JP4781704B2 - Method and apparatus for producing hydrogen-containing gas - Google Patents

Description

  The present invention provides a mixing step of mixing an oxygen-containing gas with a raw material gas in which water vapor and a hydrocarbon-based fuel are mixed, and before the mixed gas obtained in this mixing step is provided upstream of the catalytic reaction chamber. The present invention relates to a method for producing a hydrogen-containing gas, wherein the reforming step is performed through a chamber to the catalytic reaction chamber, and a mixed gas is brought into contact with the reforming catalyst to obtain a hydrogen-containing gas by a partial oxidation reaction and a steam reforming reaction. In addition, the present invention relates to a production apparatus that employs this type of method for producing a hydrogen-containing gas.

For example, as a raw gas for FT (Fischer Tropsch) synthesis, methanol synthesis, or ammonia synthesis, it has been proposed to obtain a hydrogen-rich gas by reforming a hydrocarbon fuel using a catalytic reaction.
As a catalytic reforming reaction of this type of hydrocarbon fuel, a partial oxidation reaction and a steam reforming reaction are known.
The partial oxidation reaction is in accordance with the chemical formula shown in the following chemical formula 1, and is a so-called exothermic reaction.

  The steam reforming reaction is a so-called endothermic reaction according to the chemical formula shown in Chemical Formula 2 below.

  In a certain reforming catalyst (for example, ruthenium catalyst), both the steam reforming reaction and the partial oxidation reaction occur. Further, as the reforming catalyst housed in the catalytic reaction chamber, it is conceivable to arrange a catalyst suitable for partial oxidation on the front side and a catalyst suitable for steam reforming on the rear side.

Therefore, an oxygen-containing gas (for example, pure oxygen) is mixed with the raw material gas in which water vapor and hydrocarbon-based fuel are mixed. In the obtained mixed gas, a partial oxidation reaction is performed before the catalyst layer. The hydrogen-rich gas is generated by raising the temperature of the reaction gas to the temperature required for the steam reforming reaction and causing both reactions (steam reforming reaction and partial oxidation reaction) on the rear side of the catalyst layer. It has been proposed to get
This reforming technique is also called autothermal reforming, and in this reforming, the reactions shown in Chemical Formula 1 and Chemical Formula 2 occur simultaneously.

  In this reforming mode, when the catalytic reaction chamber filled with the reforming catalyst is a single reaction chamber, as shown by the solid line in FIG. As it goes, the temperature rises and reaches the peak temperature. After that, it converges to an equilibrium temperature determined by the inlet temperature, the inlet gas composition, and the reaction pressure.

  As this type of autothermal technique, a technique disclosed in Patent Document 1 is known.

  In the technique disclosed in Patent Document 1, as shown in FIG. 2 of the specification, an upstream non-catalytic reaction chamber for performing a partial oxidation reaction is provided on the upstream side of the catalyst zone for performing a steam reforming reaction; As shown in FIGS. 3, 4, and 5 of this specification, an example is shown in which a non-catalyst chamber is provided in front of the reforming catalyst layer to perform each reaction with a reforming catalyst, and each reaction is performed. ing.

JP 2000-84410 A (FIGS. 1 to 5)

However, there are the following problems.
1 Problems of the configuration shown in FIG. 2 disclosed in Patent Document 1 In this configuration, a partial oxidation reaction is performed in a non-catalytic reaction chamber in the previous stage. Is difficult and controllability is not good.
2 Problems of configurations shown in FIGS. 3 to 5 disclosed in Patent Document 1 In these configurations, since the catalytic reaction chamber is divided into two independent chambers, the heat generated by the partial oxidation reaction is sufficiently obtained. It cannot be used for steam reforming. Further, a front chamber in which no catalyst is disposed is provided in front of the reforming catalyst layer. In this front chamber, depending on the temperature state of the catalyst layer, partial oxidation starts in this front chamber and the catalyst layer In some cases, the gas temperature in the chamber rises too much, causing problems such as the generation of carbon harmful to the reaction.

  The present invention has been made in view of the above circumstances, and allows the reforming reaction to occur stably and stably from the inlet portion of the catalytic reaction chamber, and the controllability of the reaction in the catalytic reaction chamber is maintained high and good. By obtaining a hydrogen-containing gas production technology that can maintain stable reforming performance over a long period of time by preventing problems such as a decrease in catalyst activity due to carbon deposition while realizing a high reforming efficiency. is there.

In order to achieve the above object, a mixing step of mixing an oxygen-containing gas in a mixing chamber with a raw material gas in which water vapor and hydrocarbon fuel are mixed;
The mixed gas obtained in the mixing chamber is led to the catalytic reaction chamber through a front chamber provided upstream of the catalytic reaction chamber, and the mixed gas is brought into contact with the reforming catalyst to perform partial oxidation reaction and steam reforming. The characteristic means of the method for producing a hydrogen-containing gas, wherein the reforming step of obtaining a hydrogen-containing gas by reaction is performed,
The lower limit temperature at which the reforming catalyst causes the partial oxidation reaction is defined as a partial oxidation lower limit temperature, and the lower limit temperature at which the reforming catalyst undergoes the steam reforming reaction is defined as a steam reforming lower limit temperature. At a temperature of
With respect to the self-ignition temperature that is the temperature at which the mixed gas self-ignites in the advection time required for the mixed gas to reach the catalytic reaction chamber from the mixing chamber, the temperature is lower than the self-ignition temperature.
The temperature of the mixing chamber and the front chamber is set and the mixed gas is introduced into the catalytic reaction chamber to produce a hydrogen-containing gas.

In this method, a catalyst having both partial oxidation and steam reforming ability is used as a reforming catalyst. A typical example of this type of catalyst is a ruthenium catalyst. Further, a catalyst suitable for partial oxidation and steam reforming may be used in combination.
When the catalyst is specified, the partial oxidation lower limit temperature and the steam reforming lower limit temperature are both determined as characteristic temperatures unique to the catalyst. On the other hand, from the mixing chamber to the catalytic reaction chamber, the mixed gas advection time is determined by the physical configuration of the reaction system.

Therefore, in the method of the present application, the temperature of the mixing chamber and the front chamber is set to be equal to or higher than the lower limit temperature at which the partial oxidation reaction can occur with respect to the lower limit, thereby ensuring the occurrence of the partial oxidation reaction at the catalyst reaction chamber inlet.
On the other hand, the upper limit temperature is set to a temperature lower than the steam reforming lower limit temperature and the auto-ignition temperature, so that ignition of the mixed gas is prevented from occurring in the mixing chamber or the front chamber and the system is stabilized.

  By doing so, partial oxidation is generated as a reaction in the catalytic reaction chamber, and can be controlled well in a state depending on the temperature of the inlet of the catalytic reaction chamber. Furthermore, since the inlet temperature of the catalytic reaction chamber can be optimized, the temperature distribution in the catalytic reaction chamber can be optimized as a result, and problems such as generation of carbon and catalyst deterioration due to excessive temperature rise can be reliably avoided. .

As an apparatus for producing a hydrogen-containing gas using this method,
A mixing chamber for mixing an oxygen-containing gas with a raw material gas in which water vapor and hydrocarbon fuel are mixed;
The mixed gas obtained in the mixing chamber is led to the catalytic reaction chamber through a front chamber provided upstream of the catalytic reaction chamber, and the mixed gas is brought into contact with the reforming catalyst to perform partial oxidation reaction and steam reforming. A hydrogen-containing gas production apparatus for obtaining a hydrogen-containing gas by a reaction,
The lower limit temperature at which the reforming catalyst causes the partial oxidation reaction is defined as a partial oxidation lower limit temperature, and the lower limit temperature at which the reforming catalyst undergoes the steam reforming reaction is defined as a steam reforming lower limit temperature. At a temperature of
With respect to the self-ignition temperature that is the temperature at which the mixed gas self-ignites in the advection time required for the mixed gas to reach the catalytic reaction chamber from the mixing chamber, the temperature is lower than the self-ignition temperature.
It can be set as the manufacturing apparatus of the hydrogen containing gas provided with the temperature setting means which sets the temperature of the said mixing chamber and the said front chamber.

In the above method, the temperature on the higher side with respect to the partial oxidation lower limit temperature and the dew point temperature of the mixed gas is set as the front chamber lower limit temperature, and the self-ignition temperature is set as the front chamber upper limit temperature.
It is preferable to maintain the temperature of the mixed gas flowing through the front chamber at a temperature lower than the front chamber upper limit temperature and higher than the front chamber lower limit temperature.
As an apparatus for producing a hydrogen-containing gas using this method,
The higher temperature with respect to the partial oxidation lower limit temperature and the dew point temperature of the mixed gas is set as the front chamber lower limit temperature, and the self-ignition temperature is set as the front chamber upper limit temperature.
An apparatus for producing a hydrogen-containing gas comprising a front chamber mixed gas temperature maintaining means for maintaining the temperature of the mixed gas flowing through the front chamber at a temperature lower than the upper limit temperature of the front chamber and higher than the lower limit temperature of the front chamber; it can.

  Water vapor is mixed in the mixed gas used in the method for producing a hydrogen-containing gas according to the present application, and generation of condensation (water) becomes a problem. Here, the dew point temperature of the mixed gas referred to in the present application is a temperature at which the partial pressure of water vapor at that portion becomes a saturated water vapor pressure, and is a temperature at which dew condensation occurs when only the temperature decreases in that environment. When the temperature of the reaction system is brought close to the lower limit temperature at which partial oxidation can occur in the reforming reaction, condensation may occur depending on the state of the mixed gas. When condensation occurs, it becomes an impediment to the catalytic reaction and a good gas flow cannot be secured. Therefore, regarding the state of the mixed gas, taking into consideration the dew point temperature as well, ensuring the gas state of the mixed gas in the front chamber can maintain a good operating state.

  Furthermore, in the above configuration, it is preferable that the temperature of the anterior chamber is led to the anterior chamber lower limit temperature side. As an apparatus for producing a hydrogen-containing gas that employs this configuration, the temperature of the front chamber is led to the lower limit temperature side of the front chamber.

  In the reaction system in which partial oxidation is performed as in the present application, the reaction in the catalytic reaction chamber proceeds excessively, and its peak temperature (the highest temperature in the catalytic reaction chamber) is important for maintaining a good reaction state. Element. That is, when this peak temperature reaches the vicinity of the thermal decomposition temperature of the mixed gas (especially hydrocarbon fuel), carbon is generated and the catalytic activity is affected. Since this peak temperature is governed by the inlet temperature of the catalytic reaction chamber, a lower limit is set for this inlet temperature (substantially the temperature of the front chamber) as in the present application, and control is performed so as to approach it. Thus, stable operation can be maintained.

On the other hand, it is good also as adjusting the temperature of the said mixing chamber, the said front chamber, or both according to the typical temperature of a catalyst reaction chamber, for example, peak temperature. In this case, the hydrogen-containing gas production apparatus adjusts the temperature of the mixing chamber and / or the front chamber according to the representative temperature of the catalytic reaction chamber.
As previously indicated, the reaction state of the catalytic reaction chamber follows the upstream state. Therefore, by controlling the temperature of this part according to the representative temperature of the catalytic reaction chamber, the state in the catalytic reaction chamber can be brought to a desired state.

Now, in the method described so far,
The mixing chamber is provided downstream of the source gas chamber into which the source gas is introduced, and the mixing step is performed in the mixing chamber.
In order to produce a hydrogen-containing gas by introducing the mixed gas from the mixing chamber through the front chamber into the catalytic reaction chamber,
It is preferable that the flow rate of the mixed gas in the mixing chamber and the front chamber be higher than the minimum flow rate of the raw material gas in the raw material gas chamber.
As a device for producing hydrogen-containing gas,
The mixing chamber is provided on the downstream side of the source gas chamber into which the source gas is introduced,
The flow rate of the mixed gas in the mixing chamber and the front chamber is made higher than the minimum flow rate of the raw material gas in the raw material gas chamber.

  In the state where the oxygen-containing gas is mixed with the raw material gas, if the advection to the catalytic reaction chamber is delayed, the mixed gas is self-ignited. Therefore, self-ignition can be suppressed by increasing the flow velocity in the mixing chamber and the front chamber as much as possible.

Furthermore, it is also preferable to dispose flame propagation suppressing means for suppressing flame propagation from the catalytic reaction chamber to the upstream side in the front chamber.
By disposing the flame propagation suppressing means, even if extreme local self-ignition occurs in the front chamber, the propagation can be suppressed and the reaction system can be stabilized.

Furthermore, it is preferable to dispose a heat insulating material layer at a boundary side portion of the front chamber with the catalytic reaction chamber.
By doing in this way, it can prevent that the heat | fever from a catalyst reaction chamber is transmitted to an anterior chamber, and the state in the catalyst reaction chamber entrance vicinity can be stabilized by making both chambers thermally independent.

In the method for producing a hydrogen-containing gas described so far, it is preferable that the concentration of the sulfur compound in the mixed gas introduced into the catalytic reaction chamber is 1 ppb or less.
As the sulfur compound concentration of the mixed gas supplied to the catalytic reaction chamber increases, the peak temperature of the reaction occurring in the catalytic reaction chamber tends to increase. When the reforming catalyst is ruthenium, the peak temperature in the catalytic reaction chamber can be set to a temperature at which a stable reaction can be obtained by setting the sulfur compound concentration to 1 ppb or less. Here, it may be 1 ppb or less, and the lower limit thereof is not questioned. By reducing this concentration, deterioration of the reforming catalyst can be avoided.

Hereinafter, the hydrogen containing gas manufacturing apparatus 1 which concerns on this application is demonstrated based on drawing.
[GTL manufacturing process]
FIG. 1 shows the configuration of a GTL (Gas To Liquids) production process 3 provided with a hydrogen-containing gas production apparatus 1 according to the present application on the upstream side of a GTL reactor 2 using a hydrogen-containing gas as a raw gas. . As shown in the figure, this system 3 is configured to include the hydrogen-containing gas production apparatus 1 of the present application on the upstream side of the GTL reactor 2, and the hydrogen-containing gas production apparatus 1 includes carbonization of natural gas or the like. Hydrogen-based fuel f, water vapor s and oxygen-containing gas O are supplied, and after reforming, hydrogen-rich gas h is sent to the GTL reactor 2.
In addition to the natural gas, hydrocarbon fuels include gas, alcohol, ether, LPG, naphtha, gasoline, kerosene, light oil, heavy oil, asphaltene oil, oil sand oil, coal liquefied oil, shale oil, GTL (Gas Liquid fuel manufactured by To Liquids), waste plastic oil, biofuel, etc. can be used.

The processing system for the hydrocarbon fuel f will be described. The hydrocarbon fuel f is desulfurized to 1 ppb or less by the desulfurization device 4, and then steam s is added to form the raw material gas f1 referred to in the present application. Oxygen O is further mixed with the raw material gas f1 as shown in the figure and introduced into the single catalytic reaction chamber 5. In the catalytic reaction chamber 5, a reforming catalyst c1 capable of generating an autothermal reforming reaction with respect to the mixed gas f2 in which the hydrocarbon fuel f, the steam s, and the oxygen O are mixed is disposed. In the catalytic reaction chamber 5, a partial oxidation reaction mainly occurs at the inlet side portion, and a steam reforming reaction mainly occurs at the downstream side.
Specifically, noble metal catalysts such as rhodium, iridium, platinum, palladium, and ruthenium are preferably used as this type of reforming catalyst, and nickel-based and cobalt-based catalysts can also be applied. Moreover, only 1 type may be used for a metal and it can also use 2 or more types together as needed. These catalysts may have any shape, and there is no particular limitation on the carrier. Desirably, a carrier mainly composed of one kind selected from alumina, zirconia, silica, titania, magnesia, and calcia is preferable. Then, it is preferably used in the form of a tablet-shaped, spherical, ring-shaped molded product, or molded into a honeycomb shape.
A typical example of the production of this type of catalyst will be described in the case where ruthenium is supported on an alumina support. For example, a spherical alumina support (diameter 4 to 6 mm) is immersed in an aqueous ruthenium chloride (RuCl ₃ .3H ₂ O) solution. It can be prepared by drying in air at 80 ° C. for 2 hours, followed by immobilization (treatment with aqueous NaOH) and hydrogen reduction.

  In the present application, the introduction mode of the mixed gas f2 into the catalytic reaction chamber 5 is assumed to be favorable so that the autothermal reforming reaction is favorably generated in the catalytic reaction chamber 5. Here, the favorable generation of reaction means that a partial oxidation reaction occurs only in the vicinity of the inlet 5a, and that there is no generation of carbon in the catalytic reaction chamber 5 is an important requirement. By appropriately controlling the state (particularly the temperature state) of the mixed gas f2 in 5a, it means that the state in the reaction chamber appropriately changes from the partial oxidation single state to the partial oxidation state including steam reforming.

  As shown in FIG. 1, the catalytic reaction chamber 5 is arranged in a vertical vertical direction, and a raw material gas f <b> 1 (a gas obtained by mixing water vapor s with a hydrocarbon fuel f) is supplied from the upper side. Is introduced from an inlet 5a provided on the upper side of the catalytic reaction chamber 5, finishes the reforming reaction, and the hydrogen rich gas h is sent from the lower side of the catalytic reaction chamber 5 to the GTL reactor 2 side. It is done. Hereinafter, a specific configuration of the hydrogen-containing gas production apparatus 1 according to the present application will be described with reference to FIGS.

[Hydrogen-containing gas production equipment]
The hydrogen-containing gas production apparatus 1 is configured to take steps up to desulfurization, steam addition, oxygen mixing and reforming for the hydrocarbon fuel f described above.
The desulfurization is performed in the desulfurization chamber 6, and a raw material gas f <b> 1 in which water vapor s is mixed with the hydrocarbon fuel f delivered from the desulfurization chamber 6 is generated. FIG. 2 shows a specific configuration of the source gas chamber 7, the mixing chamber 8, the front chamber 9, and the catalytic reaction chamber 5 in this apparatus 1. Since the present application is characterized by the configuration of the front chamber 9 and its usage, only the upper side of the catalytic reaction chamber 5 is shown in FIG. The outlet provided on the lower side of the catalytic reaction chamber 5 is connected to the hydrogen inlet 2a of the GTL reactor 2 through the outlet 5b through a connecting pipe 5c.

Desulfurization The desulfurization chamber 6 is provided with a desulfurization catalyst c2 such as a copper-zinc high-order desulfurization catalyst mixed with copper oxide, zinc oxide or the like. In this chamber 6, the sulfur compound concentration is set to 1 ppb or less. By desulfurizing to this concentration, the concentration of sulfur compound in the mixed gas introduced into the catalytic reaction chamber 5 is also 1 ppb or less.
In addition to the above-described copper zinc-based high-order desulfurization catalyst, silver-based catalysts, and desulfurization catalysts containing nickel, chromium, manganese, iron, cobalt, palladium, iridium, platinum, ruthenium, rhodium, gold, etc. can also be employed. .

The hydrocarbon-based fuel f that has undergone steam mixing and desulfurization is added with steam s that is separately supplied through the steam supply pipe 10. Here, the amount of water vapor s with respect to the hydrocarbon-based fuel f is 0.1 to 3.0 (preferably with the ratio of water vapor H ₂ O to carbon C contained in the fuel as a molar ratio [H ₂ O / C]. 0.1 to 1.0). Moreover, the temperature in this part is about 200-400 degreeC (preferably 200-300 degreeC). The gas thus obtained is referred to as a raw material gas f1 in the present application.

  On the other hand, as shown in FIGS. 1 and 2, the hydrogen-containing gas production apparatus 1 of the present application is supplied with a hydrocarbon-based fuel f or water vapor s, or a purge gas p such as a raw material gas f1 or an inert gas. As described so far, oxygen O is also supplied. These gases are appropriately reacted in the reforming unit 11 described in detail below.

Reforming unit 11
As shown in FIG. 2, the reforming unit 11 includes a source gas chamber 7, a mixing chamber 8, and a front chamber 9 on the upper side of the unit, and a catalytic reaction chamber 5 on the lower side. Yes.
The upper side of the reforming unit 11 has a substantially double-pipe structure, and is configured such that the purge gas p can be supplied to the lower region of the front chamber 9 through the inner pipe 11a. Further, as shown in FIG. 2, a thermocouple t1 for temperature measurement is disposed in the inner tube 11a so as to extend to the middle part of the front chamber, and the representative temperature (inlet temperature) of the front chamber 9 is set. It is configured to be measurable.

Source gas chamber 7
As shown in FIG. 2, the source gas chamber 7 has an introduction port 7a into which the source gas f1 mixed with water vapor s is introduced, an intermediate passage portion 7b in which the introduction port 7a is opened, and a flow from the intermediate passage portion 7b. The passage section 7c is configured to have a large passage section. A mixing chamber 8 is provided on the lower side of the flow path expanding portion 7c.

Mixing chamber 8
The mixing chamber 8 employs a so-called shell-and-tube type mixing structure. From the oxygen chamber 8b provided outside the channel 8a into which the raw material gas f1 flows from the channel expanding portion 7c. , Oxygen O flows in. Therefore, when oxygen O flows into the source gas f1, a mixed gas f2 in which the source gas f1 and oxygen O are mixed can be formed in the tube 8a.
As shown in the figure, the tube 8a is extended on the lower side beyond the separation distance between the partition plates 8c and 8c that divide the mixing chamber 8. By flowing down this flow path, sufficient mixing can be achieved. It is configured to obtain a state.
Here, the amount of oxygen O relative to the hydrocarbon-based fuel f is 0.05 to 1.0 (preferably 0), where the ratio of oxygen O ₂ to carbon C contained in the fuel is [O ₂ / C] in molar ratio. .3 to 0.7). Moreover, the temperature in this part is about 200-400 degreeC (preferably 200-300 degreeC). The gas thus obtained is referred to as a mixed gas f2 in the present application.

Front room 9
The front chamber 9 is provided so as to serve as an adjustment chamber for the catalyst reaction chamber 5, and the introduction portion 9 a from which the tube 8 a described above is extended, and the introduction portion 9 a and the catalyst reaction chamber 5 And an adjusting portion 9b provided therebetween.
As shown in the drawing, tubes 8a penetrate and extend downward from the introduction portion 9a, and the mixed gas f2 is discharged from the tips of these tubes 8a. The outer peripheral portion 9c of the tube 8a is solid, and gas does not stay. Further, the structure in which the purge gas p described above is supplied to the tip of the introduction portion 9a through the inner pipe 11a is adopted, and the mixed gas f2 is provided by the supply of the purge gas p and the solid structure outside the tube 8a. Ascending to the upper side and stagnation do not occur.

The adjusting portion 9b appropriately adjusts the temperature of the front chamber 9 at this portion, and further mixes the mixed gas f2 flowing through the tube 8a, which is a relatively narrow flow path, while slightly expanding the flow path. Introducing into the catalytic reaction chamber 5 is performed smoothly. Therefore, as shown in FIG. 2, in the gas flow path 9d through which the mixed gas f2 flows in the adjusting portion 9b, the cross-sectional area is slightly increased and the gas flow velocity is decreased.
In the configuration described so far, the flow path cross-sectional area is set so that the flow velocity of the mixed gas f2 in the mixing chamber 8 and the front chamber 9 is higher than the minimum flow velocity of the raw material gas f1 in the raw material gas chamber 7. Therefore, a configuration is adopted in which the residence time of the mixed gas f2 in this chamber is made as short as possible.

As shown in the figure, an alumina block 9e and a porous block 9f made of silicon nitride are provided on the upper side and the lower side of the adjustment unit 9b, respectively, in a state where the gas flow path 9d of the adjustment unit 9b is formed. ing. The reason for providing these materials is to prevent heat from the catalytic reaction chamber 5 from propagating to the upstream side and to perform heat insulation well. In the figure, a ceramic rope 9g is installed on the outer diameter side portion of the block 9f so that gas does not flow between the block 9 and the refractory material.
Further, in the example shown in FIG. 2, a heat insulating material 9 h having air permeability is disposed in the gas flow path 9 d of the adjusting portion 9 b, and the heat insulating and mixed unreacted gas at the boundary between the catalytic reaction chamber 5 and the front chamber 9 is disposed. Convection prevention is ensured.

Catalytic reaction chamber 5
The catalytic reaction chamber 5 is a main part of the hydrogen-containing gas production apparatus 1 according to the present application, and is a part where the reforming catalyst c1 is disposed as described above.
Further, the gas space velocity per a total gas flow rate supplied to the catalytic reaction chamber 5 times (however, the standard values of the state conversion) ^{750h -1} ~300000h -1 (preferably ^{10000h -1 ~300000h} -1 in, more preferably 50,000 h ^{−1 to} 300,000 h ⁻¹ ).

  There is no particular limitation on the pressure during the reaction. The reaction pressure can be changed depending on the application. As shown in the examples, when used for synthesizing liquid fuel such as GTL, it is used at about 2 to 7 MPa. On the other hand, when used for hydrogen production for fuel cells, it is used near normal pressure (for example, 1 MPa or less).

The above is the configuration of the hardware side of the hydrogen-containing gas production apparatus 1 according to the present application. However, in this apparatus configuration, the reaction state in the front chamber 9 and the catalytic reaction chamber 5 is appropriate for the apparatus of the present application. It is configured to
That is, the device 1 of the present application is devised to optimize the inlet temperature of the mixed gas f2 to the catalytic reaction chamber 5. For example, in the configuration described so far, the gas flow path 9d of the mixed gas f2 is made relatively small, and the flow rate in the flow path 9d is increased, whereby the residence time of the mixed gas f2 in the front chamber 9 is set to a fixed time. It is as follows. Further, the heat insulation at the boundary between the catalytic reaction chamber 5 and the front chamber 9 is made high so that the temperature of the catalytic reaction chamber 5 does not affect the front chamber 9. Further, a purge gas p is introduced into the front chamber 9. Thus, the hardware side in the present application is to prevent the mixed gas f2 from flowing back and staying.

In the hydrogen-containing gas production apparatus 1 of the present application, as shown in FIG. 1, a control device 13 for controlling the reaction state is provided, and the type of hydrocarbon-based fuel f and input into the system are provided. The control device 13 can monitor the amount and temperature, the amount and temperature of steam s input into the system, and the amount and temperature of oxygen input into the system.
On the other hand, as shown in FIG. 2, the inlets and outlets (catalysts) of the adjusting portion 9b of the front chamber 9 are formed by the thermocouples t1 and t2 inserted into the unit 11 from the upper and lower sides of the reforming unit 11 described above. The temperature at the inlet 5a) of the reaction chamber and the temperature in the flow direction in the catalyst reaction chamber 5 can also be monitored.
And according to the control command from the control apparatus 13, the hydrocarbon fuel injection amount, the water vapor input amount, and the oxygen input amount into the hydrogen-containing gas production device 1 can be adjusted.

Now, the configuration of the control device 13 will be described. As shown in FIGS. 1 and 3, the control device 13 has a lower limit temperature at which the reforming catalyst c1 causes a partial oxidation reaction as a partial oxidation lower limit temperature T1, a steam reforming reaction. The lower limit temperature that causes the steam reforming lower limit temperature T2 is the advection required for the mixed gas f2 to reach the catalytic reaction chamber 5 from the mixing chamber 8 at a temperature not lower than the partial oxidation lower limit temperature T1 and lower than the steam reforming lower limit temperature T2. A temperature setting means 13a for setting the temperatures of the mixing chamber 8 and the front chamber 9 to a temperature lower than the self-ignition temperature with respect to the self-ignition temperature T3, which is a temperature at which the mixed gas f2 self-ignites with time, is provided. .
Further, with respect to this temperature setting means 13a, the higher temperature with respect to the partial oxidation lower limit temperature and the dew point temperature T4 of the mixed gas f2 is set as the front chamber lower limit temperature, and the self-ignition temperature of the mixed gas f2 is set as the front chamber upper limit temperature. A front chamber mixed gas temperature maintaining means (simply referred to as temperature maintaining means in FIG. 1) 13b for maintaining the temperature of the mixed gas f2 flowing through the front chamber 9 at a temperature lower than the upper limit temperature of the front chamber and higher than the lower limit temperature of the front chamber is provided. It has been.

Hereinafter, the lower limit temperature and the upper limit temperature in the control device 13 will be described.
Lower limit temperature The partial oxidation lower limit temperature is the lower limit temperature T1 at which the mixed gas f2 comes into contact with the reforming catalyst c1 to cause a partial oxidation reaction. The lower limit temperature T1 is determined by the reforming catalyst c1 accommodated in the catalyst reaction chamber 5. . For example, when the reforming catalyst c1 is a ruthenium-based catalyst as described above, the temperature is about 200 ° C., and when the reforming catalyst c1 is a rhodium-based catalyst, the temperature is about 300 ° C. Therefore, the partial oxidation lower limit temperature is stored and stored in the storage unit 13c provided in the control device 13, and the partial oxidation lower limit temperature T1 can be appropriately read and used on the control device 13 side.

  On the other hand, for the mixed gas f2, the dew point temperature T4 of the mixed gas is determined according to the mixing ratio and pressure of the hydrocarbon fuel f, water vapor s and oxygen O. Therefore, dew point data according to the mixing ratio of each gas is stored in the storage means 13c, and by using this data, the dew point temperature T4 of the mixed gas f2 present in the front chamber 9 at present is calculated. It can be estimated from the amount of gas input.

  Therefore, in the control device 13, according to the partial oxidation lower limit temperature T1 based on the type of the reforming catalyst c1 and the dew point temperature T4 of the mixed gas f2 estimated from the composition of the mixed gas f2 estimated to exist in the front chamber, A lower limit temperature (anterior chamber lower limit temperature) is obtained as the higher temperature of both.

The upper limit temperature steam reforming lower limit temperature is the lower limit temperature T2 at which the mixed gas f2 comes into contact with the reforming catalyst c1 to cause the steam reforming reaction, and the steam reforming is performed by the reforming catalyst c1 stored in the catalyst reaction chamber 5. The lower limit temperature T2 is determined. For example, when the reforming catalyst c1 is a ruthenium-based catalyst as described above, the temperature is about 400 ° C., and when the reforming catalyst c1 is a nickel-based catalyst, the temperature is about 400 ° C. Therefore, the steam reforming lower limit temperature T2 is stored and stored in the storage means 13c provided in the control device 13, and the steam reforming lower limit temperature T2 can be appropriately read and used on the control device 13 side. Yes.

The autoignition temperature T3 of the mixed gas f2 present in the front chamber 9 is also taken into consideration for the steam reforming lower limit temperature T2. That is, the self-ignition temperature T3 is determined by the composition of the mixed gas f2 in the front chamber 9 and the residence time in the front chamber 9 (this residence time refers to the mixing chamber 8 after the oxygen O is mixed in the mixing chamber 8). It is the time from the exit to the inlet 5a of the catalytic reaction chamber 5, and in the case of the present application, the maximum required amount of the mixed gas f2 from the inside of the tube 8a on the outlet side of the mixing chamber 8 to the inlet 5a of the catalytic reaction chamber 5 Depends on time).
Accordingly, the storage means 13c stores a self-ignition temperature T3 according to the composition state of the mixed gas f2 that is ignited for the first time in the maximum required advection time (residence time). It is possible to obtain the upper limit temperature in relation to the temperature T2. FIG. 4 shows the relationship between the residence time (indicated as “ignition delay time” in the figure) and the self-ignition temperature T3 (indicated as “mixed gas temperature” in the figure) with respect to the mixed gas f2. In the figure, the mixed gas f2 is a hydrocarbon-based fuel natural gas, and [N ₂ / C] and [O ₂ / C] are (0.6 to 1.0) and (0.1 or 0.4). The pressure of the mixed gas in this state is 4 MPa.

  In the control device 13, the temperature setting means 13a and the front chamber mixed gas temperature maintaining means 13b adjust the hydrocarbon fuel input amount, the steam input amount, the oxygen input amount, etc. according to the method described above. Ensure good driving conditions.

Now, maintaining the temperature of the front chamber mixed gas f2 between the upper limit temperature and the lower limit temperature of the front chamber means that the temperature of the mixed gas at the inlet 5a of the catalytic reaction chamber 5 is adjusted appropriately. To do. This temperature leads to appropriate control of the reaction temperature in the catalytic reaction chamber 5.
Therefore, the temperature setting means 13a and the front chamber mixed gas temperature maintaining means 13b satisfy the requirements related to the front chamber upper limit temperature and the lower limit temperature, and the mixed gas f2 in the front chamber 9 according to the representative temperature of the catalytic reaction chamber 5. The structure which adjusts the temperature of is adopted. For example, with the deterioration of the catalyst c1 accommodated in the catalytic reaction chamber 5, the partial oxidation reaction is delayed, and the temperature of the catalytic reaction chamber 5 is delayed to cause the steam reforming reaction (resulting in the catalytic reaction). The peak temperature position in the chamber 5 moves downstream or the peak temperature rises). Therefore, the temperature of the front chamber can be adjusted.
This type of temperature adjustment can be performed by adjusting the amount of water vapor or oxygen with respect to the hydrocarbon fuel.

Hereinafter, the operation state of the hydrogen-containing gas production device 1 according to the present application by the control device 13 will be described.
1 When the mixed gas temperature in the front chamber 9 is within the front chamber upper limit temperature (autoignition lower limit temperature) and the front chamber lower limit temperature (the higher of the partial oxidation lower limit temperature and the dew point temperature) In this case, in the catalytic reaction chamber 5 The reaction is presumed to be in an appropriate state. However, in order to keep the state of the catalytic reaction chamber 5 stable even in such an appropriate state, the temperature of the mixed gas f2 in the front chamber 9 is set to the front chamber upper limit temperature and the front chamber lower limit temperature. In this range, the temperature is controlled according to the temperature (for example, peak temperature) of the catalytic reaction chamber 5. By doing so, a stable and proper operating state can be maintained.

[Another embodiment]
Another embodiment of the present application will be described.
(1) In the above-described embodiment, a gas flow path having substantially the same diameter as the tube extending from the mixing chamber is provided in the adjustment section of the front chamber, and the flow rate of the mixed gas is controlled via the tube and the gas flow path. Although an example in which the residence time is shortened while maintaining a relatively high level and the mixed gas is guided to the catalytic reaction chamber has been shown, as shown in FIG. 5, a combined flow path 90 is provided downstream from the outlet of the tube 8a. The mixed gas f <b> 2 may be caused to flow into the catalytic reaction chamber 5 through 90. However, the cross-sectional area of this combined flow path 90 can realize a flow velocity that reaches the catalytic reaction chamber in a time that is less than the self-ignition time under the temperature condition of this part. In this way, the properties of the mixed gas f2 can be made uniform, and the diffusion of the mixed gas f2 in the cross section direction of the catalytic reaction chamber in the vicinity of the inlet of the catalytic reaction chamber 5 can be improved.
(2) In the above embodiment, the hydrogen-containing gas production apparatus is provided with the temperature setting means 13a and the front chamber mixed gas temperature maintaining means 13b, and positively inputs water vapor and oxygen to the hydrocarbon fuel. The amount was controlled and the reaction in the catalytic reaction section was maintained in an appropriate state. However, when the normal operation state was almost fixed, the reforming unit 11 described above in each chamber 7, 8, 9 Since the flow velocity is substantially determined, the flow path cross-sectional configuration may be configured so that the temperature of the mixed gas in the front chamber 9 is appropriate.
That is, when the partial oxidation lower limit temperature is determined by the reforming catalyst c1 and the gas composition of the mixed gas f2 is determined, the dew point temperature is determined, and thus the anterior chamber lower limit temperature referred to in the present application is determined.
On the other hand, with respect to the front chamber upper limit temperature, the steam reforming lower limit temperature is determined by the reforming catalyst c1, and the mixed gas depends on the shape of the gas flow path 9d in the tube 8a through which the mixed gas f2 flows and the adjusting section 9b on the downstream side. The maximum time until f2 reaches the catalytic reaction chamber 5 from the mixing chamber 8 is determined. Therefore, the relationship between the temperature and the residence time of the mixed gas shown in FIG. 4 as described above is obtained in advance, and even when the mixed gas f2 stays in the front chamber for the residence time, the mixed gas f2 The object of the present application can be achieved by setting the temperature at which the self-ignition does not occur to the upper limit temperature of the front chamber.
(3) In the above embodiment, an example is shown in which the temperature of the mixed gas in the front chamber is controlled according to the representative temperature of the catalytic reaction chamber. Basically, partial oxidation is performed at the inlet of the catalytic reaction section. Since it is sufficient if the reaction can be generated, the temperature of the mixed gas in the front chamber is led to the front chamber lower limit temperature side in order to configure the control of the temperature setting unit 13a and the temperature maintaining unit 13b of the front chamber mixed gas described above. It can also be configured.
In this case, the reaction can be controlled in such a direction as to avoid the generation of carbon that is likely to be a problem in the catalytic reaction portion while ensuring the occurrence of the partial oxidation reaction necessary for the reforming.
(4) In the above embodiment, when the mixed gas stays in the front chamber and the mixed gas stays in the front chamber for the residence time, the mixed gas is heated to a temperature at which self-ignition does not occur. Although an example of performing reforming by setting a chamber has been shown, a means for actively preventing flame propagation may be provided in the front chamber.
FIG. 6 shows such an example. A frame arrester 60 is disposed at the tip of the tube 8a, and the inner wall 61 of the gas flow path 9d and the stagnation portion 62 are coated with gold for preventing flame propagation. A covering process w is performed. Even in this way, flame formation and propagation in the front chamber 9 can be prevented. In this way, a configuration that suppresses the flame propagation from the catalytic reaction chamber 5 to the upstream side in the front chamber 9 is referred to as flame propagation suppression means.
(5) In the embodiment described so far, an example in which a steam reforming reaction is caused after adding a steam to a hydrocarbon-based fuel and undergoing a partial oxidation reaction has been shown. A carbon dioxide reforming reaction may be caused. This carbon dioxide reforming reaction is also an endothermic reaction, and the reaction form follows the chemical formula 3 shown below.

FIG. 7 shows a configuration example of a GTL manufacturing process for performing steam reforming according to Chemical Formula 2 and carbon dioxide reforming according to Chemical Formula 3 in correspondence with FIG. Although the equipment configuration is the same as that shown in FIG. 1, in the example shown in FIG. 1, only the steam s is added to the hydrocarbon fuel f to obtain the raw material gas f1, whereas in this example, Water vapor s and carbon dioxide CO ₂ are also added to obtain a raw material gas f1. In this GTL manufacturing process, both the steam reforming reaction and the carbon dioxide reforming reaction can proceed.
Even in such a reaction mode, in the method and apparatus for producing a hydrogen-containing gas according to the present application, the state in the front chamber and the subsequent catalytic reaction chamber can be made as desired.

The figure which shows the structure of the GTL manufacturing process provided with the manufacturing apparatus of the hydrogen containing gas which concerns on this invention. Diagram showing the upper structure of the reforming unit Diagram showing the relationship between the inlet temperature in the catalytic reaction chamber and the temperature in the catalytic reaction chamber Diagram showing the relationship between the mixed gas temperature and the ignition delay time Diagram showing another configuration example of the front chamber The figure which shows the example which provided the flame propagation suppression means in the front chamber structure corresponding to FIG. The figure which shows the structural example of another implementation which adds the carbon dioxide corresponding to FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Hydrogen-containing gas production apparatus 2 GTL reactor 5 Catalytic reaction chamber 7 Raw material gas chamber 8 Mixing chamber 8a Tube 8b Oxygen chamber 9 Front chamber 11 Reforming unit 13 Controller 13a Temperature setting means 13b Temperature maintaining means 13c Storage means c1 Catalyst c2 desulfurization catalyst f hydrocarbon fuel f1 raw material gas f2 mixed gas h hydrogen rich gas O oxygen p purge gas s water vapor

Claims (15)

A mixing step of mixing an oxygen-containing gas in a mixing chamber with a raw material gas in which water vapor and hydrocarbon fuel are mixed;
The mixed gas obtained in the mixing chamber is led to the catalytic reaction chamber through a front chamber provided upstream of the catalytic reaction chamber, and the mixed gas is brought into contact with the reforming catalyst to perform partial oxidation reaction and steam reforming. A method for producing a hydrogen-containing gas, comprising performing a reforming step of obtaining a hydrogen-containing gas by a reaction,
The lower limit temperature at which the reforming catalyst causes the partial oxidation reaction is defined as a partial oxidation lower limit temperature, and the lower limit temperature at which the reforming catalyst undergoes the steam reforming reaction is defined as a steam reforming lower limit temperature. At a temperature of
With respect to the self-ignition temperature that is the temperature at which the mixed gas self-ignites in the advection time required for the mixed gas to reach the catalytic reaction chamber from the mixing chamber, the temperature is lower than the self-ignition temperature.
A method for producing a hydrogen-containing gas, wherein the temperature of the mixing chamber and the front chamber is set and the mixed gas is introduced into the catalytic reaction chamber. The higher temperature with respect to the partial oxidation lower limit temperature and the dew point temperature of the mixed gas is set as the front chamber lower limit temperature, and the self-ignition temperature is set as the front chamber upper limit temperature.
The method for producing a hydrogen-containing gas according to claim 1, wherein the temperature of the mixed gas flowing through the front chamber is maintained at a temperature lower than the upper limit temperature of the front chamber and higher than the lower limit temperature of the front chamber. The method for producing a hydrogen-containing gas according to claim 2, wherein the temperature of the front chamber is led to the lower limit temperature side of the front chamber. The method for producing a hydrogen-containing gas according to claim 1 or 2, wherein the temperature of the mixing chamber or the front chamber or both of them is adjusted according to a representative temperature in the catalytic reaction chamber . The mixing chamber is provided on the downstream side of the source gas chamber into which the source gas is introduced, and the mixing step is performed in the mixing chamber.
In order to produce a hydrogen-containing gas by introducing the mixed gas from the mixing chamber through the front chamber into the catalytic reaction chamber,
The method for producing a hydrogen-containing gas according to any one of claims 1 to 4, wherein a flow rate of the mixed gas in the mixing chamber and the front chamber is set higher than a minimum flow rate of the raw material gas in the raw material gas chamber. The method for producing a hydrogen-containing gas according to any one of claims 1 to 5, wherein a heat insulating material layer is disposed at a boundary side portion of the front chamber with the catalytic reaction chamber. The method for producing a hydrogen-containing gas according to any one of claims 1 to 6, wherein flame propagation suppression means for suppressing flame propagation from the catalytic reaction chamber to the upstream side is disposed in the front chamber. The method for producing a hydrogen-containing gas according to any one of claims 1 to 7, wherein the concentration of the sulfur compound in the mixed gas introduced into the catalytic reaction chamber is 1 ppb or less. A mixing chamber for mixing an oxygen-containing gas with a raw material gas in which water vapor and hydrocarbon fuel are mixed;
The mixed gas obtained in the mixing chamber is led to the catalytic reaction chamber through a front chamber provided upstream of the catalytic reaction chamber, and the mixed gas is brought into contact with the reforming catalyst to perform partial oxidation reaction and steam reforming. A hydrogen-containing gas production apparatus for obtaining a hydrogen-containing gas by a reaction,
The lower limit temperature at which the reforming catalyst causes the partial oxidation reaction is defined as a partial oxidation lower limit temperature, and the lower limit temperature at which the reforming catalyst undergoes the steam reforming reaction is defined as a steam reforming lower limit temperature. At a temperature of
With respect to the self-ignition temperature that is the temperature at which the mixed gas self-ignites in the advection time required for the mixed gas to reach the catalytic reaction chamber from the mixing chamber, the temperature is lower than the self-ignition temperature.
An apparatus for producing a hydrogen-containing gas, comprising temperature setting means for setting the temperature of the mixing chamber and the front chamber. The higher temperature with respect to the partial oxidation lower limit temperature and the dew point temperature of the mixed gas is set as the front chamber lower limit temperature, and the self-ignition temperature is set as the front chamber upper limit temperature.
The production of a hydrogen-containing gas according to claim 9, further comprising a front chamber mixed gas temperature maintaining means for maintaining the temperature of the mixed gas flowing through the front chamber at a temperature lower than the front chamber upper limit temperature and higher than the front chamber lower limit temperature. apparatus. The apparatus for producing a hydrogen-containing gas according to claim 10, wherein the temperature of the front chamber is led to the lower limit temperature side of the front chamber. The apparatus for producing a hydrogen-containing gas according to claim 9 or 10, wherein the temperature of the mixing chamber and / or the front chamber is adjusted according to a representative temperature in the catalytic reaction chamber . The mixing chamber is provided downstream of the source gas chamber into which the source gas is introduced,
The apparatus for producing a hydrogen-containing gas according to any one of claims 9 to 12, wherein a flow rate of the mixed gas in the mixing chamber and the front chamber is set higher than a minimum flow rate of the raw material gas in the raw material gas chamber. The apparatus for producing a hydrogen-containing gas according to any one of claims 9 to 13, further comprising a heat insulating material layer having air permeability at a boundary side portion of the front chamber with the catalytic reaction chamber. The apparatus for producing a hydrogen-containing gas according to any one of claims 9 to 14, further comprising flame propagation suppressing means for suppressing flame propagation from the catalytic reaction chamber to the upstream side in the front chamber.

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