst structure are sides (2) of the air/fuel mixture outflow catalyst structure of partially or completely burning.Therefore, " entrance side " of catalyst structure is the side (7) that unburned air/fuel mixture is initially introduced catalyst structure.
This catalyst structure can be made according to any Known designs, particularly comprises to small part scribbling a plurality of parallel longitudinal direction pipelines of catalyst or the integral catalyzer structure of passage.Typical catalyst structure is disclosed in many published reference papers, comprises people's such as Dalla Betta U.S. Patent No. 5,183,401; No.5,232,351; No.5,248,251; No.5, in 250,489 and No.5,259,754, and people's such as Young U.S. Patent No. 4,870,824.This catalyst structure can be made from cellular, corrugated plating helical coil, column (or " straw bundle ") or other metal or ceramic substrate (matrix) with configuration of pipe tunnel or passage, and these pipe tunnels or passage allow high gas space velocity and have the minimum pressure drop of crossing over catalyst structure.For example, can use as shown in Figure 2A and 2B spirality catalyst structure suitably.The manufacture method of this structure is, a metal forming (20) is bent to the ripple or the waveform of have groove (21) and fin (22), then it is wound into the big spiral shell volume (25) with corrugated foils (20) alternately and planar shaped paper tinsel (24) with a sheet of planar metal forming (sheet) (24), as a cylindrical unit.In order to prepare this catalyst structure, be wound into before the spirality catalyst structure together, this corrugated foils and/or planar shaped paper tinsel be coating a kind of platinum group metal, preferably palladium and/or platinum on its one or both sides usually.Though illustrative catalyst structure relates to a kind of metal forming of the straight trough shape wave structure that combines with the planar shaped paper tinsel, other suitable spirality catalyst structure comprises that working as two or more corrugated foils with flat or herringbone shape moire pattern is wound on the structure that a time-out obtains in non-intussusception mode.Catalyst structure supporting member of the present invention advantageous particularly under the situation of metal helical catalyst structure, because when they are exposed to fully high temperature, as 1000 ℃ or more in the high velocity air of relative superiority or inferiority and make metal structure softening or when otherwise weakening, they have the tendency of or distortion flexible along airflow direction.
Supporting structure
Supporting structure of the present invention is made up of globality open cell mesh form or alveolate texture, they are made with the strip or the floor of refractory metal or pottery, this supporting structure is near an end of catalyst structure, and along direction extension perpendicular to the catalyst structure longitudinal axis, basically cover an end face (at arrival end or the port of export or place, two ends) of catalyst structure, the periphery of this supporting structure is fixed on the reactor wall.Strip or the floor of making this supporting structure combine, and form the individual construction with grid type perforate, and the grid type perforate channel aperture as catalyst structure at least is big.The grid type perforate of this supporting structure is positioned to simultaneously with the passage of catalyst structure and exists fluid to be communicated with, thus make from catalyst structure come basically not the air communication of conversion cross this supporting structure.
Though do not expect that the open cell mesh form performance of supporting structure of the present invention can cause high strength (especially under hot environment), but supporting structure of the present invention shows structural intergrity highly and the axial intensity of force of opposing astoundingly, and this axial force is to be inclined to by the mobile or distortion of the airflow direction of catalyst structure by the edge of catalyst structure to be applied on the supporting structure.As the front is that the catalyst of 10 to 25 inches of the bigger combustion catalyst of diameter such as diameters is indicated, one typically the pressure of the 4psi by catalyst fall and can form an about axial load of 600 to about 1600lbs or power along airflow direction.Under the axial force in the above range and under about 1000 ℃ or higher temperature, supporting structure of the present invention only shows very little deflection or bending, and owing to make the even performance of a plurality of strips or the supporting member that floor provides of open cell mesh form supporting integral body, any local deformation of catalyst structure is all eliminated basically.Therefore, supporting structure of the present invention has two-fold advantage,, can support a bigger axial load that is, has very unlimited structure again, and is very little to the resistance of the air-flow by this structure.
Globality open cell mesh form supporting structure of the present invention can be pottery or metal, also can be any design comes to provide significant structural integrity and intensity under high temperature and top load any other structural material.Refractory metal material that can favourable use in supporting structure of the present invention comprises that high-temperature alloy steel such as nickel alloy, cobalt alloy or evanohm maybe can satisfy other alloy of temperature required requirement, and intermetallic material and ceramic-metal composite.Certainly, can use different materials, this depends on the position of supporting structure and temperature and the axial force that it is subjected to.For example, the supporting structure that uses at the place, inlet end of catalyst structure (or the front of multistage antigravity system what in) will can not be subjected to the outlet end that is applied to last catalyst grade on identical temperature and power, so structural material can be different.Preferred structural metallic materials comprises Fe Cr Al alloy, they comprise the Fe of about 20%Cr and about 5%Al and surplus usually, for example the Alfa IV that can buy from Allegheny Ludlum company (Pennsylvania, America Pittsburgh city), the Riverlite R20-5SR that can buy from Kawasaki iron company (Kawasakisteel, Japan Kobe) and the Aluchrom Y that can buy from VDM company (German Werdohl city).Other preferred metal alloy is a Ni Cr Al alloy, is to contain about 20%Cr and about 5%Al and surplus is the nickel based super alloy of Ni, for example the Haynes 214 that can buy from Haymes international corporation (U.S. Kokomo of Indiana State city).Suitable ceramic material comprises the Celcor cordierite bought from Corning Glass Works (New York, United States Corning city) and the cordierite globality substrate (substrate) that can buy from NGK Locke company (Michigan, USA Southfield city).
Supporting structure of the present invention can constitute with the routine techniques of any formation integral honeycomb shape structure or make, and makes with the strap or the floor (timber) of pottery or metal material, and they combine and form a monomer structure.For example, this structure can be cast individual unit in suitable mold, perhaps this structure can be made by a series of straps or floor are combined, and these straps or floor are molded in advance or crooked, can provide desired grid type perforate configuration when they combine with box lunch.In this respect, Fig. 3 A and 3B illustration are according to the manufacturing of a part of supporting structure of the present invention, and wherein this structure is the metal lump spare with the perforate of hexagon grid type.This supporting structure is made with metal sheet band (30), and these metal sheet bands have been made the fin (31) with plane and the corrugated ribbon of groove (32).These ripple strips are placed in together and form hexagon or the alveolate texture shown in Fig. 3 B, wherein Jie Chu strip planar section combine with welding or soldering (33) and form single-piece or monolithic construction.When forming a complete supporting structure, illustrative alveolate texture can center on a circular metal band (not shown) on its periphery, and the mode that the circular metal band is combined on the honeycomb peripheral part is identical with the combination of the corrugated ribbon of making honeycomb.The metal tape of a circle or metal framework are used to make supporting structure to have circular cross-section, and the cross section of this circular cross-section and cylinder catalyst structure is to have identical extension basically along the direction perpendicular to the air-flow by catalyst structure.Making with metal tape under the situation of supporting structure, preferably use soldering tech that these strips are interosculated, because this can provide than the structure of using the stronger more globality of solder technology, do not use welding as the method that these strips are combined but do not get rid of.Welding and soldering also can be used in combination, as the method that strip is combined.
Grid type perforate in the supporting structure of the present invention can have different shape, as long as their sectional area is suitably even and allow fully contact between those adjacent strips that form the grid type verge of openings or the floor, so that can produce the strong combination between strip or the floor.Suitably, the mesh shape of perforating network can be polygon, ellipse or circular, and polygonal mesh is preferably trapezoidal, triangle, rectangle, square or hexagon.From the viewpoint of the bond strength that is easy to make and between adjacent strip or floor, can produce, preferably select hexagonal grid perforate for use.In this respect, the end-view of several different open cell mesh lattices of Fig. 4 A to 4E illustration, they can be advantageously used in the supporting structure of the present invention that the cylinder catalyst structure is used as shown in Fig. 2 B.Fig. 4 A represents to have by the circle band (41) as the supporting structure framework and surrounds and the cross section of the supporting structure of the hexagon grid perforate (40) of combination, and Fig. 4 B represents a similar cross-section with supporting structure of the square net perforate (42) of being surrounded by circular frame (43).Fig. 4 C illustration is according to the cross section of a kind of supporting structure of the present invention, and wherein grid type perforate (44) also is circular in circular frame (45).At last, Fig. 4 D and 4E represent that supporting structure of the present invention has trapezoidal grid type perforate (46) or network of triangle form perforate (48), is centered on by circular frame (47) and (49) under every kind of situation.
Point out that as top crucial is, no matter its concrete shape how, the size of the grid type perforate in the supporting structure of the present invention is such, be exactly the sectional area with each vertical passage that constitutes catalyst structure is the same big at least for their sectional area.Preferably, the grid type perforate is that 1.1 times to 200 times of catalyst structure perforate are big, and the catalyst structure perforate is communicated with grid type perforate fluid, and pressure falls or other destroys the circulation problem so that reduce as far as possible.For the typical monolithic catalyst structure of using in the catalytic combustion method, the open cell mesh grid of supporting structure of the present invention or grid type perforate will have from about 0.03 square inch to about 2.0 square inches average size of mesh opening or sectional area, average size of mesh opening be preferably in about 0.05 square inch in about 0.2 square inch scope.
Make the strap of supporting structure of the present invention or the thickness of floor (being defined as any single strap) and the strap of manufacturing supporting structure of the present invention or the width (being defined as the size that strap vertically records along airflow direction) of floor and will determine that these factors relate to the size and the method parameter that uses supporting structure of reative cell and catalyst structure by many factors along the sectional dimension that records perpendicular to airflow direction.For example, the thickness of metal tape or pottery band will depend on the airflow obstruction (pressure falls) that can tolerate, axial load to be supported, catalyst structure diameter, open cell mesh lattice structure size of mesh opening and use in the desired temperature that runs into.Equally, will depend on following factor according to the width of supporting structure of the present invention, as axial load to be supported, the size of catalyst structure, in desired temperature that will run into and the reative cell to the permission space of supporting structure.Fall and compensate other method variable that runs into usually for fear of unsuitable pressure, the thickness of making the strap of supporting structure or floor should be about 0.5 to about 20 times of the passage wall thickness that longitudinally is provided with of catalyst structure.For metal structure, strap thickness is preferably between about 1 times to about 10 times of catalyst channels wall thickness, and for ceramic structure, and the thickness of strap or floor is between about 2 times to about 20 times of the passage wall thickness of catalyst structure.In catalytic combustion under the situation of normally used catalyst structure, the strap thickness optimum range of metal support structure of the present invention is about 0.0001 inch to about 0.10 inch, the preferable range of metal tape thickness is about 0.002 inch to about 0.03 inch, and most preferred range is about 0.005 inch to about 0.02 inch.For the axial load that runs into usually in the catalytic combustion, be preferably in the supporting structure of the present invention use width for about 0.25 inch to about 3 inches metal tape, if use the ceramic supporting structure, the width of strap or floor is preferably between about 0.75 inch and about 4 inches.But, in each case, local stress that selected concrete width and thickness will depend on selected structural material to a certain extent and actual surrender and creep strength.
The combining of mesh-density or grid bore size in the thickness of making the strap of supporting structure of the present invention or floor and the structure can directly influence the degree that air-flow passes in and out the catalyst structure of supported structure obstruction.Suitable is, these factors are controlled like this, makes according to airflow obstruction that any single supporting structure of the present invention produced less than about 25%.Preferably, airflow obstruction makes the gas flow capability can suitably destroy gas reaction mixture between about 5% to 15%.In addition, the gas channel in the supporting structure preferably has the flat tube of quite smooth wall, so that reduce turbulent flow and the lowest impedance that obtains air-flow in the air-flow as far as possible.
The typical case that Fig. 5,6,7 illustrates supporting structure of the present invention in the catalytic reactor uses.Fig. 5 illustrates a kind of single-stage catalytic reactor as using in the catalytic combustion system, gas reaction mixture (50) flows into catalytic reactor, the latter has a reative cell that is limited by reactor wall (51) and comprises a catalyst structure (52), reactor wall (51) will be the burner lining under the situation of catalytic burner, and catalyst structure (52) comprises a plurality of parallel vertical passages, is used to pass through gas reaction mixture.This catalyst structure utilizes globality perforate grid supporting structure of the present invention (53) to be fixed in the reative cell, this supporting structure (53) utilizes flange or fin (54) to be fixed on the reactor wall, this fin (54) is attached on the reactor wall or the part of reactor wall, and stretch out and form a lug along inward direction, settle the outer rim or the periphery of supporting structure on it.By this way, crossing the axial load that catalyst structure acts on the supporting structure by air communication transfers on the reactor wall from this supporting structure.
Fig. 6 illustrates a similar reaction system, but uses a two-stage catalytic reactor.In such cases, gas reaction mixture (60) also flows into a catalytic reactor with the reative cell that is limited by reactor wall (61), but two monolithic catalyst structures (62) and (63) are arranged in the case, they are made up of the first order and second level catalytic reaction system, in each case, this catalyst structure utilizes supporting structure of the present invention (64) and (65) to be fixed in the reative cell, and supporting structure (64) and (65) are positioned to outlet end or the exit face near each of two catalyst structures.Flange that two supporting structure utilizations that illustrate are inwardly stretched out or fin (66) and (67) are fixed on the reactor wall, make that the axial load on the catalyst structure is passed on the supporting structure, and supporting structure is delivered to this load on the reactor wall then.
At last, Fig. 7 represents a kind of two-stage catalytic reactor that does not have the inter-stage supporting, but utilizes supporting structure of the present invention to fix at the entrance side and the outlet side place of reactor.Same at this, gas reaction mixture (70) flows into a catalytic reactor, this reactor has the reative cell that is limited by reactor wall (71) and comprises the multistage catalyst of being made up of two monolithic catalysts (72) and (73), they abut one another, each has a plurality of parallel vertical passages, and these passages are communicated with passage fluid in another catalyst grade.This two-stage catalyst structure utilizes supporting structure of the present invention to be fixed in the reative cell, supporting structure is placed in the outlet end (74) of second level catalyst structure and the inlet end (75) of first order catalyst structure is located, and basically catalyst structure is clipped in it can not be moved axially along arbitrary.Fix with flange or fin (76) and (77) at the supporting structure at the supporting structure at the outlet end place of two-stage system and place, inlet end, the latter inwardly stretches out from reaction wall, thereby is used for any axial force transmission to reactor wall.
Use is with flange that inwardly stretches out or fin on the supporting structure arrangement of the present invention reactor wall in the above, in fact utilize welding or other method that the edge of supporting structure is fixed and is positioned on the reactor wall compared with (for example), have tangible service advantages.This is that supporting structure does not extend to reactor wall always because this fin or flange can hold supporting structure, thus issuable thermal expansion when providing a free space to hold supporting structure to contact with thermal current.Preferably, the size of supporting structure of the present invention and the fin of use or flange are such, make supporting structure can along peripheral direction expand into its diameter 2% and not can near or the haptoreaction wall.In a preferred embodiment, can duplicate on the position in tight the place ahead of entrance side or surface of supporting structure as shown in Fig. 5,6,7 at the flange of downstream of settling supporting structure on the reactor wall or outlet side or fin, and form a groove effectively, in groove, can settle supporting structure and still have the free degree of accommodate thermal expansion.Had this supporting structure to be fixed on method for optimizing on the reactor wall, any unexpected counter-pressure to supporting structure will can not cause the dislocation of supporting structure.
The another kind of method for optimizing that supporting structure of the present invention is fixed on the reactor wall is shown in Fig. 8, single-stage catalytic reactor of illustration among the figure, wherein gas reaction mixture (80) flows into a catalytic reactor, the latter has a reative cell that is limited by reactor wall (81), and comprises one and utilize open cell mesh form supporting structure of the present invention (83) to be securely fixed in catalyst structure (82) in the reactor.In the preferred embodiment of the present invention, the supporting structure that does not always extend to reactor wall utilizes rivet (84) to be connected on the reactor wall, these rivets stretch into by reactor wall in a series of cavitys of supporting structure, and the degree of depth of these cavitys is enough to the thermal expansion that allows supporting structure to produce when being exposed to thermal response gas.Just, rivet penetrates enough length of supporting structure, so that firmly fix supporting structure, and stays enough aperture area simultaneously at the rivet end place, allows the temperature difference heat of supporting structure to expand.
As mentioned above, an important and wonderful advantage of supporting structure of the present invention is, it presents superior intensity when running into high axial load or power, and this load or power are crossed the monolithic catalyst structure that supporting structure supports by high air communication and produced.Just, when a high axial load places on the supporting structure, supporting structure will show along applying the same direction deflection of axial force or the tendency of bending, and under the situation of supporting structure of the present invention, even when this structure also is subjected to high thermal stress outside high axial load, also can observe wonderful elasticity to this kind bending or distortion.For supporting structure of the present invention, this Fig. 9 A and 9B by the expression catalytic reactor illustrates, wherein catalyst structure (90) utilizes the supporting structure of the present invention (92) at its outlet side place to be fixed in the reaction chamber wall (91), and this supporting structure turns over and utilize the flange or the fin (93) that inwardly stretch into reative cell to be fixed on the reactor wall.In such cases, the air-flow (94) by catalyst structure makes the axial force that acts on the supporting structure cause skew or the bending (in Fig. 9 B with exaggerative form illustrate) of supporting structure along airflow direction.For purpose of the present invention, the deformation index to any given supporting structure can be expressed and be quantified as to this skew, wherein the definition of " deformation index " is to be the ratio (numerical value) of the length of the skew of the supporting structure that occurs under the 4psi or crooked diameter (or approximate diameter of non-circular supporting structure) divided by supporting structure to the load standard of catalyst or typical from axial flow at one, and it is typical that the load of this 4psi is used catalytic combustion.This skew or crooked record as Fig. 9 B as shown in is bent and be the poor of the bending that occurs under the 4psi in the standard axial load in the change that does not add the stress state lower support structure.For supporting structure of the present invention, this deformation index suitably between about 0.00001 to about 0.05, is preferably between about 0.001 to about 0.02.This extremely low deformation index (it even also still keep the supporting structure of the present invention that is exposed under the temperature in about 1000 ℃ scope), show the exceptional strength of supporting structure according to the present invention when suffering high axial load, this high axial load is the feature of the class methods of the catalytic combustion operated under high airflow rate.
Method
As mentioned above, supporting structure of the present invention can be used for hydrocarbon fuel or other fuel such as methane, ethane, H 2Or CO/H 2The catalytic combustion of mixture.In the method, a kind of oxygen-containing gas such as air mix with hydrocarbon fuel and form flammable oxygen/fuel mixture.This oxygen/fuel mixture flows through the monolithic catalyst structure that places in the reative cell as flowing gas, with burn this oxygen/fuel mixture and form a kind of partially or completely the burning hot gaseous product.
Can use various catalyst in the method.For example, can use in the present invention in the U.S. Patent No. 5 that is entitled as " catalyst structure " with overall thermal exchange, 250, the catalyst structure of describing in 489 with overall thermal exchange surface, or be entitled as the U.S. Patent No. 5,248,251 and the No.5 of " containing palladium partial combustion catalyst and using the method for this catalyst of classification ", the classification of describing in 258,349 liang of patents contains palladium partial combustion method catalyst.In addition, this method can relate to clean-burning fuel or partial combustion fuel, as is entitled as the U.S. serial number No.08/088 of " method of burning flammable mixture ", describes in 614 the common co-pending application.Secondly, this method can be a multi-stage process, wherein utilize special-purpose catalyst and catalyst structure in each stage to come the substep combustion fuel, as be entitled as the U.S. Patent No. 5 of " multi-stage process that in the heating period, utilizes the oxide catalyst combustion fuel mixture ", described in 232,357.Above-mentioned six patents and a patent application are all with reference to being incorporated into this.
This method also relates to the position of catalyst structure in the stopping reaction chamber, moves vertically so that prevent catalyst structure.This catalyst structure utilizes a globality open cell mesh format structure to stablize in reative cell, wherein the wall of grid is made with resistant to elevated temperatures metal or ceramic material and strip, so that the grid type perforate to be provided, its size passage as catalyst structure at least is big in the perforate that its place, entrance and exit end forms, and this globality open cell mesh format structure is:
(a) be placed in the place, inlet end of the outlet end place of catalyst structure or catalyst structure or the inlet end and outlet end two places of catalyst structure;
(b) location and its shape made near an end of catalyst structure and along the y direction perpendicular to catalyst structure extend, to cover the end face of catalyst structure basically, the grid type perforate of this globality open cell mesh format structure exists fluid to be communicated with the passage of catalyst structure; And
(c) its periphery is fixed on the reaction chamber wall, limits described catalyst structure thus and be parallel to moving axially of its longitudinal axis.
Should be understood that ordinary professionals of the technology can imagine equivalent with the device of narrating in claims to the back, and these equivalents will be in the scope and spirit essence of claims of the present invention.

Claims (30)

1. one kind is used for a catalyst structure is fixed on the indoor supporting structure of reaction, this catalyst structure is made the passage that longitudinally is provided with a plurality of tape entries and outlet end, these passages are used for the admixture of gas by flowing, described supporting structure comprises a kind of globality open cell mesh format structure, wherein the wall of grid is made with resistant to elevated temperatures metal or ceramic material band, so that the grid type perforate to be provided, its size passage with catalyst structure at least is the same big in the perforate that its place, entrance and exit end forms, described globality open cell mesh format structure:
(a) be placed in the place, inlet end of the outlet end place of catalyst structure or catalyst structure or the inlet end and outlet end two places of catalyst structure;
(b) locate and be configured near an end of catalyst structure and along direction extension perpendicular to the catalyst structure longitudinal axis, to cover the end face of catalyst structure basically, the grid type perforate of this globality open cell mesh format structure exists fluid to be communicated with the passage of catalyst structure; And
(c) be fixed on the reaction chamber wall with its periphery, make the axial load that is applied on this globality open cell mesh format structure be passed on this reaction chamber wall, limit described catalyst structure thus and be parallel to moving axially of its longitudinal axis.
2. supporting structure according to claim 1 is characterized in that, this globality open cell mesh format structure is placed in the outlet end place of this catalyst structure.
3. supporting structure according to claim 1 is characterized in that, this globality open cell mesh format structure is placed in the inlet end and outlet end two places of this catalyst structure.
4. according to claim 1,2 or 3 described supporting structures, it is characterized in that the grid of this open cell mesh format structure is oval or circular.
5. according to claim 1,2 or 3 described supporting structures, it is characterized in that these grids are polygon.
6. supporting structure according to claim 5 is characterized in that, these polygonal mesh are trapezoidal, triangle, rectangle, square or hexagon.
7. the described supporting structure of claim 1 is characterized in that, the flow blockage that is formed by any single globality open cell mesh format structure at the arrival end of catalyst structure or port of export place is less than about 25%.
8. the described supporting structure of claim 7 is characterized in that, this flow blockage is between about 5% to about 15%.
9. the described supporting structure of claim 1 is characterized in that, the thickness of making the metal of globality open cell mesh format structure or pottery band is about 0.5 to 20 times of wall thickness of the passage that longitudinally is provided with of catalyst structure.
10. the described supporting structure of claim 9 is characterized in that, this catalyst structure conduit wall and make globality open cell mesh format structure be with both to make by refractory metal material.
11. the described supporting structure of claim 9 is characterized in that, the width of band of making globality open cell mesh format structure is between about 0.25 to 4 inch.
12. claim 1,2,3,10 or 11 described supporting structures is characterized in that the deformation index of globality open cell mesh format structure is between about 0.0001 to about 0.05.
13. the described supporting structure of claim 1 is characterized in that, the cross-sectional area of the perforate grid of globality open cell mesh format structure is from about 0.03 square inch to about 2.0 square inches.
14. the described supporting structure of claim 1, it is characterized in that, globality open cell mesh format structure is fixed in the reative cell with a bindiny mechanism that is fixed on the reaction chamber wall, and this bindiny mechanism is held in place globality open cell mesh format structure and allows this globality open cell mesh format structure to produce the temperature difference heat expansion along outward direction towards reaction chamber wall simultaneously.
15. the described supporting structure of claim 14, it is characterized in that, this bindiny mechanism is selected from: (a) fin that inwardly stretches out on the inboard of reaction chamber wall, on this fin, settle an end face sidepiece of the periphery of globality open cell mesh format structure, expand so that adapt to the temperature difference heat of this globality open cell mesh format structure in the mode that can slide; Or (b) a series of rivets that pass in the side face upper plenum that reaction chamber wall stretches into globality open cell mesh format structure, there is difference between the degree of depth of these cavitys and the length of rivet, make the temperature difference heat that can adapt to globality open cell mesh format structure expand.
16. one kind is used for a catalyst structure is fixed on method in the reative cell, this catalyst structure is made the passage that longitudinally is provided with a plurality of tape entries and outlet end, these passages are used for the admixture of gas by flowing, this method comprises to be inserted a globality open cell mesh format structure in the reative cell, place the outlet end place of catalyst structure or place the outlet end of catalyst structure and two places, end that enter the mouth, the wall of the grid in this globality open cell mesh format structure is made with resistant to elevated temperatures metal or ceramic material band, so that the grid type perforate to be provided, its size passage with catalyst structure at least is the same big in the perforate that its place, entrance and exit end forms, described globality open cell mesh format structure:
(a) locate and be configured near an end of catalyst structure and along y direction extension perpendicular to catalyst structure, to cover the end face of catalyst structure basically, the grid type perforate of this globality open cell mesh format structure exists fluid to be communicated with the passage of catalyst structure; And
(b) be fixed on the reaction chamber wall with its periphery, make the axial load that is applied on this globality open cell mesh format structure be passed on this reaction chamber wall, limit moving axially of described catalyst structure thus.
Wherein fuel is to the method for the burned hot gaseous product of small part 17. a hydrocarbon combustion thing or other fuel are so that form, and this method comprises the following steps:
(a) form a kind of fuel mixture that has oxygen-containing gas; With
(b) make this oxygen-containing gas and fuel mixture flow through the monolithic catalyst structure that is arranged in reative cell as air flow, described catalyst structure is made has a plurality of passages that longitudinally are provided with, be used for by described air flow, described catalyst structure utilizes a globality open cell mesh format structure to come stable in described reative cell, the wall of grid is made with resistant to elevated temperatures metal or ceramic material band in this structure, so that the grid type perforate to be provided, its aperture passage with catalyst structure at least is the same big in the perforate that its place, entrance and exit end forms, described globality open cell mesh format structure:
(i) be placed in the place, inlet end of the outlet end place of catalyst structure or catalyst structure or the inlet end and outlet end two places of catalyst structure;
(ii) locate and be configured near an end of catalyst structure and along perpendicular to urging direction to extend in the agent structure longitudinal axis, to cover the end face of catalyst structure basically, the grid type perforate of this globality open cell mesh format structure exists fluid to be communicated with the passage of catalyst structure; And
(iii) be fixed on the reaction chamber wall, thus, limit described catalyst structure and be parallel to moving axially of its longitudinal axis with its periphery.
18. the described method of claim 17 is characterized in that, this globality open cell mesh format structure is placed in the outlet end place of this catalyst structure.
19. the described method of claim 17 is characterized in that, this globality open cell mesh format structure is placed in two places, entrance and exit end of this catalyst structure.
20. claim 17,18 or 19 described methods is characterized in that, the grid of this open cell mesh format structure is oval or circular.
21. claim 17,18 or 19 described methods is characterized in that these grids are polygon.
22. the described method of claim 21 is characterized in that, these polygonal mesh are trapezoidal, triangle, rectangle, square or hexagon.
23. the described method of claim 17 is characterized in that, the flow blockage that is formed by any single globality open cell mesh format structure at the arrival end of catalyst structure or port of export place is less than about 25%.
24. the described method of claim 23 is characterized in that, this flow blockage is between about 5% to about 15%.
25. the described method of claim 17 is characterized in that, the thickness of making the metal of globality open cell mesh format structure or pottery band is about 0.5 to 20 times of wall thickness of the passage that longitudinally is provided with of catalyst structure.
26, the described method of claim 25 is characterized in that, this catalyst structure conduit wall and make globality open cell mesh format structure be with both to make by refractory metal material.
27. the described method of claim 25 is characterized in that, the width of band of making globality open cell mesh format structure is between about 0.25 to 4 inch.
28. claim 17,18,19,26 or 27 described methods is characterized in that the deformation index of globality open cell mesh format structure is between about 0.0001 to about 0.05.
29. the described method of claim 17 is characterized in that, the cross-sectional area of the perforate grid of globality open cell mesh format structure is about 0.03 square inch to about 2.0 square inches.
30. one kind is used for a multistage catalyst structure is fixed on the indoor supporting structure of reaction, this multistage catalyst structure is made has a plurality of passages that longitudinally are provided with that have every grade entrance and exit end, these passages are used for the admixture of gas by flowing, described supporting structure comprises a kind of globality open cell mesh format structure, wherein the wall of grid is made with resistant to elevated temperatures metal or ceramic material band, so that the grid type perforate to be provided, its size passage with catalyst structure at least is the same big in the perforate that its place, entrance and exit end forms, described globality open cell mesh format structure:
(a) be placed in the outlet end place that comprises one or more catalyst grades of last catalyst grade in the place, inlet end of the first order of every grade outlet end place of catalyst structure or catalyst structure and the catalyst structure;
(b) locate and be configured near an end of catalyst structure and along y direction extension perpendicular to catalyst structure, to cover the end face of catalyst structure basically, the grid type perforate of this globality open cell mesh format structure exists fluid to be communicated with the passage of catalyst structure; And
(c) be fixed on the reaction chamber wall with its periphery, make the axial load that is applied on this globality open cell mesh format structure be passed on this reaction chamber wall, limit described catalyst structure thus and be parallel to moving axially of its longitudinal axis.
CN 96180325 1996-06-10 1996-06-10 Support structure for catalyst Expired - Fee Related CN1112539C (en)

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