JP2003306305A - Autothermal reforming method and its apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To smooth the temperature distribution in a catalyst bed by controlling the temperature rise at the catalyst bed inlet side and the temperature fall at the outlet side in an autothermal reforming method (ATR). <P>SOLUTION: When the cross section area and length of the catalyst bed in which a reforming material, an oxygen containing gas and steam are fed are denoted respectively as S (cm<SP>2</SP>) and L (cm) in the ATR method to produce a hydrogen-containing reformed gas, L/S=2-30 (cm<SP>-1</SP>) at 0.25<C/H≤0.40, L/S=1-20 (cm<SP>-1</SP>) at 0.40<C/H≤0.42, L/S=0.5-15 (cm<SP>-1</SP>) at 0.42<C/H≤0.47 and L/S=0.5-10 (cm<SP>-1</SP>) at 0.47<C/H≤0.58. C/H exhibits the atom ratio of carbon to hydrogen in the reforming material. L/S is optimized and variable in the ATR apparatus. <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 oxygen-containing gas such as air, and steam to a reformer equipped with a catalyst layer to oxidize a part of the raw material. , Which is a technology for balancing reaction heat by advancing SR by the heat generated at this time, and because it has a relatively short start-up time and is easy to control, has recently attracted attention as a hydrogen production method for fuel cells. ing.

[0006]

The oxidation reaction has a higher reaction rate than the reforming reaction. Therefore, in the ATR, the temperature near the portion where the oxygen-containing gas is supplied to the catalyst layer, such as near the inlet of the reformer, becomes high and a so-called hot spot occurs. This high temperature may cause the catalyst to deteriorate faster or require the use of expensive materials in the reaction tube to withstand the high temperatures. On the other hand, on the reformer outlet side of the catalyst layer, the oxidation reaction is substantially completed, and the SR reaction becomes dominant, so that the temperature drops and the raw material slip that is discharged without the raw material reacts. It is generated, a by-product is discharged, and a reformed gas having a relatively low hydrogen concentration (relatively high methane concentration) is generated due to chemical equilibrium.

An object of the present invention is to suppress a temperature increase on the oxygen-containing gas supply side of the catalyst layer and a temperature decrease on the outlet side in the ATR, and to make the temperature distribution in the catalyst layer gentle. . This suppresses catalyst deterioration, suppresses the occurrence of raw material slips and the discharge of by-products, makes it possible to use a relatively inexpensive material for the reaction tube, and to obtain a reformed gas with a high hydrogen concentration. It is possible.

[0008]

According to the present invention, an autothermal reforming method for producing a reformed gas containing hydrogen by subjecting a reforming raw material, an oxygen-containing gas and steam to an oxidation reaction and a steam reforming reaction in a catalyst layer. In, the cross-sectional area and the length of the catalyst layer to which the reforming raw material, the oxygen-containing gas and the steam are supplied are S (cm ² ) and L (c
m) and the atomic ratio of carbon and hydrogen of the reforming raw material is C / H, L / S = 2 to 30 (cm ⁻¹ ) when C / H is more than 0.25 and 0.40 or less. ), L / S = 1 to 20 (cm ⁻¹ ) when C / H is more than 0.40 and 0.42 or less,
When C / H exceeds 0.42 and is 0.47 or less, L / S =
0.5 to 15 (cm ⁻¹ ), C / H exceeds 0.47, and is 0.1.
An automatic thermal reforming method is provided, wherein L / S is 0.5 to 10 (cm ⁻¹ ) in the case of 58 or less.

According to the present invention, in an autothermal reforming method for producing a reformed gas containing hydrogen by subjecting a reforming raw material, an oxygen-containing gas and steam to an oxidation reaction and a steam reforming reaction in a catalyst layer, the reforming raw material, When the cross-sectional area and the length of the catalyst layer to which the oxygen-containing gas and steam are supplied are S (cm ² ) and L (cm), respectively, the reforming raw material is at least one selected from methanol, ethanol and dimethyl ether. And L / S =
0.5 to 10 (cm ⁻¹ ), L / S = 2 to 30 (cm ⁻¹ ) when the reforming raw material is city gas, and L / S when the reforming raw material is LPG = 1 to 20 (cm ^-1 ),
When the reforming raw material is gasoline, L / S = 0.5 to 15
(Cm ⁻¹ ), and when the reforming raw material is kerosene, L / S =
There is also provided an autothermal reforming method, which is characterized in that it is 0.5 to 10 (cm ^-1 ).

Further, according to the present invention, an auto thermal reforming apparatus equipped with a catalyst layer for obtaining a reformed gas containing hydrogen by subjecting a reforming raw material, an oxygen-containing gas and steam to an oxidation reaction and a steam reforming reaction, When the quality raw material is gasoline and the cross-sectional area and the length of the catalyst layer to which the reforming raw material, the oxygen-containing gas and steam are supplied are S (cm ² ) and L (cm), respectively, L / S =
There is provided an automatic thermal reforming device characterized by being 0.5 to 15 (cm ^-1 ).

According to the present invention, in the auto thermal reforming apparatus provided with a catalyst layer for obtaining a reformed gas containing hydrogen by subjecting a reforming raw material, an oxygen-containing gas and steam to an oxidation reaction and a steam reforming reaction, The raw material is kerosene, and the cross-sectional area and the length of the catalyst layer to which the reforming raw material, the oxygen-containing gas and the steam are supplied are S (cm).
² ) and L (cm), L / S = 0.5 to 1
There is also provided an auto-thermal reforming device characterized by being 0 (cm ^-1 ).

Further, according to the present invention, in an auto thermal reforming apparatus equipped with a catalyst layer for obtaining a reformed gas containing hydrogen by subjecting a reforming raw material, an oxygen-containing gas and steam to an oxidation reaction and a steam reforming reaction, respectively, An automatic thermal reforming apparatus having a plurality of reaction tubes provided with a catalyst layer in parallel, and a gas blocking means capable of blocking the supply of the reforming raw material, the oxygen-containing gas and the steam to the respective reaction tubes. Will be provided.

According to the present invention, a honeycomb type auto thermal reforming apparatus is provided which is provided with a catalyst layer for obtaining a reformed gas containing hydrogen by subjecting a reforming raw material, an oxygen-containing gas and steam to an oxidation reaction and a steam reforming reaction. There is also provided an auto-thermal reforming device having a catalyst, which is provided with a gas blocking means capable of blocking the supply of the reforming raw material, the oxygen-containing gas and the steam to the respective channels of the honeycomb type catalyst. .

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION As a reforming raw material, any material can be used as long as it contains a compound having carbon and hydrogen in the molecule and can cause an oxidation reaction by an oxygen-containing gas and a steam reforming reaction by steam. For example, hydrocarbons, alcohols,
Ethers can be used, and as a preferable example that can be inexpensively obtained for industrial or consumer use, methanol,
Examples thereof include ethanol, dimethyl ether, city gas, LPG (liquefied petroleum gas), gasoline, and kerosene.

Since the sulfur in the reforming raw material has an effect of deactivating the reforming catalyst, it is desirable that the concentration is as low as possible, preferably 50 mass ppm or less, more preferably 2 ppm.
It is 0 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.

There is no particular limitation on the method for carrying out the desulfurization step,
It may be carried out by a desulfurization process installed immediately before the automatic thermal reforming device according to the present invention, or a raw material treated in an independent desulfurization process may be used.

Examples of the oxygen-containing gas include oxygen, air, and oxygen-enriched air. These may include other gases such as water vapor, carbon dioxide, carbon monoxide, argon, nitrogen.

The method of supplying the oxygen-containing gas to the catalyst layer is not particularly limited, but it may be introduced into the reaction vessel at the same time as the reforming raw material, or the oxygen-containing gas and the reforming raw material may be provided at different positions in the reaction vessel. It is also possible to supply the oxygen-containing gas in several times and to introduce the oxygen-containing gas in portions.

The amount of the oxygen-containing gas supplied is the ratio of the number of moles of oxygen molecules supplied to the catalyst layer to the number of moles of carbon atoms contained in the reforming raw material supplied to the catalyst layer (oxygen / carbon ratio,
O ₂ / C) is preferably 0.05 to 1, more preferably 0.1 to 0.75, still more preferably 0.2 to 0.
It is 6. When the oxygen / carbon ratio is smaller than the above range, less heat is generated, so a large amount of heat needs to be supplied from the outside.
It has the disadvantage of approaching a situation that is virtually 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 the heat.
This is disadvantageous in that hydrogen and carbon monoxide are burned and consumed by oxygen and the modified gas yield is reduced.

The amount of water vapor introduced into the catalyst layer is the ratio of the number of moles of water molecules supplied to the catalyst layer to the number of moles of carbon atoms contained in the reforming raw material supplied to the catalyst layer (steam / carbon ratio, S / C), and this value is preferably 0.3 to 10, more preferably 0.5 to 5, and still more preferably 1 to 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 supplying steam to the catalyst layer is not particularly limited, but it may be introduced into the reaction vessel at the same time as the reforming raw material, or it may be introduced from different positions in the reaction vessel or divided into several portions. May be introduced.

The space velocity of the reforming raw material, the oxygen-containing gas and the gas containing water vapor supplied to the catalyst layer is preferably G
HSV (15 ℃, 1 atm (0.101 MPa) equivalent) in the range of 500~1,000,000h ^-1, more preferably in the range of 1,000~800,000h ^-1, more preferably 1,500～500 It is appropriately set in the range of 1,000 h ^-1 .

As the catalyst used in the catalyst layer, any catalyst that can be used for autothermal reforming, that is, one that has an oxidizing activity and a steam reforming activity can be used. For example, JP 2000-84410 A, JP 2001-80907 A, “2000 Annu”.
al Progress Reports (Official
e of Transportation Techn
It is known that nickel and precious metals such as platinum, rhodium and ruthenium have these activities, as described in U.S. Pat. No. 5,929,286. As the catalyst shape, a pellet shape, a honeycomb shape, and other conventionally known shapes can be appropriately adopted.

The temperature of the catalyst layer is preferably in the range of 200 to 1000 ° C., more preferably in the range of 300 to 900 ° C., and further preferably in the range of 500 to 800 ° C.

The pressure for the autothermal reforming reaction is not particularly limited, but is preferably atmospheric pressure to 20 MP.
a, more preferably from atmospheric pressure to 5 MPa, still more preferably from atmospheric pressure to 1 MPa.

In the present invention, the combustion reaction of the reforming raw material is performed by changing the ratio of the cross-sectional area S and the length L of the catalyst layer to which the reforming raw material, the oxygen-containing gas and the steam are supplied, depending on the properties of the reforming raw material. The temperature distribution in the catalyst layer can be made gentle by balancing the heat generation by the heat absorption by the reforming reaction and the heat absorption by the reforming reaction.

For example, the cross-sectional area and the length of the catalyst layer to which the reforming raw material, the oxygen-containing gas and the steam are supplied are S (cm ² ) and L (cm), respectively, and the carbon and hydrogen atoms of the reforming raw material are When the ratio is C / H, C / H is 0.25
L / S = 2 to 30 (c
m ⁻¹ ), C / H is more than 0.40 and 0.42 or less, L / S = 1 to 20 (cm ⁻¹ ), and C / H is more than 0.42 and 0.47 or less. L / S = 0.5 to 15 (c
If m / ^-1 ) and C / H are more than 0.47 and 0.58 or less, L / S can be set to 0.5 to 10 (cm- ¹ ).

This is to note that the reaction rate, in particular, the combustion rate and the reforming rate differ depending on the C / H of the reforming raw material, and L / S is used accordingly, whereby the temperature in the catalyst layer is changed. The distribution can be moderate. C / H is measured according to ASTM D5291-96.

Further, for example, when the reforming raw material is at least one selected from methanol, ethanol and dimethyl ether for each type of fuel, L / S = 0.5 to
10 (cm ⁻¹ ) and when the reforming raw material is city gas,
L / S = 2 to 30 (cm ⁻¹ ) and the reforming raw material is LPG
In the case of L / S = 1 to 20 (cm ⁻¹ ), and when the reforming raw material is gasoline, L / S = 0.5 to 15 (c
m ⁻¹ ), and when the reforming raw material is kerosene, L / S = 0.
It can be 5 to 10 (cm ^-1 ). This focuses on the fact that the reaction rate, especially the combustion rate and the reforming rate, differ depending on the type of fuel, and uses L / S accordingly, which makes the temperature distribution in the catalyst layer gentle. be able to.

Further, in the auto thermal reforming device in the case where the reforming raw material is gasoline, L / S is preferably 0.5 to 15 (cm ^-1 ), more preferably 0.5 to.
It is set to 10 (cm ^-1 ). Further, in the auto thermal reforming device when the reforming raw material is kerosene, L / S is preferably 0.5 to 10 (cm ^-1 ) and more preferably 0.5 to 8 (cm ^-1 ). By setting the respective ranges, it is possible to suppress the temperature increase at the catalyst layer inlet and the temperature decrease at the outlet when each reforming raw material is used, and to make the temperature distribution of the catalyst layer gentle.

In the autothermal reforming, the raw material becomes a competitive reaction of combustion reaction and steam reforming reaction. The ratio of these two reaction rates can be changed according to the gas linear velocity, and balances the rates of the combustion reaction, which is an exotherm, and the steam reforming reaction, which is an endotherm, and makes the temperature distribution of the entire catalyst layer moderate. be able to. The space velocity GHSV (converted at 15 ° C. and 1 atm (0.101 MPa)) of the reforming raw material, the oxygen-containing gas, and the steam-containing gas supplied to the catalyst layer is preferably in the range of 500 to 1,000,000 h ⁻¹ , More preferably in the range of 1,000 to 800,000 h ^-1 , and even more preferably 1,500 to 500,000 h.
^In the range of ^-1 , the length L (cm) of the catalyst layer and the cross-sectional area S
By setting the ratio L / S (cm ⁻¹ ) to (cm ² ) according to the nature and type of fuel, the balance between the above two reactions can be made desirable.

FIG. 1 shows the cross-sectional area S and the length L of the catalyst layer when the reaction vessel 11 of the auto thermal reforming apparatus has the cylindrical catalyst layer 12. The shape of the catalyst layer is not limited to the cylindrical shape. The cross section or length refers to the gas flow direction. Further, FIG. 1 shows the case where the reforming raw material, the oxygen-containing gas, and the steam are supplied to the entire catalyst layer. As will be described later, there are cases where these gases are not supplied to a part of the catalyst layer, and the cross-sectional area S in that case means the cross-sectional area of only the part to which the gas is supplied.

FIG. 2 shows one form of the automatic thermal reforming apparatus of the present invention. This reformer has a plurality of reaction tubes 21, which are connected in parallel to the raw material, oxygen-containing gas and steam streams. The reaction tubes 21 each include a catalyst layer (not shown). Furthermore, in the flow path for supplying the raw material, the oxygen-containing gas and the steam to each reaction tube,
A stop valve 23 is provided as a gas shutoff means. In addition, it is not always necessary to provide the flow path blocking means for all the flow paths.

Here, considering the case where the catalyst layers of each reaction tube have the same size, the number of reaction tubes is N, the cross-sectional area of each catalyst layer is S ', and the length of each catalyst layer is L. By switching the opening / closing of the stop valve 23 in accordance with the type and properties of the reforming raw material, it is possible to supply the gas such as the reforming raw material to the reaction tube or to stop the supply thereof. The number (n) can be changed. Therefore, the reforming raw material,
The cross-sectional area of the catalyst layer to which the oxygen-containing gas and water vapor are supplied is S = S ′ × n, and L / S can be changed.

FIG. 3 shows another form of the automatic thermal reforming device. The catalyst layer has a honeycomb type catalyst 32. The honeycomb type catalyst has independent flow paths (see FIG. 3).
In the figure, the cross section is shown as a rectangle) is a form gathered in parallel to the gas flow. Here, “independent” means that there is no gas flow between the flow paths in each flow path. The movable slit 33 is a gas blocking means capable of blocking the supply of the reforming raw material, the oxygen-containing gas and the steam to each flow path, and is arranged at a position where the inlet end face of the catalyst layer can be blocked. By moving the movable slit in the cross-sectional direction, it is possible to open and close the inlet of each channel of the honeycomb type catalyst, which can supply or stop the supply of gas to each channel. The number of flow channels can be changed. Therefore, as in the case of FIG. 2, the cross-sectional area of the catalyst layer to which the reforming raw material, the oxygen-containing gas and the steam are supplied can be changed, and L / S can be changed.

Although FIG. 3 shows a movable slit in which one plate can move in the cross-sectional direction of the catalyst layer, a band-shaped plate is arranged at the end of a plurality of honeycomb-type catalysts so that gas flows. It is also possible to use a flap type blocking means for blocking the gas by making the angle of the plate parallel with respect to allow the gas to flow.

As shown in FIG. 2 or FIG. 3, by switching the use / non-use of a part of the catalyst layer, the L / S can be adjusted according to the kind and properties of the raw material.
Even if the properties of the raw materials do not change, the temperature distribution of the catalyst layer may change due to a change in the activity of the catalyst when it is used for a long period of time. Even in such a case, the temperature distribution of the catalyst layer can be adjusted in a desired direction by changing L / S.

The autothermal reforming method and apparatus of the present invention can be used in various fields for producing hydrogen-containing gas, and can be applied to, for example, fuel reforming for fuel cells.

[0040]

[Example] [Example] A spherical catalyst 12 having an average particle diameter of 1 mmφ
0 ml was filled in a cylindrical reaction tube having an inner diameter of 4 cm (diameter). At that time, the cross-sectional area of the catalyst layer was 12.5 cm ² , the length of the catalyst layer was 9.6 cm, and L / S = 0.76 (cm ⁻¹ ). A sufficient heat insulating material was provided around the reaction tube to keep it warm.

Next, kerosene desulfurized to have a sulfur content of 1 mass ppm or less was supplied as a liquid to a 720 ml / h vaporizer, and 30
After being vaporized at 0 ° C., it was mixed with steam and air which were separately vaporized, preheated to 400 ° C., and then supplied to a reaction tube. The amount of air supplied was such that the atomic ratio of oxygen in the air to carbon in kerosene was O ₂ /C=0.4. Further, the supply amount of water vapor was set to S / C = 2. In addition, C of raw kerosene
/ H was 0.52. Further, GHSV is 15 as a space velocity for a mixed gas of kerosene, water vapor and air.
Approximately 16,000 at 1 ° C (0.101 MPa)
It was h ^-1 .

The temperature distribution of the catalyst layer at this time is shown in FIG.
The maximum temperature was 720 ° C. in a portion about 4 cm from the inlet. The lowest temperature was 660 ° C at the outlet.

The reformed gas produced had the following composition (dry base). H2; 39.9 volume% CO; 8.3 volume% CO2; 14.1 volume% CH4; 0.9 volume% undecomposed kerosene; less than 1 volume ppm [Comparative Example] 120 ml of a spherical catalyst having an average particle diameter of 1 mmφ It was filled in a cylindrical reaction tube having an inner diameter of 2 cm (diameter). At that time, the cross-sectional area of the catalyst layer was 3.1 cm ² , and the length of the catalyst layer was 39.
It was 0 cm and L / S = 12.2 (cm- ¹ ). A sufficient heat insulating material was provided around the reaction tube to keep it warm.

Next, kerosene was supplied as a liquid to a 720 ml / h vaporizer, vaporized at 300 ° C., then mixed with steam and air separately vaporized, preheated to 400 ° C. and then fed to a reaction tube. The amount of air supplied was such that the atomic ratio of oxygen in the air to carbon in kerosene was O ₂ /C=0.4.
Further, the supply amount of water vapor was set to S / C = 2.
The C / H of the raw material kerosene was 0.52. Also GHS
V was about 16,000 h ⁻¹ in terms of space velocity with respect to a mixed gas of kerosene, water vapor, and air at 15 ° C. and 1 atmospheric pressure (0.101 MPa).

Regarding the temperature distribution of the catalyst layer, the maximum temperature was 1050 ° C. at the portion about 3 cm from the inlet, and the minimum temperature was 390 ° C. at the outlet.

The reformed gas produced had the following composition (dry base). H2; 34.7 volume% CO; 4.5 volume% CO2; 15.7 volume% CH4; 4.1 volume% uncracked kerosene content; 3100 volume ppm The catalyst layer temperature distribution at this time is shown in FIG.

[0047]

EFFECTS OF THE INVENTION According to the present invention, the oxidation reaction and the reforming reaction are balanced, the generation of catalyst layer hot spots near the reactor inlet is suppressed, and the temperature from the inlet to the outlet of the reactor is made relatively uniform. it can. As a result, it is possible to suppress catalyst deterioration, suppress raw material slip, suppress by-product discharge, generate more hydrogen-rich gas, improve reforming efficiency, and configure a reactor using inexpensive materials in an automatic thermal reforming method. And equipment was provided.

[Brief description of drawings]

FIG. 1 is a schematic diagram for explaining a cross-sectional area and a length of a catalyst layer in the present invention.

FIG. 2 is a schematic view showing an embodiment of an auto thermal reforming device of the present invention.

FIG. 3 is a schematic view showing a catalyst layer portion in another embodiment of the auto thermal reforming device of the present invention.

FIG. 4 is a graph showing temperature distributions in catalyst layers of Examples and Comparative Examples.

[Explanation of symbols]

11 Reaction vessel 12 Catalyst layer 21 Reaction tube 23 Stop valve 32 Honeycomb catalyst 33 Movable slit

Claims (6)

[Claims] 1. An autothermal reforming method for producing a reformed gas containing hydrogen by subjecting a reforming raw material, an oxygen-containing gas and steam to an oxidation reaction and a steam reforming reaction in a catalyst layer, wherein the reforming raw material, oxygen-containing The cross-sectional area and length of the catalyst layer to which gas and water vapor are supplied are S and S respectively.
(Cm ² ) and L (cm), where C / H is the atomic ratio of carbon and hydrogen of the reforming raw material, and when C / H is more than 0.25 and 0.40 or less, L / S = 2-30 (c
m ⁻¹ ), C / H is more than 0.40 and 0.42 or less, L / S = 1 to 20 (cm ⁻¹ ), and C / H is more than 0.42 and 0.47 or less. L / S = 0.5 to 15 (c
m ⁻¹ ), and C / H is more than 0.47 and 0.58 or less, L / S = 0.5 to 10 (cm ⁻¹ ), an autothermal reforming method. 2. An autothermal reforming method for producing a reformed gas containing hydrogen by subjecting a reforming raw material, an oxygen-containing gas and steam to an oxidation reaction and a steam reforming reaction in a catalyst layer, the reforming raw material, oxygen-containing The cross-sectional area and length of the catalyst layer to which gas and water vapor are supplied are S and S respectively.
(Cm ² ) and L (cm), L / S = 0.5 to 10 when the reforming raw material is at least one selected from methanol, ethanol and dimethyl ether.
(Cm ⁻¹ ), and when the reforming raw material is city gas, L /
S = 2 to 30 (cm ⁻¹ ), L / S = 1 to 20 (cm ⁻¹ ) when the reforming raw material is LPG, and L / S = when the reforming raw material is gasoline. 0.5 to 15 (cm ⁻¹ ), and when the reforming raw material is kerosene, L / S = 0.5 to 10
(Cm ⁻¹ ), an autothermal reforming method. 3. An autothermal reforming apparatus provided with a catalyst layer for obtaining a reformed gas containing hydrogen by subjecting a reformed raw material, an oxygen-containing gas and steam to an oxidation reaction and a steam reforming reaction, In the case of gasoline, when the cross-sectional area and the length of the catalyst layer to which the reforming raw material, the oxygen-containing gas and steam are supplied are S (cm ² ) and L (cm), respectively, L / S = 0.5 ~ 15 (c
m ⁻¹ ), an automatic thermal reforming device. 4. An autothermal reforming apparatus equipped with a catalyst layer for obtaining a reformed gas containing hydrogen by subjecting a reformed raw material, an oxygen-containing gas and steam to an oxidation reaction and a steam reforming reaction, to obtain a reformed raw material. In the case of kerosene, the cross-sectional area and length of the catalyst layer to which the reforming raw material, oxygen-containing gas and steam are supplied are S (cm ² ) and L, respectively.
(Cm), L / S = 0.5 to 10 (cm ^-1 )
An automatic thermal reforming device characterized by: 5. An auto-thermal reforming apparatus equipped with a catalyst layer for obtaining a reformed gas containing hydrogen by subjecting a reforming raw material, an oxygen-containing gas and steam to an oxidation reaction and a steam reforming reaction, respectively. An auto-thermal reforming device comprising a plurality of reaction tubes provided in parallel, and a gas blocking means capable of blocking the supply of the reforming raw material, the oxygen-containing gas and the steam to the respective reaction tubes. 6. An autothermal reforming apparatus comprising a catalyst layer for obtaining a reformed gas containing hydrogen by subjecting a reforming raw material, an oxygen-containing gas and steam to an oxidation reaction and a steam reforming reaction to obtain a honeycomb catalyst. An auto-thermal reforming apparatus having a gas shutoff means capable of shutting off the supply of the reforming raw material, the oxygen-containing gas, and the steam to the respective channels of the honeycomb catalyst.