JPH07500659A - Multistage combustion method for fuel mixtures - Google Patents

Abstract

This invention is a combustion process having a series of stages in which a fuel/oxygen-gas-containing mixture (16, 18) is combusted stepwise using a series of specific catalysts and catalytic structures (figure 2) and, optionally, a final homogeneous combustion zone to produce a combusted gas at a selected temperature preferably between 1050 DEG and 1700 DEG C. Depending upon the pressure of operation, there may be two or three discrete catalytic stages (stages 1, 2 and 3). The choice of catalysts and the use of specific structures, including those employing integral heat exchange (44) results in a catalyst and its support which are stable due to their comparatively low temperature, do not deteriorate, and yet the product combustion gas is at a temperature suitable for use in a gas turbine, furnace, boiler, or the like, but has low NOx content. Neither fuel nor air is added to the combustion process except in the initial stage.

Description

[Detailed description of the invention] Multistage combustion method for fuel mixtures (PA-0099) Field 1 team member This application is filed against P.Tsurumi, Ezava, and Dalla Betta. ROCESS FORBURNING COMBUSTIBLE MIXTUR U.S. Patent Application No. 077617.97 entitled ES (PA-0041) No. 6; Dalla Betta, TsuruIi.

MULTISTAGE PROCESS FORCUMB against Ezaval Named USTING FUEL MIXTURES (PA-0004) U.S. Patent Application No. 617.977 and; Dalla Betta, Tsu rumi, MULTISTAGE PROCESS FO for Ezava RCOM BUSTING FUEL MIXTURES USING 0XID E CATALYSTSIN THE HOT 5TAGE (PA-0038 ) and U.S. Patent Application No. 617,980 entitled; Dalla, Be. tta, Ezava, Tsurumi, 5chlatter and N1c TWO5TAGE PROCESS PORCOMBUST for kolas INGFUEL MIXTUI’IES (PA-0030>) This is a partial continuation of patent application No. 618.301, and the above application is a reference. It will be used for this purpose.

Yoshio Yuko■ The present invention is a combustion method having a series of stages and a series of specific catalysts and catalyst structures. the fuel/oxygen gas content in stages, optionally with a final homogeneous combustion zone. combusting the mixture at a selected temperature preferably between 1050° and 1700°C to produce combustion gas. Two or three separate catalyst stages depending on operating pressure may exist. Catalyst selection, complete heat exchange (integral heat exchange) By using certain structures, including those using Due to the low temperature, stable and non-deteriorating catalysts and their supports can be obtained and manufactured. The combustion gas is at a temperature suitable for use in gas turbines, furnaces, boilers, etc. Moreover, the amount of carbon dioxide is low. Except for the initial stages, this combustion process requires no fuel. No gas is added.

15 With the advent of current pollution prevention laws in the United States and around the world, reducing various types of pollution Remarkable and novel methods are being investigated.

Fuel combustion is the main cause of the pollution problems that currently exist. This fuel is wood, coal, oil, or natural gas. produced as a result of the presence of contaminants in the fuel source Certain pollutants, such as SO2, are treated in order to remove the resulting pollution. , treat the fuel to remove contaminants, or treat the resulting exhaust gases. It can be removed by either: monoacid produced as a result of incomplete combustion Contaminants such as carbon dioxide can be removed by post-combustion oxidation or by improvements in the combustion process. , can be removed. The other major pollutant is NO, (the equilibrium mixture is mainly NO). (but also contains very small amounts of NO2) controls the combustion process to reduce its production. This can be dealt with either by allowing the problem to occur, or by removing it later. its relative stability Once formed, due to its nature and low concentration in most exhaust gases, Removal of No. is a difficult task. One of the solutions used in automobiles is - Carbon oxide is used to chemically reduce NOx to nitrogen and at the same time convert carbon monoxide to diacid. This is a method of oxidizing to carbon.

However, the need to react two pollutants means that the first combustion reaction This leads to the conclusion that it was inefficient.

Unlike the case with sulfur contaminants, where sulfur-containing contaminants can be removed from fuels, combustion Removing nitrogen from the air supplied to the process is clearly an impractical solution. I have to admit that. - Improved combustion reactions, unlike in the case of carbon oxides increases the level of NOx produced due to the associated high temperatures.

Still, the problem of reducing combustion N08 remains unresolved, and several Different methods have been proposed. The process you select should be based on the process that is generating combustion gas. materially compatible with the purpose of recovery of the heating value of the turbine, boiler or furnace. Do not go against it.

An effective means to control N08 production is the local temperature in the combustion zone and the overall The goal is to limit the temperature to 1800°C or less.

For example, Furuya et al., U.S. Pat. No. 4,731,989, column 1, 52-59. , and column 12 of Hindin et al., U.S. Pat. No. 4.088.135. Light.

Controlled combustion with one or more catalysts is achieved by dilution with excess air. by sintering or in multiple stages using various lean or rich fuel mixtures. There are many ways to control this temperature, such as by A combination of these methods also Also known.

One widely tried method is the use of multistage catalytic combustion. These people Most of the methods utilize multi-section catalysts on metal oxide or ceramic catalyst supports. are doing. Typical examples of such disclosures are shown in the table below.

(Margin below) The use of such ceramic or metal oxide supports is clearly known.

The structures formed here do not easily dissolve or oxidize, like metal supports . Carefully designed ceramic supports for use in specific temperature ranges It can function properly in the temperature range of . However, many of these substances are 11 At temperatures above 00°C, it may undergo a phase change or react with other components of the catalyst system.

For example, in this temperature range, the gamma alumina phase changes to the alpha alumina phase. .

Furthermore, such ceramic substrates are brittle to olefins and susceptible to vibrations and mechanical shocks. Easy to crack and break due to shock or thermal shock. heat shock is , is a particular problem in catalytic combustors used in gas turbines. At the start of operation and At termination, large temperature gradients can occur in the catalyst, leading to high mechanical stresses. lead to cracking and destruction.

To improve the stability of metal oxide and ceramic catalyst supports at high temperatures. Typical approaches include alkaline treatment, often along with other physical treatment steps. Incorporating earth metals or lanthanides into the support, or adding metals to the support It can be added to: Literature - or 1 Japanese Patent Publication No. 61-209044 (Babcock Hitachi Co., Ltd.) Japanese Patent Publication No. 61-209044 1-216734 (Babcock Hitachi Co., Ltd.) Japan JP 62-07153 5 (Babcock Hitachi Co., Ltd.) Japan JP 62-001454 (Babcock Hitachi Co., Ltd.) Babcock Hitachi Co., Ltd.) Japan JP 62-045343 (Babcock Hitachi Co., Ltd.) ) Japanese Patent Publication No. 62-289437 (Babcock Hitachi Co., Ltd.) Japanese Patent Publication No. 62-289437 (Babcock Hitachi Co., Ltd.) 62-221445 (Babcock Hitachi Co., Ltd.) U.S. Patent No. 4.793.7 No. 97 (Kato et al.) U.S. Patent No. 4,220.559 (Pliknkl et al.) U.S. Patent No. 3,870.455 CH5ndIn et al.) U.S. Patent No. 4. No. 711.872 (Kato et al.) UK No. 1.528,455 Ca1rn However, even with such improvements in high-temperature stability, ceramics do not easily break down. It is a substance. Japanese Patent Publication No. 60-053724 discloses a cell with holes in the column wall. A column-shaped catalyst made of ramic is used to prevent the formation of cracks between the fuel gas and the column. It teaches uniform distribution of temperature.

High temperatures (above 1100°C) are also harmful to the catalyst layer, causing loss of surface area and metal Low activity due to catalyst evaporation and reaction of catalyst components with ceramic catalyst components or cause the formation of inert substances.

Among the many catalysts disclosed in the combustion literature, the following platinum group metals are found: platinum, palladium, ruthenium iridium, and rhodium; alone or in mixtures with other metals of this type, or with co-catalysts other than the platinum group. Used with a catalyst or cocatalyst.

Other combustion catalysts include metal oxides, especially metals of group Vll+ and group 1. Examples include oxides of the genus. For example, h upper ■ hill, COMPLETE 0XIDAT ION OF METHANE 0VERPEROVSKITE 0XIDES .

Catalysis Letters I (1988) 299-306.　 J, G, Baltzer A, G.

In 5 scientific Publishing Co., the author In particular, LaI-tMexM, commonly designated as ABOa, suitable for the oxidation of tan no3, where Me is an oxide represented by the formula Ca, Sr, or Bas. A set of perovskite oxide catalysts is described.

Similarly, in many publications by groups associated with Kyushu University, Ba0.6A120 A combustion catalyst based on 3 is described: 1, PREPARATION AN D CHARACTERIZATION OF LARGESURFACE A REA BaO・6A1203. Machida et al., Bull.

Chet Soc, Jpn, 61.3659-3665 (1988).

2, HIGHTEMPERAT[IRE CATALYTICCOMBUST ION 0VERCATION-3UBSTITUTED BARIUM HE XAALUMINATES.

Machida et al., Chea+1stry Letters, 767-770° 1987° 3. ANALYTICAL ELECTRON MICROSCOPE AN ALYSIS 0F THE FORMATION OF BaO・6A1203 ．． Machida et al., J., At Cerat Coc., 71 (12) 1142-47 (1988).

4. EFFECT OF ADDITIVES ON THE 5URFAC E　AREA　0FOXIDE　SυPP0I? TS FORCATALYTI CCOM BUSTION.

J, Cat, 103.385-393 (19B?), and 5, 5tlR FACE AREAS AND CATALYTICACTIVITIES O FMn-SUBSTITUTED HEXAALUMINATES WITHV ARIOUSCAT[ON COMPOSITIONS IN THE MIR RORPLANE.

Chet Lett,, 1461-1464.1988゜Similarly, for Arai. U.S. Pat. No. 4,788,174 describes the general formula A+-xc*BxAI+2-y We propose a heat-resistant catalyst suitable for catalytic combustion that has o+9-a. The above formula smell and A is at least one element selected from Ca, Ba and Sr. ;C is X and/or Rb;B is Mn, Co, Fe, Ni, at least one selected from Cu and Cr; 2 is from zero to about 0. 4; X is a value in the range 0.1 to 4; y is approximately is a value in the range of x; a is the valence of each element of A, C, and B and 2, and the values of x, y and 2, and a-1,5(X- It is represented by z(X-Y)+xZ-3yl.

In addition to the rigorous catalytic combustion process, some methods include A final step is used to uniformly oxidize the remaining combustible materials.

Many of the three-stage catalytic combustion systems described above also have an after-combustion step. and For example, a series of publications (62-080) assigned to Nippon Shokubai Kagaku (“NSK”) 419, 62-080420, 63-080847, 63-080848 and 63-080549) uses a three-stage catalytic combustion process followed by a second combustion step. Disclosed. As mentioned above, the catalysts used in these methods are those of the present invention. The catalysts used in the process are very different. Furthermore, these publications When using the after-combustion process, the resulting gas temperature is [750°C to 1100°C]. It states that it is said that it is only a matter of time. In contrast, the method of the present invention substantially higher adiabatic combustion temperatures can be reached using a post-catalytic equalization combustion process. You will understand that.

Other combustion catalyst/postcatalyst equal combustion methods are also known. European Patent Application No. 0. No. 198.948 (also issued to NSK) states that the after-combustion process is followed by A two-stage or three-stage catalytic process is disclosed. The temperature of the post-combusted gas is 1 300℃, and the temperature flowing out of the catalyst (equal to the bulk gas phase temperature) is The temperature is 900°C. However, the catalyst structure disclosed in the NSK publication is It is not protected from the negative effects of combustion occurring within the zone and therefore this support is inferior. cause a change.

The patent to Furuya et al. (U.S. Pat. No. 4,731,989) provides additional fuel Discloses a one-stage catalyst in which catalytic gas is injected followed by post-catalytic combustion. In this case The temperature of the catalyst substrate is reduced by adding a low ratio fuel/air mixture to the catalyst. is limited to up to 900°C or 1000°C. Some types of gas turbines, etc. To obtain the high gas temperatures required for this method, additional fuel is injected after the catalyst and This fuel is combusted evenly in the post-catalyst region.

This method is complex and requires additional fuel injection equipment into the hot gas stream exiting the catalyst. It is necessary to The inventive device shown in our invention is such that the fuel injection after the catalyst is Not necessary; all fuel is added at the catalyst inlet.

An important aspect in carrying out the method of the invention is the complete heat exchange structure, preferably metal. The aim is to use the structure at least in the latter catalytic stage or combustion stage. in general, The concept is to place a catalyst layer on the wall of the catalyst structure opposite the non-catalyst surface. That is. Both sides are in contact with the flow of fuel-gas mixture.

The heat of reaction is generated on one side; the heat of reaction is transferred to the flowing gas on the other side. Ru.

Structures with perfect heat exchange characteristics are disclosed in Japanese Patent Application Laid-Open Nos. 59-136.140 and 61-25. 9. It is disclosed in O'13. Similarly, U.S. Patent No. 4 to Young et al. No. 870.824 uses a monolithic catalyst with the catalyst in selected passageway walls. A single stage catalytic combustor unit is disclosed. In addition to many other differences Therefore, this structure is disclosed when used alone and without any other catalytic steps. It is. Furthermore, the stepwise use of this structure with different catalytic metals Not shown in these documents.

In all of the above-mentioned methods, the catalyst support is made of metal, and each method has its own unique advantages. By specifically modifying the catalyst to take advantage of the Control media temperature and achieve particularly high gas temperatures while reducing NOx emissions. Demonstrates a combined catalyst system with reduced raw and catalyst (and support) temperatures not present.

Good luck! 1 The present invention allows fuel to be premixed to a specific fuel/air ratio to achieve a desired adiabatic combustion temperature. A method of combustion in which a combustible mixture having a certain temperature is produced. This flammable mixture is The reaction is then carried out in a series of catalyst structures and optionally in a homogeneous combustion zone. It will be done. This combustion occurs in stages, with catalyst and bulk gas temperatures varying depending on the catalyst selection. Depending on the selection and construction, it is controlled to a relatively low value.

We demonstrate that the palladium catalyst becomes "self-limiting" as the operating pressure increases. -11 mits) J temperature increases and the temperature at which the fuel mixture burns uniformly decreases. I found that. Above about 10 atmospheres, for most practical fuel/air ratios , the palladium catalyst self-limit temperature and the homogeneous combustion start temperature are equal or sufficiently suitable. The “hot end” fuel catalyst stage is omitted. Can be omitted.

This method has very low NOx concentrations but can be used in gas turbines, boilers, or furnaces. Produce exhaust gas at the appropriate temperature.

Ward jμλ 11 Tsui Figure 1 is a graph showing the relationship between pressure, uniform combustion temperature, and palladium temperature. Ru.

Figures 2A and 2B are close-up cutaway views of the walls of the catalyst structure with catalyst on only one side. be.

3A, 3B, 3C, 4A, 4B, 5.6A, and 6B illustrate the method of the present invention Various complete heat exchange catalyst structures that can be used in the catalyst stage are shown.

FIG. 7 is a schematic diagram of a three-stage catalytic test reactor used in the examples.

8 and 9 are graphs of various operating temperatures as a function of preheat temperature.

FIG. 10 is a graph of various operating temperatures during long term steady state operating tests.

FIG. 11 is a graph of various operating temperatures during a typical startup process.

Seal of the day The present invention allows fuel to be premixed to a specific fuel/air ratio to achieve a desired adiabatic combustion temperature. A method of combustion in which a combustible mixture having a certain temperature is produced. This flammable mixture is then in two or three separate catalyst structures and optionally in a homogeneous combustion zone. and allowed to react. This combustion takes place in stages, with the catalyst and bulk gas The temperature is controlled to a relatively low value by catalyst selection and construction. working pressure As the temperature increases, the temperature at which the palladium catalyst "self-limits" increases and the fuel mixture The temperature at which things burn uniformly decreases. As shown in Figure 1, (increase the total pressure or As the partial pressure of 02 increases (by increasing the concentration of 02), The theoretical pressure required to cause complete homogeneous combustion (to the level of carbon monoxide) is It drops to a level where the palladium catalyst starts burning. The two lines are 4 atm. Intersects between 5 atmospheres. Compressing air above about 4 to 5 atmospheres results in uniform combustion. The reaction burns out completely in about 11 microseconds. Above about 4 to 5 atmospheres, most fruit Palladium catalyst self-limiting temperature and uniform combustion for practical fuel to air ratios temperature is equal or sufficiently compatible with the third stage "hot end" ”The combustion catalyst may be omitted if desired.

Although this method has very low N(h) concentrations, it can be used in gas turbines, boilers or furnaces Produce the exhaust gas at a temperature suitable for use.

This method can be used with a variety of fuels and over a wide range of process conditions.

Common gaseous hydrocarbons, such as methane, ethane and propane, can be Although highly desirable as a fuel source for Most of the fuel you get is adequate. For example, fuel is either liquid or gas at room temperature and pressure. But that's fine. Examples include the low molecular weight hydrocarbons listed above and butane, pentane, Hexane, heptane, octane, gasoline, normal hinibenzene, toluene, ethyl Aromatic hydrocarbons such as benzene; and xylene; naphtha; diesel fuel, rosin; jet fuel; other middle distillates; heavy distillate fuel (preferably hydrogenated); treated to remove nitrogen and sulfur compounds); methanol, ethanol Oxygen-containing fuels such as alcohols, including alcohol, impropatol, butanol, etc.; Examples include ethers such as diethyl ether, ethyl phenyl ether, and MTBE. It will be done. Low BTU gases such as city gas or syngas may also be used as fuel.

The fuel is typically a catalytic or is the amount of combustion that results in a mixture with a theoretical adiabatic combustion temperature higher than the gas phase temperature. Mixed with air.

Preferably the adiabatic combustion temperature is above 900°C, most preferably 1000°C. It is above ℃. Non-gaseous fuels must be vaporized before contacting the first catalytic zone. Must be. The combustion air can be at 1 atmosphere or less (-0,25 atmospheres) , or may be compressed to a pressure of 35 atmospheres or more. (manufactured using this method) Stationary gas turbines (which can ultimately use Often operated by pressure. Therefore, the method can be applied from -0,25 atm to 3S atm. It may be operated at pressures between 0 and 17 atmospheres, preferably between 0 and 17 atmospheres.

ni mediata nie The fuel/air mixture fed to the first zone is well mixed and over the first zone catalyst. must be heated to a temperature high enough to initiate the reaction; typical For methane fuels on palladium catalysts, temperatures of at least about 325°C are usually suitable. be. This preheating can be done by partial combustion, pilot burner, heat exchange or pressurization. It can be done.

The first zone of the method is carried out on a monolithic catalyst support with low resistance to gas flow. , containing a catalytic amount of palladium.

The support is preferably made of metal. Palladium melts at 325°C and below. Very active against oxidation of tan and can "ignite" or ignite fuel at low temperatures . Also, in some cases, after the palladium starts the combustion reaction, at 1 atm, 75 The catalyst rapidly increases in temperature from 0°C to 800°C, or about 940°C at a total pressure of 10 atmospheres. was observed to increase. These temperatures are for palladium/palladium oxide below. Transition points at various pressures mentioned above in thermogravimetric analysis (TGA) of the reaction Each temperature. At this point, the catalytic reaction substantially slows down and the catalyst temperature increases with pressure. from 750°C to 800″C or 940°C.The fuel/air ratio is 900°C. Even when giving theoretical adiabatic combustion temperatures above or as high as 1700°C, this current Elephants can be seen.

One explanation for this temperature-limited phenomenon is that palladium at the above TGA transition point Examples include conversion of oxides to palladium metal. Temperature below 750℃ at 1 atm In degrees, palladium exists primarily as palladium oxide. palladium oxide appears to be an active catalyst for fuel oxidation. At temperatures above 750℃, parasitic Palladium oxide converts to palladium metal according to the equilibrium below: P　d　O---------→P　d　+1/202 Palladium metal is a hydrocarbon It has virtually no activity for combustion, with no catalytic activity at temperatures above 750°C to 800°C. is expected to decrease considerably. This conversion makes the reaction self-limiting: combustion The process involves rapidly raising the catalyst temperature from 750°C to 800°C, where temperature zero self-control begins. raise This limit temperature depends on the 02 pressure and increases as the 02 partial pressure increases. .

However, some caution is required. As the activity of palladium increases, 750 Even the low activity of palladium metal above “C” can raise the catalyst temperature above 800°C. and even approach the adiabatic combustion temperature of the above fuel/air mixture. “Runaway” combustion can occur; if the temperature exceeds 1100”C, the catalyst can be severely degraded. We limit the supply of fuel and/or oxidizer to the catalyst To achieve this, runaway combustion is controlled by adding a diffusion barrier layer on top of the catalyst layer. I found out that it can be done. Diffusion layer lowers the gas line to higher preheating temperature speed, higher fuel/air ratio ranges, and higher inlet gas temperatures. Greatly expands the operating range of the first stage catalyst. Additionally, we have palladium gold on the substrate. By limiting the concentration of ” was also found to be suppressed.

This self-limiting phenomenon maintains the temperature of the catalyst substrate substantially below the adiabatic combustion temperature. held. This prevents deterioration of the catalyst due to high temperature operation or is substantially reduced.

Palladium metal is added in an amount sufficient to impart significant activity. individual addition The amount depends on many requirements, such as economics, activity, longevity, presence of contaminants, etc. Ru. The theoretical maximum amount may lead to inappropriate metal crystallite growth and concomitant loss of activity. The amount is sufficient to cover the maximum amount of support without causing any damage. These are clear are strongly competing factors: higher surface coverage is required for maximum catalytic activity. However, high surface coverage can promote growth between adjacent crystallites. moreover , consideration must be given to the morphology of the catalyst support. Supports in high space velocity environments When used in It seems that it must be maintained. Economically, the minimum amount to do the required work The general goal is to use catalytic metals of Finally, the presence of contaminants in the fuel Then, in order to compensate for the deterioration in catalyst quality due to deactivation, the catalyst loading rate is The need arises.

The palladium metal content of this catalyst composite ranges from, for example, 0.1% to about 25%. % by weight, preferably from 0.01% to about 20% by weight, generally very low . The catalyst optionally comprises one or more noble metals of group 1B or group Vllll. may contain up to an equal or greater amount of catalyst additive. Preferred added catalysts are silver, gold , ruthenium, rhodium, platinum, iridium or osmium. most preferred The most important ones are silver and platinum.

Palladium and any additives are palladium complexes, compounds, or metal dispersions can be incorporated onto a support by a variety of different methods using materials. compound or The composite can be soluble in water or hydrocarbons. These may precipitate out of solution.

Liquid carriers are typically used to evaporate or evaporate while leaving the palladium in dispersed form on the support. is only required to be able to be removed from the catalyst support by decomposition. used in this invention Examples of palladium complexes and compounds suitable for producing catalysts used include , palladium chloride, dihedral diamine palladium nitrate, palladium tetramine chloride palladium 2-ethylhexanoate, sodium palladium chloride and There are many other palladium salts or compounds.

The preferred support for this catalyst zone is metal. However, ceramic etc. Other support materials and silica, alumina, silica-alumina, titania, silica Various inorganic oxides, such as conia, can also typically be used as supports, to provide stability. Even if it has additives such as barium, cerium, lanthanum or chromium, It can be used even if it is not evening. Honeycomb, spiral cylinder of corrugated sheet (flat sheet parators may be combined), cylindrical (i.e. “straws of bundles”), etc. or an elongated channel or passageway capable of high space velocities with minimal pressure loss. Metal supports in the form of other structures having channels are desirable for this purpose. These are soft Soft, can be more easily fixed and adhered to surrounding structures, and can be more easily cured. Gives lower flow resistance due to walls that can be manufactured thinner than Mic supports . Other practical benefits attributable to the metal support include resisting thermal shocks. It is an ability. This thermal shock occurs during gas turbine operation and starts the turbine. Occurs when moving and stopping. and, in particular, rapidly shut down the turbine. It happens when you have to. In the latter case, the fuel supply is cut off, i.e. -Bin is ``tripped>J.

Because the physical loads on the turbine - for example, the generator settings - This is because it has been removed. Fuel to the turbine to prevent overspeeding , the supply will be stopped immediately. The temperature of the combustion chamber in which the process of the invention of the present application is carried out is The temperature drops rapidly to that of compressed air. This drop is 1000° within 1 second It can reach more than C.

In any case, apply the above specified amount to the walls within the channels or passageways of the metal support. Attach or place the catalyst. The catalyst can be introduced onto the support in various ways: The entire support may be coated, a downstream portion of the support may be coated, or Coat one wall of the support to ensure complete coverage as described for the latter stages below. A heat exchange relationship may also be formed. Preferred forms increase overall activity at low temperatures , which covers the whole, but each form is uniquely effective in a particular environment. It can be. Several types of support materials are available that meet the objectives of this application, such as: Aluminum, aluminium-containing or aluminized steel, certain steel Contains stainless steel or nickel alloys that can form a catalytic layer on the metal surface Any high temperature metal alloy.

Suitable materials include Aggen et al. U.S. Pat. No. 4.414.023, Chapma U.S. Pat. No. 4,331,631 to n et al., and U.S. Pat. ．． It is an aluminum-containing steel such as that found in No. 969,082.

These steels and Kavasakj 5teel Corporation (RiverLite 20-5 SR), Vereinigte Deu tchse Metal+werke AG (Alumcbrom [RE ), and Allegheny Ludlum 5teel (Alfa-IV ) other commercially available steels contain enough molten aluminum to , when oxidized, this aluminum forms alumina whiskers on the surface of the steel, and is coarse and chemically reactive, forming crystals and having good washcoat adhesion surface.

The washcoat can be, for example, gamma-alumina sol or aluminum, Silicon, titanium, zirconium, and barium, cerium, lanthanum , chromium, or various other ingredients, such as mixed oxide sols. It can be applied using approaches such as those described in the prior art.

For better adhesion of washcoats, Chap et al., US Pat. No. 4. 729.782, such as the dilute suspension of pseudo-boehmite alumina described in 729.782. A primer layer containing a hydrous oxide such as However, preferably this The primed surface is then coated with a zirconia suspension and dried. , and can be calcined to form a high surface area adhesive oxide layer on the metal surface. .

Washcoats can be applied, for example, by spraying, directly applying, or into washcoating materials. It can be applied in the same manner as paints are normally applied to surfaces, such as by dipping the support.

Aluminum structures are also suitable for use in the present invention and can be constructed in substantially the same manner. May be treated or coated. Aluminum alloys are somewhat flexible and easily deformed . Alternatively, even the temperature of the operating envelope may melt in this process. Therefore, this Although these are not preferred as supports, they can be used as long as the temperature standards are met.

After applying the washcoat and palladium to the metal support and calcination, one or more layers of low- or non-catalytic as a diffusion barrier to prevent "runaway" A coating of chemical oxide may then be applied. This barrier layer is made of alumina, silica , zirconia, titania, or various others with low catalytic activity for fuel combustion. oxides, or mixed oxides, or additives mentioned for the washcoat layer. can be an oxide with additives similar to . Alumina is not one of the above substances. highly undesirable. The thickness of the barrier layer is 1% of the wash coat layer. - may range in thickness up to substantially greater, but preferably The thickness is 10% to 100% of the thickness of the flash coat layer. The preferred thickness is the fuel tie. catalyst, including gas flow rate, preheat temperature, and washcoat layer catalytic activity. Depends on operating conditions. Applying a diffusion barrier coating only to the downstream part of the catalyst structure, e.g. For example, by applying it to 30% to 70% of the length, under certain conditions It has also been found that sufficient protection for the catalyst is provided.

As with washcoats, barrier layers are typically used when applying paint. It can be applied using any application method.

This catalyst structure is such that the average linear velocity of the gas through the channels of the catalyst structure is so that it is about 0.2 + a/sec or more and about 40 f/sec or less in all parts of the bearing structure. The texture and form should be created. This lower limit is greater than the methane flame front velocity. This upper limit is the practical limit value for currently commercially available types of supports. Ru. These average velocities differ somewhat for fuels other than methane.

The first catalyst zone has a bulk exit temperature of gas from this zone of about 800°C or less; Preferably from 450°C to 700°C, most preferably from 500°C to 650″C. It is large enough to be enclosed.

I'm pregnant with my legs The second zone of the method takes in the partially combusted gas from the first zone and exchanges heat. In the presence of a capable catalyst structure, controlled combustion is further induced. The catalyst is , a substance selected from the noble metals of Mendeleev's 1B, V11 group Vllll. may contain. If the pressure of the method is above about 4 atmospheres, Preferably, it contains radium. Regardless of the pressure, the catalyst contains noble metals of group Vlll, such as palladium. Catalyst contains palladium Optionally, if you want! 1 selected from noble metals of Group B or Group Vllll; It may contain up to an equal amount of one or more catalyst additives. Preferred catalyst additive is silver, gold, ruthenium, rhodium, platinum, iridium, or osmium. Ru. Most preferred are silver and platinum. This zone is where the partial combustion of fuel It operates adiabatically using the heat released by the gas, increasing the gas temperature. The first catalyst zone and No air or fuel is added between the two catalyst zones.

The catalyst in this zone preferably forms the walls of a monolithic catalyst support structure. in the first catalytic zone, except that it is applied to at least a portion of only one of the surfaces. Similar to the one used. FIG. 2A shows the coating applied to one side of the metal substrate (14). a high surface area metal oxide washcoat (10) and an active metal catalyst (12). ) is shown. This structure is based on the washcoat layer ( 10) and the gas stream (16) to easily transfer the heat of reaction generated in the catalyst. conduct. Due to the relatively high heat conductivity between the wash coat (10) and the metal (14) Therefore, the heat is conducted equally to paths (A) and (B), and the heat of reaction is transferred to the gas flow (1 6) and (18). This complete heat exchange structure is expressed by the formula (1 ), the temperature rise of the wall with the base temperature, i.e. the wall temperature, is the inflow temperature and the theoretical It is equal to about half the difference from the theoretical adiabatic combustion temperature.

(Margin below) One side of the metal sheet is coated with a catalyst and the other side is uncatalyzed, and a rolled structure or Forming a layered structure, the corrugated sheet 1- (20) and the flat sheet shown in FIGS. 3A to 30 In combination with flat sheets (22), long open sheets exhibiting low resistance to gas flow. A channel structure may be formed. Corrugated metal strip coated on one side with catalyst (32) (30) as a separator strip without catalyst coating.

(34) to form the structure shown in FIG. 4A.

Alternatively, as shown in Figure 4B, both sides are coated with catalyst before assembly into the catalyst structure. The overturned wavy strip (36) and flat strip (38) are shown in Figure 4B. Can be combined as desired. This structure has a catalytic wall (40 in Figure 4A and 42 in Figure 4B). ), and a channel with non-catalytic walls (44 in Figure 4A and 46 in Figure 4B) form a le. Catalytic channels and non-catalytic channels made with this method The catalyst structure with channels is disclosed in a pending application (Attorney Directory No. PA-0097). It is described in. These structures are used to control catalyst substrate temperature and exhaust gas temperature. He has a unique ability to

A corrugated sheet (42) and a flat sheet (40) coated with catalyst on one side are shown in FIG. Therefore, it can be arranged accordingly. In this diagram, the catalytic surface of each sheet faces different channels. , so all channels have catalyst-coated walls, and all walls have It has one surface coated with catalyst and an opposing surface without catalyst. Figure 5 The structure behaves differently than the structures of FIGS. 4A and 4B. The wall of the structure in Figure 5 forms a complete heat exchanger, but since all channels contain catalyst, all combustion catalytic combustion. Since combustion occurs on the catalyst surface, the catalyst and and the temperature of the support increases, and heat is generated on both the catalytic and non-catalytic sides. Conducted and dissipated. This helps limit the temperature of the catalyst substrate and Radium controls the temperature, from 750°C to a　o　　”c in 1 atm air. Alternatively, 10 atmospheres of air can help maintain the wall temperature at 930°C.

For a sufficiently long catalyst or a sufficiently low gas flow rate, approximately 800° in air at 1 atm. Any material having an adiabatic combustion temperature above 930°C or above 930°C in air at 10 atm. At any given fuel/air, a constant exhaust gas of 750°C to 800°C is obtained. Figure 4 The structures shown in A and 4B include each catalytic channel and each non-catalytic channel. An equal amount of gas flow flows through. The maximum gas temperature rise for these structures is It occurs when 50% of the amount is burned.

The structures shown in Figures 4A and 4B contain catalytic and non-catalytic channels. By changing the ratio of fuel and oxygen passing through the Can be modified to control Figure 6A shows that the corrugated foil alternates with narrow corrugations (50) and A structure with a wide corrugation (52) structure is shown. If you cover one side of this corrugated foil, , a large catalytic channel (54) and a small non-catalytic channel (56) can get. In this configuration, approximately 80% of the gas flow passes through the catalytic channels and and 20% passes through non-catalytic channels. The maximum exhaust gas temperature is This is about 80% of the expected temperature rise when the firing temperature is reached. Conversely, the other side of the foil (Figure 6B), the gas flow through the catalytic channels (58) is small. 20%, and the maximum exhaust gas temperature rise is 20% of the adiabatic combustion temperature rise. structure is obtained. Proper design of wave shape and size to incorporate perfect heat exchange Any level of conversion from 5% to 95% can be achieved. Maximum exhaust gas temperature can be calculated using the following equation (2): To illustrate the operation of this complete heat exchange zone, a portion from the first catalytic zone Assume that the combusted gas flows into the structure of FIG. 4A. With this structure, the touch The gas flow through the media channel is 50% of the total flow rate.

Approximately half of the gas flow passes through the channel with catalytic walls (42) and half passes through a channel with non-catalytic walls (46). Fuel combustion occurs on the catalyst surface , and heat is transferred to the gas flowing through both catalytic and non-catalytic channels. Dissipate. The incoming gas from zone (1) is at 500°C and the fuel/air ratio is 1. If the fuel in the catalytic channel corresponds to the theoretical adiabatic combustion temperature of 300 °C The combustion of increases the temperature of all flowing gases. This heat can be used for both catalytic and non-catalytic dissipates into the gas flowing through both channels. Calculated L-IHE wall temperature :T1. Ia) lIII standing l2-teching and l=900℃To-s-a-=1 500°C + [1300°C -500°C], 5-900°C. but, At 1 atm air pressure, palladium limits the wall temperature to 750°C to 800°C; The maximum exhaust gas temperature is approximately 800°C. As you can see from this case, Paragiu The system limit controls the maximum exhaust gas temperature and thereby limits the wall temperature.

The situation is different at an air pressure of 10 atmospheres. The limiting temperature of palladium is about 930℃ . The walls are controlled at 900°C by the L-IHE structure.

In this case, the L-IRE structure limits the wall a degree and gas temperature.

The catalyst structure in this zone has a similar catalyst loading as the structure in the trough zone. must be present on the surface. This catalyst structure directs the flow into the first zone. The third catalyst stage should be sized to maintain the same average linear velocity as the If the bulk outlet temperature is below 800°C, preferably in the range from 600°C , most preferably in the range of 700°C to 800°C. . The catalyst has a non-catalytic diffusion barrier layer as described for the first catalytic zone. You can also

As a design matter, if a method using only two distinct catalyst structures is desired, , the second catalyst zone (if a uniform combustion zone is desired) flows out of the zone The design shall be such that the bulk temperature of the gas used is above the self-ignition temperature. .

The temperature of the support and catalyst is determined by the relative dimensions of the catalytic and non-catalytic channels. , moderate, determined by the introduction temperature, the theoretical adiabatic combustion temperature, and the length of the second zone. maintained at a suitable temperature.

The linear velocity of the gas in the second catalytic zone is the same as in the first zone .

1st limb lenii In use, the third zone of the method collects partially burned gas from the second zone. with full heat exchange capacity and preferably containing metal oxide catalytic material. further controlled in the presence of a catalytic structure containing platinum as a catalytic material. cause combustion. Metal oxide materials are classified into Mendeleev's group VIII and and one or more metals selected from Group 1. Yes. These substances are desirable because their activity is relatively stable even at high temperatures. pa Other combustion catalysts such as radium, rhodium, osmium, and iridium also It can be used instead of or in addition to platinum.

This zone may be essentially adiabatic during operation and contain at least one portion of the fuel. catalytic combustion at a point where uniform combustion can occur, or where the gas is The gas temperature is further increased to the point where it can be used directly in the bottle.

The catalyst structure in this zone can be the same as that used in the second zone . As mentioned above, the catalyst used in this zone can be a metal-oxygen catalyst material or a white It is desirable that the material contains gold. Suitable metal-oxygen catalyst materials include Mende Leev group V (especially Nb or ■), group Vl (especially Cr), group Vllll transition metals (especially Fe, Co, Ni), and first series lanthanides (especially Ce , Pr, Nd, Sa, Tb, La) from metal oxides or mixed oxides Selected ones are listed. Additionally, this catalytic material is a perovskite in the form of ABO3. may be selected from skite-form materials, where A is a Group 11A or Group 1A metal. Selected from the genus (Ca%Bas　Srs　Mg5Be, KSRbSNa or Cs) B is a group VIII transition metal, a group VIB or a group 1B (particularly Fe, Co, Ni, Mn, Cr, Cu). What are these substances? I have not yet discovered that it is important whether they are combined like this. base Impregnating the body with a solution of salts or with a complex of the desired metal and then calcining it is It is appropriate, as has been proposed in the These materials are suitable for temperatures above 650°C. It is generally active as a combustion catalyst only at show. These materials do not exhibit temperature-limiting effects like palladium; catalytic substrate If care is not taken, temperatures can rise to over 800°C.

The L-IHE catalyst structure of Figure 6 allows 50% gas flow through catalyst channels (3). , with 50% gas flow through the non-catalytic channel (4) and the catalytic channel (4). Once combustion is completed in the third zone, the temperature of the exiting gas from the third zone will be as described above. is the average of the inlet temperature and the adiabatic combustion temperature. Wall temperature and gas temperature are as above. is defined by equations (1) and (2). Incomplete reaction occurs within the catalyst channel As a result, the temperature of the outflow gas decreases.

The exhaust gas from the second zone is at a temperature above about 800°C and the fuel/air mixture is It has a theoretical adiabatic combustion temperature of 300°C, with 50% of the gas mixture inside the catalyst channels. When completely combusted at (average of 0°C and 1300°C). This exit gas temperature results in rapid, uniform combustion is obtained.

In order to combust at least a portion of the fuel entering the third zone, the structure of the third zone must be The structure can take many forms and the catalyst can be applied in a variety of ways. For example, in the above Using the structure described for Figures 6A and 6B, respectively, entering the third zone. A conversion of 80% or 20% of the gas mixture is possible. Outflow gas temperature from third zone The degree can be adjusted by the design of the catalyst support.

Therefore, as a design issue, (if a fourth zone homogeneous combustion zone is desired) ) The bulk temperature of the gas exiting the third zone exceeds the autoignition temperature. Three zones should be designed. The temperature of the support and catalyst is relative dimensions of the and non-catalytic channels, inlet temperature, theoretical adiabatic combustion temperature, and third zone. maintained at a moderate temperature determined by the length of the tube. Gas in the third catalyst zone The linear velocity of the is higher, so it is clearly faster.

two anus The gas that has flowed out from the previous combustion zone can be used as is if the temperature is correct. the gas may be in suitable conditions for The medium and catalyst support are maintained at a temperature that allows long-term stability. but , many applications require even higher temperatures. For example, many gasters The bottle is designed for an inlet temperature of approximately 1260'C. Therefore, the homogeneous combustion zone It may be appropriate to add .

The homogeneous combustion zone does not have to be large. Virtually complete combustion (i.e. carbon monoxide gas within this zone to achieve a The residence time of the flash should be less than about 11 or 12 milliseconds.

The table below shows the results for achieving various adiabatic combustion temperatures (as a function of fuel/air ratio). and fuel-(methane)/air to achieve near-complete combustion. as a function of the ratio, the bulk temperature of the gas exiting the third catalytic zone, and the pressure: Shows the calculated residual time. These reaction times are based on the homogeneous combustion model and Kee et al. Kinetic rate constants (Sa ndia National Laboratory Report No. 5AND　8O-8003).

Obviously, for the methods used in gas turbine substrates (e.g. catalytic gas bulk outflow temperature = 900°C, F/A ratio 0.043, pressure = 10 atm), The maximum combustion temperature and residence time to achieve complete combustion are less than 5 milliseconds.

If the bulk linear gas velocity is less than 40 m/s (as described above for the catalyst stage) ), the length of the homogeneous combustion zone may be less than 0.2 m.

In summary, this method uses a carefully crafted catalyst structure and catalytic method to Produces a working gas that is qualitatively NOx-free and has a temperature comparable to that of conventional combustion methods. Ru. However, it may inhibit the catalyst or support or shorten its useful life. , the catalyst and its support are not exposed to harmful high temperatures.

fresh blood and Soaring soil This example shows the assembly of a three-stage catalyst system.

Anti-staircase The first step was prepared as follows: 13% palladium/ZrO2 sol was prepared. Manufactured. A sample of 145 g of ZrO2 powder with a surface area of 45 m2/g+o was dissolved in HNO3. 0.83 g/m prepared by dissolving Pd(HN3)2(NO2)2 It was impregnated with 45 ml of palladium solution containing 1 ml of palladium. Dry this solid Then, it was calcined in air at 500℃, and 230ml of 820 and 2.01 of concentrated HNO3 were added. A polymer-lined ball mill was filled with a cylindrical zirconia medium. .

This mixture was mixed and ground for 8 hours.

To 50 cc of this sol (containing approximately 35% solids by weight), add 36+ ml of palladium The solution was added. The p■ was adjusted to about 9 and 1.0μl of hydrazine was added. room temperature The palladium was reduced by stirring. up to 100 square cells per square inch (SCS I) A cordierite monolith type ceramic honeycomb structure having the above parameters It was immersed in the Dium/ZrO2 sol and the excess sol was blown out of the channel. child The monolith was dried and calcined at 850°C. The monolith contains 6.1% ZrO2 and 1.5% palladium.

This monolith was immersed again in the same palladium/ZrO2 sol to a depth of 101 m. Then, it was taken out, blown dry, and calcined.

The final catalyst consisted of 25% ZrO2 and 6.2% palladium in the io, Omm portion of the introduction. It contained mu.

limited skin appearance The second stage catalyst was prepared as follows: A colloidal sol of 2zrO2 was prepared.

Approximately 66 g of zirconium isopropoxide was hydrolyzed with 75 cc of water to determine the surface area. 100 g of ZrO2 powder at 100 2/g was mixed with a further 56 l of water. child The slurry was transferred to a polymer-lined ball using a cylindrical medium of ZrO2. The mixture was mixed and ground in a mill for 8 hours. By adding water to this colloidal sol, the ZrO2 concentration is 1. Diluted to 5%.

Wave the Fe/Cr/Al alloy foil in a herringbone shape and oxidize it in air at 900°C. Then, alumina whiskers were formed on the foil surface.

The above zr02 sol was sprayed onto corrugated foil. Dry the coated foil at 850°C It was calcined in The final foil had 12 g of ZrO2 per surface IC12. Ta.

Dissolve palladium bovine acid into 2-ethyl toluene and place on one side of the paralyzed metal foil. It was sprayed on only the surface, dried and calcined at 850°C in air. The final foil is , had 0.5 B palladium per few'' surface.

Wrap the corrugated foil so that the waves do not interlock, 2 inches in diameter and 2 inches long. It has elongated channels axially throughout the structure, with approximately 150 channels per square inch. A final metal structure was formed with cells of . This foil only has palladium on one side /ZrO2 catalyst, and each channel is coated with a catalyst as shown in Figure 3A. It consists of a surface and a non-catalytic surface.

R1 main The third stage catalyst was prepared as follows: An alumina sol was prepared. Surface area 180 Approximately 125g of gamma alumina of m2/g, 21ml of concentrated nitric acid, and 165+el of water. was charged into a half gallon ball mill with cylindrical alumina grinding media and mixed for 24 hours. Shattered. This sol was diluted to a solids concentration of 20%.

The Fe/Cr/A1 alloy foil is corrugated to form uniform straight channels in the foil piece. Ta. When rolled together with flat foil strips, the helical structure forms a honeycomb with straight channels. formed the structure. First, spray 5% colloidal boehmite sol onto a corrugated piece of foil. Then, the alumina sol prepared above was sprayed. Same goes for flat metal foil. I sprayed it like that. Each foil was thus coated on only one side. and , the foil was dried and calcined at 1100°C.

Pt(NH3)2(NO2)2 was dissolved in nitric acid, containing 0.13g/sl of platinum. I made a solution with Spray this solution onto the coated foil and treat the foil with gaseous H2S. The mixture was washed, dried, and calcined at 1100°C. The "thickness" of the alumina coating on the metal foil is It was about 4 mg/cm2 on a flat foil surface.

The amount of platinum added was about 20% of the alumina.

= system The above three catalysts are arranged inside a ceramic cylinder as shown in Figure 7. Beta. In this system, thermocouples were placed at the locations shown. placed on the catalyst part The thermocouple is enclosed in a channel with ceramic cement and measures the temperature of the catalyst substrate. It was measured. A gas thermocouple was suspended in a gas stream. The diameter of the insulated catalyst part in Figure 7 is It was installed in a reactor with 50 liters of gas flow path. 150SLPM sky Air was passed through an electric heater, a static gas mixer, and into the catalyst system. 67 SLPM natural gas was added just upstream of the static gas mixer. electric heater power By increasing the force, the air temperature was slowly raised.

At 368 °C, the gas temperature exiting from stages 1.2 and 3 is as shown in Figure 8. It started to rise. Above the preheat temperature of 380°C, the gas temperature from stage 1 is approximately 530°C. °C, the gas temperature exiting from stage 2 is approximately 780"C, and from stage 3 the gas temperature is approximately 780"C. The temperature of the gas flowing out was about 1020°C. The catalyst increases the gas temperature to approximately 1250°C. After that, uniform combustion occurs. This temperature is close to the adiabatic combustion temperature for this fuel/air ratio. The temperature is high. These three stages of substrate temperature are shown in FIG.

As mentioned above, the Stage I catalyst ignites at low temperatures and the substrate temperature is self-limiting at about 750°C. It was done. The catalyst cell concentration and gas flow rate were determined with an intermediate gas temperature of 540°C. . Similarly, stage 2 also self-limits the substrate temperature at 780°C and the gas temperature at 750°C. Ta. Stage 3 was limited to a wall temperature of 1100"C.

By limiting the substrate temperature in stages 1 and 2 to 750°C to 780°C, Catalyst stability was obtained with Cₛ stiffness for a very long period. This stability is shown in Figure 10. This was shown to be the case over a period of 100 hours. Maintain the inlet air temperature at 400°C. This catalytic system can be improved by increasing the fuel/air ratio by increasing the methane flow rate. I started the system again. This starting process is shown in FIG. Stage 1 is fuel/air = , the exit gas temperature reached 540 °C at 033, and this temperature remained until the fuel/air ratio, O45. was maintained. Complete homogeneous combustion in the region after the catalyst is achieved at a fuel/air ratio of 045 It was done.

The invention has been illustrated by direct description and examples.

The examples are not intended to limit the invention as claimed below, but are merely illustrative. Only. Furthermore, those skilled in the art will be able to find equivalents that implement the invention recited in these claims. You will notice the method. Such equivalent methods are considered to be within the spirit of the present invention. think.

End defense muscle h “suji tsui” Ke ÷ Shito f6.10c 1? 6 C31A 10c 41 major tests on CH, Ft io Struggle 1m 1,000m/81 international search report Continuation of front page (31) Priority claim number: 617,980 (32) Priority date: November 2, 1990 6th (33) Priority claim country: United States (US) (31) Priority claim number: 618,301 (32) Priority date: November 2, 1990 6th (33) Priority claim country: United States (US) (81) Designated countries EP (AT, BE, CH, DE.

DK, ES, FR, GB, GR, IT, LU, NL, SE), AT, AU, BB , BG, BR, CA, CH, DE, DK, ES, FI, GB, HU, JP, KP , KR, LK, LU, MC, MG, MW, NL, No, RO.

SD, SE, SU, US (72) Inventor Nobuo Ezawa 3-1-502 Sengoku, Koto-ku, Tokyo (72) Inventor: Schlazter, James C.

United States California 94087゜Sunnyvale, Chitamukko 1718 (72) Inventor Nicholas, Salento Gee.

Wagoner Drive, Livermore, California 94550, United States 1158

Claims (1)

[Claims] 1. A method of combusting a combustible mixture comprising: a. reaching the desired temperature during combustion A combustible mixture containing the fuel and oxygen-containing gas necessary for The fuel is brought into contact with a catalytic structure having a catalytic material therein without contacting the catalyst. Only a portion is combusted in the catalytic structure and partially combusted flows out of the catalytic structure. a step in which the temperature of the combustible mixture is lower than a desired temperature; b. The remainder of the fuel in the combustible mixture is burned outside the catalyst structure to reduce its temperature. and increasing the temperature to a desired temperature. 2. The catalyst structure is divided into three stages, the first stage contacting the combustible mixture comprising: having a catalyst containing palladium, the second stage catalyst having palladium, and the third stage having a catalyst containing palladium; 2. The method of claim 1, wherein the catalyst comprises platinum. 3. The temperature of the combustible mixture flowing out from the first stage is between 500°C and 650°C. and the amount flowing out from the second stage is in the range of 750g°C to 800°C. and the temperature of what flows out from the third stage is in the range of 850°C to 1050°C. , the method according to claim 2. 4. 2. The desired temperature is in the range of 1050<0>C to 1700<0>C. the method of. 5. A catalyst having a catalytic material inside so that a part of the combustible mixture does not come into contact with the catalyst. The media structure includes a catalyst support having a plurality of elongated passageways for passage of the fuel mixture. 2. A catalyst according to claim 1, wherein only a portion of the passageway has a catalytic material therein. How to put it on. 6. 6. The method of claim 5, wherein the catalyst support is a corrugated metal structure. 7. A catalyst having a catalytic material inside so that a part of the combustible mixture does not come into contact with the catalyst. Claim 1, wherein the medium structure contains a catalyst support having a catalyst with expanded burrs 7 inside. The method described in. 8. 8. A method of combusting a combustible mixture, comprising: oxygen-containing gas at relatively high pressure mixing with the fuel under force to form a high pressure combustible mixture; b. reaction conditions sufficient to combust at least some, but not all, of the fuel; , the high pressure combustible mixture is applied to a first zone combustion catalyst containing palladium. a step of contacting the C. Complete reaction conditions are sufficient to combust at least a portion of the fuel. a second zone having a second zone combustion catalyst on a support having a heat exchange surface; The process of contacting partially combusted gas from one zone with a second zone combustion catalyst and how to encompass it. 9. 9. The method of claim 8, wherein the second zone combustion catalyst contains palladium. 10. The bulk temperature of the gas exiting the second zone is about 750°C to 950°C. 9. The method according to claim 8, wherein the temperature is in the range of <0>C. 11. said oxygen-containing gas is air, up to a pressure of at least 4 atmospheres (gauge); 9. The method of claim 8, wherein the method is compressed. 13. Claim wherein the first zone combustion catalyst contains palladium in a metal support. The method according to item 8. 13. A first zone combustion catalyst containing palladium on the metal support further comprises: 13. The palladium according to claim 12, further comprising a barrier layer covering at least a portion of the palladium. Method described. 14. 14. The method of claim 13, wherein the barrier layer contains zirconia. 15. Furthermore, in the third zone, the remaining unburned fuel is burned, having a temperature higher than the temperature of the gas exiting from the second zone and lower than about 1700°C. 9. The method of claim 8, comprising the step of producing a gas that is 16. A method of combusting a fuel mixture comprising: a. Mix oxygen-containing gas with fuel forming a combustible mixture; b. reaction conditions sufficient to combust at least a portion, but not all, of the fuel; Contacting the combustible mixture in a first zone with a first zone combustion catalyst containing bardium. C. Burning at least some of the fuel, but not all of it The second zone combustion catalyst, which has a complete maturation exchange surface, is contacting the partially combusted gas from the combustion zone in a second zone; d. a third zone at reaction conditions sufficient to combust at least a portion of the fuel; The partially combusted gas from the second zone contacts the combustion catalyst in the third zone. A method comprising: 17. The first zone combustion catalyst further comprises one or more Group IB metals. or a Group VIII metal. 18. Claim 1, wherein the first zone combustion catalyst further contains silver or platinum. The method described in 7. 19. the first zone combustion catalyst is on a support having a complete heat exchange surface; 17. The method according to claim 16. 20. 17. The method of claim 16, wherein the second zone combustion catalyst contains palladium. Law. 21. The bulk temperature of the gas flowing out from the second zone is approximately 750°C to 800°C. 21. The method of claim 20. 22. The second zone combustion catalyst further comprises one or more Group IB metal scraps. or a Group VIII metal. 23. 23. The first zone combustion catalyst further contains silver or platinum. Method described. 24. 17. The method of claim 16, wherein the third zone combustion catalyst contains platinum. 25. the third zone combustion catalyst is on a support having a complete heat exchange surface; 25. The method according to claim 24. 26. The third zone combustion catalyst comprises Mendeleev group V (particularly Nb or V ), Group VI (especially Cr), Group VIII transition metals (especially Fe, Co, Ni), and first series wotanide (particularly Ce, Pr, Nd, Sa, Tb, La) metal acids oxide, or mixed oxide, or berovskite-form material represented by AB03. one or more selected metal-element catalyst materials, in the above formula: A is Group IIA or Group IA (Ca, Ba, Sr, Mg, Be, K, Rb, N a, or Cs); B is a Group VIII transition metal, Group VIB or is selected from Group 1B (particularly Fe, Co, Ni, Mn, Cr, CU). The method according to item 16. 27. the third zone combustion catalyst is on a support having a complete heat exchange surface; 27. The method according to claim 26. 28. The oxygen-containing gas is air, and the pressure is from zero to 35 atmospheres (gauge). 17. The method of claim 16, wherein the method is compressed. 29. The first zone combustion catalyst comprises palladium on a metal support. The method according to claim 16. 30. A first zone combustion catalyst containing palladium on the metal support further comprises: Claim 2 further comprising a barrier layer covering at least a portion of the palladium-containing catalyst. 9. 31. 31. The method of claim 30, wherein the barrier layer contains zirconia. 32. Furthermore, the remaining fuel is burned in the fourth zone, and the gas flowing out from the third zone is It includes the process of producing a gas having a temperature higher than that of the gas and lower than about 1700°C. 17. The method of claim 16, comprising: