JP5165832B2 - Hydrogen generating apparatus and method - Google Patents

Description

  The present invention uses hydrocarbon compound gas such as natural gas, propane gas, gasoline, naphtha, kerosene, methanol, biogas and water and air or oxygen as raw materials to supply hydrogen to hydrogen-using equipment such as fuel cells. The present invention relates to a hydrogen generation apparatus and method.

  Hydrogen is attracting attention as one of the promising energy sources to replace fossil fuels, but social infrastructure such as hydrogen pipelines is required for its effective use. One way to do this is to use natural gas, other fossil fuels, alcohol, and other infrastructure that has already been built, such as transportation and transportation, and reform the fuel where hydrogen is needed to generate hydrogen. A method is being considered.

As the hydrogen generator as described above, for example, one disclosed in Patent Document 1 below is disclosed. This hydrogen generator introduces a mixed gas of hydrocarbon gas and steam into a reformer as a raw material, and separates and purifies hydrogen gas from hydrogen-rich reformed gas obtained by a reforming reaction using a catalyst. In this hydrogen generator, since the reforming reaction is an endothermic reaction, the reformer is equipped with a burner and supplies the heat energy necessary for the reforming reaction from the outside.
JP 2002-53307 A

  However, in the hydrogen generator of Patent Document 1, since it is necessary to provide a heating furnace equipped with a burner around the reformer, the structure of the reformer itself is complicated, and heat resistance and pressure resistance are provided. There are problems that the structure is complicated, the equipment cost is high, and the maintenance requires labor and cost. In addition, since heat energy necessary for the reforming reaction is supplied from the outside, there is a problem that heat efficiency is poor, energy cost is increased, and nitrogen oxides and sulfur oxides are generated.

  The present invention has been made to solve such a problem, and an object of the present invention is to provide a hydrogen generation apparatus and method that are excellent in energy efficiency and can reduce facility costs.

To achieve the above object, the hydrogen generator of the present invention is a hydrogen generator that reforms a hydrocarbon-based gas to produce a hydrogen-rich reformed gas,
Comprising a reformer that causes the hydrocarbon gas to contact and react with the catalyst together with water vapor and oxygen to burn and reform the hydrocarbon gas;
In the reformed gas path provided on the downstream side of the reformer,
A heat exchanger for water heating that heats water as a water vapor source by heat exchange with the reformed gas;
A heat exchanger for heating a hydrocarbon gas that heats the hydrocarbon gas by heat exchange with the reformed gas is provided,
Further, heating with the hydrocarbon gas heating heat exchanger is performed upstream of the water heating heat exchanger and the hydrocarbon gas heating heat exchanger in the reformed gas path by heat exchange with the reformed gas. A raw material gas heating heat exchanger for heating a raw material gas that is a mixed gas of the hydrocarbon-based gas and water vapor obtained from water heated by the water heating heat exchanger,
Further, the raw material gas supply path for supplying the raw material gas is provided with a raw material heater for heating the raw material gas introduced into the reformer in the initial operation of the hydrogen generator in which the temperature of the reformer has not sufficiently increased. ,
The water-heating heat exchanger, hydrocarbon gas heat exchanger for heating, without introducing oxygen gas into the heat exchanger and the raw material for the heater material gas heating, Rukoto to introduce oxygen gas into the raw material gas supply passage Is the gist.

In order to achieve the above object, the hydrogen generation method of the present invention is a hydrogen generation method for reforming a hydrocarbon gas to generate a hydrogen-rich reformed gas,
A reforming step of bringing the hydrocarbon gas into contact with a catalyst together with water vapor and oxygen to burn and reform the hydrocarbon gas;
On the downstream side of the reforming step,
A heat exchange process for water heating that heats water as a water vapor source by heat exchange with the reformed gas;
A heat exchange process for heating a hydrocarbon gas that heats the hydrocarbon gas by heat exchange with the reformed gas,
Further, heating is performed in the hydrocarbon gas heating heat exchange step by heat exchange with the reformed gas upstream of the water heating heat exchange step and the hydrocarbon gas heating heat exchange step in the reformed gas path. Performing a raw material gas heating heat exchange step of heating a raw material gas which is a mixed gas of the hydrocarbon-based gas and water vapor obtained from the water heated in the water heating heat exchange step,
Further, the raw material gas supply step of supplying the raw material gas, the operation initial hydrogen generator reformer is not sufficiently rise in temperature, line physician raw material heating step of heating the raw material gas to be introduced into the reformer ,
Introducing oxygen gas in the raw material gas supply step without introducing oxygen gas in the water heating heat exchange step, hydrocarbon gas heating heat exchange step, raw material gas heating heat exchange step and raw material heating step Is the gist.

In the reformer, the hydrocarbon gas is contacted with a catalyst together with water vapor and oxygen to cause combustion and reforming of the hydrocarbon gas, and the reformed gas provided on the downstream side of the reformer. The raw material gas introduced into the reformer is heated by exchanging heat between the reformed gas and the raw material gas in the channel. In this way, the raw material gas to be introduced into the reformer is heated by the heat of the reformed gas obtained by combustion and reforming, instead of supplying the heat energy necessary for reforming from the outside by a burner or the like. Therefore, it is extremely energy efficient. In addition, it is no longer necessary to provide a heating furnace with a burner around the reformer, simplifying the structure of the reformer itself, and simplifying the structure to provide heat resistance and pressure resistance, thereby reducing equipment costs. it can.
In addition, heat is exchanged with the reformed gas on the upstream side of the water heating heat exchanger and the hydrocarbon gas heating heat exchanger in the reformed gas path, and the hydrocarbon gas heating heat exchanger is heated. Since a raw material gas heating heat exchanger for heating a raw material gas that is a mixed gas of water vapor obtained from water heated by a heated hydrocarbon gas and water heated by a water heating heat exchanger is provided. Since hydrocarbon gas and water vapor, which require relatively large heat energy, are heated by the heat exchanger for heating the raw material gas and then introduced into the reformer, the raw material gas is brought to the required gas temperature at the reformer inlet. Can be raised.
In addition, since a water heating heat exchanger that heats water as a water vapor source is provided by heat exchange with the reformed gas, heat exchange with the raw material gas in the raw material gas heating heat exchanger is performed to some extent. Energy efficiency can be further improved by heat-exchanging the reformed gas whose temperature has decreased with water using a water heating heat exchanger.
In addition, since a hydrocarbon gas heating heat exchanger that heats the hydrocarbon gas by heat exchange with the reformed gas is provided, heat exchange with the raw material gas in the raw material gas heating heat exchanger is possible. The energy efficiency can be further improved by exchanging the reformed gas whose temperature has decreased to some extent with the hydrocarbon-based gas in the hydrocarbon-gas heating heat exchanger.
The raw material gas supply path is provided with a raw material heater for heating the raw material gas introduced into the reformer at the initial operation of the hydrogen generator in which the temperature of the reformer has not sufficiently increased. As a result, at the initial stage of operation of the hydrogen generator, the reformer is not sufficiently heated, and the source gas is heated by the source heater at a stage where the source gas cannot be sufficiently heated by the heat exchanger. Even in the initial operation of the apparatus, a sufficient reforming reaction can be secured by preventing the reforming reaction from being lowered due to insufficient temperature rise in the reformer.

In the present invention, a plurality of the water heating heat exchangers may be provided in the reformed gas path.

In the present invention, a plurality of the hydrocarbon-based gas heating heat exchangers may be provided in the reformed gas path.

  In the present invention, when an adsorption device for adsorbing impurities in the reformed gas is provided and the adsorption device is a pressurized vacuum pressure swing adsorption device, the pressurized vacuum pressure swing adsorption device is modified in a pressurized state. Since the impurities in the gas are adsorbed and the impurities adsorbed in a vacuum state are desorbed, the amount of impurities remaining in the adsorbent after desorption is significantly less than the pressure-pressure swing type adsorption device that desorbs at atmospheric pressure. Become. For this reason, the purge gas amount can be significantly reduced in the product hydrogen gas purge after the desorption is completed, and the amount of purge gas discharged as off-gas can be reduced. In addition, since desorption is performed in a vacuum state, the adsorption amount of impurities to the adsorbent also increases, and as a result, the amount of adsorbent filling can be reduced. As a result, the purge gas amount can be further reduced and the off gas amount can be reduced. become. Furthermore, if the amount of adsorbent filling is not reduced, the amount of impurities adsorbed in one adsorption can be increased. As a result, the pressure swing period is extended and the number of purges per hour is reduced, thereby reducing the amount of off-gas. It can also be reduced. In the present invention, since there is no reformer heating burner capable of burning off gas, the effect of improving the treatment efficiency by reducing the amount of off gas is very remarkable.

In the present invention, the reformer uses a Rh-modified (Ni—CeO ₂ ) —Pt catalyst so that the hydrocarbon combustion reaction and the reforming reaction are simultaneously performed in the same reaction region. In some cases, the combustion reaction, which is an exothermic reaction, and the reforming reaction, which is an endothermic reaction, are simultaneously performed in the same reaction region, so that the heat energy generated in the combustion reaction can be used as a heat source for the reforming reaction. Will be better. Furthermore, since the exothermic reaction and the endothermic reaction occur simultaneously in the reaction region, thermal neutralization occurs. For example, the temperature of the reaction region is higher than that in the case where a region for performing the catalytic combustion reaction alone is provided in the reformer. The rise is considerably suppressed, and it is not necessary to select a heat-resistant material used for the reformer and the heat-resistant structure of the reformer itself to have a high temperature specification, so that the equipment cost can be reduced.

  Next, the best mode for carrying out the present invention will be described.

  FIG. 1 is a configuration diagram showing an example of a hydrogen generator to which the present invention is applied.

  This hydrogen generator is a hydrogen generator that reforms a hydrocarbon-based gas to generate a hydrogen-rich reformed gas. The source gas may be a hydrocarbon gas such as natural gas or methane, as well as a hydrocarbon gas generally supplied as social infrastructure such as propane gas or city gas. In the following description, an example in which natural gas is used as the hydrocarbon-based gas will be described.

  The hydrogen generator includes a reformer 1 that reforms natural gas by introducing natural gas, water vapor, and oxygen as raw material gases, and a CO shift that converts the reformed gas discharged from the reformer 1 to CO. And an adsorption device 5 for adsorbing impurities in the reformed gas that has been CO-transformed.

  Further, the hydrogen generator includes a natural gas supply path 22 through which the natural gas supplied to the reformer 1 is circulated, and a water supply through which water for generating water vapor to be introduced into the reformer 1 is supplied and circulated. A passage 23 and an oxygen supply passage 24 for introducing oxygen into the reformer 1 are provided. The water supply path 23 is provided with a steam heater 6 that converts the supplied water into water vapor.

  The steam supply path 23 a for supplying water vapor from the steam heater 6 and the natural gas supply path 22 merge with the raw material gas supply path 10, and an oxygen supply path 24 further merges with the raw material gas supply path 10. . And the said raw material gas supply path 10 is connected to the reformer 1, and introduce | transduces into the reformer 1 the mixed gas of natural gas, water vapor | steam, and oxygen as raw material gas.

  The reformed gas reformed by the reformer 1 flows through the reformed gas path 25 and is introduced into the CO converter 4, and the reformed gas transformed by the CO converter 4 is converted into the modified gas path 26. Is distributed and introduced into the adsorption device 5. The hydrogen gas from which impurities are adsorbed and removed by the adsorption device 5 is supplied from a product gas passage 29 to a predetermined hydrogen gas use facility.

The reformer 1 causes the natural gas to come into contact with a reforming catalyst together with oxygen and water vapor to burn and reform the natural gas. Specifically, the reformer 1 uses an Rh-modified (Ni—CeO ₂ ) —Pt catalyst, and this one type of catalyst allows the hydrocarbon combustion reaction and the reforming reaction to be performed in the same reaction region. At the same time.

  As shown in FIG. 2, the reformer 1 has a double structure of an inner cylinder 34 and an outer case 33, and a reforming catalyst 31 is disposed inside the inner cylinder 34, The hydrocarbon combustion reaction and the reforming reaction are simultaneously performed in the same reaction region.

  In this way, the combustion reaction, which is an exothermic reaction, and the reforming reaction, which is an endothermic reaction, are simultaneously performed in the same reaction region, so that the heat energy generated by the combustion reaction can be used as a heat source for the reforming reaction, which is extremely energy efficient Will be better. Furthermore, since the exothermic reaction and the endothermic reaction occur simultaneously in the reaction region, thermal neutralization occurs. For example, compared with the case where a region for performing the catalytic combustion reaction alone is provided in the reformer 1, The temperature rise is considerably suppressed, and it is not necessary to select the heat-resistant material used for the reformer 1 and the heat-resistant structure of the reformer 1 itself so as to have a high-temperature specification, so that the equipment cost can be reduced. Details of the reformer 1 will be described later.

  In the reformed gas path 25 connecting the reformer 1 and the CO converter 4 on the downstream side of the reformer 1, heat exchange between the reformed gas and the source gas flowing through the source gas supply path 10 is performed. A first heat exchanger 3 for heating the raw material gas introduced into the reformer 1 is provided. The first heat exchanger 3 heats a mixed gas of natural gas and water vapor as a raw material gas.

  In this way, the heat energy necessary for reforming is not supplied from the outside by a burner or the like, but the raw material gas introduced into the reformer 1 is heated by the heat of the reformed gas obtained by combustion and reforming. Therefore, energy efficiency is extremely improved. In addition, it is not necessary to provide a heating furnace with a burner around the reformer 1, the structure of the reformer 1 itself is simplified, and the structure for providing heat resistance and pressure resistance is also simplified. Can also save.

  Moreover, in the said 1st heat exchanger 3, in order to heat the mixed gas of hydrocarbon type gas and water vapor | steam, the hydrocarbon gas and water vapor | steam which require comparatively big heat energy in order to heat are heated by the 1st heat exchanger 3. Since it introduce | transduces into the reformer 1 after heating, source gas can be raised to gas temperature required for the reformer 1 inlet_port | entrance.

  Further, the first heat exchanger 3 is arranged on the upstream side closest to the reformer 1 than other heat exchangers described later. Thereby, the raw material gas that must be heated to the highest temperature immediately before being introduced into the reformer 1 is heated by the first heat exchanger 3 on the most upstream side. It can be introduced into the reformer 1, and the raw material gas can be raised to the gas temperature required at the inlet of the reformer 1.

  The raw material gas supply path 10 is provided with a raw material heater 2 for heating the raw material gas introduced into the reformer 1. Thereby, at the initial stage of operation of the hydrogen generator, the temperature of the reformer 1 is not sufficiently increased, and the raw material heater 2 supplies the raw material gas when the raw material gas cannot be sufficiently heated in the first heat exchanger 3. The gas can be heated, and even in the initial operation of the apparatus, it is possible to prevent the reforming reaction from being lowered due to insufficient temperature rise in the reformer 1 and to ensure a sufficient reforming reaction.

  On the downstream side of the first heat exchanger 3 in the reformed gas path 25, a second heat exchange is performed in which the natural gas flowing through the natural gas supply path 22 and the reformed gas are subjected to heat exchange to heat the natural gas. A vessel 9 is provided. In this way, by heat exchange with the raw material gas in the first heat exchanger 3, the heat of the reformed gas whose temperature has decreased to some extent is further exchanged with natural gas in the second heat exchanger 9. Furthermore, energy efficiency can be improved.

  Further, on the downstream side of the reformed gas path 25 from the first heat exchanger 3 and downstream of the second heat exchanger 9, the water and the reformed gas flowing through the water supply path 23 serving as water vapor are provided. A third heat exchanger 11 that heats the water by performing heat exchange is provided. By doing so, the heat of the reformed gas whose temperature has been lowered to some extent by heat exchange with the raw material gas in the first heat exchanger 3 and heat exchange with the natural gas by the second heat exchanger 9 is further increased. Energy exchange can be further improved by exchanging heat with water in the third heat exchanger 11.

  On the downstream side of the second heat exchanger 9 in the natural gas supply path 22, a preheating heater 8 for further preheating the natural gas heated by the second heat exchanger 9, and a natural gas preheated by the preheating heater 8. A desulfurizer 7 is provided for removing sulfur additives from the reactor. The desulfurizer 7 is not particularly limited, and may be one that physically adsorbs on the adsorbent, or one that performs hydrodesulfurization.

  Further, a steam heater (steam generator) 6 that converts water heated by the third heat exchanger 11 into steam is provided downstream of the third heat exchanger 11 in the water supply path 23. . The leading end of the steam supply path 23 a extending from the steam heater 6 and the leading end of the natural gas supply path 22 extending from the desulfurizer 7 join the raw material gas supply path 10 and are connected to the first heat exchanger 3.

  The water supply path 23 is provided with a pure water device 12 that makes the supplied tap water pure water, and a pure water pump 13 that pumps pure water discharged from the pure water device 12. . The natural gas supply path 22 is provided with a compressor 19 for pumping the natural gas supplied from the supply source.

  Further, the reformed gas passage 26 through which the reformed gas discharged from the CO transformer 4 circulates is supplied by the pure water pump 13 and circulated through the water supply passage 23, and the modified gas passage 26 circulates through the modified gas passage 26. The 4th heat exchanger 14 and the 5th heat exchanger 15 which heat-exchange with quality gas and heat the said water are provided.

  The water supply path 23 is provided with a pure water heater 16 for heating pure water on the downstream side of the fifth heat exchanger 15 and the upstream side of the fourth heat exchanger 14. The water fed by the pure water pump 13 is preheated by the fifth heat exchanger 15, the pure water heater 16, and the fourth heat exchanger 14, and then introduced into the third heat exchanger 11. It has become.

  Further, the natural gas that is compressed by the compressor 19 and sent to the downstream side of the fourth heat exchanger 14 and the fifth heat exchanger 15 and the modified gas passage 26 are circulated in the modified gas passage 26. A sixth heat exchanger 17 is provided that heat-exchanges with the reformed gas to heat the natural gas. The natural gas sent in by the compressor 19 is preheated by the sixth heat exchanger 17 and then introduced into the second heat exchanger 9.

  Thus, since the water and natural gas supplied using the heat of the reformed gas discharged from the CO converter 4 are preheated, the thermal efficiency is further improved.

  A gas-liquid separator 18 that separates and removes water vapor remaining in the reformed gas is provided further downstream of the sixth heat exchanger 17 in the modified gas path 26. The water separated and removed by the gas-liquid separator 18 is drained from the drainage channel 27.

On the downstream side of the gas-liquid separator 18, an adsorption device 5 that adsorbs CO and CO ₂ that are impure components in the reformed gas is provided.

  The adsorption apparatus is a pressure swing type adsorption apparatus in which a first adsorption tower 20a and a second adsorption tower 20b each filled with an adsorbent are present in parallel, and one of the adsorption towers is in a high-pressure state and the reformed gas is circulated. While the impurity is adsorbed on the adsorbent, the other adsorption tower is evacuated by the vacuum pump 21 to desorb the impurity gas adsorbed on the adsorbent, thereby performing vacuum desorption. Adsorption device. Although the illustrated example has two adsorption towers, the number of adsorption towers may be three or more.

  Thus, the pressurized vacuum pressure swing type adsorption device 5 adsorbs impurities in the reformed gas in a pressurized state and desorbs the impurities adsorbed in a vacuum state, so that the desorption is performed at atmospheric pressure. Compared with the pressure-and-pressure swing type adsorption apparatus, impurities remaining in the adsorbent after desorption are remarkably reduced. For this reason, the purge gas amount can be significantly reduced in the product hydrogen gas purge after the desorption is completed, and the amount of purge gas discharged as off-gas can be reduced. In addition, since desorption is performed in a vacuum state, the adsorption amount of impurities to the adsorbent also increases, and as a result, the amount of adsorbent filling can be reduced. As a result, the purge gas amount can be further reduced and the off gas amount can be reduced. become. Furthermore, if the amount of adsorbent filling is not reduced, the amount of impurities adsorbed in one adsorption can be increased. As a result, the pressure swing period is extended and the number of purges per hour is reduced, thereby reducing the amount of off-gas. It can also be reduced. In the present invention, since there is no reformer heating burner capable of burning off gas, the effect of improving the treatment efficiency by reducing the amount of off gas is very remarkable.

  Here, the reformer 1 will be described in detail.

  As shown in FIG. 2, the reformer 1 includes an inner cylinder 34 that reforms the raw material gas introduced from the upstream end and discharges the reformed gas to the downstream end, and the inner cylinder 34 and a predetermined heat insulating space. And an outer case 33 that accommodates the inner cylinder 34 in a state where the inner cylinder 34 is separated, and has a double structure of the inner cylinder 34 and the outer case 33, and the reforming catalyst 31 is disposed inside the inner cylinder 34. ing. The upper side in the figure is the upstream side, and the lower side is the downstream side.

  The outer case 33 has a bottomed cylindrical shape, and a disk-like flange 36a is formed on the periphery of the upper end portion. Similarly, a plate-like flange 36b is disposed above the flange 36a, and a cylindrical introduction tube 35 is disposed on the flange 36b so as to be substantially concentric with the outer case.

  The introduction cylinder 35 has a smaller diameter than the outer case 33 and is set to be substantially the same diameter as the inner cylinder 34 accommodated therein. The introduction cylinder 35 is joined and fixed to the flange 36b and protrudes upstream of the flange 36b. . The upstream end opening of the introduction cylinder 35 is covered with a flange 36c. The raw material gas supply path 10 is connected to the flange 36c, and a mixed gas of natural gas, water vapor and oxygen is introduced into the internal space of the introduction cylinder 35. A certain raw material gas is supplied.

  On the other hand, a reformed gas path 25 for circulating reformed gas is connected to the bottom of the outer case, and the first heat exchanger 3 and the second heat exchanger 9 are provided in the reformed gas path 25. (The third heat exchanger 11 is not shown).

  Further, a support cylinder 38 into which the inner cylinder 34 is fitted is provided at the bottom of the outer case so as to protrude inward. A catalyst seat 32 on which a large number of flow holes 32 a are formed and the catalyst 31 is placed is provided at the upper portion of the support cylinder 38.

  The inner cylinder 34 is fixed to the outer case 33 at the upstream end of the source gas. That is, the upstream end portion of the inner cylinder 34 is welded and joined to the downstream end of the introduction cylinder 35 to be fixed. In this state, the catalyst 31 is placed on the catalyst seat 32, and the downstream end on the opposite side of the fixed end of the inner cylinder 34 is fitted into the support cylinder 38.

  In this state, the inner cylinder 34, the catalyst seat 32, and the support cylinder 38 are not fixed, and the inner cylinder 34 can slide relative to the catalyst seat 32 and the support cylinder 38. Further, the downstream end opposite to the fixed end of the inner cylinder 34 is not fixed to the outer case 33 with a predetermined gap 40 between the outer case 33 and the downstream end.

  Further, the heat insulating space 37 between the inner cylinder 34 and the outer case 33 is filled with a heat insulating material (not shown).

  The outer case 33, the introduction cylinder 35, and the flanges 36a, 36b, 36c are made of a stainless material having a thickness capable of withstanding a predetermined pressure in order to provide a pressure resistant structure. On the other hand, a heat resistant alloy such as Inconel is used for the inner cylinder 34 so as to withstand the high temperature of the reforming reaction. At this time, since the outer case 33 has a pressure-resistant structure, the inner cylinder 34 does not need to be pressure-resistant designed. Therefore, the plate pressure is set to be thinner than the members constituting the outer case 33 and the like.

  With such a structure, in the reformer 1, the raw material gas supplied from the raw material gas supply path 10 is reformed by bringing the raw material gas into contact with the catalyst 31 in the inner cylinder 34, and the resulting reformed gas is converted into the inner cylinder 34. The flow holes 32 a and the support cylinders 38 are passed through the reformed gas passage 25.

As the catalyst 31, an Rh-modified (Ni—CeO ₂ ) —Pt catalyst is used. With this one type of catalyst, a hydrocarbon combustion reaction and a reforming reaction are performed in one reaction region in the inner cylinder 34. The hydrocarbon combustion reaction and the reforming reaction are simultaneously performed in the same reaction region.

  The reformer 1 includes an inner cylinder 34 that has a catalyst disposed therein, reforms the raw material gas introduced from the upstream end, and discharges the reformed gas to the downstream end, and the inner cylinder 34 and a predetermined heat insulating space. And the outer case 33 that accommodates the inner cylinder 34 in a state where the inner cylinder 34 is separated, even if the reformed gas flows and the inside of the inner cylinder 34 becomes hot, the outer case 33 is interposed via the heat insulating space 37. Since 33 exists, the outer case 33 does not become so hot as compared with the inner cylinder 34. Therefore, it is possible to use a material having a high temperature durability only for the inner cylinder 34 and to use a relatively inexpensive material such as stainless steel for the outer case 33, so that the equipment cost can be greatly reduced. In addition, since the outer case 33 has a pressure-resistant structure, it is not necessary to consider the pressure resistance of the inner cylinder 34, so that the thickness of the inner cylinder 34 formed from a relatively expensive high-temperature durable material can be reduced. Therefore, the facility cost can be further reduced.

  Further, the inner cylinder 34 is fixed to the outer case 33 at the upstream end of the source gas, and the outer case 33 has a predetermined gap 40 between the end opposite to the fixed end and the outer case 33. Therefore, even if a large difference in thermal expansion occurs between the inner case 34 and the outer case 33 in which the temperature rise is suppressed, the inner case 34 and the outer case 33 are heated. Is absorbed by the predetermined gap 40 between the outer case 33 and the inner cylinder 34. Accordingly, there is no concentration of stress between the inner tube 34 that is at a high temperature and the outer case 33 that is at a relatively low temperature, and creep fatigue failure is caused by repeated start and stop, which has been a problem in the past. Disappear.

  Further, in the reformer 1, since the fixed end of the inner cylinder 34 is the upstream end, damage to the joint portion at the fixed end of the inner cylinder 34 can be prevented in advance. That is, when the end opposite to the fixed end of the inner cylinder 34 fixed to the outer case 33 is the upstream end, a predetermined gap between the end and the outer case 33 when the source gas flows. The flow of the raw material gas is disturbed in the portion 40, and vibration is generated in the inner cylinder 34 itself, and stress is applied to the fixed end and the joint is easily damaged. However, the predetermined gap 40 is formed with the fixed end as an upstream end. By disposing on the downstream side, the flow of the raw material gas is made smooth to prevent the vibration of the inner cylinder 34, the stress applied to the fixed end is greatly reduced, and the joint portion is prevented from being damaged.

  Further, in the reformer 1, the support cylinder 38 provided in the outer case 33 is fitted and inserted into the inner cylinder 34 at the end opposite to the fixed end of the inner cylinder 34. It functions as a displacement prevention member that prevents displacement of the portion. For this reason, damage to the joint portion at the fixed end of the inner cylinder 34 can be prevented in advance. That is, when the end opposite to the fixed end of the inner cylinder 34 fixed to the outer case 33 is a free end, the inner cylinder 34 itself is applied when an external force is applied to the reformer 1 itself. Vibrates, a large stress is applied to the fixed end, and the joint is easily damaged. However, by providing a support tube 38 (displacement prevention member) that is fitted into the end opposite to the fixed end, the modification is improved. Even if an external force is applied to the vessel 1, the vibration of the inner cylinder 34 is prevented, the stress applied to the fixed end is greatly reduced, and damage to the joint can be prevented.

  In the above-described example, the case where the fixed end of the inner cylinder 34 is the upstream end has been described. However, the inner cylinder 34 is connected to the outer case 33 at either one of the upstream end and the downstream end of the source gas. If it is fixed with respect to it, it is the meaning included in this invention.

  FIG. 3 shows a second example of the reformer 1 to which the present invention is applied. In this example, the catalyst seat 32 is fixed to the inside of the inner cylinder 34 by welding, and the catalyst 31 is placed. Further, the outer case 33 is formed in a cylindrical shape, and the downstream end of the inner cylinder 34 is greatly opened in the first heat exchanger 3. A disc-like member 39 that protrudes inward is attached to a portion near the downstream end of the outer case 33, and this disc-like member 39 functions as a displacement prevention member. Other than that, it is the same as that of the said 1st example, and attaches | subjects the same code | symbol to the same part.

  For example, hydrogen is generated by the hydrogen generator as follows.

  That is, the natural gas supplied as a raw material is heat-exchanged with the reformed gas flowing through the modified gas path 26 by the sixth heat exchanger 17 in the process of being compressed by the compressor 19 and flowing through the natural gas supply path 22. The second heat exchanger 9 exchanges heat with the reformed gas flowing through the reformed gas path 25 and is heated. Further, it is heated by the preheating heater 8 and the sulfur additive is removed by the desulfurizer 7 and introduced into the raw material gas supply path 10.

  On the other hand, tap water supplied as a raw material is made pure water by the pure water device 12 and then pumped by the pure water pump 13 to circulate through the water supply path 23. In the process, the fifth heat exchanger 15 and the fourth heat exchanger 14 are heated by being exchanged with the reformed gas flowing through the shift gas passage 26 and heated by the pure water heater 16. The heat is exchanged with the reformed gas flowing through the reformed gas path 25 in the three heat exchanger 11 and heated, steamed by the steam heater 6, and introduced into the raw material gas supply path 10 through the steam supply path 23a.

  The natural gas and water vapor introduced into the source gas supply path 10 become a mixed gas while flowing through the source gas path, and are heat-exchanged with the reformed gas flowing through the reformed gas path 25 in the first heat exchanger 3. Heated. Oxygen supplied to the oxygen supply path 24 is further introduced into the source gas supply path 10, and a mixed gas of natural gas, water vapor, and oxygen is supplied to the reformer 1 as a source gas.

In the reformer 1, the hydrocarbon combustion reaction and the reforming reaction are performed by the Rh-modified (Ni—CeO ₂ ) -Pt catalyst, and the hydrocarbon combustion reaction and the reforming reaction are performed in one reaction region in the inner cylinder 34. Are performed simultaneously in the same reaction zone.

That is, a combustion reaction in which part of the hydrocarbon is completely burned to convert the hydrocarbon into CO and H ₂ O, and each of CO ₂ and H ₂ O generated by this combustion reaction is further reacted with the remaining hydrocarbon. the reforming reaction and for converting by the H ₂ and CO, is allowed to proceed over the catalyst, it is of to convert hydrocarbons to H ₂ and CO.

For example, the case where the hydrocarbon is methane will be described as an example, and the reaction is generally expressed as in the following formula (1), but in reality, it is a combustion reaction as expressed in the formulas (2) to (4). This is a sequential reaction in which the produced CO ₂ and H ₂ O further undergo a reforming reaction with CH ₄ and are converted to CO and H ₂ .
CH ₄ + 2O ₂ → 4CO + 8H ₂ (1)
CH ₄ + 2O ₂ → CO ₂ + 2H ₂ O (2)
CH ₄ + CO ₂ → 2CO + 2H ₂ (3)
2CH ₄ + 2H ₂ O → 2CO + 6H ₂ (4)

In the contact reaction between CH ₄ and O ₂ , CO ₂ or 2H ₂ O can be further supplied to the system. In this case, the supply amount of O ₂ can be reduced in accordance with the supply amount of CO ₂ or 2H ₂ O.

The reaction temperature is suitably from 350 to 800 ° C, particularly from about 400 to 750 ° C. Although the reaction temperature is partially compensated by the reaction of CH ₄ and O ₂ , the shortage is externally heated. When the reaction temperature is too low, the reforming reaction of CH ₄ itself does not proceed smoothly. On the other hand, when the reaction temperature is too high, it is disadvantageous in terms of thermal energy, and carbon deposition occurs due to thermal decomposition of CH _4. Tend. The reaction pressure is usually a pressurizing condition, but may be normal pressure.

The composition of the reformed gas obtained by this reforming process is approximately 70% H ₂ + 15% CO + 15% CO _{2 on} a dry basis, with the remainder being impure. This reforming process is an exothermic reaction on the catalyst, and the temperature of the reformed gas at the outlet is about 700 to 800 ° C.

The Rh-modified (Ni—CeO ₂ ) -Pt catalyst is obtained, for example, by supporting Rh on an alumina support surface having an appropriate porosity, then supporting Pt, and simultaneously supporting Ni and CeO _2. It is done. However, various variations are possible for the selection of the material and shape of the carrier, the presence / absence of coating formation, and the selection of the material.

Rh is supported by impregnating an aqueous solution of a water-soluble salt of Rh, followed by drying, firing, and hydrogen reduction. Pt is supported by impregnating an aqueous solution of a Pt water-soluble salt, followed by drying, firing, and hydrogen reduction. Simultaneous loading of Ni and CeO ₂ is performed by impregnating a mixed aqueous solution of a water-soluble salt of Ni and a water-soluble salt of Ce, followed by drying, firing, and hydrogen reduction.

The target Rh-modified (Ni—CeO ₂ ) -Pt catalyst is obtained by the procedure exemplified above. The composition of each component is Rh: Ni: CeO ₂ : Pt = (0.05-0.5) :( 3.0-10.0) :( 2.0-8.0) :( 0 .3-5.0), preferably Rh: Ni: CeO ₂ : Pt = (0.1-0.4) :( 4.0-9.0) :( 2.0-5.0): It is preferable to set to (0.3-3.0).

  In addition, the hydrogen reduction process in each step in the above may be omitted, and the catalyst 31 may be used after being reduced with hydrogen at a high temperature in actual use. Even when the hydrogen reduction treatment is performed at each stage, the catalyst 31 can be further reduced with hydrogen at a high temperature before use.

In the CO converter 4, a CO conversion process for converting CO in the reformed gas into CO ₂ is performed.

That is, about 10 to several tens percent of CO and steam (H ₂ O) in about 15% of CO contained in the reformed gas are reacted as shown in the following reaction formula to be converted into CO ₂ and H ₂ . Through this CO conversion step, the composition of the reformed gas becomes approximately 77% H ₂ + 22% CO ₂ + 1% CO + remaining impurity content on a dry basis.
CO + H ₂ O → CO ₂ + H ₂

If necessary, a CO selective oxidizer may be provided on the downstream side of the CO converter 4 to oxidize the CO remaining after the CO conversion step to CO ₂ . That is, CO and O ₂ in the air are reacted as shown in the following reaction formula to form CO ₂ . By this CO selective oxidation, the residual CO content is 10 ppm or less, and the reformed gas composition is approximately 77% H ₂ + 23% CO ₂ + the remaining impure component, which is supplied to hydrogen gas utilization equipment such as fuel cells. The
2CO + O ₂ → 2CO ₂

In the above-described example, the Rh-modified (Ni—CeO ₂ ) —Pt catalyst is used as the reforming catalyst. However, the hydrocarbon combustion reaction and the reforming reaction can be performed simultaneously in the same reaction region. Other catalysts can be used as long as they are suitable.

  As described above, the hydrogen generation apparatus and method perform the combustion reaction, which is an exothermic reaction, and the reforming reaction, which is an endothermic reaction, simultaneously in the same reaction region, thereby converting the thermal energy generated in the combustion reaction to the reforming reaction. Since it can be used as a heat source, it is extremely energy efficient. Furthermore, since the exothermic reaction and the endothermic reaction occur simultaneously in the reaction region, thermal neutralization occurs. For example, compared with the case where a region for performing the catalytic combustion reaction alone is provided in the reformer 1, The temperature rise is considerably suppressed, and it is not necessary to select the heat-resistant material used for the reformer 1 and the heat-resistant structure of the reformer 1 itself so as to have a high-temperature specification, so that the equipment cost can be reduced.

  In addition, the reformer 1 has an outer case 33 through the heat insulating space 37 even when the reformed gas flows and the inside of the inner cylinder 34 becomes hot. Case 33 does not become so hot. Therefore, it is possible to use a material having a high temperature durability only for the inner cylinder 34 and to use a relatively inexpensive material such as stainless steel for the outer case 33, so that the equipment cost can be greatly reduced. In addition, since the outer case 33 has a pressure-resistant structure, it is not necessary to consider the pressure resistance of the inner cylinder 34, so that the thickness of the inner cylinder 34 formed from a relatively expensive high-temperature durable material can be reduced. Therefore, the facility cost can be further reduced. Furthermore, even if the inner cylinder 34 becomes hot and thermally expands and a large difference in thermal expansion occurs between the outer case 33 and the temperature rise is suppressed, the difference in thermal expansion between the inner cylinder 34 and the outer case 33 is It is absorbed in the predetermined gap 40 between the outer case 33 and the inner cylinder 34. Accordingly, there is no concentration of stress between the inner tube 34 that is at a high temperature and the outer case 33 that is at a relatively low temperature, and creep fatigue failure is caused by repeated start and stop, which has been a problem in the past. Disappear.

FIG. 4 shows a third example of the reformer 1 to which the present invention is applied. In this example, so-called autothermal reforming is performed, and the above-described Rh-modified (Ni—CeO ₂ ) —Pt catalyst or the like allows a hydrocarbon combustion reaction and a reforming reaction to be simultaneously performed in the same reaction region. Instead, the combustion catalyst 41 is disposed upstream of the raw material gas as a catalyst, and the reforming catalyst 42 is disposed downstream thereof.

  In the reformer 1, the thermal energy necessary for the reforming reaction in the reforming catalyst 42 is supplemented by the combustion energy obtained by burning the raw material gas with the combustion catalyst 41.

  For example, when methane is used as the raw material gas and a part of the methane is burned at a stoichiometric ratio or less, the fuel gas undergoes the following reaction.

CH ₄ + 1 / 2O ₂ = 2H ₂ + CO (1)
CH ₄ + 2O ₂ = CO ₂ + 2H ₂ O (2)
The reaction at this time is an exothermic reaction and has an advantage that hydrogen required in the fuel cell is generated.

  In the process where a part of the raw material gas is partially burned by the combustion catalyst and hydrogen is generated by the reaction of the equations (1) and (2), the vapor generated by the reaction of the equation (2) reacts with the remaining raw material gas. However, hydrogen is generated by the reforming reaction of the following formula.

CH ₄ + H ₂ O = 3H ₂ + CO (3)
That is, when the steam and the remaining raw material gas react in the reforming catalyst, a hydrogen-rich reformed gas is generated.

  Other than that, it is the same as that of the above-mentioned Example, and there exists the same effect.

  The present invention can be applied not only to hydrogen generators for household fuel cells, but also to hydrogen generators for automobiles, plants, and other fuel cells, and for hydrogen gas utilization equipment other than fuel cells. The present invention can also be applied to a hydrogen generator for supplying hydrogen gas.

It is a figure which shows one Example of the hydrogen generator to which this invention is applied. It is sectional drawing which shows one Example of the reformer to which this invention is applied. It is sectional drawing which shows the 2nd example of the said reformer. It is sectional drawing which shows the 3rd example of the said reformer.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Reformer 2 Raw material heater 3 1st heat exchanger 4 CO converter 5 Adsorption device 6 Steam heater 7 Desulfurizer 8 Preheating heater 9 2nd heat exchanger 10 Raw material gas supply path 11 3rd heat exchanger 12 Pure water apparatus DESCRIPTION OF SYMBOLS 13 Pure water pump 14 4th heat exchanger 15 5th heat exchanger 16 Pure water heater 17 6th heat exchanger 18 Gas-liquid separator 19 Compressor 20a 1st adsorption tower 20b 2nd adsorption tower 21 Vacuum pump 22 Natural gas Supply path 23 Water supply path 23a Steam supply path 24 Oxygen supply path 25 Reformed gas path 26 Metamorphic gas path 27 Drainage path 29 Product gas path 31 Reformed catalyst 32 Catalyst seat 32a Flow hole 33 Outer case 34 Inner cylinder 35 Introducing cylinder 36a Flange 36b Flange 36c Flange 37 Heat insulation space 38 Bearing cylinder 39 Disc member 40 Predetermined gap 41 Combustion catalyst 42 Reforming catalyst

Claims (5)

A hydrogen generator for reforming a hydrocarbon gas to produce a hydrogen-rich reformed gas,
Comprising a reformer that causes the hydrocarbon gas to contact and react with the catalyst together with water vapor and oxygen to burn and reform the hydrocarbon gas;
In the reformed gas path provided on the downstream side of the reformer,
A heat exchanger for water heating that heats water as a water vapor source by heat exchange with the reformed gas;
A heat exchanger for heating a hydrocarbon gas that heats the hydrocarbon gas by heat exchange with the reformed gas is provided,
Further, heating with the hydrocarbon gas heating heat exchanger is performed upstream of the water heating heat exchanger and the hydrocarbon gas heating heat exchanger in the reformed gas path by heat exchange with the reformed gas. A raw material gas heating heat exchanger for heating a raw material gas that is a mixed gas of the hydrocarbon-based gas and water vapor obtained from water heated by the water heating heat exchanger,
Further, the raw material gas supply path for supplying the raw material gas is provided with a raw material heater for heating the raw material gas introduced into the reformer in the initial operation of the hydrogen generator in which the temperature of the reformer has not sufficiently increased. ,
The water-heating heat exchanger, hydrocarbon gas heat exchanger for heating, without introducing oxygen gas into the heat exchanger and the raw material for the heater material gas heating, Rukoto to introduce oxygen gas into the raw material gas supply passage A hydrogen generator characterized by   The hydrogen generator according to claim 1, wherein a plurality of the water heating heat exchangers are provided in the reformed gas path.   The hydrogen generator according to claim 1 or 2, wherein a plurality of the hydrocarbon-based gas heating heat exchangers are provided in the reformed gas path. The hydrogen generator according to any one of claims 1 to 4 , further comprising an adsorption device that adsorbs impurities in the reformed gas, wherein the adsorption device is a pressurized vacuum pressure swing adsorption device. A hydrogen generation method for reforming a hydrocarbon gas to produce a hydrogen-rich reformed gas,
A reforming step of bringing the hydrocarbon gas into contact with a catalyst together with water vapor and oxygen to burn and reform the hydrocarbon gas;
On the downstream side of the reforming step,
A heat exchange process for water heating that heats water as a water vapor source by heat exchange with the reformed gas;
A heat exchange process for heating a hydrocarbon gas that heats the hydrocarbon gas by heat exchange with the reformed gas,
Further, heating is performed in the hydrocarbon gas heating heat exchange step by heat exchange with the reformed gas upstream of the water heating heat exchange step and the hydrocarbon gas heating heat exchange step in the reformed gas path. Performing a raw material gas heating heat exchange step of heating a raw material gas which is a mixed gas of the hydrocarbon-based gas and water vapor obtained from the water heated in the water heating heat exchange step,
Further, the raw material gas supply step of supplying the raw material gas, the operation initial hydrogen generator reformer is not sufficiently rise in temperature, line physician raw material heating step of heating the raw material gas to be introduced into the reformer ,
Introducing oxygen gas in the raw material gas supply step without introducing oxygen gas in the water heating heat exchange step, hydrocarbon gas heating heat exchange step, raw material gas heating heat exchange step and raw material heating step A method for generating hydrogen.

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