JP2004217505A - Method for operating reformed gas production unit - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for operating a reformed gas production unit where the reduction of catalytic activity caused by the precipitation of carbon can be prevented while realizing high reforming efficiency. <P>SOLUTION: The fluid to be reformed comprising water vapor, carbon dioxide, ≥2C hydrocarbon fuel and oxygen is fed to a reaction chamber in a low temperature reformer 1 incorporated with a catalyst for reforming, and temperature control is performed in such a manner that the maximum temperature of the fluid to be reformed in contact with the catalyst for reforming is regulated to the temperature range of 200 to 800°C, and also, to the thermal decomposition temperature of the fuel or lower, so that a reformed gas comprising methane, hydrogen and carbon monoxide is produced. Further, gaseous oxygen and the second fluid to be reformed are fed to a second reaction chamber in a high temperature reformer 2 incorporated with a second catalyst for reforming, and temperature control is performed in such a manner that the maximum temperature of the second fluid to be reformed in contact with the second catalyst for reforming is held to the temperature range of 400 to 1,200°C, and also, the outlet temperature in the second reaction chamber is made higher than the outlet temperature in the reaction chamber, so that a second reformed gas comprising hydrogen, and carbon monoxide is produced. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention relates to a method for operating a reformed gas producing apparatus for reforming a hydrocarbon-based fuel to generate a synthesis gas containing hydrogen and carbon monoxide.

The above-mentioned synthesis gas can be produced by reforming hydrocarbon or methanol, and a reformed gas production apparatus for producing synthesis gas by such fuel reforming is capable of producing liquid fuel (GTL) from natural gas. It can be used in the field of syngas production such as production, and in the field of hydrogen production such as for fuel cells.
Currently, three main reforming methods for hydrocarbon fuels are steam reforming, partial oxidation, and autothermal reforming in which these are combined.
Steam reforming process is described as shown in the chemical formula 1 below, since H _{2 /} CO ratio of the resulting synthesis gas is high, which is mainly applied in hydrogen manufacturing field, there are a number of results. Hydrogen is generated not only from hydrocarbons but also from water vapor, resulting in a high H ₂ / CO ratio, which is advantageous for hydrogen production. On the other hand, the endothermic reaction limits the rate of external heating, and the gas space velocity (gas flow rate / catalyst) Volume) cannot be increased.

[Formula 1]
_{C n H 2n + 2 + nH} 2 O → (2n + 1) H 2 + nCO

  The partial oxidation method (also referred to as a partial combustion method) is an exothermic reaction in which fuel is partially oxidized (partial combustion) to generate hydrogen as shown in the following Chemical Formula 2, and has a high reaction rate and a high gas space velocity. Although it has advantages, it has the disadvantage of low thermal efficiency.

[Formula 2]
C _n H _{2n + 2} +0.5 nO ₂ → (n + 1) H ₂ + nCO

Part synthesis gas obtained by the oxidation method is low as compared to synthesis gas H _{2 /} CO ratio is obtained by steam reforming process, if H _{2 /} CO ratios desired in the utilization side of the synthesis gas is low is effective . However, in the case of fuel reforming by the partial oxidation method, continuous operation is difficult because hydrocarbons such as methane are reformed at the same time and undergo oxidative dehydrogenation to become heavy hydrocarbons and carbon, Also, as described above, the thermal efficiency is not good, and it is difficult to commercialize the method for reforming natural gas, naphtha, and the like.

  The autothermal reforming method is a composite system in which a partial oxidation reaction and a steam reforming reaction proceed in series or simultaneously, and heat required for the endothermic steam reforming reaction is covered by heat generated by the partial oxidation reaction. Generally, there are two types, one is a method of performing a partial oxidation reaction in a gas phase using a burner or the like, and then performing a series of steam reforming (hereinafter abbreviated as ATR). One is a method of simultaneously performing partial oxidation and steam reforming using a catalyst (hereinafter abbreviated as CPO). Methods for producing hydrogen or synthesis gas using the autothermal reforming method are disclosed in various documents (for example, see Patent Documents 1 and 2).

  As a problem of fuel reforming by the autothermal reforming method, when hydrocarbons having 2 or more carbon atoms are used as a raw material, carbon deposition occurs more violently near the inlet of the reformer than when the raw material is methane. Point. That is, as shown in FIG. 19, the temperature near the inlet of the reformer rapidly rises due to the partial combustion reaction of hydrocarbons with oxygen, and hydrocarbons having 2 or more carbon atoms are thermally decomposed into carbon. It is. For example, in Examples and Comparative Examples of Patent Document 2, an example in which carbon deposition was confirmed is described. The cause is that the temperature of the inlet of the catalyst layer in the reaction chamber suddenly becomes high, and hydrocarbons are generated. Is thought to be due to the thermal decomposition of carbon.

  In order to solve the problem (carbon deposition) of the fuel reforming by the autothermal reforming method, a technique of installing a pre-reformer in a preceding stage may be used. As reforming methods using a pre-reformer, there are a method of performing steam reforming and a method of performing CPO (see Patent Document 3). As a steam reforming prereformer, for example, an autothermal reformer with a prereformer as shown in FIG. 20 has been proposed. That is, in a pre-reformer, hydrocarbons are reformed to methane at a low temperature at which carbon deposition does not occur due to a steam reforming reaction, and then methane is reformed in an autothermal reformer to convert the hydrogen into hydrogen and carbon monoxide. . Patent Document 3 discloses a CPO prereformer + ATR technology, and describes that all higher hydrocarbons are converted in CPO, and that a saturated hydrocarbon having 2 or more carbon atoms is converted by CPO. You can see that the concept is being implemented.

JP-A-2000-84410 (pages 2-14) JP 2001-146406 A (pages 2-6) JP-A-2002-97479 (pages 2 to 5)

  However, in the autothermal reformer with a pre-reformer, when steam reforming is applied to the pre-reformer, a large amount of catalyst is required because the steam reforming reaction, which has a lower reaction rate than the partial oxidation reaction, is performed at a low temperature. There is a problem that the reformer cannot be downsized. In addition, when this auto-thermal reformer with pre-reformer is applied to a reforming system for automobile fuel cells or household fuel cells that require daily startup and shutdown, it takes a long time to start up from room temperature. There is a problem in that the hydrocarbon fuel as the reforming raw material must be constantly burned in order to maintain the reformer near the reforming temperature.

  In addition, when CPO is applied to the pre-reformer, the reforming efficiency can be increased, but on the other hand, as shown in Patent Document 2, for example, the temperature at the inlet of the catalyst layer rapidly increases. In addition, there is a problem that hydrocarbons having 2 or more carbon atoms are thermally decomposed and carbon deposition occurs, so that they cannot be used stably for a long time.

The present invention has been made in view of the above circumstances, and a first object of the present invention is to solve the problems of the conventional autothermal reformer with a pre-reformer and realize a high reforming efficiency while achieving a high reforming efficiency. It is an object of the present invention to provide a method for operating a reformed gas production apparatus capable of preventing a decrease in catalyst activity due to precipitation and maintaining stable performance for a long period of time.
A second object is to provide an operation method of a reformed gas production device that can shorten a start-up time.

  A first characteristic configuration of the operation method of the reformed gas production apparatus according to the present invention for achieving the above object includes a gas containing at least one of steam and a carbon dioxide-containing gas and a hydrocarbon having 2 or more carbon atoms. A fluid containing a fuel to be reformed and an oxygen-containing gas is supplied as a reforming fluid to a reaction chamber containing a reforming catalyst, and the maximum temperature of the reforming fluid in contact with the reforming catalyst is 200 to 800. A reformed gas containing methane, hydrogen and carbon monoxide is produced by adjusting the temperature of the reaction chamber so that the temperature is within a temperature range of 200 ° C. (preferably 200 to 750 ° C.) and equal to or lower than a thermal decomposition temperature of the fuel. On the point.

  The second characteristic configuration is, in addition to the first characteristic configuration, a supply amount ratio to the fuel of at least one of the oxygen-containing gas, the water vapor, and the carbon dioxide-containing gas supplied to the reaction chamber. That is, the temperature of the reaction chamber is adjusted by changing the temperature.

  The third characteristic configuration is that, in addition to the second characteristic configuration, control is performed to adjust a supply amount ratio to the fuel based on detection information of a temperature sensor that detects a temperature in the reaction chamber. .

  The fourth characteristic configuration is that, in addition to any one of the first to third characteristic configurations, the temperature of the reaction chamber is adjusted by a temperature adjustment mechanism capable of cooling or heating the reaction chamber.

  The fifth feature is that, in addition to any of the first to fourth features, a hydrogen-containing gas is supplied to the reaction chamber.

  The sixth characteristic configuration is characterized in that, in addition to the fifth characteristic configuration, the hydrogen-containing gas and the oxygen-containing gas are supplied to the reaction chamber until the temperature of the reaction chamber reaches an appropriate operating temperature required for reforming the fuel. Hydrogen is burned by supplying a contained gas, and the temperature of the reaction chamber is raised to the proper operating temperature by the heat of combustion of the hydrogen.

  The seventh characteristic configuration is that, in addition to any one of the first to sixth characteristic configurations, the reforming catalyst is a catalyst containing a metal having steam reforming performance as a main component.

  The eighth characteristic configuration is, in addition to any one of the first to seventh characteristic configurations, by a desulfurization device provided in front of the reaction chamber, the fuel supplied to the reaction chamber, the gases, and the fuel. The point is that at least one of the steam is subjected to the desulfurization treatment.

  The ninth feature is that, in addition to the eighth feature, the sulfur concentration in the total gas supplied to the reaction chamber is 5 vol. The point is to operate the desulfurization device so as to be ppb or less.

  The tenth feature configuration is, in addition to the first to ninth feature configurations, a fluid containing an oxygen-containing gas and the reformed gas generated in the reaction chamber as a second fluid to be reformed. Supplying the second catalyst for reforming to the second reaction chamber containing the second catalyst for reforming, the maximum temperature of the second fluid to be reformed in contact with the second catalyst for reforming is maintained in a temperature range of 400 to 1200 ° C., and By adjusting the temperature of the second reaction chamber so that the outlet temperature of the second reaction chamber is higher than the outlet temperature of the reaction chamber, to produce a second reformed gas containing hydrogen and carbon monoxide is there.

  The eleventh feature is that, in addition to the tenth feature, at least one of steam and a carbon dioxide-containing gas is supplied to the second reaction chamber.

  The twelfth characteristic configuration is, in addition to the eleventh characteristic configuration, at least one of the oxygen-containing gas, the steam, and the carbon dioxide-containing gas supplied to the second reaction chamber. The point is to adjust the temperature of the second reaction chamber by changing the supply ratio to the gas.

  The thirteenth characteristic configuration is that, in addition to the twelfth characteristic configuration, a supply amount ratio to the reformed gas is adjusted based on detection information of a temperature sensor that detects a temperature in the second reaction chamber. The point is to control.

  The fourteenth characteristic configuration is characterized in that, in addition to any one of the tenth to thirteenth characteristic configurations, a temperature of the second reaction chamber is controlled by a second temperature adjustment mechanism capable of cooling or heating the second reaction chamber. The point is to adjust.

  The fifteenth feature is, in addition to any one of the tenth to fourteenth features, a desulfurization device provided in front of the second reaction chamber, wherein each of the components supplied to the second reaction chamber is provided. The desulfurization treatment is performed on at least one of the gases.

  The sixteenth characteristic configuration is the same as the fifteenth characteristic configuration, except that the sulfur concentration in the total gas supplied to the second reaction chamber is 5 vol. The point is to operate the desulfurization device so as to be ppb or less.

  The seventeenth characteristic configuration is, in addition to any one of the tenth to sixteenth characteristic configurations, the second reforming catalyst is a catalyst mainly composed of a metal having steam reforming performance. On the point.

Wherein configuration of the eighteenth, said from the first addition to any of the characteristic feature of the seventeenth, the reaction per the total gas flow time is supplied to the chamber gas space velocity in 750h ^-1 ~300000h ^-1 In the range.

  A nineteenth feature of the present invention resides in that the nineteenth feature is used for a mobile object or for stationary use in addition to any one of the first to eighteenth features.

The constituent fluids such as steam, fuel, and oxygen-containing gas that constitute the above-mentioned fluid to be reformed or the second fluid to be reformed may be mixed before reaching the catalyst section of the reaction chamber or the second reaction chamber. For this purpose, mixing may be performed before entering each reaction chamber, or may be performed after entering each reaction chamber and arriving at the catalyst section.
In addition, the characteristic configuration of the present invention (the first to nineteenth characteristic configurations) is defined as an operation method of the reformed gas producing apparatus, but when the reformed gas producing apparatus is operated according to the present invention, the reformed gas is produced. Therefore, the characteristic configuration of the present invention is also a reformed gas production method.

The operation and effect will be described below.
According to the first characteristic configuration of the operation method of the reformed gas production device according to the present invention, at least one of steam and carbon dioxide-containing gas, a fuel containing a hydrocarbon having 2 or more carbon atoms, and oxygen A fluid to be reformed containing a contained gas is supplied to a reaction chamber containing a reforming catalyst, and the maximum temperature of the fluid to be reformed in contact with the reforming catalyst is in a temperature range of 200 to 800 ° C. and the fuel The temperature of the reaction chamber is adjusted so as to be equal to or lower than the thermal decomposition temperature of, and a reformed gas containing methane, hydrogen and carbon monoxide is generated. In other words, the present invention having the first characteristic configuration (the same applies to the second to nineteenth characteristic configurations) is also a method for producing a reformed gas.

  That is, when a fuel containing a hydrocarbon having 2 or more carbon atoms is reformed into methane, hydrogen, and carbon monoxide, the fuel reacts with an oxygen-containing gas in a reaction chamber containing the reforming catalyst. To cause the exothermic partial oxidation reaction to generate hydrogen and carbon monoxide, and at the same time, using the heat generated by this partial oxidation reaction, the fuel reacts with water or carbon dioxide to produce methane and hydrogen having 1 carbon atom. And a steam reforming reaction for reforming into carbon monoxide or the like. At this time, the temperature in the reaction chamber is set so that the maximum temperature of the fluid to be reformed in contact with the reforming catalyst is in the temperature range of 200 to 800 ° C (preferably 200 to 750 ° C) and the hydrocarbon has 2 or more carbon atoms. By suppressing the temperature below the thermal decomposition temperature of the fuel containing, it is possible to prevent the thermal decomposition of the fuel containing a hydrocarbon having 2 or more carbon atoms. If the conditions are selected, it is possible to balance the heat generation of the partial oxidation reaction and the heat absorption of the steam reforming reaction, and it is also possible to eliminate external heat supply.

  Here, thermal decomposition means that hydrocarbons are decomposed into carbon, hydrogen, acetylene, etc. in a gas phase or on a solid surface, and the thermal decomposition temperature is a lower limit temperature at which the above-mentioned phenomenon is remarkably observed. Means The pyrolysis temperature is a physical property value unique to hydrocarbons and is a fixed value. The pyrolysis temperature differs depending on the type of hydrocarbon. The higher the number of carbon atoms, the lower the pyrolysis temperature. Is low. The thermal decomposition temperature of a fuel containing two or more hydrocarbons having two or more carbon atoms is generally the lowest thermal decomposition temperature among the thermal decomposition temperatures of hydrocarbons contained in the fuel. Note that, regarding the specific thermal decomposition temperature of hydrocarbons, the Dictionary of Chemistry describes 1200 ° C. for methane and 800 ° C. for ethane. In addition, the book “Tables of Chemical Kinetics Homogeneous Reaction” (Circular of the National Bureau of Standards 510,1951) summarizes the study on thermal decomposition temperature, From the thermal decomposition temperatures of ethane and ethane, the thermal decomposition temperature of propane is about 755 ° C, and the thermal decomposition temperature of butane is about 690 ° C. The thermal decomposition temperature of hexane is estimated to be between 634 ° C and 665 ° C.

  From the above, as in the present invention, in order to prevent a decrease in catalytic activity due to carbon deposition and to maintain stable performance over a long period of time, the temperature of the hydrocarbon in contact with the reforming catalyst is specific to the hydrocarbon. Performing the reforming reaction at a temperature not exceeding the thermal decomposition temperature is the safest and most reliable method. Incidentally, the above-mentioned prior art does not disclose that autothermal reforming is performed under the condition that the temperature of the hydrocarbon in contact with the catalyst layer is equal to or lower than the thermal decomposition temperature. For example, in Patent Document 1, autothermal reforming is performed at 800 ° C. using naphtha (including a hydrocarbon having 5 or more carbon atoms) as a hydrocarbon fuel, and the reaction temperature is the thermal decomposition temperature of naphtha. As described above, carbon is deposited depending on the catalyst. In Patent Document 2, judging from the fact that the reforming reaction is performed at 550 ° C. inlet temperature and 680 ° C. outlet temperature of the catalyst layer using heavy hydrocarbon as a raw material, the temperature of the catalyst layer becomes higher, It is estimated that the temperature exceeds the thermal decomposition temperature of heavy hydrocarbons in contact with the catalyst layer, and carbon deposition has actually been confirmed. Patent Literature 3 includes methane, ethane, propane, butane, and pentane as the hydrocarbon components. However, judging from the fact that the outlet temperature is 705 ° C. or higher, the temperature of the hydrocarbon in contact with the catalyst layer is further increased. Therefore, it is expected that the temperature exceeds the thermal decomposition temperature of butane (690 ° C.).

  The carbonization of hydrocarbons is more likely to occur as the temperature increases, and the reforming reaction does not proceed if the reaction temperature is too low. Therefore, the reaction is performed at an operating temperature of 200 ° C. or more and 800 ° C. or less. However, it is possible to raise the maximum temperature somewhat depending on the thermal decomposition behavior of the raw hydrocarbon.

  Therefore, there is provided a method for operating a reformed gas production apparatus that can prevent a decrease in activity of a reforming catalyst due to carbon deposition and maintain stable performance over a long period of time while realizing high reforming efficiency. Is done.

According to the second feature, the supply ratio of the oxygen-containing gas, the water vapor and the carbon dioxide-containing gas to be supplied to the reaction chamber to at least one of the fuels is changed to change the supply amount ratio of the reaction chamber. Adjust the temperature.
That is, since the temperature in the reaction chamber is related to the balance between the heat generation of the partial oxidation reaction and the endothermic heat of the steam reforming reaction, the temperature in the reaction chamber is in the temperature range of 200 to 800 ° C and the hydrocarbon having 2 or more carbon atoms is The supply ratio of at least one of oxygen-containing gas, water vapor, and carbon dioxide-containing gas to the fuel is adjusted so as to maintain a temperature lower than the thermal decomposition temperature of the contained fuel.

  For example, when the supply ratio of the oxygen-containing gas to the fuel is increased, the ratio of the oxygen-containing gas amount to the carbon amount in the hydrocarbon-based fuel is increased, and the partial oxidation reaction of the hydrocarbon-based fuel is promoted. Therefore, when the temperature of the reaction chamber rises, while decreasing the supply ratio of the oxygen-containing gas to the fuel, the ratio of the oxygen-containing gas amount to the carbon amount in the hydrocarbon-based fuel decreases, and the Since the partial oxidation reaction of the system fuel is suppressed, the temperature of the reaction chamber decreases. Similarly, when the supply ratio of the steam or the carbon dioxide-containing gas to the fuel is increased, the endothermic reforming reaction of the hydrocarbon-based fuel is promoted, so that the temperature of the reaction chamber decreases, while the steam to the fuel decreases. Alternatively, when the supply ratio of the carbon dioxide-containing gas is reduced, the endothermic reforming reaction of the hydrocarbon-based fuel is suppressed, so that the temperature of the reaction chamber increases.

  Therefore, for example, by changing the supply amount of at least one of the oxygen-containing gas, the water vapor, and the carbon dioxide-containing gas in a state where the supply amount of the hydrocarbon-based fuel is constant (a state in which the carbon amount is fixed), A preferred embodiment of a method for operating a reformed gas production device capable of adjusting the temperature of a reaction chamber to an appropriate temperature is provided.

  According to the third characteristic configuration, at least one of the oxygen-containing gas, water vapor, and carbon dioxide-containing gas supplied into the reaction chamber based on the detection information of the temperature sensor that detects the temperature in the reaction chamber. The supply ratio to the fuel is adjusted and controlled.

That is, the supply ratio of at least one of oxygen-containing gas, water vapor, or carbon dioxide-containing gas supplied into the reaction chamber to the fuel is adjusted based on the detected temperature in the reaction chamber. If the supply ratio (O ₂ / C) of the oxygen-containing gas to the fuel is too high, temperature control becomes difficult. Therefore, in a large-sized apparatus, the supply ratio (O ₂ / C) is 0.01 to 0. .5.
Therefore, a preferred embodiment of the operating method of the reformed gas production apparatus that enables accurate automatic temperature control of the temperature in the reaction chamber based on the detection information of the temperature in the reaction chamber is provided.

According to the fourth characteristic configuration, the temperature can be adjusted by cooling or heating the reaction chamber by the temperature adjustment mechanism.
That is, when the temperature in the reaction chamber is too high, the reaction chamber is cooled so as not to exceed the thermal decomposition temperature of a fuel containing a hydrocarbon having 2 or more carbon atoms, and the temperature in the reaction chamber becomes low. If the reaction does not proceed smoothly after that, the reaction chamber is heated. The cooling or heating of the reaction chamber is performed, for example, by cooling or heating the entire reaction chamber, or by lowering or increasing the inlet temperature of the reaction chamber.
Accordingly, there is provided a preferred embodiment of a method for operating a reformed gas production apparatus capable of maintaining the reaction temperature of the reaction chamber so as not to fall out of an appropriate temperature range.

According to the fifth characteristic configuration, a hydrogen-containing gas is supplied to the reaction chamber, and the temperature of the reaction chamber can be quickly increased.
That is, for example, when a hydrogen-containing gas, the fuel, and the oxygen-containing gas are supplied to the reaction chamber, hydrogen having a combustion start temperature lower than that of the hydrocarbon-based fuel reacts with oxygen and burns, and the temperature in the reaction chamber also increases. However, when the temperature is about 300 ° C. or higher, hydrogen is burned on a catalyst having high combustion activity even in the presence of a large excess of steam, so that the heat of combustion of the hydrogen rapidly raises the temperature of the reaction chamber without depositing carbonaceous material, thereby improving steam reforming. In addition, the partial oxidation reaction can smoothly proceed.
Therefore, a preferred embodiment of the operating method of the reformed gas production device that enables a quick temperature increasing operation is provided.

According to the sixth characteristic configuration, the hydrogen-containing gas and the oxygen-containing gas are supplied to the reaction chamber to burn hydrogen until the temperature of the reaction chamber reaches a proper operation temperature required for reforming the fuel. Then, the temperature of the reaction chamber is raised to the appropriate operating temperature by the heat of combustion of the hydrogen.
That is, at the time of startup, a hydrogen-containing gas and an oxygen-containing gas are supplied to the reaction chamber, and the temperature of the reaction chamber is quickly increased to an appropriate operation temperature by heat generated by a combustion reaction of hydrogen and oxygen by a catalyst in a short time. To rise.
Therefore, a preferred embodiment of the operation method of the reformed gas production apparatus having excellent startability is provided.

According to the seventh characteristic configuration, the reaction chamber is provided with a reforming catalyst mainly composed of a metal having steam reforming performance. As a desirable metal, a catalyst mainly containing one selected from Ni, Co, Ru, Rh, Pt, and Pd is preferable. The carrier is not particularly limited, but is preferably a carrier containing one selected from alumina, zirconia, silica, titania, magnesia, and calcia as a main component.
Accordingly, a preferred embodiment of a method for operating a reformed gas producing apparatus including a reforming catalyst for satisfactorily exhibiting the reforming performance of the reaction chamber is provided.

According to the eighth characteristic configuration, the hydrocarbon fuel, the oxygen-containing gas, and the water vapor to be supplied to the reaction chamber, when the water vapor is supplied, and when the carbon dioxide-containing gas is supplied, the carbon dioxide-containing gas is supplied. When gas and hydrogen are supplied, at least one of the hydrogen is desulfurized by a desulfurization device provided in front of the reaction chamber.
That is, the sulfur component in each gas is removed and then supplied to the reaction chamber so that the activity of the reforming catalyst provided in the reaction chamber does not decrease due to the high concentration of the sulfur component. The desulfurization apparatus may employ, for example, a copper-zinc-based high-order desulfurization technique in which copper oxide CuO and zinc oxide ZnO are mixed.
Accordingly, there is provided a preferred embodiment of a method for operating a reformed gas producing apparatus in which the reforming performance of a reforming catalyst provided in the reaction chamber is not reduced by sulfur poisoning.

According to the ninth aspect, the desulfurization apparatus is operated to reduce the sulfur concentration in the total gas supplied to the reaction chamber to 5 vol. ppb or less.
That is, as a specific value of the sulfur concentration in the total gas in which the sulfur poisoning of the reforming catalyst provided in the reaction chamber does not occur, 5 vol. Make the concentration less than ppb. Preferably, 2 vol. ppb or less, more preferably 1 vol. Make the concentration less than ppb.
Therefore, there is provided a preferred embodiment of a method for operating a reformed gas production apparatus capable of reliably preventing sulfur poisoning of a reforming catalyst provided in the reaction chamber.

  According to the tenth characteristic configuration, the second reforming fluid containing the oxygen-containing gas and the reformed gas generated in the reaction chamber is supplied to the second reaction chamber containing the second reforming catalyst, The maximum temperature of the second fluid to be reformed in contact with the second reforming catalyst is maintained in the temperature range of 400 to 1200 ° C (preferably 500 to 1100 ° C), and the outlet temperature of the second reaction chamber is set to The temperature of the second reaction chamber is adjusted so as to be higher than the outlet temperature of the second reaction chamber, and a second reformed gas containing hydrogen and carbon monoxide is generated.

  That is, when a fuel containing a hydrocarbon having 2 or more carbon atoms is reformed into hydrogen and carbon monoxide, a two-stage reaction chamber configuration of a first-stage reaction chamber and a second-stage reaction chamber of a second stage is used to form a first-stage reaction chamber. In the chamber, as described above, the temperature in the reaction chamber is controlled to a temperature lower than the thermal decomposition temperature of the hydrocarbon fuel having 2 or more carbon atoms, thereby preventing the thermal decomposition of the fuel and producing methane (1 carbon number). At the same time, in the second reaction chamber in the second stage in which the second reforming catalyst is built, an endothermic steam reforming reaction in which methane reacts with steam proceeds simultaneously with the exothermic partial oxidation reaction in which the methane reacts with the oxygen-containing gas. In this case, the temperature of the second reaction chamber can be suppressed to a temperature lower than 1200 ° C. at which thermal decomposition of methane occurs remarkably, thereby preventing thermal decomposition of methane. On the other hand, if the reaction temperature in the second reaction chamber is too low, the reforming reaction of methane does not proceed. Therefore, the lower limit temperature is set to 400 ° C, and the operating temperature of the second reaction chamber is set in the range of 400 to 1200 ° C.

  Further, when the temperature of the second reaction chamber is adjusted so that the outlet temperature of the second reaction chamber is higher than the outlet temperature of the reaction chamber, a portion of the reformed gas generated in the reaction chamber in the second reaction chamber is adjusted. As a result of the accelerated oxidation reaction, in the composition of the reformed gas generated from the second reaction chamber, the proportion of hydrogen decreases, and the proportion of carbon monoxide can increase.

  Therefore, when reforming a fuel containing hydrocarbons having 2 or more carbon atoms to hydrogen and carbon monoxide, the catalyst activity due to carbon deposition is realized while realizing high reforming efficiency in the second reaction chamber at the subsequent stage. It is possible to prevent the catalyst from deteriorating due to reduction and overheating, and to maintain stable performance over a long period of time.Furthermore, the ratio of hydrogen to carbon monoxide is low. A preferred embodiment of a method for operating a reformed gas production device that can be produced is provided.

According to the eleventh feature, at least one of steam and a carbon dioxide-containing gas is supplied to the second reaction chamber.
That is, when the reformed gas generated in the previous reaction chamber in the second reaction chamber is reformed into a synthesis gas containing hydrogen and carbon monoxide, the reformed gas reacts with the oxygen-containing gas to generate hydrogen. And the exothermic partial oxidation reaction that produces carbon monoxide proceeds, and at the same time, using the heat of this partial oxidation reaction, the reformed gas reacts with steam or carbon dioxide to produce hydrogen and carbon monoxide. The reforming reaction proceeds. Further, if conditions are selected, it is possible to balance the heat generation of the above-mentioned partial oxidation reaction with the endothermic heat of the subsequent reforming reaction, and it is also possible to eliminate external heat supply. In this case, when the supply ratio of the water vapor and the carbon dioxide-containing gas supplied to the second reaction chamber is changed, the ratio of hydrogen and carbon monoxide in the generated synthesis gas changes.
Therefore, when reforming a reformed gas consisting of methane, hydrogen, and carbon monoxide into a synthesis gas containing hydrogen and carbon monoxide, it is possible to achieve a high reforming efficiency and achieve a high reforming efficiency, while achieving a high reforming efficiency. A preferred embodiment of a method for operating a reformed gas production device that enables the ratio of carbon oxide to be adjusted as needed is provided.

According to the twelfth characteristic configuration, the supply amount ratio to the reformed gas of at least one of the oxygen-containing gas, the water vapor, and the carbon dioxide-containing gas supplied to the second reaction chamber is changed. And adjusting the temperature of the second reaction chamber.
That is, the temperature in the second reaction chamber is related to the balance between the heat generated in the partial oxidation reaction and the endotherm in the steam reforming reaction. A supply ratio of at least one of the gases to the reformed gas is adjusted.

  For example, when the supply ratio of the oxygen-containing gas to the reformed gas is increased, the ratio of the oxygen-containing gas amount to the carbon amount in the methane contained in the reformed gas is increased, and the partial oxidation reaction of methane is promoted. Therefore, the temperature of the second reaction chamber rises, while reducing the supply ratio of the oxygen-containing gas to the reformed gas reduces the ratio of the oxygen-containing gas amount to the carbon amount in the methane, Since the partial oxidation reaction of methane is suppressed, the temperature of the second reaction chamber decreases. Similarly, if the supply ratio of the steam or the carbon dioxide-containing gas to the reformed gas is increased, the steam reforming reaction of endothermic methane is accelerated, so that the temperature of the second reaction chamber decreases, while the reforming temperature decreases. If the supply ratio of the steam or carbon dioxide-containing gas to the gas is reduced, the endothermic steam reforming reaction of methane is suppressed, and the temperature of the second reaction chamber rises.

  Therefore, for example, by changing the supply amount of at least one of the oxygen-containing gas, the water vapor, and the carbon dioxide-containing gas in a state where the supply amount of methane in the reformed gas is kept constant (in a state where the carbon amount is fixed). A preferred embodiment of a method for operating a reformed gas production apparatus that enables the temperature of the second reaction chamber to be adjusted to an appropriate temperature is provided.

  According to the thirteenth characteristic configuration, based on the detection information of the temperature sensor that detects the temperature in the second reaction chamber, the oxygen-containing gas, water vapor, and carbon dioxide-containing gas supplied into the second reaction chamber The supply ratio to at least one of the reformed gases is adjusted and controlled.

That is, the supply ratio of at least one of the oxygen-containing gas, steam, and carbon dioxide-containing gas supplied to the second reaction chamber to the reformed gas is adjusted based on the detected temperature in the second reaction chamber. If the supply ratio (O ₂ / C) of the oxygen-containing gas to methane in the reformed gas is too high, it becomes difficult to control the temperature. Therefore, in a large-sized apparatus, the supply ratio (O ₂ / C) is large. It is desirable to be in the range of 0.01 to 0.5.
Therefore, a preferred embodiment of the operating method of the reformed gas production device capable of realizing accurate automatic temperature control of the temperature in the second reaction chamber based on the detection information of the temperature in the second reaction chamber is provided.

According to the fourteenth characteristic configuration, the temperature can be adjusted by cooling or heating the second reaction chamber by the second temperature adjustment mechanism.
That is, when the temperature in the second reaction chamber is too high, the second reaction chamber is cooled so that the temperature does not exceed 1200 ° C. at which thermal decomposition of methane occurs remarkably, and the temperature in the second reaction chamber becomes too low. If the reaction does not proceed smoothly, the second reaction chamber is heated. The cooling or heating of the second reaction chamber is performed, for example, by cooling or heating the entire second reaction chamber, or by lowering or increasing the inlet temperature of the second reaction chamber.
Therefore, a preferred embodiment of the method for operating the reformed gas production device capable of maintaining the reaction temperature of the second reaction chamber so as not to fall out of an appropriate temperature range is provided.

According to the fifteenth feature, the oxygen-containing gas to be supplied to the second reaction chamber, the water vapor when the water vapor is supplied, and the carbon dioxide-containing gas when the carbon dioxide-containing gas is supplied Is desulfurized by a desulfurization device provided in front of the second reaction chamber.
That is, the sulfur component in each gas is removed and then supplied to the second reaction chamber so that the activity of the second reforming catalyst provided in the second reaction chamber does not decrease due to the high concentration of the sulfur component. The desulfurization apparatus may employ, for example, a copper-zinc-based high-order desulfurization technique in which copper oxide CuO and zinc oxide ZnO are mixed.
Therefore, a preferred embodiment of the operating method of the reformed gas producing apparatus is provided in which the reforming performance of the second reforming catalyst provided in the second reaction chamber is not reduced by sulfur poisoning.

According to the sixteenth aspect, the desulfurization device is operated to reduce the sulfur concentration in the total gas supplied to the second reaction chamber to 5 vol. ppb or less.
That is, as a specific value of the sulfur concentration in the total gas in which the sulfur poisoning of the second reforming catalyst provided in the second reaction chamber does not occur, 5 vol. Make the concentration less than ppb. Preferably, 2 vol. ppb or less, more preferably 1 vol. Make the concentration less than ppb.
Therefore, a preferred embodiment of the operating method of the reformed gas production device which can surely prevent the sulfur poisoning of the second reforming catalyst provided in the second reaction chamber is provided.

According to the seventeenth characteristic configuration, the second reaction chamber is provided with a second reforming catalyst mainly composed of a metal having steam reforming performance. As a desirable metal, a catalyst mainly containing one selected from Ni, Co, Ru, Rh, Pt, and Pd is preferable. The carrier is not particularly limited, but is preferably a carrier containing one selected from alumina, zirconia, silica, titania, magnesia, and calcia as a main component.
Therefore, a preferred embodiment of the operating method of the reformed gas producing apparatus including the reforming second catalyst for satisfactorily exhibiting the reforming performance of the second reaction chamber is provided.

According to a feature configuration of the eighteenth, the range of ^{750h -1 ~300000h} -1 at a gas space velocity per a total gas flow rate supplied into the reaction chamber time.
That is, in the reaction chamber, since the partial oxidation reaction having a high reaction rate simultaneously proceeds with the steam reforming reaction, the total gas flow rate supplied to the reaction chamber is set to a gas hourly space velocity of 750 h ^{-1 to} 300,000 h ^-1. The reforming reaction in the reaction chamber can be properly performed even if the amount of the reformed gas to be generated is increased or decreased by changing in a wide range.
Therefore, a preferred embodiment of the operating method of the reformed gas producing apparatus that enables a stable reforming reaction to be performed under a wide range of gas flow conditions is provided.

According to the nineteenth characteristic configuration, the reformed gas production device is used for a mobile object or a stationary object.
That is, by simultaneously proceeding the partial oxidation reaction and the steam reforming reaction in the reaction chamber and the second reaction chamber, the reaction speed is increased while the reformed gas production apparatus is formed in a small size as a whole, and hydrogen and the like are produced. A large amount of reformed gas can be generated. Further, in the case of a small reformed gas producing apparatus for a moving object or stationary, water is heated by heat recovered from a high-temperature reformed gas generated in the second reaction chamber by a heat exchanger or the like, and the reaction chamber is heated. And the steam to be supplied to the second reaction chamber can be easily generated, so that a special heat source for generating steam is not required, and the apparatus can be made compact in this respect as well.
Accordingly, a preferred embodiment of a method for operating a reformed gas producing apparatus which is small, has high performance, and is suitable for a moving object or stationary is provided.

An embodiment of a method for operating a reformed gas producing apparatus (hereinafter, referred to as a fuel reforming apparatus) according to the present invention will be described.
FIG. 1 is a conceptual diagram of a fuel reforming apparatus, which includes a two-stage reforming section including a low-temperature reforming section 1 and a high-temperature reforming section 2. That is, in the former low-temperature reforming section 1 (hereinafter, referred to as low-temperature reformer 1), at least one of steam and carbon dioxide-containing gas and a fuel containing a hydrocarbon having 2 or more carbon atoms (hereinafter, carbon A fluid containing a hydrocarbon-based fuel having a number of 2 or more) and an oxygen-containing gas is supplied as a fluid to be reformed to a reaction chamber containing a reforming catalyst, and the fluid in contact with the reforming catalyst is supplied to the reaction chamber. The temperature of the reaction chamber is adjusted so that the maximum temperature of the reforming fluid is in the temperature range of 200 to 800 ° C. (preferably 200 to 750 ° C.) and equal to or lower than the thermal decomposition temperature of the fuel. A reformed gas containing carbon oxide (hereinafter, referred to as a first reformed gas) is produced.

  Further, in the subsequent high-temperature reforming section 2 (hereinafter, referred to as high-temperature reformer 2), a fluid containing an oxygen-containing gas and the first reformed gas generated in the reaction chamber is used as a second reformed fluid. The maximum temperature of the second fluid to be reformed, which is supplied to the second reaction chamber containing the second reforming catalyst and is in contact with the second reforming catalyst, is maintained in a temperature range of 400 to 1200 ° C., and A second reformed gas containing hydrogen and carbon monoxide is produced by adjusting the temperature of the second reaction chamber so that the outlet temperature of the second reaction chamber is higher than the outlet temperature of the reaction chamber. Furthermore, in addition to the supply of the first reformed gas and the oxygen-containing gas to the second reaction chamber, at least one of water vapor and a carbon dioxide-containing gas can be supplied.

  As shown in FIG. 1, the fuel, the oxygen-containing gas, and the fuel supplied to the reaction chamber of the low-temperature reformer 1 by the desulfurization devices 3A, 3B, and 3C provided in front of the reaction chamber of the low-temperature reformer 1. A desulfurization treatment is performed on the carbon dioxide-containing gas. Further, since steam is produced using ion-exchanged water as a raw material, it is desulfurized to a low sulfur concentration of ppb level.

The desulfurizer 3B for the oxygen-containing gas is also used as a desulfurizer for the oxygen-containing gas supplied to the high-temperature reformer 2, and the desulfurizer 3C for the carbon dioxide-containing gas is used for the sulfur dioxide supplied to the high-temperature reformer 2. The desulfurized steam is also supplied to the high-temperature reformer 2, which is also used as a desulfurization device for carbon-containing gas. That is, the desulfurization devices 3B and 3C provided in front of the second reaction chamber of the high temperature reformer 2 apply the oxygen-containing gas and the carbon dioxide-containing gas supplied to the second reaction chamber of the high temperature reformer 2 to each other. Then, desulfurization treatment is performed.
In addition, since the sulfur content contained in the fluid to be reformed may be set to a desired value or less, it is not essential to perform the desulfurization treatment on all of the plurality of supply fluids.

  As shown in FIG. 2, the fuel reformer operates the low-temperature reformer 1 in a temperature range of 200 to 800 ° C. (preferably 400 to 750 ° C., more preferably 400 to 700 ° C.), The porcelain vessel 2 is operated in a temperature range of 400 to 1200C (preferably 500 to 1100C, more preferably 600 to 1000C). For example, when gasoline is supplied as a hydrocarbon-based fuel, the reaction temperature in the reaction chamber of the low-temperature reformer 1 is maintained at a temperature lower than the thermal decomposition temperature of the hydrocarbon component in the gasoline, and The reaction temperature in the second reaction chamber of the vessel 2 is maintained at a temperature lower than the thermal decomposition temperature of methane (1200 ° C.). That is, the temperature does not exceed 1200 ° C., which is the temperature at which the thermal decomposition of methane in the first reformed gas is remarkably generated.

  The reaction of the low-temperature reformer 1 is performed by changing a supply ratio of at least one of the oxygen-containing gas, water vapor, and carbon dioxide-containing gas to the reaction chamber of the low-temperature reformer 1 to the hydrocarbon-based fuel. The temperature of the room can be adjusted. Specifically, the temperature of the reaction chamber of the low-temperature reformer 1 is adjusted by changing the ratio of the supply amount of the oxygen-containing gas to the hydrocarbon-based fuel supplied to the low-temperature reformer 1, The temperature of the reaction chamber of the low-temperature reformer 1 is adjusted by changing the ratio between the amount of carbon in the fuel and the amount of oxygen in the oxygen-containing gas.

  A hydrogen-containing gas can be supplied to the reaction chamber of the low-temperature reformer 1. The hydrogen-containing gas supplied to the low-temperature reformer 1 may be an off-gas of a fuel cell, a reformed gas, or the like. Although there is no particular limitation on the hydrogen concentration, it is preferable that the hydrogen concentration be 30% or more. Further, as shown in FIG. 1, a desulfurization device 3 </ b> D for the hydrogen-containing gas supplied to the low-temperature reformer 1 is provided in front of the low-temperature reformer 1.

  The reforming catalyst incorporated in the reaction chamber of the low-temperature reformer 1 is a catalyst mainly composed of a metal having steam reforming performance. Similarly, the reforming second catalyst contained in the second reaction chamber of the high-temperature reformer 2 is also a catalyst mainly composed of a metal having steam reforming performance. The reforming catalyst and the second reforming catalyst are preferably reforming catalysts having high steam reforming activity and high carbon deposition resistance, and specifically, a noble metal catalyst such as ruthenium or a nickel catalyst. The catalyst is filled. These catalysts may be of any shape, but preferably are supported on a carrier such as alumina and used in the form of tablets, spheres, rings, or formed into honeycombs. preferable.

Further, the low-temperature gas space velocity per the total gas flow supplied to the reaction chamber time of the reformer 1 (however, the standard values of the state conversion) ^{750h -1} ~300000h -1 (preferably at ^10000h -1 ^{~300000h - 1} , more preferably 50,000 h ^{-1 to} 300,000 h ^-1 ). That is, it is possible to change the total gas flow rate in such a wide gas space velocity range.

  There is no particular limitation on the pressure during the reaction. The reaction pressure can be changed depending on the application. For example, when used for hydrogen production for fuel cells, it can be used near normal pressure (for example, 1MPs or less), and when used for liquid fuel synthesis such as GTL, it can be used at about 2 to 7MPa. .

  When the fuel reformer is started, the temperature of the reaction chamber (reaction temperature) of the low-temperature reformer 1 reaches a proper operating temperature (for example, 400 ° C.) required for reforming the hydrocarbon-based fuel. The hydrocarbon-based fuel, the hydrogen-containing gas, and the oxygen-containing gas are supplied to the reaction chamber of the reformer 1 to burn the hydrogen, and the heat of combustion of the hydrogen is used to raise the temperature of the reaction chamber of the low-temperature reformer 1 to the above-described proper operation. The temperature is rising. In the course of raising the temperature to the appropriate operating temperature (for example, when the reaction temperature reaches 300 ° C.), steam is additionally supplied, and hydrogen combustion is continued in the presence of steam. After the temperature of the reaction chamber of the low-temperature reformer 1 reaches the appropriate operating temperature, the supply of the hydrogen-containing gas to the reaction chamber of the low-temperature reformer 1 is stopped, and the hydrocarbon-based fuel and the oxygen-containing gas are stopped. Operate to switch to gas and steam supply.

  As described above, at the time of startup, the hydrocarbon-based fuel, the hydrogen-containing gas, and the oxygen-containing gas can be supplied to the reaction chamber of the low-temperature reformer 1. It is also possible to supply only the contained gas. In addition, during the heating to the proper operating temperature, additional carbon dioxide is supplied instead of steam, both steam and carbon dioxide are additionally supplied, or steam or carbon dioxide is added during the heating to the proper operating temperature. It is also possible not to supply additional carbon.

Next, with respect to an example of a reforming experiment using the low-temperature reformer 1, an experimental result performed using the experimental apparatus shown in FIG. 3 will be described.
The experimental apparatus includes a reactor 4 having a reaction chamber 4A (hereinafter, referred to as a microreactor) filled with a reforming catalyst, a temperature recorder 5 for measuring and recording the temperature in the microreactor 4A, and an output gas from the reactor 4. A water condenser 6 for condensing the water therein, an automatic sampler 7 for sampling the output gas passing through the water condenser 6, a gas chromatograph 8 for analyzing the sample gas, and the like are provided for the catalyst packed bed of the reaction chamber 4A. Supply sources of the hydrocarbon fuel gas, oxygen or air as an oxygen-containing gas, hydrogen as a hydrogen-containing gas, water vapor, carbon dioxide as a carbon dioxide-containing gas, and dimethyl sulfide (DMS) at a concentration of 10 ppm in methane Is supplied after passing through on-off valves V1 to V6. The catalyst packed bed of the reaction chamber 4A is surrounded by an electric furnace 4B, and is provided with a lash ring on the inlet side and quartz wool on the outlet side.

  That is, the reaction chamber 4A corresponds to the reaction chamber of the low-temperature reformer 1, and the temperature of the reaction chamber 4A can be adjusted by the electric furnace 4B as a temperature adjustment mechanism capable of heating the reaction chamber 4A. Further, the temperature of the fluid to be reformed supplied to the reaction chamber 4A and in contact with the reforming catalyst can be measured by the temperature recorder 5. In the following examples, the on-off valves V1 to V6 were manually operated to adjust the supply amount of each gas and water vapor, and the pressure during the reaction was all normal pressure.

(Example 1) Start-up experiment of reformer when propane is used as fuel gas In order to confirm the start-up situation due to catalytic combustion of hydrogen, temperature rise characteristics were measured. Into the microreactor 4A, 33 ml of a ruthenium-based reforming catalyst Ru / Al ₂ O ₃ (2 wt% Ru / alumina supported, particle size: 0.5 to 1.0 mm) was filled. Other conditions are a propane (C ₃ H ₈ ) supply rate of 176 ml / min, a hydrogen supply rate of 158 ml / min, and an oxygen supply rate of 79 ml / min. Under these conditions, when a mixed gas of hydrogen, oxygen, and propane was introduced into the reactor 4 at room temperature, the catalyst packed bed was heated and increased in temperature due to the hydrogen combustion reaction by the catalyst. FIG. 4 shows the temperature rise characteristic of the catalyst packed bed inlet at this time, and it has reached 400 ° C. (appropriate operating temperature) in about 40 minutes.
During the above operation, the temperature of the electric furnace 4B surrounding the catalyst layer was heated to a temperature lower by 5 ° C. than the catalyst layer temperature to prevent heat radiation from the reactor 4 (otherwise, the reactor 4 and the catalyst The temperature of the bed does not rise).

(Example 2) Reforming of propane with a ruthenium-based catalyst Using the same apparatus as in Example 1, partial oxidation of propane gas and a steam reforming reaction were performed. In this experiment, air was used as the oxygen-containing gas. The experimental conditions in the reforming stage are shown in Table 1 of FIG. 5, and the four conditions C2-1, C2-2, C2-3, and C2-4 were changed by changing the SV, the O ₂ / C ratio, and the inlet temperature Tin. Is set.
The results such as the composition of the reformed gas at the reforming stage in which the temperature is stable under each condition are shown in Tables 2-1 to 4 in FIGS.
Table 2-1 shows the experimental results for the condition C2-1 in which the O ₂ / C ratio was changed in the range of 0.3 to 1.4 at SV = 10000 h ⁻¹ and Tin 300 ° C.
Table 2-2 shows the experimental results for C2-2 in which the O ₂ / C ratio was changed in the range of 0.3 to 1.4 at SV = 10000 h ⁻¹ and Tin 400 ° C.
Table 2-3 shows the experimental results for C2-3 in which the O ₂ / C ratio was changed in the range of 0.3 to 1.2 at SV = 20,000 h ⁻¹ and Tin 300 ° C.
SV = 20,000 h ⁻¹ , Tin 400 ° C., the O ₂ / C ratio was changed in the range of 0.3 to 1.0, and further, the C / C was changed to 2.0 / 2.5. The experimental results are shown in Table 2-4.

The following can be seen from the above experimental results.
Under each condition, as the O ₂ / C ratio is increased, the maximum temperature Tmax in the catalyst layer and the catalyst layer outlet temperature Tout are higher than the inlet temperature Tin. Thus, it was found that the reaction temperature could be controlled by the O ₂ / C ratio.
Comparing the results of C2-1 and C2-2, the higher temperature C2-2 has higher concentrations of hydrogen and carbon monoxide (excluding the hydrogen concentration of O ₂ /C=1.4) and the methane concentration Is low, it is understood that the reforming of propane is progressing.
Comparing the results of C2-1 and C2-3, it can be seen that C2-3, which has a larger SV, has half the effect of heat radiation and the catalyst layer temperature has increased.
From the result of C2-4, as the S / C ratio decreases, the temperature increases. Thus, it was found that the reaction temperature could be controlled by the S / C ratio. When the S / C ratio decreases, the amount of carbon monoxide increases, but the amounts of hydrogen and methane decrease. This indicates that the outlet gas composition can be controlled by the S / C ratio.
It is shown that the maximum temperature Tmax of the catalyst layer is lower than the thermal decomposition temperature of propane.
After reacting for 5 hours, the reactor was returned to normal temperature and disassembled and observed. As a result, no carbon deposition on the inside of the reactor or on the catalyst surface was observed in any case.

(Example 3) Reforming of n-hexane with ruthenium-based catalyst Regarding the reforming reaction when n-hexane was used as a fuel gas instead of propane, the temperature was fixed at Tin 400 ° C, and as shown in Table 3 of FIG. The partial oxidation of n-hexane and the steam reforming reaction were performed using the same apparatus as in Example 1 with SV10000h- ¹ . In this embodiment, air was used as the oxygen-containing gas.
Table 4 in FIG. 9 shows the results such as the composition of the reformed gas when the O ₂ / C ratio was changed in the range of 0.1 to 0.6.

The following can be seen from the above experimental results.
As the O ₂ / C ratio increases, the maximum temperature Tmax and the outlet temperature Tout become higher than the inlet temperature Tin. Thus, it was found that the reaction temperature could be controlled by the O ₂ / C ratio. Also, the H ₂ / CO ratio decreases as the O ₂ / C ratio increases. This indicates that the outlet gas composition can be controlled by the O ₂ / C ratio.
In this example, a small amount of hexane remained at the outlet, but it is easy to reform hexane entirely by reducing the SV (or increasing the amount of catalyst). After the reaction, the reactor was returned to room temperature and disassembled and observed. As a result, no carbon deposition was observed inside the reactor or on the catalyst surface in any case.

(Example 4) Durability test of ruthenium-based catalyst Since ruthenium-based catalyst Ru / Al ₂ O ₃ showed excellent performance in the reforming reaction of propane and hexane, next, using hexane as fuel gas, The durability was confirmed. In this embodiment, air was used as the oxygen-containing gas. The results of the durability test are shown in FIG. 10. In the hexane reforming reaction, even after 110 hours, the catalyst layer temperature Tmax (maximum temperature), Tmid (intermediate temperature), Tout (outlet temperature), and It was found that both the pressures P (MPa) were stable, the carbon did not precipitate, and the reforming reaction proceeded stably.
After the reaction, the reactor was returned to room temperature and disassembled and observed. As a result, no carbon deposition was observed inside the reactor or on the catalyst surface.

(Example 5) nickel catalyst Ni / Al 2 _O 3 in place of the reforming ruthenium-based catalysts propane by nickel catalysts _(nickel concentration of 22 wt%, alumina support) was used to the same apparatus as in Example 1, Partial oxidation of propane gas and steam reforming reaction were performed. The experimental conditions and results are shown in Table 5 of FIG. It can be seen that propane gas is stably reformed to hydrogen, methane, and the like.
The Ni catalyst was reduced by a nitrogen gas containing 10% of hydrogen at 400 ° C. for 1 hour after filling the microreactor.
After the reaction, the reactor was returned to room temperature and disassembled and observed. As a result, no carbon deposition was observed inside the reactor or on the catalyst surface.

The same apparatus as reforming Example 1 of n- hexane by Example 6 nickel catalyst, a nickel catalyst Ni / _Al 2 _{O 3} (nickel concentration 22 wt%, alumina support, particle size 0.5 to 1.0 mm) 2.2 ml was filled in the microreactor 4A, and a partial oxidation of n-hexane and a steam reforming reaction were performed. In this embodiment, air was used as the oxygen-containing gas.
The Ni catalyst was reduced at 530 ° C. for 1 hour with a nitrogen gas containing 10% of hydrogen after filling the microreactor. The experimental conditions and results are shown in Table 6 in FIG.
In this example, a small amount of hexane remained at the outlet, but it is easy to reform hexane entirely by reducing the SV (or increasing the amount of catalyst). After the reaction, the reactor was returned to room temperature and disassembled and observed. As a result, no carbon deposition was observed inside the reactor or on the catalyst surface.

(Example 7) by the same experimental apparatus as reforming Example 1 of n- hexane by ruthenium-based catalyst, a ruthenium catalyst Ru _/ Al _{2 O} 3 ₍₂ wt% Ru / alumina supported, particle size: 0.5 (0.0 mm) into the microreactor 4A to perform a partial oxidation of n-hexane and a steam reforming reaction. In this embodiment, pure oxygen was used as the oxygen-containing gas. The experimental conditions and results are shown in Table 7 in FIG.
In this example, a small amount of hexane remained at the outlet, but it is easy to reform hexane entirely by reducing the SV (or increasing the amount of catalyst). After the reaction, the reactor was returned to room temperature and disassembled and observed. As a result, no carbon deposition was observed inside the reactor or on the catalyst surface.

(Comparative Example 1) High-temperature reforming of n-hexane with a ruthenium-based catalyst Ruthenium-based catalyst Ru / Al ₂ O ₃ (2 wt% Ru / alumina supported, particle size: 0.5 to (1.0 mm) of 2.4 ml was charged into the microreactor 4A, and a partial oxidation of n-hexane and a steam reforming reaction were performed. In this embodiment, pure oxygen was used as the oxygen-containing gas. In Example 7, the reaction temperature was 594 ° C, but in Comparative Example 1, the reaction temperature was 665 ° C. The experimental conditions and results are shown in Table 8 in FIG.
After the reaction, the reactor was returned to room temperature and disassembled and observed. As a result, carbon deposition on the catalyst was observed. This is considered to be because the reaction temperature is higher than the thermal decomposition temperature of n-hexane.

Comparative Example 2 High-Temperature Reforming of n-Hexane with Ruthenium-Based Catalyst Ruthenium-based catalyst Ru / Al ₂ O ₃ (2% by weight Ru / alumina supported, particle size: 0.5 to 5%) by the same experimental device as in Example 1. (1.0 mm) 3.3 ml was charged into the microreactor 4A, and a partial oxidation of n-hexane and a steam reforming reaction were performed. In this embodiment, air was used as the oxygen-containing gas. The reaction temperature was raised to 669 ° C. The experimental conditions and results are shown in Table 9 in FIG.
After the reaction, the reactor was returned to room temperature and disassembled and observed. As a result, carbon deposition on the catalyst was observed. Then, using a carbon analyzer (EMIA-820) manufactured by HORIBA, Ltd., the amount of carbon in the catalyst extracted after the reaction was analyzed, and a value of 0.42 wt% was obtained. The carbon content of the new catalyst before the reaction was also analyzed at the same time, and it was 0.16 wt%. Therefore, it was determined that the carbon deposition of the difference in carbon content before and after the reaction (0.26 wt%) occurred. But it was clear. It is considered that the cause of the carbon precipitation is that the reaction temperature is higher than the thermal decomposition temperature of n-hexane.

  That is, considering the thermal decomposition temperature of hexane, the results of Example 3 (see FIG. 9) show that no carbon deposition was observed at the catalyst layer maximum temperature Tmax of 634 ° C. From the results of Examples 1 and 2 (see FIG. 12), no carbon deposition was observed when the catalyst layer maximum temperature Tmax was 530 ° C. and 594 ° C., and carbon deposition was observed when the catalyst layer maximum temperature Tmax was 665 ° C. and 699 ° C.

(Example 8) by the same experimental apparatus as reforming the first embodiment of simulated natural gas by a ruthenium-based catalyst, a ruthenium catalyst Ru _/ Al _{2 O} 3 ₍₂ wt% Ru / alumina supported, particle size: 0.5 (0.0 mm) into the microreactor 4A, and a partial oxidation of simulated natural gas (methane concentration 88%, ethane 6%, propane 4%, butane 2%) and a steam reforming reaction were performed. In this embodiment, pure oxygen was used as the oxygen-containing gas. The experimental conditions and results are shown in Table 10 of FIG.
The maximum temperature Tmax of the catalyst layer is 505 ° C., which indicates that it is lower than the thermal decomposition temperature of butane having the highest carbon number in the simulated natural gas.
After the reaction, the reactor was returned to room temperature and disassembled and observed. As a result, no carbon deposition was observed inside the reactor or on the catalyst surface.

(Example 9) by the same experimental apparatus as reforming the first embodiment of simulated natural gas by a ruthenium-based catalyst, a ruthenium catalyst Ru _/ Al _{2 O} 3 ₍₂ wt% Ru / alumina supported, particle size: 0.5 2.0 mm) into a microreactor 4A, and simulated natural gas (methane concentration 88%, ethane 6%, propane 4%, butane 2%), partial oxidation, steam reforming, CO ₂ reforming reaction Was done. In this embodiment, pure oxygen was used as the oxygen-containing gas. The experimental conditions and results are shown in Table 11 of FIG.
As compared with Example 8, it was found that the H ₂ / CO ratio could be reduced by adding carbon dioxide. The maximum temperature Tmax of the catalyst layer is 504 ° C., which indicates that the maximum temperature Tmax is lower than the thermal decomposition temperature of butane having the highest carbon number in the simulated natural gas. After the reaction, the reactor was returned to room temperature and disassembled and observed. As a result, no carbon deposition was observed inside the reactor or on the catalyst surface.

  In the above Examples 1 to 9, the reforming experiment was performed only in the former reforming section (low-temperature reformer 1), but in the following Example 10, the former reforming section (low-temperature reformer 1) and the latter reformer were used. The results of a reforming experiment using a two-stage reforming section of the reforming section (high-temperature reformer 2) will be described.

(Example 10) Reforming of simulated natural gas with ruthenium-based catalyst As shown in FIG. 14, a ruthenium-based reforming catalyst Ru / Al ₂ O ₃ ( 2.9 ml of 2 wt% Ru / alumina supported, particle size: 0.5 to 1.0 mm) was placed in the microreactor 4A in the former stage, and 2.9 ml of the same ruthenium-based catalyst Ru / Al ₂ O ₃ was used for reforming. The two-catalyst is charged into the latter microreactor 9A to perform partial oxidation, steam reforming, and CO ₂ reforming of simulated natural gas (methane concentration 88%, ethane 6%, propane 4%, butane 2%). Was. The reactor 9 at the latter stage is composed of a microreactor 9A, an electric furnace 9B and the like having the same configuration as the reactor 4 at the former stage (see FIG. 3), and a temperature for measuring the temperature inside the microreactor 9A. A recorder 10 is provided. In Example 10, pure oxygen was used as the oxygen-containing gas. Then, the output gas from the latter-stage reactor 9 is sampled and analyzed.

  That is, the microreactor 9A corresponds to the second reaction chamber of the high-temperature reformer 2, and the temperature of the second reaction chamber 4A is adjusted by the electric furnace 9B as a temperature adjustment mechanism capable of heating the second reaction chamber 9A. can do. Further, the temperature of the second fluid to be reformed supplied to the reaction chamber 9A and in contact with the second reforming catalyst can be measured by the temperature recorder 10.

The experimental conditions and results are shown in Table 12 of FIG. The conditions of the first-stage microreactor 4A are as shown in Table 12, and between the first-stage microreactor 4A and the second-stage microreactor 9A, as shown in FIG. ~ V9. With respect to the simulated natural gas introduced into the microreactor 4A inlet, the total amount of water vapor added to the microreactor 4A inlet and 9A inlet was described as the S / C ratio in the microreactor 4A + 9A conditions. Similarly, the total amount of oxygen or carbon dioxide added to the microreactor 4A inlet and the 9A inlet is defined as the O ₂ / C ratio or the CO ₂ / C ratio with respect to the simulated natural gas introduced into the microreactor 4A inlet. The conditions were described in the microreactor 4A + 9A conditions.

The maximum temperature of the catalyst layer of the first stage reformer (microreactor 4A) is 512 ° C, and the maximum temperature of the catalyst layer of the second stage reformer (microreactor 9A) is 895 ° C. did it. Thus, the temperature of the second reaction chamber (microreactor 9A) is adjusted so that the outlet temperature of the second reaction chamber (microreactor 9A) is higher than the outlet temperature of the reaction chamber (microreactor 4A). I understand.
The maximum temperature Tmax of the former reforming catalyst layer is 512 ° C., which is lower than the thermal decomposition temperature of butane having the highest carbon number in the simulated natural gas. The maximum temperature Tmax of the second reforming second catalyst layer is 895 ° C., which is lower than the thermal decomposition temperature of methane. The outlet temperature Tout of the second reforming catalyst layer at the subsequent stage is 843 ° C., which is higher than the outlet temperature Tout of the first reforming catalyst layer at 500 ° C. After the reaction, the reactor was returned to room temperature and disassembled and observed. As a result, no carbon deposition was observed inside the reactor or on the catalyst surface of any of the microreactors 4A and 9A.

  Next, the description returns to the results of the reforming experiment performed by the former reforming section (low-temperature reformer 1).

(Examples 11 to 15) Reforming experiment of simulated natural gas containing sulfur by ruthenium-based catalyst Ruthenium-based reforming catalyst Ru / Al ₂ O ₃ (2% by weight Ru / alumina supported by the same experimental apparatus as in Example 1) , 2.4-ml in the microreactor 4A and partial oxidation of simulated natural gas (methane concentration 88%, ethane 6%, propane 4%, butane 2%), A steam reforming reaction was performed to determine a reforming rate (%). In this embodiment, pure oxygen was used as the oxygen-containing gas. The experimental conditions and results are shown in Table 13 of FIG. In Examples 11 to 15, the DMS concentration was 5 vol. ppb or less, Example 11 had no DMS added, and Example 12 had a DMS concentration of 0.9 vol. ppb, Example 13 shows a DMS concentration of 1.3 vol. ppb, Example 14 shows a DMS concentration of 2.4 vol. ppb, Example 15 has a DMS concentration of 4.8 vol. Performed under ppb conditions.
The reforming rate in Table 13 is obtained by the following equation, and represents the ratio of carbon in the raw material gas converted to CO and CO ₂ gas without remaining as a hydrocarbon in the output gas. .

[Equation 1]
Reformation rate (%) = (outlet CO concentration + outlet CO ₂ concentration) × 100 / (outlet methane concentration + outlet CO concentration + outlet CO ₂ concentration + outlet C2 component concentration × 2 + outlet C3 component concentration × 3 + outlet C4 component concentration × 4)

  As shown in Table 13, 5 vol. At any DMS concentration of ppb or less, no sharp decrease in the activity (reduction of the reforming rate) was observed, but particularly at 1.3 vol. It was found that there is no effect (the reforming ratio does not change) when the content is less than ppb. Therefore, the sulfur concentration in the total gas supplied to the first-stage reforming section (low-temperature reformer 1) is 5 vol. The present fuel reformer is operated so as to be ppb or less. Note that the above results can be similarly applied to the second-stage reforming section (high-temperature reformer 2). Therefore, when the sulfur concentration in the total gas supplied to the second-stage reforming section (high-temperature reformer 2) is 5 vol. The present fuel reformer is operated so as to be ppb or less. The maximum temperature Tmax of the catalyst layer is 504 ° C to 507 ° C, which is lower than the thermal decomposition temperature of butane. After the reaction, the reactor was returned to normal temperature and disassembled and observed. As a result, no carbon deposition was observed inside the reactor or on the catalyst surface in any of the examples.

The above Examples 1 to 15 and Comparative Examples 1 and 2 were performed at normal pressure using the experimental apparatus shown in FIG. 3 or FIG. Therefore, when the heat insulation performance and the reaction pressure of the reactors 4 and 9 change, the maximum temperature Tmax of the catalyst layer and the outlet gas composition can change even under the same conditions as those in Examples 1 to 15 and Comparative Examples 1 and 2. There is. However, even in such a case, the maximum temperature of the catalyst layer is changed by changing at least one of the S / C ratio, O ₂ / C ratio, and CO ₂ / C ratio in the inlet gas, or by heating or cooling from the outside. It is possible to control Tmax below the pyrolysis temperature of the raw hydrocarbon.

  As described above, the fuel reformer according to the present invention can be used under the condition of a large gas space velocity and can be miniaturized, so that it can be used for a moving body such as an automobile (for mounting on a moving body) or stationary (for example, , For stationary small power supplies). For mounting on a moving body, it can be used to supply hydrogen fuel to a fuel cell, for example, as a power unit of an automobile, and for a stationary small power source, a fuel used for power generation at a small business establishment or the like It can be used to supply hydrogen fuel to batteries.

[Another embodiment]
Next, another embodiment of the operation method of the reformed gas producing apparatus according to the present invention will be described.
In the above-described embodiment, the reformed gas production device (fuel reforming device) has a two-stage configuration including the former low-temperature reforming unit 1 (reaction chamber) and the latter high-temperature reforming unit 2 (second reaction chamber). It is also possible to configure so that only the former low-temperature reforming section 1 (reaction chamber) is provided. In the operation method of the reformed gas producing apparatus, the former low-temperature reforming section 1 (reaction chamber) is operated in a temperature range of 200 to 800C (preferably 400 to 700C).

In the above embodiment, the temperature of the reaction chamber 4A of the experimental reactor 4 corresponding to the reaction chamber of the low-temperature reformer 1 is measured (see FIG. 3), and the O ₂ / C ratio is determined while observing the measured temperature. Was manually changed (ie, the supply amount of the oxygen-containing gas (air) was adjusted) to adjust the temperature of the reaction chamber 4A, but this adjustment operation is automatically performed as follows. You may do so.
In this alternative embodiment, as shown in FIG. 17, a multi-point system for detecting the temperature in the reaction chamber of the low-temperature reforming section 1, for example, Tin (inlet temperature), Tmax (maximum temperature), Tout (outlet temperature), and the like. A temperature sensor, and control means for performing control to adjust a supply ratio of at least one of the oxygen-containing gas, water vapor, and carbon dioxide-containing gas to the hydrocarbon-based fuel based on detection information of the temperature sensor. 11 are provided. In the figure, 13a to 13e are solenoid valves for adjusting the flow rate of each gas.

  Then, based on the temperatures Tin, Tmax, and Tout of the respective sections in the reaction chamber, the control means 11 controls the amount of the oxygen-containing gas, the amount of the water vapor-containing gas, and the amount of the carbon dioxide-containing gas with respect to the supply amount of the hydrocarbon-based fuel. At least one of the amounts is adjusted so that the temperature in the reaction chamber is equal to or lower than the thermal decomposition temperature of hydrocarbon gas as a fuel, and is controlled to a temperature at which the reforming reaction is properly performed. For example, when the temperature of the reaction chamber is lower than the appropriate temperature, increase the supply ratio of the oxygen-containing gas or decrease the supply ratio of the steam-containing gas to increase the temperature, and conversely, the temperature of the reaction chamber Is higher than the appropriate temperature, the supply ratio of at least one of the water vapor-containing gas and the carbon dioxide-containing gas is increased, or the supply ratio of the oxygen-containing gas is decreased to lower the temperature.

Further, as an operation method of the reformed gas production apparatus of the present invention, the oxygen-containing gas supplied to the subsequent high-temperature reforming section 2 (second reaction chamber) as in the preceding low-temperature reforming section 1 (reaction chamber). An operation method of adjusting the temperature of the second reaction chamber by changing a supply ratio of at least one of the steam and the carbon dioxide-containing gas to the reformed gas is possible.
Although not shown, the temperatures of the respective sections Tin, Tmax, and Tout in the second reaction chamber in the second reforming section (high-temperature reforming section 2) are also the same as in the first reforming section (low-temperature reformer 1). Is supplied to the high-temperature reforming section 2 by the control means based on the detection information of the temperature sensor for detecting the supply rate ratio of at least one of the oxygen-containing gas, steam, and carbon dioxide-containing gas to the first reformed gas. Can be changed to perform control for adjusting the temperature of the second reaction chamber.

  Further, in an actual reformer, a temperature adjusting mechanism 15 capable of forcibly cooling or heating the former low-temperature reformer 1 (reaction chamber) from the outside, and the latter high-temperature reformer 2 (second reaction chamber) ) May be provided with a second temperature adjustment mechanism 15 capable of forcibly cooling or heating from outside. Specifically, as illustrated in FIG. 18, a temperature adjustment mechanism 15 for the low-temperature reformer 1 (reaction chamber) and a second temperature adjustment mechanism 15 for the high-temperature reformer 2 (second reaction chamber), respectively. Is composed of a heating gas burner 15A and a cooling pipe 15B through which a cooling fluid flows for cooling.

  In the above embodiment, the reforming catalyst and the second reforming catalyst are metal catalysts having steam reforming performance, but the reforming catalyst and the second reforming catalyst have partial oxidation performance together with steam reforming performance. You may have.

Conceptual diagram of a reformed gas production device according to the present invention 4 is a graph showing a configuration and a temperature distribution of a reformer of the reformed gas production device according to the present invention. Configuration diagram of test equipment for checking characteristics of low-temperature reformer Graph showing temperature rise result (Example 1) due to hydrogen combustion in low-temperature reformer Diagram showing conditions for propane reforming experiment (Example 2) using ruthenium-based catalyst Diagram showing the results of a propane reforming experiment (Example 2) using a ruthenium-based catalyst Diagram showing the results of a propane reforming experiment (Example 2) using a ruthenium-based catalyst The figure which shows the conditions of the n-hexane reforming experiment (Example 3) with a ruthenium-based catalyst The figure which shows the result of the reformation experiment (Example 3) of n-hexane with a ruthenium-based catalyst Graph showing the results of the durability test (Example 4) of the reforming catalyst of the low-temperature reformer Diagram showing conditions and results of propane reforming experiment (Example 5) using nickel-based catalyst Diagram showing conditions and results of an experiment for reforming n-hexane using nickel-based catalyst and ruthenium-based catalyst (Examples 6 and 7) Diagram showing the conditions and results of a simulated natural gas reforming experiment (Examples 8 and 9) using a ruthenium-based catalyst Configuration diagram of test equipment for confirming characteristics of two-stage reformer consisting of low-temperature reformer and high-temperature reformer Diagram showing conditions and results of a characteristic confirmation experiment (Example 10) of a two-stage reformer including a low-temperature reformer and a high-temperature reformer Diagram showing conditions and results of a reforming experiment of simulated natural gas containing sulfur with a ruthenium-based catalyst (Examples 11 to 15) FIG. 4 is a block diagram illustrating a temperature control configuration of a low-temperature reformer according to another embodiment. The figure which shows the temperature adjustment mechanism of the reformed gas manufacturing apparatus which concerns on another embodiment. Graph showing the configuration and temperature distribution of a conventional partial oxidation reformer Graph of configuration and temperature distribution of conventional partial oxidation reformer with prereformer

Explanation of reference numerals

3A to 3D Desulfurizer 4A Reaction chamber 4B Temperature adjustment mechanism 9A Second reaction chamber 9B Second temperature adjustment mechanism 12 Temperature sensor 15 Temperature adjustment mechanism 15 Second temperature adjustment mechanism

Claims (19)

  Reaction chamber containing a reforming catalyst, using a fluid containing at least one of steam and carbon dioxide-containing gas, a fuel containing hydrocarbons having 2 or more carbon atoms, and an oxygen-containing gas as a fluid to be reformed The temperature of the reaction chamber is adjusted so that the maximum temperature of the fluid to be reformed in contact with the reforming catalyst is within a temperature range of 200 to 800 ° C. and equal to or lower than the thermal decomposition temperature of the fuel. An operating method of a reformed gas producing apparatus for producing a reformed gas containing methane, hydrogen and carbon monoxide.   2. The modification according to claim 1, wherein a temperature of the reaction chamber is adjusted by changing a supply ratio of at least one of the oxygen-containing gas, the water vapor, and the carbon dioxide-containing gas to be supplied to the reaction chamber. Method of operating a high quality gas production system   3. The operating method of the reformed gas production apparatus according to claim 2, wherein control is performed to adjust a supply amount ratio to the fuel based on detection information of a temperature sensor that detects a temperature in the reaction chamber.   The method according to any one of claims 1 to 3, wherein the temperature of the reaction chamber is adjusted by a temperature adjustment mechanism capable of cooling or heating the reaction chamber.   The method for operating a reformed gas production apparatus according to any one of claims 1 to 4, wherein a hydrogen-containing gas is supplied to the reaction chamber.   Until the temperature of the reaction chamber reaches a proper operating temperature required for the reforming of the fuel, the hydrogen-containing gas and the oxygen-containing gas are supplied to the reaction chamber to burn hydrogen, and the combustion heat of the hydrogen causes the heat of combustion. The method according to claim 5, wherein the temperature of the reaction chamber is raised to the proper operating temperature.   The method for operating a reformed gas producing apparatus according to any one of claims 1 to 6, wherein the reforming catalyst is a catalyst containing a metal having steam reforming performance as a main component.   The desulfurization device provided in front of the reaction chamber performs desulfurization processing on at least one of the fuel, each of the gases, and the steam supplied to the reaction chamber. Method for operating a reformed gas production apparatus of the present invention.   When the sulfur concentration in the total gas supplied to the reaction chamber is 5 vol. The method for operating a reformed gas production apparatus according to claim 8, wherein the desulfurization apparatus is operated so as to be ppb or less.   A fluid containing an oxygen-containing gas and the reformed gas generated in the reaction chamber is supplied to a second reaction chamber containing a second reforming catalyst as a second fluid to be reformed, The second temperature is set such that the maximum temperature of the second fluid to be reformed in contact with the catalyst is maintained in the temperature range of 400 to 1200 ° C., and the outlet temperature of the second reaction chamber is higher than the outlet temperature of the reaction chamber. The method for operating a reformed gas producing apparatus according to any one of claims 1 to 9, wherein the temperature of the reaction chamber is adjusted to produce a second reformed gas containing hydrogen and carbon monoxide.   The method according to claim 10, wherein at least one of steam and a carbon dioxide-containing gas is supplied to the second reaction chamber.   The temperature of the second reaction chamber is adjusted by changing a supply ratio of at least one of the oxygen-containing gas, the water vapor, and the carbon dioxide-containing gas to the reformed gas to be supplied to the second reaction chamber. An operation method of the reformed gas production apparatus according to claim 11.   13. The operating method of the reformed gas production apparatus according to claim 12, wherein control for adjusting a supply amount ratio to the reformed gas is performed based on detection information of a temperature sensor that detects a temperature in the second reaction chamber.   The method for operating a reformed gas production apparatus according to any one of claims 10 to 13, wherein the temperature of the second reaction chamber is adjusted by a second temperature adjustment mechanism capable of cooling or heating the second reaction chamber.   15. The modification according to claim 10, wherein at least one of the gases supplied to the second reaction chamber is subjected to a desulfurization treatment by a desulfurization device provided in front of the second reaction chamber. Method of operating a high quality gas production device.   The sulfur concentration in the total gas supplied to the second reaction chamber is 5 vol. The method for operating a reformed gas production apparatus according to claim 15, wherein the desulfurization apparatus is operated so as to be ppb or less.   The method for operating a reformed gas producing apparatus according to any one of claims 10 to 16, wherein the second catalyst for reforming is a catalyst containing a metal having steam reforming performance as a main component. How the operation of the reformed gas manufacturing apparatus according to any one of claims 1 to 17 in the range of the reaction chamber to supply the total gas flow rate ^{750h -1 ~300000h} -1 at a gas hourly space velocity.   The method for operating a reformed gas production apparatus according to any one of claims 1 to 18, wherein the method is used for a moving object or a stationary object.

Images