JP4464230B2 - Reforming apparatus and method, and fuel cell system - Google Patents

Description

  The present invention relates to a reformer that reforms a raw material for hydrogen production such as kerosene using steam to obtain a reformed gas containing hydrogen. The present invention also relates to a fuel cell system including this reformer.

  In recent years, fuel cells have attracted attention as environmentally friendly energy conversion technologies. In many types of fuel cells, such as solid polymer forms, it is hydrogen that actually undergoes an electrode reaction at the fuel electrode of the fuel cell. However, because hydrogen production raw materials such as kerosene are superior to hydrogen in terms of supply system and handling, the hydrogen production raw materials such as kerosene are reformed to produce hydrogen-containing gas, which is used as a fuel cell. A fuel cell system for supplying fuel to the fuel electrode has been developed.

It is known to perform steam reforming to reform the raw material for hydrogen production. For example, Patent Documents 1 and 2 disclose techniques for producing a hydrogen-containing gas by reforming a mixture of kerosene or the like and steam under a reforming catalyst.
JP 2004-175621 A JP 2002-2014478 A

  When the raw material for hydrogen production is mixed with water vapor, heated to an appropriate temperature and introduced into the reforming catalyst layer, the mixture is uniform even if the mixture of the raw material for hydrogen production and water vapor is at an appropriate temperature. If it is not mixed in a gaseous state, coke may precipitate. Since coke hinders the functioning of the reforming catalyst and also causes channel blockage, coke deposition hinders long-term operation of the reformer.

  For example, when the raw material for hydrogen production is simply combined with steam in the piping, coke deposition on the reforming catalyst due to the heterogeneity of the mixture is observed, or the fluctuations in CO concentration and methane concentration are large. Driving may become unstable. Such a tendency is particularly strong when the raw material for hydrogen production is a hydrocarbon oil such as kerosene.

  The reformed gas obtained in the reformer is further processed by a CO converter or the like as necessary to reduce the CO concentration, and then used as fuel for fuel cells. Such fluctuations may also affect processing devices such as CO converters and fuel cells.

  An object of the present invention is to provide a reforming apparatus and a reforming method that can suppress the above-described phenomenon and can be stably operated for a long period of time.

  Another object of the present invention is to provide a fuel cell system that can be stably operated for a long period of time.

According to the present invention, in a reformer for mixing a raw material for hydrogen production and steam, and reforming the mixture by steam to obtain a reformed gas containing hydrogen,
Mixing means for mixing the raw material for hydrogen production with water vapor;
A mixing promoting means for promoting the mixing of the raw material for hydrogen production and steam disposed downstream of the mixing means; and a reforming means for reforming the mixture promoted by the mixing promoting means in the presence of the reforming catalyst. It has a quality instrument,
A reformer is provided in which the cross-sectional area of the mixing means is 1.5 to 3 times the cross-sectional area of the mixing promoting means .

  In the above reformer, it is preferable that the mixing promoting means has a structure in which a baffle plate is arranged inside the tubular member.

  It is preferable that the reformer further includes a heating unit for heating the mixture of the raw material for hydrogen production and water vapor downstream of the mixing promoting unit and upstream of the reforming catalyst.

In the reformer, the reformer has a combustion means for generating heat necessary for steam reforming,
The heating means is preferably a heat exchange means that is disposed in a flow path through which the combustion gas of the combustion means flows and heats the mixture of the raw material for hydrogen production and water vapor with the combustion gas.

  The heat exchange means may have a structure in which a tube is wound in a coil shape or a structure in which a plurality of straight tubes are connected in parallel.

According to the present invention, in a reforming method of mixing a raw material for hydrogen production and steam, and steam reforming the mixture to obtain a reformed gas containing hydrogen,
A reforming apparatus for mixing a raw material for hydrogen production with steam and steam reforming the mixture to obtain a reformed gas containing hydrogen, the mixing means for mixing the raw material for hydrogen production with steam; A mixing promoting means for promoting the mixing of the raw material for hydrogen production and water vapor, and a reformer for reforming the mixture whose mixing is promoted by the mixing promoting means in the presence of the reforming catalyst. Using a reformer having a flow path cross-sectional area of the mixing means that is 1.5 to 3 times the flow path cross-sectional area of the mixing promoting means,
Mixing step of mixing raw material for hydrogen production and water vapor;
After the mixing step, a mixing promotion step for promoting mixing of the raw material for hydrogen production and steam; and a reforming step for reforming the mixture whose mixing has been promoted in the mixing promotion step in the presence of the reforming catalyst. A reforming method is provided.

  In the above reforming method, it is preferable that the temperature of the raw material for hydrogen production mixed in the mixing step is 300 ° C. or lower and the temperature of the water vapor is 100 ° C. or higher.

  Preferably, the reforming method further includes a heating step of heating the mixture of the raw material for hydrogen production and water vapor by heat exchange after the mixing promotion step and before the reforming step.

  In the heating step, the residence time of the mixture heated by heat exchange is preferably 0.1 seconds or more.

  In the heating step, the linear velocity of the mixture heated by heat exchange is preferably 10 m / s or more.

  In the heating step, the mixture is preferably heated to 300 ° C. or higher and 600 ° C. or lower.

In order to generate heat necessary for steam reforming in the reforming step, combustion is performed,
It is preferable to use the combustion gas of the combustion at 300 ° C. or higher and 700 ° C. or lower as the heat transfer fluid used for the heat exchange.

According to the present invention, a fuel having a reforming device that mixes a raw material for hydrogen production and steam, steam reforms the mixture to obtain a reformed gas containing hydrogen, and a fuel cell using the reformed gas as fuel. In battery systems,
A fuel cell system in which the reformer is the above reformer is provided.

  The present invention provides a reformer and a reforming method that can be stably operated for a long period of time.

  The present invention also provides a fuel cell system that can be stably operated for a long period of time.

  Hereinafter, the present invention will be described with reference to the drawings, but the present invention is not limited thereto.

  As shown in FIG. 1, the reforming apparatus of the present invention promotes the mixing of the hydrogen production raw material and steam, which is arranged downstream of the mixing means 1001 for mixing the hydrogen production raw material and steam, and the mixing means. It has a mixing promoting means 1002 and a reformer 1003 for reforming the mixture whose mixing has been promoted by the mixing promoting means in the presence of the reforming catalyst. Here, kerosene is used as a raw material for hydrogen production. In addition, a steam reformer is used as the reformer, and in particular, an externally heated steam reformer that supplies heat necessary for reforming with combustion gas is used.

  The raw material for hydrogen production introduced into the mixing means 1001 may be liquid, gas, or gas-liquid mixed phase. When the hydrogen production raw material introduced into the mixing means is gas, a vaporizer for vaporizing the hydrogen production raw material can be provided upstream of the mixing means as necessary. When the raw material for hydrogen production to be introduced into the mixing means is a liquid, no vaporizer is provided, and the raw material for hydrogen production can be introduced into the mixing means at room temperature (without particular heating). Alternatively, the raw material for hydrogen production can be preheated within a range where it does not vaporize and then introduced into the mixing means. As the vaporizer, a known vaporizer capable of vaporizing a raw material for hydrogen production can be appropriately used. As the preheater for the preheating, a known preheater such as a heat exchanger capable of preheating the raw material for hydrogen production can be appropriately used.

  As a structure of the mixing means, a known mixing technique capable of mixing fluids can be employed. From the viewpoint of ease of production, a structure in which a steam pipe and a hydrogen production raw material pipe are connected can be preferably employed. For example, as shown in FIG. 1, the structure of the mixing means can be a structure in which a pipe (straight pipe) for introducing kerosene is connected in the middle of a pipe (straight pipe) through which water vapor flows.

  The temperature of the raw material for hydrogen production introduced into the mixing means is preferably set to a temperature at which thermal decomposition of the raw material for hydrogen production can be satisfactorily suppressed. From this viewpoint, the temperature of the raw material for hydrogen production introduced into the mixing means is preferably 350 ° C. or lower, and more preferably 300 ° C. or lower. It should be noted that this temperature may be normal temperature or higher because there is no meaning to cool.

  Although the temperature of the water vapor introduced into the mixing means depends on the pressure, it is preferably at least 100 ° C. from the viewpoint of at least the boiling point of water at atmospheric pressure. Moreover, since the evaporation of kerosene is promoted by the heat of steam, the higher one is desirable. Practically, it is preferably about 450 ° C. or less, and more preferably 400 ° C. or less.

  The mixing ratio of the raw material for hydrogen production and steam can be appropriately determined in consideration of S / C (steam / carbon ratio) suitable for reforming.

  As the mixing promoting means, a known technique that can promote mixing of gases or a known technique that can promote mixing of gas and liquid can be used.

  It is preferable that the mixing promoting means has a structure in which a baffle plate is arranged inside the tubular member because no separate power is required and a good mixing promoting effect can be expected. As such a mixing means, a static mixer in which baffle plates for geometrically mixing substances more uniformly are arranged in a tube such as a circular tube can be used.

From the viewpoint of suppressing pressure fluctuation, the channel cross-sectional area of the mixing unit is preferably 1.5 times or more, more preferably 2 times or more than the channel cross-sectional area of the mixing promoting unit. In addition, this ratio is preferably 3 times or less, more preferably 2.5 times or less from the viewpoint of maintaining the linear velocity of the fluid. For example, when the raw material for hydrogen production is kerosene, some kerosene is vaporized by mixing with steam, and the volume of fluid changes due to partial condensation of steam. The pulsation accompanying the volume change can be suppressed. In the present invention, this ratio is particularly 1.5 times or more and 3 times or less.

  For example, when the mixing means has a structure in which a pipe through which the raw material for hydrogen production flows is connected in the middle of a pipe through which water vapor flows, and the mixing promoting means has a structure having a baffle plate in the pipe, water vapor flows. The channel cross-sectional area of the tube is preferably 1.5 times or more and 3 times or less, and more preferably 2 times or more and 2.5 times or less the channel cross-sectional area of the tube forming the mixing promoting means. When considering the cross-sectional area of the flow path, the baffle plate is ignored.

  As the reformer, a known reformer utilizing a steam reforming reaction can be used. A reformer that utilizes a partial oxidation reaction in addition to the steam reforming reaction can also be used.

  The steam reforming reaction is accompanied by a violent endotherm. In order to advance the reforming reaction, heat is supplied. For this purpose, an externally heated reformer equipped with combustion means is known. The external heat type reformer has a combustion means such as a burner for burning combustion fuel with an oxygen-containing gas such as air, and a reaction tube filled with, for example, a reforming catalyst by the combustion heat generated by the combustion means. Heat.

  FIG. 1 also shows an external heat type reformer, which burns with a burner 1003a, heats the reaction tube 1003b filled with the reforming catalyst with its radiant heat, and also transfers the combustion gas to the reaction tube 1003b. The reaction tube is heated by contact. As the combustion fuel, a known fuel may be appropriately selected and used. However, it is preferable to use a hydrogen production raw material used as a reformed gas raw material as a combustion fuel in order to simplify the entire apparatus.

  At the stage of supplying to the reforming catalyst, the mixture of the raw material for hydrogen production and water vapor is made a gas. Therefore, when the mixture extracted from the mixing promoting means contains a liquid, the liquid is vaporized in advance. Moreover, it is preferable to preheat the temperature of the mixture supplied to the reforming catalyst to a temperature suitable for the reforming reaction.

  For this vaporization and / or preheating, a heating means for heating the mixture of the raw material for hydrogen production and water vapor can be provided. The combustion gas can be used for this heating. As the heating means, heat exchange means using combustion gas as a heat transfer fluid and a mixture of a raw material for hydrogen production and water vapor as a heat reception fluid can be used.

  For example, the heat exchange means 1004 having a structure in which a tube is wound in a coil shape or a structure in which a plurality of straight pipes are connected in parallel can be arranged in a flow path through which combustion gas in the reformer flows. . As a structure in which a plurality of straight pipes are connected in parallel, a structure in which both ends of a straight pipe having a deflection in consideration of heat shrinkage at the intermediate portion are respectively attached to an inlet header and an outlet header is preferable.

  In this heat exchange means, it is heated by heat exchange from the viewpoint of homogeneously mixing the raw material for hydrogen production and water vapor, and from the viewpoint of promoting vaporization when the raw material for hydrogen production is a liquid such as kerosene. The residence time of the mixture is preferably 0.1 seconds or more, and more preferably 0.2 seconds or more. In other words, in order to mix kerosene or other hydrocarbon oil with steam and evaporate it uniformly, the residence time when the mixture passes through the heat exchange means is set to 0.1 seconds or more to promote heat exchange with the combustion gas. It is preferable to make it. The linear velocity of the fluid passing through the heat exchange means is preferably 10 m / s or more in order to reduce the film coefficient and promote heat exchange. More preferably, it is 20 m / s or more.

  For example, when the hydrogen production raw material is kerosene, the steam temperature at the heat exchange means inlet is preferably 100 ° C. or higher, more preferably 150 ° C. or higher from the viewpoint of promoting evaporation.

  The temperature of the mixture at the outlet of the heat exchange means is preferably 300 ° C. or higher, more preferably 450 ° C. or higher from the viewpoint of promoting the reforming catalyst reaction. Moreover, it is preferable to set it as 600 degrees C or less from a viewpoint of the coke precipitation prevention by thermal decomposition, and 550 degrees C or less is more preferable.

  On the other hand, the temperature of the flue gas used for heat exchange is preferably 450 ° C. or higher, and more preferably 550 ° C. or higher from the viewpoint of more uniformly vaporizing and mixing kerosene and steam when the raw material for hydrogen production is kerosene. Moreover, 700 degrees C or less is preferable from a viewpoint of the heat balance of a system, and 650 degrees C or less is more preferable.

  As explained above, by using the mixing promoting means, when the mixture mixed by the mixing means is a gas, the mixing becomes more uniform, and even if this mixture is a gas-liquid mixed phase, it is probably in the liquid. Mixing is promoted in a form in which bubble-like gas is taken in. As a result, when the mixture is supplied to the reforming catalyst, the uniformity of the mixture becomes excellent, the above-mentioned coking and the like are suppressed, and long-term stable operation is possible.

  Generally, when the raw material for hydrogen production is a hydrocarbon oil such as kerosene, long-term stable operation tends to be difficult because coking is likely to occur. Moreover, when mixing gas and liquid, it is more difficult to make the mixture uniform in the stage supplied to a reforming catalyst compared with the case where gas is mixed. According to the present invention, even in such a case, the uniformity of the mixture at the stage of being supplied to the reforming catalyst can be improved, and a stable operation can be performed for a longer period of time. That is, the effect of the present invention is particularly remarkable when the raw material for producing hydrogen is a hydrocarbon oil such as kerosene, and further when the hydrocarbon oil introduced into the mixing means is a liquid.

[Raw materials for hydrogen production]
As a raw material for hydrogen production, any substance that can obtain a reformed gas containing hydrogen by a steam reforming reaction can be used. For example, compounds having carbon and hydrogen in the molecule, such as hydrocarbons, alcohols, and ethers, can be used. Alternatively, a hydrocarbon oil that is liquid at 25 ° C. and 0.101 MPa, includes a compound having carbon and hydrogen in the molecule, and is an organic compound capable of generating hydrogen by a steam reforming reaction can be used.

  Preferable examples of raw materials for hydrogen production that can be obtained at low cost for industrial use or consumer use include methanol, ethanol, dimethyl ether, methane, city gas, LPG (liquefied petroleum gas), and gasoline obtained from petroleum, naphtha. And hydrocarbon oils such as kerosene and light oil. Of these, kerosene is preferable because it is easily available for industrial use and consumer use, and is easy to handle.

  In addition, in order to suppress catalyst poisoning, such as a reforming catalyst, the desulfurization which reduces the sulfur content in the raw material for hydrogen production can be performed as needed. For this purpose, the raw material for hydrogen production can be desulfurized and introduced into the mixing means.

[Hydrogen production equipment]
The reformer of the present invention can be suitably used in a fuel cell system. It is also possible to use the reformed gas obtained in the reformer as fuel for the fuel cell without passing through another reactor. However, when the fuel cell is of a solid polymer type, for example, a CO converter or a selective oxidizer is usually provided to reduce the CO concentration in the reformed gas. Hereinafter, the present invention will be described in more detail by taking such a case as an example. In the following description, an apparatus having a CO converter and a selective oxidizer in addition to the reformer is referred to as a hydrogen production apparatus.

  The hydrogen production apparatus described here is a hydrogen production apparatus that has the effects of improving thermal efficiency, reducing the occupied volume, extending the life span and operating conditions.

Specifically, this hydrogen production apparatus includes a reformer having a reforming pipe that obtains a reformed gas containing hydrogen by steam reforming hydrocarbon oil, and a burner that heats the reforming pipe; Steam generator for generating steam necessary for quality; CO converter for reducing CO concentration in reformed gas by shift reaction; and selective oxidation of CO concentration in reformed gas whose CO concentration is reduced by CO converter A hydrogen production apparatus having a selective oxidizer that is further reduced by reaction,
A first region that is a vertical cylindrical region, a second region that is an annular region that is concentric with the first region and located on the outer peripheral side of the first region, and a concentric with the first region that is located on the outer peripheral side of the second region A third region that is an annular region of the second region, and a fourth region that is an annular region that is located on the outer peripheral side of the third region and is concentric with the first region,
Having the burner in a first region;
Having the reforming tube in the second region;
Having the steam generator in a third region;
The fourth region includes the CO converter and the selective oxidizer. And this hydrogen production apparatus has a mixing means for mixing the steam generated by the steam generator and the hydrocarbon oil, and a mixing promoting means for promoting the mixing of the mixture obtained by the mixing means.

  In this hydrogen production apparatus, the first region, the second region, and the third region are formed in one sealable container, and the fourth region is formed in a sealable container different from the container. There are different forms.

  Further, there is a form in which the first region, the second region, the third region, and the fourth region are formed in one sealable container.

  The hydrogen production apparatus preferably has a combustion gas flow path for heating the reforming pipe, the steam generator, the CO converter and the selective oxidizer in this order by the combustion gas of the burner.

  Furthermore, a desulfurizer for desulfurizing hydrocarbon oil can be provided in the third region and in the combustion gas flow path.

Alternatively, it further comprises a desulfurizer filled with a desulfurizing agent in a sealable container in which none of the first region, the second region, the third region, and the fourth region is formed,
A flow path for heating the desulfurizer can be provided by the combustion gas obtained by heating the reforming pipe, the steam generator, the CO converter, and the selective oxidizer.

  It is preferable that the burner is arranged vertically downward and has a combustion cylinder.

  In the fourth region, the CO transformer and the selective oxidizer are arranged in the vertical direction.

  Alternatively, in the fourth region, the CO transformer and the selective oxidizer are arranged in the circumferential direction.

  It is preferable to have a cooling line that cools the CO converter and the selective oxidizer with water vapor generated by the steam generator.

  It is preferable that water having a pressure of 500 kPa to 1000 kPa is supplied to the steam generator.

  A fuel cell system including the hydrogen production apparatus and a fuel cell using the hydrogen-containing gas produced by the hydrogen production apparatus as a fuel is a highly efficient and compact fuel cell system.

In this fuel cell system, a combustion catalyst is disposed in the second region, and
There is a form having a line for guiding the anode off gas of the fuel cell to the combustion catalyst.

  Alternatively, there is a mode in which the burner is a mixed combustion burner capable of combusting an anode off gas and hydrocarbon oil of a fuel cell, and has a line for guiding the anode off gas of the fuel cell to the burner.

[Desulfurization]
Since sulfur has an effect of inactivating the steam reforming catalyst, the sulfur concentration in the hydrocarbon oil supplied to the steam reforming reactor is preferably as low as possible. Preferably it is 50 mass ppm or less, More preferably, it is 20 mass ppm or less. For this reason, if necessary, the hydrocarbon oil can be desulfurized before the steam reforming. A hydrocarbon oil that has been desulfurized before being supplied to the hydrogen production apparatus may be used, or a desulfurizer may be provided in the hydrogen production apparatus. When providing a desulfurizer, the hydrocarbon oil supplied to a desulfurizer can use suitably what can be desulfurized, for example to the said sulfur concentration in a desulfurizer.

  As the desulfurization method, a method of sorbing a sulfur component in the presence of a sorption-type desulfurization catalyst is preferable from the viewpoint of simplification of the system, ease of control method, and ease of catalyst pretreatment. The sorption-type desulfurization catalyst removes sulfur by adsorption and / or absorption. For example, a catalyst containing Zn / ZnO, Cu / CuO, Ni / NiO or the like is preferable from the viewpoint of sulfur adsorption capacity.

  When a sorption type desulfurization catalyst is used, the desulfurization temperature is preferably 100 to 350 ° C. from the viewpoint of causing the desulfurization catalyst to function well.

  In addition, the desulfurization catalyst may accelerate the decomposition reaction of hydrocarbon oil as well as the detachable sulfur. In this case, the desulfurizer serves as a pre-reformer that partially decomposes the hydrocarbon oil.

[Reform tube]
In the reforming tube that performs the steam reforming reaction, hydrocarbon oil and water react to obtain carbon monoxide and hydrogen. Since this reaction involves a large endotherm, heating from the outside is necessary. For this reason, the hydrogen production apparatus is provided with a burner, and the reforming pipe is heated from the outside by combustion heat.

  For example, hydrocarbon oil and steam can be supplied to a reforming catalyst layer formed by filling a reforming tube with a reforming catalyst, and the reforming catalyst layer can be heated from the outside of the reforming tube.

  The steam reforming reaction can be performed in the presence of a metal catalyst, typically a Group VIII metal such as nickel, cobalt, iron, ruthenium, rhodium, iridium and platinum.

  The reaction temperature can be 450 ° C to 900 ° C, preferably 500 ° C to 850 ° C, more preferably 550 ° C to 800 ° C.

  The pressure of the reforming reaction can be appropriately set, but is preferably in the range of atmospheric pressure to 20 MPa, more preferably atmospheric pressure to 5 MPa, and still more preferably atmospheric pressure to 1 MPa.

The amount of steam introduced into the reaction system is defined as the ratio of the number of moles of water molecules to the number of moles of carbon atoms contained in the hydrocarbon oil (steam / carbon ratio), and this value is preferably 0.5 to 10, more preferably. Is 1-7, more preferably 2-5. The liquid space velocity (LHSV) at this time can be expressed as A / B when the flow rate in the liquid state of the hydrocarbon fuel is A (L / h) and the catalyst layer volume is B (L). Preferably, it is set in the range of 0.05 to 20 h ⁻¹ , more preferably 0.1 to 10 h ⁻¹ , and still more preferably 0.2 to 5 h ⁻¹ .

  The form of the reforming tube is preferably a double tube reactor from the viewpoint of heat balance. In the double tube reactor, the reforming catalyst is filled in the outer ring portion of the double tube, and the catalyst is not filled in the inner tube. The reforming raw material is introduced into the outer ring portion, undergoes a steam reforming reaction when passing through the catalyst layer, turns back at the end opposite to the introduced side, and passes through the inner tube to introduce the raw material. Discharged from the end of the side.

〔burner〕
As the fuel supplied for burning the burner, combustible materials can be used as appropriate. For example, it is preferable to use a hydrocarbon oil used as a raw material for hydrogen production for combustion from the viewpoint of simplification of the hydrogen production apparatus or its incidental facilities. Moreover, when using a hydrogen production apparatus for a fuel cell system, it is preferable from an energy efficiency viewpoint to use anode off gas discharged | emitted from the anode (fuel electrode) of a fuel cell.

  The maximum combustion temperature of the burner is preferably 800 to 1000 ° C. from the viewpoint of the heat resistance temperature of the reformed pipe material.

[CO transformer]
The reformed gas generated in the reforming tube contains carbon monoxide, carbon dioxide, methane, and steam in addition to hydrogen. The CO converter converts carbon monoxide with water to convert it into hydrogen and carbon dioxide in order to increase the hydrogen concentration and carbon monoxide may be a catalyst poison. . Fe-Cr mixed oxide, Zn-Cu mixed oxide, platinum, ruthenium, iridium and other noble metal-containing catalysts are used, and the carbon monoxide content (mol% in dry base) is preferably 2% or less, more Preferably it can be reduced to 1% or less, more preferably 0.5% or less.

  The shift reaction can also be carried out in two stages, in which case the CO converter is divided in two. One is a high temperature CO transformer with a relatively high rated operating temperature, and the other is a low temperature CO transformer with a relatively low rated operating temperature. The high-temperature CO conversion can be performed using a high-temperature CO conversion catalyst having a preferable use temperature of 300 to 500 ° C, and the low-temperature CO conversion is performed using a low-temperature CO conversion catalyst having a preferable use temperature of 100 to 300 ° C. be able to. The high-temperature CO converter and the low-temperature CO converter are installed in this order from the upstream with respect to the reformed gas flow.

The CO conversion is preferably performed at a gas space velocity GHSV (15 ° C., 0.101 MPa conversion) 800 to 3000 h ⁻¹ .

[High temperature CO transformer]
For the high temperature CO converter, a high temperature CO conversion catalyst which is a catalyst having shift reaction activity at 300 to 500 ° C. can be used.

  As the high-temperature CO conversion catalyst, a catalyst containing at least one metal selected from iron, chromium and copper in addition to sulfur is preferable from the viewpoint of shift reaction activity at 300 to 500 ° C. For example, as a mass composition on the oxide basis of a high-temperature shift catalyst, one containing sulfur and 60 to 95% iron, 1 to 30% chromium, and 0.1 to 10% copper is preferable. The shape is preferably spherical, columnar, massive, or ring-shaped, and any molding method may be used, but tablet molding and extrusion molding are preferable.

In the high-temperature CO conversion step, GHSV is preferably 200 to 10,000 h ⁻¹ (GHSV represents a gas space velocity in terms of 15 ° C. and 0.101 MPa. The same applies hereinafter). When it is 200 h ⁻¹ or more, the gas treatment capacity and economy can be improved, and when it is 10000 h ⁻¹ or less, the CO concentration reduction ability is excellent.

[Low-temperature CO transformer]
For the low temperature CO converter, a low temperature CO conversion catalyst which is a catalyst having a shift reaction activity at 100 to 300 ° C. can be used.

  As the low-temperature modification catalyst, a catalyst containing at least one metal selected from copper, zinc, nickel, iron, manganese, platinum, gold, ruthenium, rhodium and rhenium is preferable from the viewpoint of shift reaction activity. The total amount of metal contained is preferably 5 to 90% by mass on the oxide basis, and the shape is preferably spherical, cylindrical, massive, or ring-shaped, and any molding method may be used, but tablet molding and extrusion Molding is preferred. The catalyst preparation method is not particularly limited, but a coprecipitation method, a gel kneading method, and an impregnation method are preferable.

  The gas supplied to the low temperature CO converter preferably has a CO concentration (mol% of dry base) of 2% or more from the viewpoint of preventing the burden on the high temperature CO conversion catalyst from increasing and preventing deterioration. From the viewpoint of preventing an increase in the burden of the low-temperature CO conversion catalyst and preventing catalyst deterioration, the CO concentration (mol% in dry base) is preferably 20% or less. Therefore, it is preferable to reduce the CO concentration to this range in a high temperature CO transformer.

As for the gas supplied to the low-temperature CO converter, the GHSV is preferably 200 to 50000 h ⁻¹ . 200h ^-1 or more and can be made good gas throughput and economy by, excellent CO concentration reduction ability as long 50000h ^-1 or less.

[Selective oxidizer]
For example, in the polymer electrolyte fuel cell system, it is preferable to further reduce the concentration of carbon monoxide, and for this purpose, the outlet gas of the CO converter can be treated with a selective oxidizer. In the selective oxidizer, CO is selectively oxidized to carbon dioxide.

  For this reaction, a catalyst containing iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, silver, gold, etc. is used, and preferably 0.5 mol relative to the number of moles of carbon monoxide remaining. The carbon monoxide concentration is reduced by selectively converting carbon monoxide to carbon dioxide by adding 10 to 10 times mol, more preferably 0.7 to 5 times mol, and still more preferably 1 to 3 times mol. Preferably, it is reduced to 10 ppm (mol basis of dry base) or less. In this case, the carbon monoxide concentration can be reduced by reacting with the coexisting hydrogen simultaneously with the oxidation of carbon monoxide to generate methane. For example, air can be used as the oxygen source.

The selective oxidation can be performed using a selective oxidation catalyst having a suitable use temperature of 100 to 200 ° C. The molar ratio of oxygen to be supplied and CO (O ₂ / CO ratio) is preferably 1.0 to 2.0, and preferably 7000 to 10,000 h ^{−1 in} terms of GHSV (15 ° C., 0.101 MPa conversion).

[Water / steam system]
In order to supply steam necessary for steam reforming, the hydrogen production apparatus includes a water evaporator (steam generator). Further, from the viewpoint of stable operation, the water evaporator preferably has a superheat section that superheats the generated water vapor.

  About the temperature of the water supplied to a hydrogen production apparatus, normal temperature water can be used, without heating in particular, or it can be 35-60 degreeC, for example. The pressure can be appropriately set, but is preferably 500 kPa to 1000 kPa from the viewpoint of improving thermal efficiency by promoting heat recovery.

  The water vapor to be generated may be, for example, saturated water vapor depending on the pressure, but this can be superheated to, for example, 250 to 450 ° C.

[Arrangement]
FIG. 2 schematically shows an outline of the hydrogen production apparatus. The hydrogen production apparatus has four regions. The first region 1 is a columnar region arranged vertically, the second region 2 is an annular region disposed on the outer periphery thereof, and the third region 3 is an annular region disposed further on the outer periphery thereof. In addition, the fourth region 4 is an annular region disposed on the outer periphery thereof.

  A burner is provided in the first region, a reforming tube is provided in the second region, a steam generator is provided in the third region, and a CO converter and a selective oxidizer are provided in the fourth region.

  All the first to fourth regions may be formed in one sealable container. In this case, a cylindrical container can be used as the container. In this form, the whole region can be kept in one container and the outside is covered with a heat insulating material and / or the outer wall of the container has a vacuum heat insulating structure. This is preferable from the viewpoint of reducing the space for the heat insulating material. In the vacuum heat insulating structure, the container wall has a double structure of an inner wall and an outer wall, and a vacuum is formed between the inner wall and the outer wall.

  Further, it is not necessary that all the regions are in one container. For example, the first to third regions are formed in one sealable container, and the fourth region is sealed independently from this container. It can also be formed in a possible container. In this case, the former container can be cylindrical, the latter container can be annular, and both containers can be installed with a space therebetween, and a flow path connecting the two containers can be provided. Both containers preferably have a vacuum heat insulating structure on the outer wall. This configuration is preferably employed when it is better not to conduct heat directly between the third region and the fourth region, for example, in order to avoid overheating of the CO converter and the selective oxidizer in the fourth region. At this time, it is preferable from the viewpoint of thermal efficiency and the reduction of the space for the heat insulating material that the two containers are collectively kept warm.

[First form of hydrogen production apparatus]
FIG. 3 schematically shows a vertical section and FIG. 4 shows a schematic horizontal section of one embodiment of the hydrogen production apparatus. The following drawings are for illustration purposes and do not necessarily represent the apparatus strictly. In this embodiment, the first to third regions are formed adjacent to each other in one cylindrical container 101, the fourth region is formed in an independent annular container 102, and the third region and the fourth region are connected. Connecting portion 103 to be connected. The central axes of all regions are coincident.

  In the first region 1, a burner 11 passes through the upper surface of the container 101 and is provided downward, and a flame 12 is formed during combustion. It is preferable for the burner to face downward because it can effectively prevent dripping. Moreover, it has the combustion cylinder 13, and a 1st area | region and a 2nd area | region are divided by the combustion cylinder. The combustion cylinder reaches the bottom of the container, but has an opening 14 near the lower end, and the combustion gas of the burner flows through the opening to the adjacent second region 2. The burner is provided at a position along the central axis of all regions.

  For example, a ceramic cylinder can be used as the combustion cylinder, and an opening is formed in the lower part. By using the combustion cylinder, the reforming pipe in the second region can be uniformly heated by the combustion gas. The openings can be appropriately provided so that the combustion gas uniformly heats the reforming tube. For this purpose, for example, a plurality of openings can be provided from the lower portion of the combustion cylinder length of about 30% to the lower end. Moreover, the heat insulating material 15 can be provided in the bottom face of a 1st area | region.

  When this hydrogen production apparatus is used in a fuel cell system, the burner can be a mixed combustion burner capable of combusting both hydrocarbon oil and anode off-gas of the fuel cell. This makes it possible to effectively use the anode off gas, reduce the consumption of hydrocarbon oil, and is preferable from the viewpoint of thermal efficiency.

  In the second region, a double pipe type reforming pipe 21 having a closed lower end is provided, and the reforming pipe is heated by the combustion gas. On the other hand, a raw material gas in which hydrocarbon oil and water vapor are mixed is supplied from the raw material gas manifold 22 to the outer ring portion of the reforming pipe, and a reforming reaction occurs in the reforming catalyst layer 21a provided in the outer ring portion. The reformed gas is converted into the reformed gas, and the reformed gas ascends the inner pipe portion of the reformer tube and reaches the reformed gas manifold 36 through the communication portion 24. The partition wall 23 partitions the second region and the third region. A partition can be formed with a heat insulating material.

  In addition, it is preferable from a viewpoint of thermal efficiency to provide the heat insulating material 110 in the bottom face of the 1st area | region and 2nd area | region of the container 101. FIG.

  In addition, an orifice can be attached to the reforming pipe outlet reforming gas flow path, and the pressure loss of the plurality of reforming pipes can be made uniform to achieve stability. For example, an orifice can be attached to each reforming pipe outlet (inner pipe outlet). The orifice diameter is set such that the differential pressure at the orifice portion is preferably about 50% to 300%, more preferably about 100% to 150% of the differential pressure of the reforming pipe filled with the catalyst. By attaching the orifice, the distribution of the raw material gas to the plurality of reforming tubes becomes uniform and the variation of the reforming tube temperature is reduced, so that the reforming tube temperature control is easy and a homogeneous reformed gas can be obtained. it can.

  A plurality of reforming tubes are provided along a circumference centering on the central axis of the entire region so as to surround the burner. The number is preferably 6 to 12 in consideration of the size of the second region and the flow rate dispersibility of the source gas. Here, nine reforming pipes are provided. Also, fins can be provided on the outer surface of the reforming tube. This is preferable because the heat of the combustion gas is more easily transmitted to the catalyst inside the reforming tube.

  A water evaporator 31 and a raw material gas preheater 32 are provided in the third region. The combustion gas supplied from the second region contacts the raw material gas preheater and the steam generator in this order, heats them, and is discharged out of the container 101 from the combustion gas discharge port 33. On the other hand, the water supplied from the water supply pipe 34 is steamed by the water evaporator, and this steam cools the selective oxidizer and the CO converter in the fourth region as will be described later and passes through the steam supply pipe 35. Is heated, mixed with the raw material in the mixer 51, and further supplied to the raw material gas preheater 32 after passing through the static mixer 120 which is a mixing promoting means. When the mixture supplied to the source gas preheater contains a liquid, the source gas preheater also serves as a vaporizer. The raw material gas (mixed gas of vaporized hydrocarbon oil and water vapor) heated by the raw material gas preheater is supplied to the raw material gas manifold 22 and subjected to reforming. In FIG. 4, for the sake of explanation, the third region is divided into two parts so as to show whether the reformed gas manifold 36 and the water evaporator 31 are arranged in the horizontal direction, but actually, as shown in FIG. These are arranged one above the other.

  The water evaporator and the raw material gas preheater have a form in which a single tube is wound in a coil shape in the circumferential direction of the third region.

  Furthermore, in order to improve thermal efficiency, an air preheater for preheating the air for burner combustion can be provided in the third region. For example, a single pipe wound in a coil shape in the circumferential direction of the third region is provided on the most downstream side with respect to the reformed gas flow in the third region. Can be supplied to.

  The inside of the fourth region is partitioned in the circumferential direction by vertical partition walls, and a high-temperature CO converter 41, a reformed gas cooler 42, a low-temperature CO converter 43, and a first chamber in which each partition is filled with a catalyst as necessary. The reformed gas / air mixer 44, the first selective oxidizer 45, the second reformed gas / air mixer 46, and the second selective oxidizer 47 are arranged in the circumferential direction. The reformed gas supplied from the reformed gas manifold 36 through the connecting portion 103 is first reduced in its CO concentration by a shift reaction in the high temperature CO shift catalyst layer 41a in the high temperature CO shift converter 41 filled with the high temperature CO shift catalyst. Is done. At this time, the high temperature CO transformer is cooled by the steam flowing through the cooling pipe 48 penetrating the inside of the high temperature CO transformer. The reformed gas that has passed through the high-temperature CO converter is cooled to a temperature suitable for low-temperature CO conversion by steam flowing through the cooling pipe in the reformed gas cooler 42 (the catalyst is not filled), and is filled with the low-temperature CO conversion catalyst. Is supplied to the low-temperature CO transformer 43. Here, the CO concentration of the reformed gas is further reduced by a shift reaction. At this time, the low temperature CO converter is cooled by the steam flowing through the cooling pipe passing through the inside of the low temperature CO converter. The reformed gas exiting the low temperature CO converter is mixed with air for CO selective oxidation in a first reformed gas air mixer 44 (not packed with catalyst). The reformed gas mixed with air is further reduced in CO concentration by oxidation of CO in the first selective oxidizer 45 filled with the selective oxidation catalyst. The reformed gas leaving the first selective oxidizer is further mixed with air in a second reformed gas air mixer 46 (not filled with catalyst), and the second selection filled with the selective oxidation catalyst. The CO concentration is reduced by oxidation of CO in the oxidizer 47, and is taken out from the hydrogen-containing gas outlet 50 as a hydrogen-containing gas having a low CO concentration. Note that the reformed gas flow paths connecting the devices 41 to 47 such as the reformed gas flow paths connecting the high temperature CO converter 41 and the reformed gas cooler 42 are not shown.

  From the viewpoint of better mixing of the reformed gas and air, it is preferable that baffle plates are respectively disposed in the first and second reformed gas air mixers to form a so-called static mixer. Each of the first and second selective oxidizers is cooled by steam flowing through a cooling pipe penetrating the first and second selective oxidizers. In addition, it is not necessary to provide a cooling pipe in the reformed gas air mixer.

  Although it is possible to perform CO selective oxidation in one stage, as shown above, when CO selective oxidation is performed in two stages, for example, the CO concentration (on a dry basis, molar basis) can be easily reduced from 1% to 10 ppm. Therefore, it is preferable. For example, the first CO selective oxidation can reduce the CO concentration (dry basis molar basis) from 1% to 5000 ppm, and the second CO selective oxidation can reduce it to 10 ppm.

  On the other hand, the steam generated in the water evaporator 31 is supplied from the steam supply pipe 35 to the steam manifold 49a, and the high temperature CO converter 41, the reformed gas cooler 42, the low temperature CO converter 43, the first selective oxidizer 45, And the hydrocarbon gas cooled by the reformed gas when it passes through the cooling pipe disposed in the second selective oxidizer 47 and heated by itself, gathered in the steam manifold 49b, and desulfurized in the mixer 51; Mixed. The cooling pipes are a plurality of pipes provided in the vertical direction like a so-called shell and tube type heat exchanger, and only a part is shown in FIG.

  The desulfurization of the hydrocarbon oil is performed in a desulfurizer (not shown) independent of the containers 101 and 102. This desulfurizer is heated by the combustion gas discharged from the combustion gas discharge port 33. The structure of this desulfurizer is, for example, a double pipe structure, the outer side is a desulfurization catalyst layer, the raw material flows from the lower part to the upper part, and the combustion flows through the inner pipe part so that the desulfurization reaction temperature is 100 ° C to 350 ° C Temperature can be adjusted by gas.

[Second form of hydrogen production apparatus]
FIG. 5 shows another form of the hydrogen production apparatus. In this embodiment, a combustion catalyst layer 25 is provided in the second region which is a reformer portion, and an anode off gas supply pipe 26 for supplying an anode off gas of the fuel cell to the combustion catalyst. The burner need only burn hydrocarbon oil and need not be a mixed burner. The burner combustion gas in which oxygen remains and the anode off-gas are combusted by the combustion catalyst, and the combustion gas is supplied to the second region. The combustion catalyst layer can be provided so that all the combustion gas of the burner passes through the combustion catalyst layer. For example, it can be provided around the reforming pipe 21 over the entire combustion gas flow path cross section of the burner.

  This form is preferable in terms of homogenizing the reforming tube temperature distribution and improving the exhaust gas properties.

  The combustion catalyst can be appropriately selected from known combustion catalysts. For example, an active carrier such as silica or alumina is supported on a honeycomb carrier such as ceramics or metal, and a noble metal or composite oxide such as Pt or Pd is supported thereon. Can be used.

  Other than the above, the second embodiment is the same as the first embodiment.

  In the above-described hydrogen production apparatus including the first and second embodiments, heat exchange is performed for reactors necessary for hydrogen production, reactors such as a CO converter, selective oxidizer, water evaporator, preheater, etc. The equipment can be configured as a single unit, and the life of the catalyst is defined by the equipment structure and equipment layout that makes the reaction conditions such as the operating temperature and space velocity of each catalyst appropriate. Longer service life and extended operating conditions can be achieved. Therefore, this hydrogen production apparatus is a hydrogen production apparatus that is compact and excellent in thermal efficiency, has a long service life and a wide range of operating conditions. In addition, since the mixing of a mixture of hydrocarbon oil and water vapor is promoted in this hydrogen production apparatus, coke deposition and gas composition fluctuations are suppressed, and the hydrogen production apparatus can be operated stably for a long period of time.

[Fuel cell system]
A fuel cell system including the above-described hydrogen production apparatus and a fuel cell using a hydrogen-containing gas obtained from the hydrogen production apparatus as a fuel electrode supply gas includes means for supplying an oxygen-containing gas such as air to the cathode, a fuel cell A known device or the like can be appropriately provided as a device conventionally provided in a fuel cell system, such as a means for extracting electricity from an instrument and an instrumentation control device.

  The anode off-gas of the fuel cell can be burned by a burner when the hydrogen production apparatus has a mixed combustion burner (for example, the first embodiment described above). When a hydrogen production apparatus has a combustion catalyst (for example, the above-mentioned 2nd form), it can be made to burn with a combustion catalyst. For this reason, the fuel cell system can have a line for guiding the anode off gas to the mixed combustion burner and a line for guiding the anode off gas to the combustion catalyst. This line can be appropriately formed by piping or valves.

  With such a configuration, for example, hydrocarbon oil is combusted when the fuel cell system is started, but only anode off gas is combusted during rated operation, and consumption of hydrocarbon oil for combustion can be suppressed.

  The fuel cell system is a fuel cell system that is highly efficient, compact, has a long lifetime, and has a wide range of operating conditions. Further, coke deposition and fluctuations in gas composition are suppressed, and the fuel cell system can be stably operated for a long time.

  The reformer of the present invention can be suitably used for hydrogen production and can be suitably used for a fuel cell system. The fuel cell system of the present invention can be suitably used as a power generation system or a cogeneration system.

It is a schematic diagram which shows one form of the reforming apparatus of this invention. It is a conceptual diagram which shows a hydrogen production apparatus. It is explanatory drawing which shows a vertical direction cross section typically about the 1st form of the said hydrogen production apparatus. It is explanatory drawing which shows a horizontal-vertical direction cross section typically about the 1st form of the said hydrogen production apparatus. It is explanatory drawing which shows a vertical direction cross section typically about the 2nd form of the said hydrogen production apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 1st area | region 2 2nd area | region 3 3rd area | region 4 4th area | region 11 Burner 12 Flame 13 Combustion cylinder 14 Opening 15 Heat insulating material 21 Reforming pipe 21a Reforming catalyst layer 22 Raw material gas manifold 23 Partition 24 Communication part 25 Combustion catalyst layer 26 Anode off gas supply pipe 31 Water evaporator 32 Raw material gas preheater 33 Combustion gas outlet 34 Water supply pipe 35 Steam supply pipe 36 Reformed gas manifold 41 High temperature CO converter 41a High temperature CO conversion catalyst layer 42 Reformed gas cooler 43 Low-temperature CO converter 44 First reformed gas air mixer 45 First selective oxidizer 46 Second reformed gas air mixer 47 Second selective oxidizer 48 Cooling pipes 49a, b Steam manifold 50 Hydrogen-containing gas 51 Outlet 51 Mixer 101 Cylindrical container for storing the first to third areas 102 Independently collecting the fourth area That the annular container 103 connection portion 110 heat insulator 120 mixing acceleration means 1001 mixing unit 1002 mixing acceleration means 1003 reformer 1003a burner 1003b reaction tube 1004 heat exchange means

Claims (13)

In a reformer for mixing a raw material for hydrogen production and steam, and steam reforming the mixture to obtain a reformed gas containing hydrogen,
Mixing means for mixing the raw material for hydrogen production with water vapor;
A mixing promoting means for promoting the mixing of the raw material for hydrogen production and steam disposed downstream of the mixing means; and a reforming means for reforming the mixture promoted by the mixing promoting means in the presence of the reforming catalyst. It has a quality instrument,
A reformer in which the flow channel cross-sectional area of the mixing means is 1.5 to 3 times the flow cross-sectional area of the mixing promoting means .   The reforming apparatus according to claim 1, wherein the mixing promoting means has a structure in which a baffle plate is arranged inside a tubular member. Further, downstream of the mixing acceleration means, and upstream of the reforming catalyst, the reforming apparatus according to claim 1 or 2, wherein a heating means for heating the mixture of hydrogen-producing feedstock and steam. The reformer has combustion means for generating heat necessary for steam reforming;
The reforming apparatus according to claim 3 , wherein the heating means is a heat exchange means that is disposed in a flow path through which the combustion gas of the combustion means flows, and that heats a mixture of the raw material for hydrogen production and water vapor with the combustion gas. The reforming apparatus according to claim 4 , wherein the heat exchange means has a structure in which a tube is wound in a coil shape or a structure in which a plurality of straight tubes are connected in parallel. In a reforming method of mixing a raw material for hydrogen production and steam, and steam reforming the mixture to obtain a reformed gas containing hydrogen,
A reforming apparatus for mixing a raw material for hydrogen production with steam and steam reforming the mixture to obtain a reformed gas containing hydrogen, the mixing means for mixing the raw material for hydrogen production with steam; A mixing promoting means for promoting the mixing of the raw material for hydrogen production and water vapor, and a reformer for reforming the mixture whose mixing is promoted by the mixing promoting means in the presence of the reforming catalyst. Using a reformer having a flow path cross-sectional area of the mixing means that is 1.5 to 3 times the flow path cross-sectional area of the mixing promoting means,
Mixing step of mixing raw material for hydrogen production and water vapor;
After the mixing step, a mixing promotion step for promoting mixing of the raw material for hydrogen production and steam; and a reforming step for reforming the mixture whose mixing has been promoted in the mixing promotion step in the presence of the reforming catalyst. Modification method. The reforming method according to claim 6 , wherein the temperature of the raw material for producing hydrogen mixed in the mixing step is set to 300 ° C. or lower, and the temperature of the water vapor is set to 100 ° C. or higher. The reforming method according to claim 6 or 7 , further comprising a heating step of heating the mixture of the raw material for hydrogen production and steam by heat exchange after the mixing promotion step and before the reforming step. The reforming method according to claim 8 , wherein in the heating step, the residence time of the mixture heated by heat exchange is 0.1 seconds or more. The reforming method according to claim 8 or 9 , wherein in the heating step, the linear velocity of the mixture heated by heat exchange is set to 10 m / s or more. The reforming method according to any one of claims 8 to 10 , wherein in the heating step, the mixture is heated to 300 ° C or higher and 600 ° C or lower. In order to generate heat necessary for steam reforming in the reforming step, combustion is performed,
The reforming method according to any one of claims 8 to 11 , wherein a combustion gas of the combustion at 300 ° C or higher and 700 ° C or lower is used as the heat transfer fluid used for the heat exchange. In a fuel cell system comprising a reforming device that mixes raw materials for hydrogen production and steam, reforms the steam to obtain a reformed gas containing hydrogen, and a fuel cell using the reformed gas as a fuel,
A fuel cell system, wherein the reformer is the reformer according to any one of claims 1 to 5 .

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