JP2011088778A - Hydrogen production apparatus and fuel cell system - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogen production apparatus which is less in maintenance frequency, and also is high in the activity of a shift reaction and a selective oxidation reaction. <P>SOLUTION: The hydrogen production apparatus 10 includes a reforming part 11 for producing a reformed gas by reforming a raw material for hydrogen production which contains hydrocarbon with a reforming catalyst and hydrogen sulfide removing parts 12, 14 for removing hydrogen sulfide. The hydrogen reforming catalyst is obtained by supporting one or more kinds of active metals selected from a group comprising rhodium, platinum and palladium on an alumina-containing support having fine pores of ≥50 nm pore diameter and ≥0.2 ml/g pore volume and containing alumina in a ratio of ≥0.3 mass% and ≤5 mass% per 100 mass% alumina-containing support. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a hydrogen production apparatus for reforming hydrocarbons to produce hydrogen. The present invention also relates to a fuel cell system that generates power using hydrogen.

In recent years, in order to reduce the burden on the environment, the spread of fuel cell systems has been promoted, and household fuel cell systems have also been developed.
In a household fuel cell system, hydrogen is produced from reforming and shift reactions from raw materials for hydrogen production such as city gas containing hydrocarbons and petroleum-based fuels, and electricity is generated by the fuel cell using the hydrogen. (For example, refer to Patent Documents 1 and 2).

By the way, an odorant made of a sulfur compound such as mercaptan is added to city gas supplied to households in order to facilitate detection of gas leakage. Petroleum fuel contains a sulfur compound in the production process.
However, in general, the reforming reaction catalyst has low sulfur resistance and is easily deactivated by a sulfur compound. In addition, a selective oxidation reaction may be performed after the shift reaction in order to remove residual carbon monoxide, but the selective oxidation reaction catalyst used at that time was also easily deactivated by the sulfur compound. Furthermore, platinum-based catalysts used for fuel cells were also easily deactivated by sulfur compounds.
For this reason, when city gas or petroleum-based fuel is used as a raw material for hydrogen production, a desulfurization step using an adsorbent was provided before the reforming step.

JP 2002-362902 A International Publication WO2008 / 001632

However, removal of sulfur compounds with the adsorbent requires replacement of the adsorbent after breakthrough or immediately before breakthrough, and because the life of the adsorbent is short, maintenance must be performed with high frequency. There wasn't. For this reason, a hydrogen production apparatus that can reduce the frequency of maintenance has been demanded.
An object of the present invention is to provide a hydrogen production apparatus and a fuel cell system that can be operated stably over a long period of time with low maintenance frequency.

[1] A raw material for hydrogen production containing hydrocarbons is reformed using a reforming catalyst to remove a hydrogen sulfide from a reforming section that generates a reformed gas containing hydrogen and carbon monoxide. A hydrogen production apparatus having a hydrogen sulfide removal unit,
In the steam reforming catalyst, one or more active metals selected from the group consisting of rhodium, platinum and palladium are contained in an alumina-containing support in an amount of 0.3 to 5% by mass with respect to 100% by mass of the alumina-containing support. % Or less,
The alumina-containing support is an α-alumina having a pore volume of 50 nm or more and a pore volume of 0.2 ml / g or more and 1.0 ml / g or less, and 2 to 25% by mass of rare earth based on 100% by mass of α-alumina. An apparatus for producing hydrogen, comprising a carrier on which an elemental oxide and an alkaline earth elemental oxide in an amount of 0.1% by mass to 15% by mass are supported.
[2] A fuel cell system comprising the hydrogen production apparatus according to [1].

  The hydrogen production apparatus and fuel cell system of the present invention have a low maintenance frequency and can be stably operated over a long period of time.

1 is a schematic view of an embodiment of a hydrogen production apparatus and a fuel cell system of the present invention. It is the schematic of the other embodiment of the hydrogen production apparatus and fuel cell system of this invention. It is the schematic of the other embodiment of the hydrogen production apparatus and fuel cell system of this invention. It is the schematic of the other embodiment of the hydrogen production apparatus and fuel cell system of this invention.

(Hydrogen production equipment)
An embodiment of the hydrogen production apparatus of the present invention will be described.
FIG. 1 shows a hydrogen production apparatus according to this embodiment. This hydrogen production apparatus 10 is an apparatus for producing a fuel cell supply gas containing hydrogen from a hydrogen production raw material containing hydrocarbons, and reforming the hydrogen production raw material to obtain a reformed gas The reforming unit 11, the first hydrogen sulfide removing unit 12 that removes hydrogen sulfide in the reformed gas generated by the reforming unit 11, and the shift reaction of the reformed gas that has passed through the first hydrogen sulfide removing unit 12 are performed. The shift reaction unit 13 that obtains the shift gas, the second hydrogen sulfide removal unit 14 that removes hydrogen sulfide contained in the shift gas, and the selective oxidation reaction of the shift gas that has passed through the second hydrogen sulfide removal unit 14 are performed to supply the fuel cell. And a selective oxidation unit 15 for obtaining gas.

The hydrocarbons contained in the raw material for hydrogen production are organic compounds having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms. Specific examples include saturated aliphatic hydrocarbons, unsaturated aliphatic hydrocarbons, and aromatic hydrocarbons. In addition, saturated aliphatic hydrocarbons and unsaturated aliphatic hydrocarbons can be used regardless of chain or cyclic. Aromatic hydrocarbons can be used regardless of whether they are monocyclic or polycyclic.
The hydrocarbons may have a substituent. The substituent may be either a chain or a ring, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group, and an aralkyl group. Further, it may be substituted with a substituent containing a hetero atom such as a hydroxy group, an alkoxy group, a hydroxycarbonyl group, an alkoxycarbonyl group, or a formyl group.

Specific examples of hydrocarbons include saturated aliphatics such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, and eicosane. Examples thereof include hydrocarbons, unsaturated aliphatic hydrocarbons such as ethylene, propylene, butene, pentene and hexene, cyclic hydrocarbons such as cyclopentane and cyclohexane, and aromatic hydrocarbons such as benzene, toluene, xylene and naphthalene.
Specific examples of hydrocarbons having a substituent containing a hetero atom include oxygen-containing compounds such as methanol, ethanol, propanol, butanol, dimethyl ether, phenol, anisole, acetaldehyde, and acetic acid.
Also, a mixture of these hydrocarbons can be used preferably. For example, natural gas, petroleum-based fuel (LP gas, naphtha, gasoline, kerosene, light oil, etc.) such as gas and oil that can be obtained industrially at low cost can be used.

  Further, the raw materials for producing hydrocarbons from hydrogen may include hydrogen, water, carbon dioxide, carbon monoxide, nitrogen, oxygen, and the like.

Specifically, city gas, LP gas, kerosene, gasoline, and the like are used as raw materials for hydrogen production used in the hydrogen production apparatus 10, but city gas, LP gas, and kerosene are preferable for household use.
Note that city gas and LP gas contain, for example, a sulfur compound as an odorant. Examples of sulfur compounds added to city gas include lower mercaptans such as ethyl mercaptan, isopropyl mercaptan, and t-butyl mercaptan, and lower sulfides such as dimethyl sulfide, ethyl methyl sulfide, and tetrahydrothiophene.
LP gas includes lower mercaptans such as methyl mercaptan, ethyl mercaptan, and propyl mercaptan, lower sulfides such as dimethyl sulfide, carbonyl sulfide, carbon disulfide, and disulfides in which carbon mercaptans are oxidatively coupled. included.
The sulfur concentration of the raw material for hydrogen production is preferably 0.1 ppm or more and 100 ppm or less. A raw material for hydrogen production having a sulfur concentration of the raw material for hydrogen production of 0.1 ppm or more can be easily obtained. If the sulfur concentration of the raw material for hydrogen production is 100 ppm or less, the activity of the reforming catalyst can be prevented from decreasing.

[Modification section]
In the reforming unit 11, the raw material for hydrogen production that has not been subjected to the desulfurization treatment is reformed using the reforming catalyst.
Specifically, a reforming gas containing carbon monoxide and hydrogen is obtained by reacting a raw material for hydrogen production containing hydrocarbons with steam in the presence of a reforming catalyst. When reacting with steam, an oxygen-containing gas may be accompanied (autothermal reforming reaction).

  In the reforming reaction using the reforming catalyst, a flow type fixed bed reactor, a fluidized bed reactor, or the like is used as a reactor. The shape of the reactor may be appropriately selected according to the purpose of the reforming reaction, and for example, a cylindrical shape, a flat plate shape, or the like is applied.

In the reforming reaction, as a method of supplying steam to the raw material for hydrogen production, for example, a method of supplying steam simultaneously with the raw material for hydrogen production in the reaction zone, a separate position in the reactor zone or several times For example, a method of supplying steam part by part.
The amount of steam to be supplied is a value defined as the ratio of the number of moles of water molecule to the number of moles of carbon atoms contained in the hydrocarbons (hereinafter referred to as “steam / carbon ratio”), preferably 2.0 or more and 10 In the following, it is more preferable that the amount be in the range of 2.5 to 5. If the steam / carbon ratio is 2.0 or more, it is difficult for carbon to precipitate on the reforming catalyst surface, and the hydrogen fraction can be easily increased. On the other hand, when the steam / carbon ratio is 10 or less, it is possible to avoid an increase in the size of the steam generating equipment and the steam collecting equipment.

In the reforming reaction, the space velocity of the hydrogen-producing feedstock introduced into the reactor at GHSV, preferably ^{10h -1} over 10,000 h ^-1 or less, more preferably ^{50h -1} over 5,000H ^-1 or less, More preferably, it is the range of 100h- ¹ or more and 3,000h- ¹ or less. In LHSV, preferably 0.05 h ^-1 or 5.0 h ^-1 or less, more preferably 0.1 h ^-1 or 2.0 h ^-1 or less, more preferably 0.2 h ^-1 or 1.0 h ^-1 or less of It is a range.
The reaction temperature is preferably in the range of 300 ° C to 900 ° C, more preferably 400 ° C to 800 ° C, and still more preferably 400 ° C to 800 ° C.
The reaction pressure is preferably at least atmospheric pressure.

  The reforming catalyst is a catalyst (hereinafter referred to as “reforming catalyst (A)”) in which one or more active metals selected from the group consisting of rhodium, platinum, and palladium are supported on an alumina-containing support. Used.

Among the active metals of the reforming catalyst (A), rhodium is preferred because of its superior reforming activity and sulfur resistance.
The content of the active metal in the reforming catalyst (A) is 0.3% by mass or more and 5% by mass or less, and 0.4% by mass or more and 4% by mass or less when the alumina-containing support is 100% by mass. It is preferable that it is 0.5 mass% or more and 3 mass% or less. If the content of the active metal is 0.3% by mass or more, sufficient catalytic activity can be obtained, and the amount of the reforming catalyst (A) used can be reduced. Metal aggregation can be reduced and the amount of active metal exposed on the surface can be increased.

The alumina-containing support in the reforming catalyst (A) is a support in which a rare earth element oxide and an alkaline earth metal element oxide are supported on α-alumina. This alumina-containing carrier is excellent in strength against thermal fluctuation.
Here, α-alumina preferably has pores (macropores) having a pore diameter of 50 nm or more, and the pore volume is 0.2 ml / g or more and 1.0 ml / g or less.
When the volume of pores having a pore diameter of 50 nm or more is smaller than 0.2 ml / g, the catalytic activity may be insufficient, and when the volume of pores having a pore diameter of 50 nm or more is larger than 1.0 ml / g, the catalyst strength is increased. It may be insufficient.
The BET specific surface area of α-alumina is preferably 3 m ² / g or more and 30 m ² / g or less. When the BET specific surface area of α-alumina is 3 m ² / g or more, the catalytic activity is high, and when the BET specific surface area is 30 m ² / g or less, the catalyst strength is higher.

As the rare earth element, it is preferable to use one or more rare earth elements selected from scandium, yttrium, lanthanum, and cerium, and lanthanum and cerium are more preferable because the effect of suppressing carbon deposition is more excellent.
The content of rare earth elements in the alumina-containing support is 2% by mass or more and 25% by mass or less, preferably 5% by mass or more and 20% by mass or less, when the mass of alumina is 100% by mass, preferably 10% by mass. More preferably, it is 15 mass% or less. If the content of the rare earth element oxide is 2% by mass or more, the effect of suppressing the carbon precipitation by the rare earth element becomes higher, and if it is 25% by mass or less, the rare earth element oxide is less likely to aggregate and is exposed to the surface. The amount of active metal can be increased.

As the alkaline earth metal element, it is preferable to use one or more alkaline earth metals selected from magnesium, calcium, strontium, and barium, because the carbon precipitation suppression effect and the activity improvement effect are more excellent. More preferred are magnesium and strontium.
The content of the alkaline earth metal element in the alumina-containing carrier is 0.1% by mass or more and 15% by mass or less, preferably 0.5% by mass or more and 12% by mass or less, more preferably 100% by mass of alumina. Is 1 mass% or more and 10 mass% or less. When the content of the alkaline earth metal element oxide is 0.1% by mass or more, the carbon precipitation suppressing effect and the activity improving effect of the alkaline earth metal element are further increased. The metal group element is less likely to aggregate, and the amount of active metal exposed on the surface can be increased.

  In the reforming catalyst (A), the combination of the active metal, rare earth element and alkaline earth metal element is preferably a combination of rhodium, cerium and strontium because of its particularly excellent catalytic activity and sulfur resistance.

  The catalyst strength of the reforming catalyst (A) used in the reforming section 11 is preferably such that the catalyst crushing strength according to the Kiya measurement method is 50 N or more per catalyst particle. If the catalyst crushing strength is 50 N or more, the catalyst is difficult to break during operation of the fuel cell system, and powdering can be prevented.

The reforming catalyst (A) may be in the form of a powder or may be a molded body that is molded into a predetermined shape. Examples of the shape of the molded body include a spherical shape, a ring shape, a tablet shape, a cylindrical shape, and a flake shape.
Examples of the method for obtaining a molded article include a method of tableting and reforming the reforming catalyst (A), pulverizing and then granulating, a method of adding a binder to the reforming catalyst, and extrusion molding. . In addition, after compressing, molding, and sizing the alumina-containing carrier, a method of supporting the active metal, a method of adding a binder to the alumina-containing carrier, extrusion molding, and then supporting the active metal Can be applied.
The reforming catalyst (A) may be monolithic or honeycomb-shaped. Further, the reforming catalyst (A) may be used by coating a monolithic or honeycomb structure.

[First hydrogen sulfide removal section]
The first hydrogen sulfide removing unit 12 is a part that removes hydrogen sulfide generated by the reaction of the sulfur compound in the raw material for hydrogen production with hydrogen in the reforming unit 11.
In the first hydrogen sulfide removing unit 12, the sulfur concentration is preferably 5 ppm or less as the mass of sulfur atoms. If the sulfur concentration is 5 ppm or less, the activity of the shift reaction catalyst can be sufficiently prevented from decreasing. However, in order to reduce the sulfur concentration to less than 5 ppm, the sulfur removal conditions must be severe.
Examples of the method for removing hydrogen sulfide include an adsorbent mainly composed of zinc oxide, an adsorbent composed mainly of copper-zinc, and an adsorbent composed mainly of nickel-zinc. .

  The temperature at which hydrogen sulfide is removed by the first hydrogen sulfide removing unit 12 is preferably 100 ° C. or more and 500 ° C. or less. If the hydrogen sulfide removal temperature in the first hydrogen sulfide removal unit 12 is 500 ° C. or less, the amount of adsorption of hydrogen sulfide is increased in equilibrium, and the sulfur concentration can be easily reduced to 5 ppm or less. However, if the hydrogen sulfide removal temperature in the first hydrogen sulfide removal unit 12 is less than 100 ° C., the sulfidation reaction of the adsorbent becomes difficult to occur, and the removal amount of hydrogen sulfide becomes insufficient.

[Shift reaction section]
In order to increase the hydrogen concentration of the reformed gas and reduce the carbon monoxide concentration, the shift reaction unit 13 reacts the carbon monoxide contained in the reformed gas with water to perform hydrogen and carbon dioxide shift reaction. It is a part to do.
When performing the shift reaction, a shift reaction catalyst is usually used. Examples of the shift reaction catalyst include iron-chromium mixed oxides, zinc-copper mixed oxides, and catalysts containing noble metals such as platinum, ruthenium and iridium.
In the shift reaction unit 13, the carbon monoxide content (mol% calculated excluding water vapor) is preferably reduced to 2% by mass or less, more preferably 1% by mass or less, and further preferably 0.5% by mass or less. .
The shift reaction may be a two-stage process, for example, a two-stage process of a high temperature shift reaction and a low temperature shift reaction.

  Since the shift reaction is an exothermic reaction, operation conditions at low temperatures are preferable in terms of equilibrium, but heating is performed according to the temperature at which the activity of the catalyst used is developed. Specifically, when the shift is performed in a single stage, the temperature is usually 100 ° C. or higher and 450 ° C. or lower, preferably 120 ° C. or higher and 400 ° C. or lower, more preferably 150 ° C. or higher and 350 ° C. or lower. If it is 100 degreeC or more, a catalyst activity will become high and can react carbon monoxide more. If it is 450 degrees C or less, the catalyst deterioration by a heat | fever can be suppressed and high durability can be given.

[Second hydrogen sulfide removal section]
The second hydrogen sulfide removing unit 14 is a part that removes hydrogen sulfide that has passed through the first hydrogen sulfide removing unit 12.
In the second hydrogen sulfide removing unit 14, the sulfur concentration is preferably set to 0.1 ppm or less as the mass of sulfur atoms. If the sulfur concentration is 0.1 ppm or less, it is possible to sufficiently prevent the activity of the selective oxidation catalyst and the fuel cell body from decreasing. However, in order to reduce the sulfur concentration to less than 0.1 ppm, the sulfur removal conditions must be severe.
As a method for removing hydrogen sulfide in the second hydrogen sulfide removing unit, a method similar to that for the first hydrogen sulfide removing unit 12 can be applied.

  The temperature at which hydrogen sulfide is removed by the second hydrogen sulfide removing unit 14 is preferably lower than the temperature of the first hydrogen sulfide removing unit 12 and is 100 ° C. or more and 250 ° C. or less. If the hydrogen sulfide removal temperature in the second hydrogen sulfide removal unit 14 is 250 ° C. or lower, the amount of adsorption of hydrogen sulfide is increased in equilibrium, and the sulfur concentration can be easily reduced to 0.1 ppm or lower. However, if the hydrogen sulfide removal temperature in the second hydrogen sulfide removal unit 14 is less than 100 ° C., the sulfidation reaction of the adsorbent becomes difficult to occur, and the removal amount of hydrogen sulfide becomes insufficient.

[Selective oxidation part]
The selective oxidation unit 15 is a part that further reduces the remaining carbon monoxide by a selective oxidation reaction. Specifically, the carbon monoxide concentration is preferably reduced to 10 ppm by mass or less.
In the selective oxidation reaction, a selective oxidation reaction catalyst is usually used. Examples of the selective oxidation reaction catalyst include a catalyst containing iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, silver, or gold. Among these, a catalyst containing ruthenium is preferable.
When the selective oxidation reaction catalyst contains ruthenium, the ruthenium content is preferably 0.02% by mass or more and less than 1% by mass, and 0.05% by mass or more and 0.75% by mass or less. Is more preferable, and 0.1% by mass or more and 0.5% by mass or less is particularly preferable.
In the selective oxidation reaction, the number of moles of carbon monoxide is preferably 0.5 times to 10 times, more preferably 0.7 times to 5 times, more preferably 1 times to 3 times. Add the following oxygen.
The selective oxidation reaction is usually performed in the range of 50 ° C. to 250 ° C., preferably 60 ° C. to 220 ° C., more preferably 80 ° C. to 200 ° C. If it is 50 degreeC or more, a catalyst activity becomes high and can reduce carbon monoxide more, and if it is 250 degrees C or less, since selectivity improves, hydrogen consumption can be decreased.
The selective oxidation reaction can also be performed in two steps.

In addition, a third hydrogen sulfide removing unit can be provided downstream of the selective oxidation unit 15 in order to reduce the hydrogen sulfide content in the fuel cell supply gas.
As a method for removing hydrogen sulfide in the third hydrogen sulfide removing unit, a method similar to that for the first hydrogen sulfide removing unit 12 can be applied.

In the hydrogen production apparatus 10 described above, the reforming catalyst used in the reforming reaction in the reforming unit 11 is excellent in sulfur resistance. Therefore, even if a sulfur compound is contained in the hydrogen production raw material, the reforming reaction catalyst. The decrease in activity is prevented. Further, since the first hydrogen sulfide removing unit 12 removes the hydrogen sulfide generated in the reforming unit 11, the activity of the shift reaction catalyst is prevented from being lowered. Further, since the second hydrogen sulfide removing unit 14 removes the hydrogen sulfide that has passed through the first hydrogen sulfide removing unit 12, the activity of the selective oxidation reaction catalyst is prevented from being lowered. Therefore, the fuel cell can be stably operated for a long time.
Further, in the hydrogen production apparatus 10, instead of desulfurizing the raw material for hydrogen production before the reforming unit 11, the reforming unit 11 is desulfurized by the first hydrogen sulfide removing unit 12 and the second hydrogen sulfide removing unit 14. Since the adsorbent for desulfurization before is omitted, the maintenance frequency can be reduced.
In general, removal of hydrogen sulfide is easier than removing sulfur compounds other than hydrogen sulfide. Therefore, the efficiency of desulfurization is also high.

  The hydrogen production apparatus of the present invention is not limited to the above embodiment, and a desulfurization unit for adsorbing and removing sulfur compounds contained in the raw material for hydrogen production may be provided before the reforming unit 11. Absent.

(Fuel cell system)
An embodiment of the fuel cell system of the present invention will be described.
FIG. 1 shows a fuel cell system according to this embodiment. The fuel cell system 1 includes a hydrogen production apparatus 10 and a fuel cell unit 20.

  As the fuel cell unit 20, a cell stack of a solid polymer type (PEFC), a phosphoric acid type (PAFC), a solid oxide type (SOFC), a molten carbonate type (MCFC) or the like can be used. The polymer form is preferred.

The solid polymer fuel cell has an anode (fuel electrode), a cathode (air electrode), and a solid polymer electrolyte sandwiched between these electrodes. A fuel cell supply gas obtained by the hydrogen production apparatus 10 is supplied to the anode, and an oxygen-containing gas such as air is supplied to the cathode. The hydrogen-containing gas and the oxygen supply gas may be humidified as necessary.
The anode includes platinum black, activated carbon-supported platinum catalyst, platinum-ruthenium alloy catalyst, and the like, and the cathode includes platinum black, activated carbon-supported platinum catalyst, and the like. Usually, the catalyst contained in the anode and the catalyst contained in the cathode are each contained in polytetrafluoroethylene, a low molecular weight polymer electrolyte membrane, activated carbon, or the like to form a porous catalyst layer.
An electrical load is electrically connected to the anode and the cathode.

Examples of the solid polymer electrolyte membrane include Nafion (Nafion, DuPont, registered trademark), Gore (Gore, Gore, registered trademark), Flemion (Flemion, Asahi Glass, registered trademark), Aciplex (Aciplex, Asahi Kasei). For example, a polymer electrolyte membrane such as a registered trademark of the company can be used.
By laminating the porous catalyst layer on both sides of the solid polymer electrolyte membrane, an MEA (Membrane Electrode Assembly) is formed. Further, the fuel cell unit 20 is formed by sandwiching the MEA with a separator having a gas supply function, a current collection function, particularly an important drainage function in the cathode, and the like made of a metal material, graphite, carbon composite and the like.

  In the fuel cell system 1, the fuel cell supply gas obtained by the hydrogen production apparatus 10 is supplied to the fuel cell unit 20. Since the fuel cell supply gas obtained by the hydrogen production apparatus 10 has few impurities such as hydrogen sulfide and carbon monoxide, it can be stably operated over a long period of time.

Note that the present invention is not limited to the above embodiment. For example, since the hydrogen production apparatus 10 of the present invention only needs to have one or more hydrogen sulfide removing units downstream from the reforming unit 11, as shown in FIG. 2, the hydrogen sulfide removing unit (first hydrogen sulfide removing unit) The part 12) may be provided only between the reforming part 11 and the shift reaction part 13.
In addition, as shown in FIG. 3, a hydrogen sulfide removing unit (first unit) is provided between the reforming unit 11 and the shift reaction unit 13, between the shift reaction unit 13 and the selective oxidation unit 15, and downstream of the selective oxidation unit 15. A first hydrogen sulfide removing unit 12, a second hydrogen sulfide removing unit 14, and a third hydrogen sulfide removing unit 16) may be provided.
Further, as shown in FIG. 4, a hydrogen sulfide removal unit (first hydrogen sulfide removal unit 12, second hydrogen sulfide removal) is provided between the reforming unit 11 and the shift reaction unit 13 and downstream of the selective oxidation unit 15. Part 16) may be provided.
In the hydrogen production apparatus 10 of the present invention, the selective oxidation unit 15 may be omitted. However, in order to minimize the carbon monoxide content contained in the fuel supplied to the fuel cell, it is preferable to have the selective oxidation unit 15.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.

[Example 1]
Α-alumina having a pore volume of 50 nm or more and a volume of 0.4 ml / g and a surface area of 5 m ² / g was impregnated with cerium nitrate and strontium nitrate. At that time, the supported amount of cerium oxide is 13% by mass when the mass of α-alumina is 100% by mass, and the supported amount of strontium oxide is 5% by mass when the mass of α-alumina is 100% by mass. Thus, impregnation with cerium nitrate and strontium nitrate was performed.
Subsequently, after drying at 150 degreeC for 8 hours or more, it baked at 800 degreeC in the air atmosphere for 8 hours, and obtained the alumina containing support | carrier.
The alumina-containing support is impregnated with rhodium chloride so that the amount of rhodium supported is 3% by mass when the mass of the alumina-containing support is 100% by mass, dried at 120 ° C. for 12 hours or more, and then at 1 ° C. at 500 ° C. Reforming catalyst A was obtained by hydrogen reduction for a period of time.
As shown in FIG. 1, a reforming unit 11 filled with the reforming catalyst A, a first hydrogen sulfide removing unit 12, a shift reaction unit 13, a second hydrogen sulfide removing unit 14, and a selective oxidation unit 15 are provided. Using the hydrogen production apparatus 10, LP gas having a sulfur content of 5 ppm was reformed to produce a fuel cell supply gas containing hydrogen.
At that time, the temperature of the first hydrogen sulfide removing unit 12 was set to 400 ° C., and the temperature of the second hydrogen sulfide removing unit 14 was set to 180 ° C.
Further, the inlet reaction temperature of the reforming reaction is 500 ° C. (the outlet reaction temperature is adjusted so that the inlet reaction temperature is 500 ° C.), the reaction pressure is 0.1 MPa, the steam / carbon ratio is 3.0 mol / mol, and GHSV 300h ⁻¹ . did.
Further, the inlet reaction temperature of the shift reaction was 300 ° C., the outlet reaction temperature was 200 ° C., the reaction pressure was 0.1 MPa, and GHSV1100h ⁻¹ (wet base).
Moreover, the inlet reaction temperature of the selective oxidation reaction was 160 ° C., the outlet reaction temperature was 140 ° C., the reaction pressure was 0.1 MPa, and GHSV 6500 h ⁻¹ (wet base).

[Comparative Example 1]
In Example 1, ruthenium chloride was used instead of rhodium chloride, and the amount of ruthenium supported was impregnated so as to be 3% by mass when the mass of the alumina-containing carrier was 100% by mass, and dried at 120 ° C. for 12 hours or more. Thereafter, a fuel cell supply gas was produced in the same manner as in Example 1 except that the reforming catalyst B obtained by hydrogen reduction at 500 ° C. for 1 hour was used.

The components contained in the obtained fuel cell supply gas were quantitatively analyzed with a gas chromatograph to evaluate the activity of the reforming reaction, shift reaction and selective oxidation reaction, and the ability to remove hydrogen sulfide. The results are shown in Table 1.
As shown in Table 1, in Example 1, even after 100 hours from the start of production, the amount of unreacted hydrocarbons, residual carbon monoxide and residual hydrogen sulfide was small, and the amount of hydrogen produced was large. Further, when the fuel cell system was used to generate power using the fuel cell supply gas obtained in Example 1, it was possible to operate stably over a long period of time.
On the other hand, in Comparative Example 1, the amount of residual carbon monoxide was large and the amount of hydrogen produced was small. In addition, when the fuel cell supply gas obtained in Comparative Example 1 was used to generate power with the fuel cell system, the amount of power generation was small, and operation was not possible for a long time.

DESCRIPTION OF SYMBOLS 1 Fuel cell system 10 Hydrogen production apparatus 11 Reforming part 12 1st hydrogen sulfide removal part 13 Shift reaction part 14 2nd hydrogen sulfide removal part 15 Selective oxidation part 16 3rd hydrogen sulfide removal part 20 Fuel cell part

Claims (2)

A reforming section that produces a reformed gas containing hydrogen and carbon monoxide by steam reforming a raw material for producing hydrogen containing hydrocarbons using a steam reforming catalyst, and a sulfurization that removes hydrogen sulfide A hydrogen production apparatus having a hydrogen removal unit,
In the steam reforming catalyst, one or more active metals selected from the group consisting of rhodium, platinum and palladium are contained in an alumina-containing support in an amount of 0.3 to 5% by mass with respect to 100% by mass of the alumina-containing support. % Or less,
The alumina-containing support is an α-alumina having a pore volume of 50 nm or more and a pore volume of 0.2 ml / g or more and 1.0 ml / g or less, and 2 to 25% by mass of rare earth based on 100% by mass of α-alumina. An apparatus for producing hydrogen, comprising a carrier on which an elemental oxide and an alkaline earth elemental oxide in an amount of 0.1% by mass to 15% by mass are supported.   A fuel cell system comprising the hydrogen production apparatus according to claim 1.

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