JP2003306310A - Autothermal reforming device and method of autothermal reforming using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an autothermal reforming device in which, when a honeycomb catalyst is used, the occurrence of hot spots and cold spots depending on the cells in the honeycomb is prevented and the slippage of raw materials and the production of byproducts are reduced. <P>SOLUTION: The autothermal reforming device 1 contains a honeycomb catalyst layer 2, and a reforming raw material, steam and an oxygen-containing gas are supplied from the inlet side of the catalyst layer to produce a reformed gas. The honeycomb catalyst layer 2, at the prestage thereof, is provided with a pre-catalyst layer 3 filled with a particulate or a foam catalyst. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an autothermal reforming reformer for converting hydrocarbons into a mixed gas containing carbon monoxide and hydrogen by an autothermal reforming reaction.

[0002]

2. Description of the Related Art Steam reforming (SR) and auto thermal reforming (AT) are used as techniques for reforming reforming raw materials such as hydrocarbons into synthesis gas and hydrogen.
Various methods such as R) and partial oxidation (POX) have been developed.

Of these, many technologies have already been put to practical use for SR, but since it is a reaction involving a relatively large amount of heat absorption, the load on the heat supply system such as a heat exchanger is large and it takes time to start. Is inferior in terms of.

On the other hand, contrary to SR, POX has a very short start-up time, but it is difficult to control because of large heat generation due to oxidation, and there are problems such as suppression of soot generation.

On the other hand, the ATR supplies a reforming raw material such as hydrocarbon, an oxidizing agent such as air, and steam to a reformer having a catalyst layer to oxidize a part of the raw material. This is a technique for balancing the reaction heat by advancing SR by the heat generated at this time. Since it has a relatively short start-up time and is easy to control, it has been particularly noted in recent years as a hydrogen production method for fuel cells. There is.

[0006]

The shape of the catalyst is
Honeycomb type, pellet type and the like are used. As shown in FIG. 3, the honeycomb catalyst has the cells 11 communicating with each other and can reduce the differential pressure between the upstream side and the downstream side. Therefore, the loads of the raw material pump, the water pump, and the air blower can be reduced. However, in the honeycomb catalyst, the gas is divided by the cells and the raw material, steam, and air do not mix between the cells in the honeycomb, so hot spots and cold spots are generated by the cells in the honeycomb, and raw material slips and by-products are generated. Object generation occurs. In order to avoid this, a gas mixer may be installed before the honeycomb catalyst, but there is a problem that the device becomes large.

Further, since the honeycomb has a low heat storage property, there is a risk of misfire due to load fluctuation (the risk of a sudden temperature decrease and reaction stop).

Further, at the time of starting, the reformer must be heated until the raw material gas reaches the combustion temperature, so that there is a problem that it takes time to start.

The present invention has been made to solve such problems, and when a honeycomb type catalyst is used,
An object of the present invention is to provide an autothermal reforming reformer that prevents hot spots and cold spots from being generated by cells in a honeycomb and reduces raw material slips and by-products.

Another object of the present invention is to provide an auto-thermal reforming reformer capable of effectively preventing a misfire due to load fluctuation and performing stable operation.

Another object of one aspect of the present invention is to provide an auto-thermal reforming reformer that can be started up quickly by shortening the startup time.

[0012]

The present invention relates to the following items.

1. In an autothermal reforming reformer for producing a reformed gas by supplying a reforming raw material, a gas containing steam and oxygen from the inlet side of the catalyst layer in the honeycomb type catalyst layer, An autothermal reforming reformer characterized in that a pre-catalyst layer filled with a granular or foamed catalyst is provided.

2. 1. The above-mentioned 1. characterized in that the catalyst filled in the preceding catalyst layer is an oxidation catalyst. The described autothermal reforming reformer.

3. 1. The above-mentioned 1 or 2, wherein the pre-catalyst layer has a higher heat storage property than the honeycomb-type catalyst layer. The described autothermal reforming reformer.

4. The volume ratio of the pre-stage catalyst layer to the honeycomb type catalyst layer is in the range of 0.1: 9.9 to 3: 7, and the above 1-3. 5. The auto thermal reforming reformer according to any one of 1.

5. 1. A burner that is ignited at least at startup is provided upstream of the front catalyst layer. 5. The auto thermal reforming reformer according to any one of 1.

6. 4. The above-mentioned 5. characterized in that the burner is a surface burner. The described autothermal reforming reformer.

7. 1 to 6 above, wherein the reforming raw material is kerosene. 5. The auto thermal reforming reformer according to any one of 1.

8. 1 to 7 above. An auto-thermal reforming method for producing a reformed gas by supplying a gas containing a reforming raw material, steam and an oxygen amount using the auto-thermal reforming reformer according to any one of 1.

9. The above 5 or 6. An auto-thermal reforming method, characterized in that a burner is ignited at the time of startup by using the auto-thermal reforming reformer described above, and combustion gas is supplied to the preceding catalyst layer.

10. Using the autothermal reforming reformer described in 5 or 6, the burner is ignited at the time of start-up to supply combustion gas to the preceding catalyst layer, and the burner is extinguished at the steady state, or Bypassing the burner, reforming raw material in the preceding catalyst layer,
An autothermal reforming method comprising supplying a gas containing water vapor and oxygen.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION As a reforming raw material, any material containing carbon and hydrogen and capable of causing an oxidation reaction by oxygen and a steam reforming reaction by steam can be used. Methanol, ethanol, dimethyl ether, city gas, LPG (liquefied petroleum gas), gasoline, kerosene, etc. can be mentioned as examples that can be inexpensively obtained for industrial or consumer use. Among these, kerosene is suitable.

Further, the above raw materials include hydrogen, water, carbon dioxide,
A raw material containing carbon monoxide, oxygen, etc. can also be used. For example, when hydrodesulfurization is performed as a pretreatment of the raw material, the residual hydrogen used in the reaction can be mixed with the raw material without being particularly separated.

On the other hand, the sulfur concentration in the raw material is desirably as low as possible because it has the effect of deactivating the reforming catalyst, and is preferably 50 mass ppm or less, more preferably 20 mass ppm or less. Therefore, if necessary, the raw material can be desulfurized in advance.

The sulfur concentration in the raw material to be subjected to the desulfurization step is not particularly limited, and any raw material having a sulfur concentration such that it can be converted to the above sulfur concentration in the desulfurization step can be used.

The desulfurization method is also not particularly limited, but an example is a method in which hydrodesulfurization is carried out in the presence of a suitable catalyst and hydrogen and the produced hydrogen sulfide is absorbed in zinc oxide or the like. In this case, examples of catalysts that can be used include catalysts containing nickel-molybdenum, cobalt-molybdenum, or the like. On the other hand, if necessary, a method of sorbing a sulfur content in the presence of hydrogen in the presence of an appropriate sorbent can also be adopted. As sorbents that can be used in this case, Japanese Patent Nos. 2654515 and 26
Examples thereof include a sorbent containing copper-zinc as a main component or a sorbent containing nickel-zinc as a main component as disclosed in Japanese Patent No. 88749.

The method for carrying out the desulfurization step is not particularly limited, either.
It may be carried out by a desulfurization process installed immediately before the autothermal reforming reactor according to the present invention, or a raw material treated in an independent desulfurization process may be used.

Oxygen is usually added to the reaction raw material in an amount that can generate a heat quantity capable of balancing the endothermic reaction of SR, but the addition amount is appropriately determined in relation to heat loss and external heating installed as necessary. . The amount is preferably 0.05 to 1, as a ratio (oxygen / carbon ratio) of the number of moles of oxygen molecules supplied to the ATR reaction region to the number of moles of carbon atoms contained in the reforming raw material supplied to the ATR reaction region. More preferably 0.1 to 0.75, even more preferably 0.2 to
It is preferably 0.6. When the oxygen / carbon ratio is smaller than the above range, a small amount of heat is generated and a large amount of heat needs to be supplied from the outside, which is disadvantageous in that the situation is substantially the same as SR. On the other hand, when the oxygen / carbon ratio is larger than the above range, heat generation becomes large and it is difficult to balance heat, and it is disadvantageous in that hydrogen and carbon monoxide are burned and consumed by oxygen and the modified gas yield is reduced. is there.

The oxygen may be pure oxygen, but those diluted with other gas can also be used suitably, such as water vapor,
It may contain carbon dioxide, carbon monoxide, argon, nitrogen, etc. For example, from the viewpoint of easy availability, air, oxygen-enriched air, etc. are preferably used as a gas containing oxygen.

The amount of steam introduced into the reaction system depends on the ATR
It is defined as the ratio of the number of moles of water molecules supplied to the ATR reaction region to the number of moles of carbon atoms contained in the reforming raw material supplied to the reaction region (steam / carbon ratio), and this value is preferably 0.3 to 10 , More preferably 0.5 to 5,
More preferably, it is 1-3. If this value is smaller than the above range, coke tends to precipitate on the catalyst, and the hydrogen content obtained tends to decrease, while it is disadvantageous if the value is larger. However, it is disadvantageous in that it may lead to enlargement of steam generation equipment and steam recovery equipment.

The method of adding steam to the hydrocarbon compounds is not particularly limited, but it may be introduced into the reaction region at the same time as the starting hydrocarbon compound, or it may be introduced from different positions in the reaction region or divided into several times. You may introduce them part by part.

The oxygen supply amount and the steam supply amount can be appropriately determined in consideration of the composition of the reforming raw material, the composition of the reformed gas to be produced, the heat balance in the catalyst layer, the generation of coke, and the like. .

Further, the space velocity of the reforming raw material, the mixed gas containing steam and oxygen is GH on the basis of the total amount of the catalyst and converted into standard temperature / pressure (15 ° C., 1 atm {0.101 MPa}).
The SV is preferably set in the range of 500 to 1,000,000 h ^-1 , more preferably 1,000 to 800,000 h ^-1 , and most preferably 1,500 to 500,000 h ^-1 . At this time, the temperature in the reformer is preferably set to 2 by appropriately controlling the oxygen / carbon ratio and the space velocity.
00-1000 ° C, more preferably 300-900 ° C,
More preferably, the temperature is controlled to 500 to 800 ° C.

In the present invention, as described above, the honeycomb type catalyst layer is used as the main catalyst, and the granular or foamed catalyst (hereinafter, the catalyst used in the pre-stage catalyst layer is referred to as the pre-stage catalyst) is used in the pre-stage catalyst layer. It is a thing. At least the honeycomb-type catalyst is a catalyst for autothermal reforming (ATR catalyst), has an oxidizing activity and a steam reforming activity, and has a catalyst component on a honeycomb carrier having a cross-sectional shape such as a triangle, square, or hexagon. It is a supported catalyst.
In addition, Japanese Patent Laid-Open Nos. 2000-84410 and 2001
-80907, "2000 Annual Pr"
ogress Reports (Office of
Transportation Technology
es) ”, US Pat. No. 5,929,286, etc., nickel and precious metals such as platinum, rhodium, ruthenium, etc. are known to have these activities, and these are supported as catalyst components. Can be used. In the present invention, a known honeycomb type ATR catalyst can be used. The honeycomb carrier is usually made of a material selected from the group consisting of ceramics such as alumina, silica, magnesia, zirconia, titania, or a combination of two or more thereof, or a heat-resistant metal material.

On the other hand, the pre-stage catalyst may be either an ATR catalyst or an oxidation catalyst (generally a partial oxidation catalyst (POX catalyst)). However, the POX catalyst is preferable in order to raise the gas temperature reaching the honeycomb-type ATR catalyst which is the main catalyst.

The shape of the pre-stage catalyst is granular or foam. Here, the term “granular” means a ball shape (sphere, ellipsoidal sphere, etc.),
It has a shape including a tablet shape (cylindrical shape), a ring shape, and the like, and includes all granular shapes that can be filled while maintaining voids. Generally, a ball shape (sphere, elliptical sphere, etc.), a tablet shape (cylindrical shape), or a ring shape is used. The granular form may be a carrier selected from alumina, silica, zirconia, titania, magnesia, or the like, even if the catalyst component itself forms the shape.
It may be either a catalyst in which a catalyst component is supported on a carrier which is a combination of two or more species.

Further, the foam-like material is a porous material in which the respective pores communicate with each other so that gas can pass therethrough, and a catalyst in which a catalyst component is carried on such a foam-like carrier is used. You can As the granular or foamed catalyst used in the present invention, a known catalyst can be used.

The pre-catalyst layer preferably has a high heat storage property. When the heat storage property of the front catalyst layer is high, the amount of raw material gas supplied,
Even if there is a load change such as pressure, the temperature does not change abruptly, so that the temperature of the honeycomb catalyst does not suddenly drop and the reaction does not stop, and stable operation can be performed. Materials with high heat storage properties include alumina, silica,
1 selected from zirconia, titania, magnesia, etc.
One or a combination of two or more thereof is preferable.

FIG. 1 shows how the ATR reformer 1 is filled with the honeycomb catalyst 2 and the pre-catalyst layer 3. In this way, the upstream catalyst is packed on the upstream side of the honeycomb catalyst. The particle size of the pre-stage catalyst is selected so that the reforming raw material, steam and a gas containing oxygen (air) can be sufficiently mixed. The particle size of the pre-catalyst is selected so that it does not enter the pores of the honeycomb catalyst, or an appropriate mesh division may be provided between the pre-catalyst and the honeycomb catalyst. The size of the pre-catalyst is, for example, in the case of a ball, its diameter, and in the case of an ellipsoid, the major axis and the minor axis are, for example, 0.5.
It is -20 mm, preferably 1-10 mm, and the major axis / minor axis ratio is 1-5. In the case of tablets or rings, the height and bottom diameter are, for example, 0.5.
~ 20 mm, preferably 1-10 mm, and the height / diameter ratio is 1-20.

The filling height of the pre-catalyst layer needs to be high enough to allow the reforming raw material, the gas containing steam and oxygen to be sufficiently mixed while the feed gas passes between them. The volume ratio of the pre-catalyst to the honeycomb catalyst is preferably in the range of 0.1: 9.9 to 3: 7, particularly 0.5: 9.5 to 2:
A range of 8 is preferred.

In addition, in one embodiment of the present invention, a burner can be provided further upstream of the pre-stage catalyst. The burner may be a diffusion combustion (nozzle type) burner conventionally used for partial oxidation of reforming raw materials such as hydrocarbons, but the point that the partial oxidation reaction is stable and the flame length is short and the device can be made compact with a simple configuration. A surface burner is preferable in that respect.

FIG. 2 is a diagram showing an example of the above.
The reformer 4 is filled with the honeycomb catalyst layer 2 and the pre-catalyst layer 3, a surface burner 5 is provided on the upstream side of the pre-catalyst 3, and a spark plug 6 for ignition is provided.
In a normal configuration, even if the pre-stage catalyst is a partial oxidation catalyst,
It is necessary to heat it up to the combustion temperature. However, in the configuration of this ATR reformer, at the time of startup, the burner is ignited to burn at least a part of the raw material gas to raise the gas temperature,
By supplying the high temperature gas to the pre-stage catalyst and the honeycomb catalyst, the temperatures of both catalysts are rapidly raised, so that the normal operation can be started in a short start-up time. A with burner
Also in the case of the TR reformer, the honeycomb type catalyst layer and the pre-stage catalyst layer may have the same structure as the burner is not provided, and the pre-stage catalyst is preferably a partial oxidation catalyst.

The surface burner is a porous plate (hereinafter referred to as a porous plate) having pores in which a premixed gas such as fuel and oxygen (air) communicates with the front and back.
The burner mat is supplied from the back surface (upper surface in FIG. 2) and passed to the front surface (lower surface in FIG. 2), and is ignited in the vicinity of the surface to burn the entire surface of the burner mat. The surface burner itself has been conventionally used and has features such as low NOx, uniform surface combustion, and low noise.

From the viewpoint of pressure loss, the average porosity of the burner mat is preferably 20% or more, more preferably 30% or more. For the burner mat, a non-woven fabric or woven fabric of metal fibers, or a non-woven fabric or woven fabric of fibers made of ceramics such as cordierite, titania, mullite, alumina, silica, and alumina-silica can be used.

Examples of the method for producing the above metal fibers include processing methods such as a drawing method, a melt spinning method, a wire cutting method, a coil material cutting method, a chatter vibration cutting method, a coating method and a whisker method. The average diameter of the metal fibers is 5 to 200
μm, more preferably 10 to 100 μm.

The main component of the raw material of the above fibers is Fe-Cr-S.
In the case of i or Fe-Cr-Al, it is possible to heat-treat in an oxidizing atmosphere after the sintering treatment to form an alumina layer or a silica layer on the surface and improve the high temperature heat resistance. Even if other materials are used, the oxidation resistance can be improved by coating the surface of the combustion burner mat with alumina or the like.

When the metal fibers are molded into a mat and then sintered, 800 to 1 in a vacuum or a non-oxidizing atmosphere.
It can be heated in the range of 200 ° C. for 10 minutes to 10 hours. It is also preferable to perform sintering while applying a load to the fibers, but it is preferable to adjust the load so that the preferable porosity is obtained.

In the present invention, the burner mat used for the surface burner preferably carries a substance having a catalytic action for improving the activity of partial oxidation reforming and / or improving the combustibility, particularly metal. As the supported metal, a known active metal used for catalytic partial oxidation of hydrocarbons or catalytic combustion can be selected.

As an active metal for catalytic partial oxidation, rhodium, ruthenium, palladium, platinum and the like are preferable. Nickel, which is inexpensive in cost, is also suitable.

From the viewpoint of the reaction accelerating effect and the economical efficiency, the amount of metal supported is 0.
1-30 mass% is preferable. A known method can be applied as a method for supporting the metal without particular limitation. For example, after the burner mat is immersed in an aqueous solution of a metal salt and 0.1 to 30% by mass of the active metal is attached to the burner mat as a carrier. It can be prepared by carrying out the steps of drying, thermal decomposition and pyrolysis.
When the amount of metal supported on the burner mat cannot be increased, a plurality of burner mats supporting active metal can be stacked to carry out the reaction as long as the flow of the premixed gas is not hindered.

The shape of the burner mat is usually matched with the sectional shape of the reactor, but it may be appropriately changed if necessary. That is, when the surface load is small with respect to the burner mat area, it is disadvantageous in that the partial oxidation reaction tends to be difficult to occur, and when the surface load is large, an excessive load is applied to the burner mat, resulting in damage to the mat. There is a disadvantage in that there is a tendency. From such a viewpoint, the surface load is preferably 100 to 10,000 kW / m ² , and 1000
˜5000 kW / m ² is more preferable.

As the spark plug 6, a known one for a surface burner can be used.

Thus, by using the surface burner at least at the time of starting, the reforming reaction can be started in a short time.

In the present invention, it is also possible to use the burner only at the time of starting and not use the burner after starting.
As one method, there is a method of igniting the burner only at start-up and turning off the burner when a steady state (stable operation) is reached. Further, when the gas including the reforming raw material bypasses the burner and enters the catalyst layer when the steady state is reached, the pressure loss due to the burner, particularly the surface burner can be reduced. For example, as shown in FIG. 4, with respect to the ATR reformer 7 having the honeycomb catalyst 2, the pre-catalyst layer 3, and the surface burner 5 and the spark plug 6 upstream thereof, the valve 8 is opened at startup and the valve is opened. 9 is closed, the raw material mixed gas containing the reforming raw material and the like is guided to the surface burner, the burner is ignited and started, and when operating in a steady state, the valve 8 is closed and the valve 9 is opened to change the raw material. The mixed gas may be supplied from upstream of the front catalyst layer 3 without passing through the surface burner. At this time, the surface burner is usually extinguished.

Since the reformed gas produced by using the above apparatus contains hydrogen and carbon monoxide, it is suitable for applications requiring a lower carbon monoxide concentration such as when used for fuel cells. Is a known shift process reactor or CO
Carbon monoxide can be reduced and used through a selective oxidation device.

[0057]

EXAMPLES Example 1 In this example, the apparatus configuration shown in FIG. 2 was used. That is, a cordierite honeycomb catalyst supporting Rh (diameter 5 cm, height 10 cm, cell number 40
0 cpi) was charged in a reaction tube, and P was used as a pre-stage catalyst.
20 ml of γ-alumina spheres carrying t (diameter: 2 mm, catalyst layer height: 1 cm). As a surface burner, the diameter is 5
cm, thickness 1 mm, average porosity 40%, Fe-Cr-A
A metal fiber non-woven fabric made of 1 supporting 0.5 mass% of Pt was used.

In this reformer, desulfurized kerosene (sulfur content 1 mass p
pm or less) was used as a raw material, and a steam / carbon ratio of 2 and air of an oxygen / carbon ratio of 0.5 were supplied. At this time, the space velocity in the honeycomb catalyst was 6,000 h.
^-1 (space velocity for mixed gas of kerosene, water vapor, and air, converted to 15 ° C and 1 atm).

The ignition plug was ignited, the operation was started, and changes with time in the honeycomb catalyst outlet temperature and the gas composition were measured. As a result, the temperature and the gas composition were stable in about 10 minutes, and the steady operation was reached. As a result of measuring the temperature distribution in the cross-sectional direction at the honeycomb catalyst outlet, the maximum temperature was 630 ° C and the minimum temperature was 627 ° C.

The composition of the gas further produced is as follows.
It was Ri. H₂  40.0 vol% (dry) CO; 8.9 vol% CO₂; 12.3 vol% CH_Four0.8 vol% Undegraded kerosene content: 1 volppm or less <Example 2> Supply of desulfurized kerosene, steam and air of Example 1
The supply amount was rapidly tripled without changing the supply ratio.
At this time, the space velocity in the honeycomb catalyst was 18,000.
0h ^-1(Empty against mixed gas of kerosene, water vapor and air
Inter-speed, converted to 15 ° C and 1 atm). Honeycomb touch
The medium outlet temperature and gas composition are about 5 minutes after changing the supply amount.
It was stable and stable operation could be continued.

Comparative Example 1 A reaction tube was filled with a Rh-supported cordierite honeycomb catalyst (diameter 5 cm, height 10 cm, cell number 400 cpi).

In this reformer, desulfurized kerosene (sulfur content 1 mass p
pm or less) was used as a raw material, and a steam / carbon ratio of 2 and air of an oxygen / carbon ratio of 0.5 were supplied. At this time, the space velocity in the honeycomb catalyst was 6,000 h.
^-1 (space velocity for mixed gas of kerosene, water vapor, and air, converted to 15 ° C and 1 atm).

The ignition plug was ignited, the operation was started, and the changes with time of the honeycomb catalyst outlet temperature and the gas composition were measured. As a result, the temperature and the gas composition were stable in about 12 minutes, and the steady operation was reached. As a result of measuring the temperature distribution in the cross-sectional direction at the honeycomb catalyst outlet, the maximum temperature was 675 ° C and the minimum temperature was 595 ° C.

The composition of the gas produced further is as follows.
It was Ri. H₂  38.9 vol% (dry) CO: 8.0 vol% CO₂; 13.3 vol% CH_Four1.0 vol% Undegraded kerosene content: 250 volppm <Comparative Example 2> Desulfurization kerosene of Comparative Example 1, supply of steam and air
The supply amount was rapidly tripled without changing the supply ratio.
At this time, the space velocity in the honeycomb catalyst was 18,000.
0h ^-1(Empty against mixed gas of kerosene, water vapor and air
Inter-speed, converted to 15 ° C and 1 atm). Honeycomb touch
The medium outlet temperature dropped rapidly and the reaction stopped.

[0065]

EFFECTS OF THE INVENTION According to the present invention, even if a honeycomb type catalyst is used, generation of heat spots and cold spots is suppressed, and as a result, stable operation can be performed without deterioration or misfire of the catalyst, and at the same time, the raw material can be used. It is possible to provide an apparatus and a reforming method having high reforming efficiency, which can suppress gas slip and obtain a reformed gas having a high hydrogen content.

Further, according to one aspect of the present invention, it is possible to provide an apparatus and a reforming method which have a high reforming efficiency and can be started quickly and can start stable operation in a short time.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of an autothermal reforming reformer of the present invention.

FIG. 2 is a diagram showing an example of an autothermal reforming reformer of the present invention.

FIG. 3 is a view showing a honeycomb type catalyst.

FIG. 4 is a diagram showing an example of an autothermal reforming reformer of the present invention.

[Explanation of symbols]

1 ATR reformer 2 Honeycomb catalyst layer 3 First stage catalyst layer 4 ATR reformer 5-sided burner 6 spark plugs 7 ATR reformer 8 valves 9 valves

Claims (10)

[Claims] 1. An auto-thermal reforming reformer comprising a honeycomb type catalyst layer, and a reforming gas is produced by supplying a reforming raw material, a gas containing steam and oxygen from the inlet side of the catalyst layer. An autothermal reforming reformer, characterized in that a pre-stage catalyst layer filled with a granular or foam-like catalyst is provided in front of the mold catalyst layer. 2. The autothermal reforming reformer according to claim 1, wherein the catalyst filled in the front catalyst layer is an oxidation catalyst. 3. The heat storage property of the pre-catalyst layer is higher than that of the honeycomb-type catalyst layer.
The described autothermal reforming reformer. 4. The volume ratio of the pre-catalyst layer to the honeycomb-type catalyst layer is in the range of 0.1: 9.9 to 3: 7, and the volume ratio is in the range of 0.1: 9.9 to 3: 7. Auto thermal reforming reformer. 5. The autothermal reforming reformer according to claim 1, wherein a burner that is ignited at startup is provided at least upstream of the front catalyst layer. 6. The autothermal reforming reformer according to claim 5, wherein the burner is a surface burner. 7. The autothermal reforming reformer according to claim 1, wherein the reforming raw material is kerosene. 8. An autothermal manufacturing method for producing a reformed gas by using the autothermal reforming reformer according to claim 1 to supply a gas containing a reforming raw material, steam and an oxygen amount. Reforming method. 9. An autothermal reforming method using the autothermal reforming reformer according to claim 5 or 6, wherein a burner is ignited at the time of start-up and combustion gas is supplied to the preceding catalyst layer. . 10. The autothermal reforming reformer according to claim 5, wherein the burner is ignited at the time of start-up to supply combustion gas to the pre-catalyst layer.
In a steady state, the burner is extinguished, or the burner is bypassed to supply a reforming raw material, a gas containing steam and oxygen to the pre-catalyst layer, and an auto-thermal reforming method.