JP2008133143A - Apparatus and method for producing hydrogen - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an apparatus for producing hydrogen which prevents a radiant heat to a hydrogen producing reaction tube and has a simple composition and a method for producing hydrogen. <P>SOLUTION: The apparatus for producing hydrogen 10A consists of a hydrogen producing reaction tube 101 which is installed in the main body of the apparatus for producing hydrogen 100a and has a preparatory reforming catalyst part 107 in its inside containing a preparatory reforming catalyst which preparatorily reforms a raw material gas G where the raw material gas G is reformed into hydrogen and only the hydrogen formed is collected, a burner 113 which is installed at the main body of the apparatus for producing hydrogen 100a and heats the hydrogen producing reaction tube 101, and a steam generating part 12 which is installed at the main body of the apparatus for producing hydrogen 100a and generates steam 11 to be supplied to the raw material gas G. The burner 113 is installed opposite to the preparatory reforming catalyst part 107 which is located in the hydrogen producing reaction tube 101 and the steam generating part 12 is installed between the hydrogen producing reaction tube 101 and the burner 113. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a hydrogen production apparatus and a hydrogen production method for producing hydrogen using hydrocarbons such as city gas and steam as raw materials.

Development of a hydrogen production system that produces hydrogen using hydrocarbons such as city gas and steam as raw materials is underway, and steam reforming reaction on a reforming catalyst in a hydrogen production reaction tube is one way to obtain hydrogen. and it generates the hydrogen (H ₂₎ by CO shift reaction, only the generated hydrogen (H ₂₎ by the recovering, hydrogen production apparatus is used for producing high-purity hydrogen (H _2).

As an example of a conventional hydrogen production apparatus, a conventional hydrogen production apparatus is shown in FIG. FIG. 5 is a diagram showing a configuration of a conventional hydrogen production apparatus (left), a gas temperature in a hydrogen production reaction tube, and an active state of a catalyst (right). As shown in the left side view of FIG. 5, a conventional hydrogen production apparatus 100 includes a hydrogen production reaction tube 101 and a combustion chamber 102 in a hydrogen production apparatus main body 100a. The hydrogen production reaction tube 101 is a raw material that supplies, into the hydrogen production reaction tube 101, a mixed gas 105 obtained by mixing steam 104 supplied from a steam generator 103 with a raw material gas G made of hydrocarbon such as city gas. A gas supply pipe 106; and a pre-reforming catalyst unit 107 filled with a pre-reforming catalyst for pre-reforming the raw material gas G in the mixed gas 105 fed into the hydrogen production reaction pipe 101; A hydrocarbon or oxygen-containing hydrocarbon in the raw material gas G is converted in the reforming catalyst unit 108 to generate hydrogen (H ₂ ), and a hydrogen separation membrane 109a through which only the generated hydrogen (H ₂ ) can pass is formed. the hydrogen separation membrane module 109 having, for recovering the hydrogen withdrawing pipe 110 for recovering hydrogen (H ₂₎ which has passed through the hydrogen separation membrane 109a, the raw material gas G and the off-gas 111 unreacted Ofuga Consisting of the discharge pipe 112.. The combustion chamber 102 is provided with a burner 113 for burning hydrocarbons or oxygen-containing hydrocarbons in the combustion gas supplied to the combustion chamber 102.

  By the burner 113, when the high-temperature combustion gas burned passes through the hydrogen production reaction tube 101, it comes into contact with the outer wall of the hydrogen production reaction tube 100 and heats the hydrogen production reaction tube 101. The reforming catalyst unit 108 is set to a temperature suitable for reforming the hydrocarbon in the raw material gas G.

Further, the mixed gas 105 fed into the hydrogen production reaction tube 101 is preliminarily stored in the preliminary reforming catalyst unit 107 provided on the combustion chamber 102 side in the hydrogen production reaction tube 101 in advance. Part of hydrocarbons such as methane and methanol in the raw material gas G is pre-reformed and converted into hydrogen, and hydrogen at the inlet of the hydrogen separation membrane 109a installed on the upper side of the pre-reform catalyst part 107 Increase partial pressure. Then, the reforming catalyst unit 108 mainly generates hydrogen and carbon dioxide from the hydrocarbons in the raw material gas G by a steam reforming reaction and a CO shift reaction, and generates hydrogen (H ₂ ) is selectively separated and recovered effectively.

  In addition, the temperature of the hydrogen separation membrane module 109 is preferably controlled to 500 to 550 ° C. from the viewpoint of the catalyst life of the reforming catalyst unit 108 and the pre-reforming catalyst unit 107 and the hydrogen permeation performance. Since the temperature on the combustion chamber 102 side of the reaction tube 101 for hydrogen production, which tends to be high, can be lowered by the endothermic reaction by the steam reforming reaction, local heating of the hydrogen separation membrane module 109 is suppressed, and the hydrogen The temperature in the production reaction tube 101 is kept uniform to improve the heat resistance of the hydrogen production reaction tube 101 (see, for example, Patent Document 1).

JP 2004-345926 A

  Here, the composition of the raw material gas G at the outlet of the pre-reforming catalyst unit 107 has almost reached the equilibrium composition at the gas temperature.

  For example, as shown in the right side of FIG. 5, the equilibrium composition is reached at the outlet of the pre-reforming catalyst unit 107 when the gas temperature is, for example, 550 ° C. Then, the reforming reaction further proceeds as the steam reforming reaction proceeds, and the temperature decreases due to the endotherm. Therefore, in order to obtain a sufficient endothermic amount by the endothermic reaction by the steam reforming reaction at the inlet portion of the hydrogen separation membrane 109a, the gas temperature of the source gas G at the inlet portion of the hydrogen separation membrane 109a is It is necessary to control the temperature to 550 ° C. or lower, preferably 500 to 530 ° C.

  However, in the actual operation of the hydrogen production apparatus 100, the temperature and flow rate vary for each of the hydrogen production reaction tubes 101, and the gas temperature of the mixed gas 105 is, for example, due to direct radiant heat transfer from the burner 113. The temperature may exceed 550 ° C., and abnormal heat generation of the preliminary reforming catalyst portion 107 below the hydrogen production reaction tube 101 cannot be prevented. There is a problem that the catalyst is easily deactivated, and deterioration cannot be prevented.

  Further, when the activity of the pre-reforming catalyst layer of the pre-reforming catalyst unit 107 is reduced due to radiant heat transfer from the burner 113, the pre-reforming catalyst is extracted from the reaction tube 101 for hydrogen production and replaced with a new one. There is also a problem that it is not easy to do.

  In view of the above problems, an object of the present invention is to provide a hydrogen production apparatus and a hydrogen production method that have a simple configuration by suppressing direct radiant heat to a hydrogen production reaction tube.

  The first invention of the present invention for solving the above-described problem has a pre-reforming catalyst portion provided in the hydrogen production apparatus main body and having a pre-reforming catalyst for pre-reforming the raw material gas, A hydrogen production reaction tube that reforms the raw material gas into hydrogen and collects only the produced hydrogen, a combustion section that is provided in the hydrogen production apparatus main body and heats the hydrogen production reaction tube, and the hydrogen production The hydrogen production apparatus is characterized in that it comprises a steam generating section that is provided in the apparatus main body and generates steam for supplying the raw material gas.

  According to a second invention, in the first invention, the combustion section is provided to face the preliminary reforming catalyst section disposed in the hydrogen production reaction tube, and the steam generation section is used for the hydrogen production. The hydrogen producing apparatus is provided between a reaction tube and the combustion section.

  According to a third aspect of the present invention, there is provided the hydrogen production apparatus according to the first aspect, wherein the steam generation unit and the combustion unit are provided via the hydrogen production reaction tube and a partition wall. .

  A fourth invention is characterized in that, in any one of the first to third inventions, the preliminary reforming catalyst section is provided outside the reaction tube for hydrogen production. In production equipment.

  A fifth aspect of the invention relates to the hydrogen production according to the third or fourth aspect of the invention, comprising a damper that controls the flow rate of the combustion gas supplied from the combustion section to the steam generation section. In the device.

  According to a sixth invention, in any one of the first to fifth inventions, the reaction tube for producing hydrogen selectively reforms the raw material gas into hydrogen, and selectively transmits only hydrogen. And a hydrogen separation membrane module having a hydrogen separation membrane.

  According to a seventh aspect of the invention, there is provided a hydrogen production method characterized in that hydrogen is produced using any one of the hydrogen production apparatuses according to the first to sixth aspects.

  According to the present invention, by providing the steam generation unit between the hydrogen production reaction tube and the combustion unit, the hydrogen production reaction tube and the preliminary reforming catalyst unit directly from the combustion unit. Radiant heat transfer can be suppressed. In addition, since steam can be generated in the hydrogen production apparatus main body and the source gas G in the hydrogen production reaction tube can be heated, the apparatus can be made simple and compact and supplied. Since the raw material gas and water can be efficiently heated, the thermal efficiency of the apparatus can be improved.

  Further, by providing the steam generating part and the combustion part via the hydrogen production reaction pipe and a partition wall, direct radiation transmission from the combustion part to the hydrogen production reaction pipe and the pre-reforming catalyst part. Heat can be suppressed. In addition, since steam can be generated in the hydrogen production apparatus main body and the source gas G in the hydrogen production reaction tube can be heated, the apparatus can be made simple and compact and supplied. Since the raw material gas and water can be efficiently heated, the thermal efficiency of the apparatus can be improved.

  Hereinafter, the present invention will be described in detail with reference to the drawings. Note that the present invention is not limited to the embodiments. In addition, constituent elements in the following embodiments include those that can be easily assumed by those skilled in the art or those that are substantially the same.

A hydrogen production apparatus according to Example 1 of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic diagram illustrating a configuration of a hydrogen production apparatus according to the present embodiment.
As shown in FIG. 1, a hydrogen production apparatus 10A according to this embodiment includes a preliminary reforming catalyst unit 107 that is provided in a hydrogen production apparatus main body 100a and has a preliminary reforming catalyst that preliminarily reforms a raw material gas G. The hydrogen production reaction tube 101 that reforms the raw material gas G into hydrogen and collects only the produced hydrogen, and the hydrogen production apparatus main body 100a are provided to heat the hydrogen production reaction tube 101. And a steam generator 12 that is provided in the hydrogen production apparatus main body 100a and generates steam 11 to be supplied to the source gas G. The burner 113 is used for the hydrogen production. The steam generator 12 is provided opposite to the pre-reforming catalyst unit 107 disposed in the reaction tube 101, and the steam generating unit 12 is disposed between the hydrogen production reaction tube 101 and the burner 113. One in which vignetting composed.
The steam generator 12 and the burner 113 are provided in the combustion chamber 102 below the reaction tube 101 for hydrogen production.

The hydrogen production apparatus 10 </ b> A according to this embodiment supplies the mixed gas 105 obtained by mixing the steam 11 generated in the steam generation unit 12 with the source gas G to the hydrogen production reaction tube 101. Then, in the preliminary reforming catalyst unit 107 in the reaction tube 101 for hydrogen production, a part of hydrocarbons in the raw material gas G is preliminarily reformed in advance at a predetermined temperature of 500 to 550 ° C., for example. Convert to hydrogen. After that, for example, hydrogen is generated using the reforming catalyst unit 108 as shown in FIG. 5, and only the generated hydrogen (H ₂ ) is selectively recovered.

  When the preliminary reforming catalyst unit 107 is provided below the hydrogen production reaction tube 101 as in the hydrogen production apparatus 10A according to the present embodiment, the burner 113 is placed in the hydrogen production reaction tube 101. It is provided below the hydrogen production reaction tube 101 that faces the pre-reforming catalyst unit 107 disposed. At this time, by providing the steam generator 12 between the hydrogen production reaction tube 101 and the burner 113, direct radiation heat transfer from the burner 113 to the lower side of the hydrogen production reaction tube 101 is achieved. Can be suppressed. As a result, a rapid temperature rise of the catalyst in the hydrogen production reaction tube 101 can be prevented, and deterioration of the pre-reforming catalyst can be prevented.

  Further, unlike the conventional hydrogen production apparatus 100 shown in FIG. 5, the hydrogen production apparatus 10A according to the present embodiment does not need to be provided with a boiler for generating the steam 104 in the steam generation apparatus 103, and the combustion The steam 11 can be generated only by the burner 113 in the chamber 102, and the mixed gas 105 in the hydrogen production reaction tube 101 can be heated. For this reason, 10 A of hydrogen production apparatuses which concern on a present Example can make an apparatus compact.

  In the hydrogen production apparatus 10A according to the present embodiment, only one combustion chamber 102 for heating the mixed gas 105 in the hydrogen production reaction tube 101 and the water 13 to be the steam 11 is sufficient. The mixed gas 105 and the water 13 in the reaction tube 101 for hydrogen production can be heated together by the burner 113. Therefore, since the mixed gas 105 and the water 13 in the hydrogen production reaction tube 101 can be efficiently heated, the thermal efficiency of the entire apparatus can be improved.

  Thus, according to the present embodiment, by providing the steam generating section 12 between the hydrogen production reaction tube 101 and the burner 113, the hydrogen production reaction tube 101 is connected to the hydrogen production reaction tube 101 from the burner 113. Since direct radiant heat transfer can be suppressed, deterioration of the catalyst in the hydrogen production reaction tube 101 can be prevented. Moreover, since the steam 11 can be generated only by the burner 113 and the mixed gas 105 in the reaction tube 101 for hydrogen production can be heated, the apparatus can be made compact and the entire apparatus can be reduced. Thermal efficiency can be improved.

  Further, in the present embodiment, the hydrogen production reaction tube 101 uses the reforming catalyst section 108 for reforming the source gas G to hydrogen as shown in FIG. The hydrogen separation membrane module 109 having the hydrogen separation membrane 109a that selectively permeates may be used, but the present invention is not limited to this, and hydrogen is generated and generated hydrogen. Any device that can collect only the water may be used.

  In the present embodiment, the raw material gas G may be a raw material gas containing hydrocarbons, such as city gas, methane, ethane, propane, butane, LP gas, natural gas, and a mixture of two or more other hydrocarbons. Hydrocarbon gas containing may be used.

  Further, in this embodiment, the pre-reforming catalyst unit 107 is arranged below the hydrogen production reaction tube 101, but the present invention is not limited to this, and the hydrogen production You may make it arrange | position to the side in the reaction tube 101 for an object.

A hydrogen production apparatus according to Embodiment 2 of the present invention will be described with reference to FIG.
FIG. 2 is a schematic diagram illustrating the configuration of the hydrogen production apparatus according to the present embodiment.
Since the hydrogen production apparatus according to the present embodiment is the same as the configuration of the hydrogen production apparatus according to the first embodiment, the same members are denoted by the same reference numerals, and redundant description is omitted.
As shown in FIG. 2, the hydrogen production apparatus 10 </ b> B according to the present embodiment is configured such that the steam generation unit 12 and the burner 113 of the hydrogen production apparatus 10 </ b> A according to the first embodiment shown in FIG. And provided on the side of the reaction tube 101 for hydrogen production via the partition wall 20. Moreover, the damper 21 which controls the flow volume of the combustion gas supplied to the said steam generation part 12 from the said burner 113 is comprised.
In the figure, reference numeral 22-1 is a first thermometer for measuring the gas temperature of the combustion gas supplied to the steam generator 12, and reference numeral 22-2 is a combustion released from the steam generator 12. Reference numeral 22-3 denotes a third thermometer for measuring the gas temperature of the mixed gas 105 in the pre-reforming catalyst of the pre-reforming catalyst unit 107. Each is illustrated.

Similarly to the hydrogen production apparatus 10A according to the first embodiment, the hydrogen production apparatus 10B according to the present embodiment uses the mixed gas 105 obtained by mixing the steam 11 generated in the steam generation unit 12 with the source gas G as the hydrogen. It is fed to the production reaction tube 101. Then, in the preliminary reforming catalyst unit 107 in the reaction tube 101 for hydrogen production, a part of hydrocarbons in the raw material gas G is preliminarily reformed in advance at a predetermined temperature of 500 to 550 ° C., for example. Convert to hydrogen. After that, for example, hydrogen is generated using the reforming catalyst unit 108 as shown in FIG. 5, and only the generated hydrogen (H ₂ ) is selectively recovered.

  In the hydrogen production apparatus 10B according to the present embodiment, the steam generation unit 12 and the burner 113 are provided on the side of the hydrogen production reaction tube 101 via the hydrogen production reaction tube 101 and the partition wall 20, respectively. Direct radiant heat transfer from the burner 113 can be suppressed. Therefore, an increase in the gas temperature of the mixed gas 105 supplied to the hydrogen production reaction tube 101 can be prevented, and the catalyst temperature of the catalyst in the hydrogen production reaction tube 101 is controlled to, for example, 500 to 550 ° C. can do. As a result, the rapid temperature rise of the catalyst in the hydrogen production reaction tube 101 can be prevented, and the deterioration of the catalyst can be prevented.

  Further, the hydrogen production apparatus 10B according to the present embodiment provides the damper 21 for controlling the flow rate of the combustion gas flowing from the burner 113 in the combustion chamber 12 to the steam generation unit 12, thereby reducing the flow rate of the combustion gas. Can be controlled. For this reason, the gas temperature of the mixed gas 105 in the reaction tube 101 for hydrogen production can be adjusted by adjusting the gas temperature generated in the steam generator 12.

  For this reason, for example, when the amount of the generated steam 11 cannot be adjusted even if the water 13 is supplied, or when the temperature of the reaction tube 101 for hydrogen production is high, the damper 21 is opened and closed, By controlling the flow rate of the combustion gas, the gas temperature of the combustion gas released from the steam generator 12 is adjusted, and the gas temperature of the mixed gas 105 in the hydrogen production reaction tube 101 is adjusted. it can.

  Further, in the hydrogen production apparatus 10B according to the present embodiment, the first thermometer 22-1 for measuring the gas temperature of the combustion gas supplied to the steam generation unit 12, and the combustion released from the steam generation unit 12 A second thermometer 22-2 for measuring the gas temperature of the gas, and a third thermometer 22-3 for measuring the gas temperature of the mixed gas 105 in the pre-reforming catalyst of the pre-reforming catalyst unit 107. To have.

  The damper 21 controls the flow rate of the combustion gas by detecting the gas temperature of the combustion gas supplied from the burner 113 with the first thermometer 22-1. The gas temperature generated in the steam generator 12 is adjusted by detecting the gas temperature of the combustion gas discharged from the steam generator 12 with the second thermometer 22-2. The gas temperature supplied to the hydrogen production reaction tube 101 is adjusted by detecting the gas temperature at the inlet of the hydrogen production reaction tube 101 with the third thermometer 22-3. ing.

  Accordingly, the hydrogen separation membrane module includes the hydrogen production reaction tube 101 having, for example, the reforming catalyst unit 108 that reforms the source gas G into hydrogen, and the hydrogen separation membrane 109a that selectively transmits only hydrogen. 109, the gas temperature of the mixed gas 105 in the hydrogen production reaction tube 101 is adjusted, and the temperature of the reforming catalyst used in the reforming catalyst unit 108 is, for example, 500 to 550 ° C. Can be controlled.

  Further, the hydrogen production apparatus 10B according to the present embodiment generates the steam 11 only by the burner 113 in the combustion chamber 102 and heats the mixed gas 105 in the hydrogen production reaction tube 101. Therefore, the apparatus can be made compact.

  Further, in the hydrogen production apparatus 10B according to the present embodiment, the mixed gas 105 in the hydrogen production reaction tube 101 and the water 13 that becomes the steam 11 can be heated together. The mixed gas 105 and the water 13 in the pipe 101 can be efficiently heated, and the thermal efficiency of the entire apparatus can be improved.

Thus, according to the present embodiment, the steam generating unit 12 and the burner 113 are provided on the side of the hydrogen production reaction tube 101 via the hydrogen production reaction tube 101 and the partition wall 20. Since the direct radiant heat transfer from the burner 113 to the hydrogen production reaction tube 101 can be suppressed, deterioration of the catalyst in the hydrogen production reaction tube 101 can be prevented.
Further, since the flow rate of the combustion gas can be controlled by controlling the flow rate of the combustion gas flowing from the burner 113 to the steam generating unit 12 by the damper 21, the combustion gas released from the steam generating unit 12 The temperature in the reaction tube 101 for hydrogen production can be adjusted by adjusting the gas temperature.

  Further, in the hydrogen production apparatus 10B according to the present embodiment, the pre-reforming catalyst unit 107 is disposed below the reaction tube 101 for hydrogen production, but the present invention is limited to this. Instead, the partition 20 may not be able to suppress the heat from the burner 113, so that the pre-reforming catalyst unit 107 may be disposed on the side of the hydrogen production reaction tube 101. Good.

  Further, the partition wall 20 used in the present embodiment prevents direct radiant heat transfer from the burner 113, but the present invention is not limited to this. For example, the combustion chamber You may make it have a communicating port through which the combustion gas from the said burner 113 in 102 distribute | circulates.

A hydrogen production apparatus according to Example 3 of the present invention will be described with reference to FIG.
FIG. 3 is a schematic diagram illustrating the configuration of the hydrogen production apparatus according to the present embodiment.
Since the hydrogen production apparatus according to the present embodiment is the same as the configuration of the hydrogen production apparatus according to the first embodiment, the same members are denoted by the same reference numerals, and redundant description is omitted.
As shown in FIG. 3, the hydrogen production apparatus 10 </ b> C according to the present embodiment is such that the pre-reforming catalyst unit 107 of the hydrogen production apparatus 10 </ b> A according to the first embodiment shown in FIG. Is provided. Further, the preliminary reforming catalyst unit 107 is provided between the hydrogen production reaction tube 101 and the steam generating unit 12.

  In the hydrogen producing apparatus 10C according to the present embodiment, the mixed gas 105 obtained by mixing the steam 11 generated in the steam generating unit 12 and the raw material gas G is mixed in the pre-reforming catalyst unit 107 at a predetermined temperature of, for example, 500 to 550 ° C. After the preliminary reforming to the above temperature, the mixed gas 105 at a predetermined temperature is supplied to the hydrogen production reaction tube 101.

  Like the hydrogen production apparatus 10 </ b> C according to the present embodiment, by providing the preliminary reforming catalyst unit 107 between the hydrogen production reaction tube 101 and the steam generation unit 12, the hydrogen production reaction tube 101 is provided. The direct radiant heat transfer from the burner 113 can be suppressed. Thereby, the rapid temperature rise of the reforming catalyst arranged in the reaction tube 101 for hydrogen production can be prevented, and deterioration of the catalyst can be prevented.

Further, in the conventional hydrogen production apparatus 100 as shown in FIG. 5, the preliminary reforming catalyst unit 107 decomposes CO ₂ in the raw material gas G, and sets the hydrogen partial pressure at the inlet of the hydrogen separation membrane module 109. The mixture gas outlet temperature of the pre-reforming catalyst unit 107 is adjusted to about 550 ° C., which is the ideal temperature at the inlet of the hydrogen separation membrane module 109. However, in the hydrogen production apparatus 10C according to the present embodiment, the inlet temperature of the mixed gas 105 of the pre-reforming catalyst unit 107 becomes high due to direct radiant heat transfer from the burner 113, and the hydrogen production reaction tube The catalyst in 101 is not deactivated.

  Further, by providing the preliminary reforming catalyst portion 107 separately outside the hydrogen production reaction tube 101, even if the preliminary reforming catalyst of the preliminary reforming catalyst portion 107 is deactivated, the preliminary reforming catalyst is provided. Can be easily replaced.

  Further, unlike the conventional hydrogen production apparatus 100 shown in FIG. 5, the hydrogen production apparatus 10C according to the present embodiment does not need to be provided with a boiler for generating the steam 104 in the steam generation apparatus 103, and the combustion The steam 11 can be generated only by the burner 113 in the chamber 102, and the mixed gas 105 in the hydrogen production reaction tube 101 can be heated. For this reason, 10 C of hydrogen production apparatuses which concern on a present Example can make an apparatus compact.

  In the hydrogen production apparatus 10C according to the present embodiment, only one combustion chamber 102 for heating the mixed gas 105 in the hydrogen production reaction tube 101 and the water 13 to be the steam 11 is sufficient. The mixed gas 105 and the water 13 in the reaction tube 101 for hydrogen production can be heated together by the burner 113. Therefore, since the mixed gas 105 and the water 13 in the hydrogen production reaction tube 101 can be efficiently heated, the thermal efficiency of the entire apparatus can be improved.

  As described above, according to this embodiment, the hydrogen generating reaction tube 101 and the burner 113 provided below the hydrogen manufacturing reaction tube 101 are provided with the steam generating unit 12, thereby Since direct radiant heat transfer from the burner 113 to the production reaction tube 101 and the pre-reforming catalyst unit 107 can be suppressed, deterioration of the catalyst in the hydrogen production reaction tube 101 can be prevented. it can. Further, since the preliminary reforming catalyst portion 107 is provided separately from the outside of the hydrogen production reaction tube 101, the preliminary reforming catalyst can be easily replaced.

A hydrogen production apparatus according to Embodiment 4 of the present invention will be described with reference to the drawings.
FIG. 4 is a schematic diagram illustrating the configuration of the hydrogen production apparatus according to the present embodiment.
The reaction tube for hydrogen production according to the present embodiment is the same as the configuration of the hydrogen production apparatus according to Embodiments 1 to 3, and therefore, the same members are denoted by the same reference numerals and redundant description is omitted.
As shown in FIG. 4, the hydrogen production apparatus 10 </ b> D according to this embodiment is configured such that the preliminary reforming catalyst unit 107 of the hydrogen production apparatus 10 </ b> B according to the second embodiment shown in FIG. It is provided.

  The hydrogen production apparatus 10D according to the present embodiment uses, for example, 500 to 550 ° C. in the pre-reforming catalyst unit 107 by the mixed gas 105 obtained by mixing the steam 11 generated in the steam generating unit 12 with the raw material gas G. After the preliminary reforming to a predetermined temperature, the mixed gas 105 at a predetermined temperature is supplied to the reaction tube 101 for hydrogen production.

  As in the hydrogen production apparatus 10D according to the present embodiment, the steam generation unit 12 and the burner 113 are provided on the side of the hydrogen production reaction tube 101 via the hydrogen production reaction tube 101 and the partition wall 20. Thus, direct radiant heat transfer from the burner 113 to the hydrogen production reaction tube 101 can be suppressed. Thereby, the rapid temperature rise of the catalyst in the reaction tube 101 for hydrogen production can be prevented.

  Further, in the hydrogen production apparatus 10D according to the present embodiment, when the damper 21 is provided, for example, when the amount of the steam 11 cannot be adjusted even when the water 13 is supplied, the hydrogen production reaction tube When the gas temperature of the mixed gas 105 in 101 is high, the damper 21 can be opened and closed to control the flow rate of the combustion gas. For this reason, the gas temperature of the mixed gas 105 in the hydrogen production reaction tube 101 can be adjusted by adjusting the gas temperature of the combustion gas released from the steam generator 12.

  Therefore, the hydrogen separation membrane includes the hydrogen production reaction tube 101 including, for example, the reforming catalyst unit 108 that reforms the source gas G into hydrogen, and the hydrogen separation membrane 109a that selectively permeates only hydrogen. In the case of the module 109, the gas temperature of the mixed gas 105 in the hydrogen production reaction tube 101 is adjusted, and the temperature of the reforming catalyst used in the reforming catalyst unit 108 is, for example, 500 to 550 ° C. Can be controlled.

  Here, the hydrogen separation membrane in the case where the hydrogen separation membrane module 109 of the hydrogen production reaction tube 101 of the conventional hydrogen production apparatus 100 as shown in FIG. The temperature change due to the reaction in the module 109 will be described.

Using 13A gas as the source gas and the outlet gas (CH ₄ , CO, CO ₂ , H ₂ , H ₂ O) of the hydrogen production reaction tube 101, S / C was 3 mol at a flow rate of 10.6 Nm ³ / h. / Mol as a pressure of 0.8 MPa · G.
Further, the mixed gas outlet temperature T _p of the mixed gas 105 at the outlet of the pre-reforming catalyst unit 107 is set to 600 ° C., and the mixed gas inlet temperature T _{m of the} mixed gas 105 at the inlet of the hydrogen separation membrane module 109 is set. Table 1 shows the heat amounts of CH ₄ , CO, CO ₂ , H ₂ , and H ₂ O in the mixed gas 105.

The reaction at the reforming catalyst unit 108 in the hydrogen separation membrane module 109 is performed by an equilibrium reaction by a forward reaction of the following formula (1) and a reverse reaction of the formula (2). Moreover, the forward reaction of Formula (1) is an endothermic reaction, and the reverse reaction of Formula (2) is an exothermic reaction.
CH ₄ + 2H ₂ O → CO ₂ + 4H ₂ (1)
CO ₂ + 4H ₂ → CH ₄ + 2H ₂ O (2)

The mixed gas outlet temperature T _{p of the} mixed gas 105 at the outlet of the pre-reforming catalyst unit 107 and the mixed gas inlet temperature T _{m of the} mixed gas 105 at the inlet of the hydrogen separation membrane module 109 are equal. For example, since the endothermic reaction, which is the positive reaction of the formula (1), further proceeds as much as hydrogen (H ₂ ) is removed, hydrogen is produced and the mixed gas in the reforming catalyst unit 108 is also produced. The gas temperature of 105 can be prevented from exceeding 550 ° C., for example.

Further, the mixed gas outlet temperature T _{p of the} mixed gas 105 at the outlet of the pre-reforming catalyst unit 107 is higher than the mixed gas inlet temperature T _{m of the} mixed gas 105 at the inlet of the hydrogen separation membrane module 109. In this case, an exothermic reaction that is a reverse reaction proceeds and generates heat, so that the gas temperature of the mixed gas 105 in the hydrogen separation membrane module 109 increases.

In the hydrogen separation membrane module 109, as shown in Table 1, the mixed gas outlet temperature T _{p of the} mixed gas 105 at the outlet of the pre-reforming catalyst unit 107 is, for example, 600 ° C., and the hydrogen separation membrane module 109 When the mixed gas inlet temperature T _{m of the} mixed gas 105 at the inlet of the gas is, for example, 550 ° C., CO and CO ₂ contained in the mixed gas 105 are reacted with the following formulas (3) and (4). It proceeds to generate CH ₄ and generate heat.
_{CO + 3H 2 → CH 4 +} H 2 O -164.63kJ / mol ··· (3)
CO ₂ + 4H ₂ → CH ₄ + 2H ₂ O−241.82 kJ / mol (4)

At this time, CO is reduced by, for example, 23.71 mol / h, and CO ₂ is reduced by, for example, 28.94 mol / h, and, for example, 2.68 kW is generated. Due to this heat generation, the mixed gas 105 is heated, and the mixed gas inlet temperature T _m that is the gas temperature of the mixed gas 105 at the inlet of the hydrogen separation membrane module 109 exceeds 550 ° C., for example.

Therefore, in order to prevent the catalyst temperature of the reforming catalyst unit 108 in the hydrogen separation membrane module 109 from exceeding, for example, 550 ° C., the mixing of the mixed gas 105 at the outlet of the pre-reforming catalyst unit 107 is performed. The gas outlet temperature T _p and the mixed gas inlet temperature T _{m of the} mixed gas 105 at the inlet of the hydrogen separation membrane module 109 are made equal, and the damper 21 adjusts the flow rate of the combustion gas from the burner 113. There is a need.

  Further, in the hydrogen production apparatus 10D according to the present embodiment, the preliminary reforming catalyst unit 107 is separately provided outside the hydrogen production reaction tube 101, so that the preliminary reforming catalyst of the preliminary reforming catalyst unit 107 is provided. Even if the catalyst is deactivated, the pre-reforming catalyst can be easily replaced.

  Further, the hydrogen production apparatus 10D according to the present embodiment generates the steam 11 only by the burner 113 in the combustion chamber 102 and heats the mixed gas 105 in the hydrogen production reaction tube 101. Therefore, the apparatus can be made compact.

  Further, in the hydrogen production apparatus 10D according to the present embodiment, the mixed gas 105 in the hydrogen production reaction tube 101 and the water 13 that becomes the steam 11 can be heated together at one time. The mixed gas 105 and the water 13 in the reaction tube 101 can be efficiently heated, and the thermal efficiency of the entire apparatus can be improved.

  Thus, according to the present embodiment, the steam generation unit 12 and the burner 113 are provided on the side of the hydrogen production reaction tube 101 via the hydrogen production reaction tube 101 and the partition wall 20. Since direct radiant heat transfer from the burner 113 to the hydrogen production reaction tube 101 can be suppressed, deterioration of the catalyst in the hydrogen production reaction tube 101 can be prevented. Further, since the preliminary reforming catalyst portion 107 is provided separately from the outside of the hydrogen production reaction tube 101, the preliminary reforming catalyst can be easily replaced.

  As mentioned above, although the Example of this invention was described, this invention is not limited to the said Example, A various deformation | transformation and change are possible based on the technical idea of this invention.

  As described above, in the hydrogen production apparatus and the hydrogen production method according to the present invention, the steam generation unit is provided between the hydrogen production reaction tube and the combustion unit, so that the hydrogen production reaction tube and the preliminary production method are provided. The direct heat transfer from the combustion section to the reforming catalyst section can be suppressed and the supplied raw material gas and water can be efficiently heated, so that the durability of the catalyst is improved and simplified. It is compact with a simple structure and suitable for use in a hydrogen production apparatus with good thermal efficiency.

  In addition, since the steam generation unit and the combustion unit are provided via the hydrogen production reaction tube and a partition wall, the hydrogen production reaction tube and the preliminary reforming catalyst unit 107 directly from the combustion unit. As well as being able to suppress the radiant heat transfer, the supplied raw material gas and water can be efficiently heated, so the durability of the catalyst is improved, the structure is simple and compact, and the hydrogen production apparatus has high thermal efficiency. Suitable for use in.

1 is a schematic diagram illustrating a configuration of a hydrogen production apparatus according to Example 1. FIG. FIG. 3 is a schematic diagram illustrating a configuration of a hydrogen production apparatus according to a second embodiment. FIG. 5 is a schematic diagram illustrating a configuration of a hydrogen production apparatus according to a third embodiment. FIG. 6 is a schematic diagram illustrating a configuration of a hydrogen production apparatus according to Example 4. It is a figure which shows the structure of the conventional hydrogen production apparatus, the temperature in the reaction tube for hydrogen production, and the active state of a catalyst.

Explanation of symbols

10A to 10D Hydrogen production apparatus 11 Steam 12 Steam generation unit 13 Water 20 Bulkhead 21 Damper 22-1 First thermometer 22-2 Second thermometer 22-3 Third thermometer G Raw gas 100a Hydrogen production apparatus main body 101 hydrogen production reaction tube 102 combustion chamber 105 the gas mixture 107 pre-reforming catalyst 113 burner T _m mixed gas inlet temperature T _p mixed gas outlet temperature

Claims (7)

It has a pre-reforming catalyst part that has a pre-reforming catalyst that pre-reforms the raw material gas inside the main body of the hydrogen production device, reforms the raw material gas into hydrogen, and collects only the generated hydrogen. A reaction tube for hydrogen production,
A combustion section provided in the hydrogen production apparatus main body, for heating the hydrogen production reaction tube;
A hydrogen production apparatus comprising: a steam generation unit that is provided in the hydrogen production apparatus main body and generates steam for supplying the raw material gas. In claim 1,
The combustion section is provided opposite to the pre-reforming catalyst section disposed in the hydrogen production reaction tube;
The hydrogen production apparatus, wherein the steam generation part is provided between the hydrogen production reaction tube and the combustion part. In claim 1,
The hydrogen production apparatus, wherein the steam generation unit and the combustion unit are provided through the hydrogen production reaction tube and a partition wall. In any one of Claims 1 thru | or 3,
The hydrogen production apparatus according to claim 1, wherein the pre-reforming catalyst section is provided outside the reaction tube for hydrogen production. In claim 3 or 4,
2. A hydrogen production apparatus comprising a damper for controlling a flow rate of combustion gas supplied from the combustion section to the steam generation section. In any one of Claims 1 thru | or 5,
The hydrogen production reaction tube comprises a reforming catalyst section for reforming the raw material gas into hydrogen and a hydrogen separation membrane module having a hydrogen separation membrane that selectively permeates only hydrogen. To produce hydrogen.   A method for producing hydrogen, comprising producing hydrogen using the hydrogen production apparatus according to any one of claims 1 to 6.

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