JP2007326756A - Porous body material for honeycomb, porous body material mixture, suspension to be supported on honeycomb, catalytic body, and method of manufacturing mixed reaction gas using the catalytic body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a porous body for honeycomb which can be industrially mass-produced and has excellent sulfur poisoning resistance, a porous body material mixture using the porous body, a honeycomb catalytic body, and a method of producing the mixed reaction gas of C1 components and hydrogen from a hydrocarbon raw material containing sulfur using the honeycomb catalytic body. <P>SOLUTION: The porous body material for honeycomb is a multiple oxide comprising at least aluminum and magnesium and has 10-300 m<SP>2</SP>/g BET specific surface area, ≤300 Å fine pore diameter and ≥0.1 cm<SP>3</SP>/g fine pore volume. A catalyst used for converting the sulfur-containing hydrocarbon into the mixed reaction gas of the C1 component and hydrogen is prepared by mixing silica, boehmite, titania, zirconia or the like with a porous support and supporting active metallic species on the porous support. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a porous material for a honeycomb excellent in sulfur poisoning resistance that can be industrially produced in large quantities, a porous material mixture using the porous material, a catalyst body, and sulfur using the catalyst It aims at providing the manufacturing method of the mixed reaction gas of C1 component and hydrogen from the hydrocarbon raw material containing this.

  The current situation of biasing to coal and oil as an energy source using a large power generation device is easily affected by natural disasters such as earthquakes, rising raw material prices, terrorism and war. Screamed.

  Rather than generating electrical energy at a power plant and allocating it to households and business establishments via transmission lines and electric wires, it is more efficient to use a cogeneration system to generate electricity with hot water in places where electricity is needed. Because it can reduce the amount of carbon dioxide generated, there are great expectations from the viewpoint of global environment and resource depletion. Of these, the most promising is power generation by a fuel cell system using hydrogen, which is being put into practical use in recent years.

  As a fuel source for generating hydrogen used in fuel cells, a wide range of hydrocarbon raw materials such as petroleum, such as kerosene, isooctane, and gasoline, LPG, and city gas have been studied.

  However, petroleum-based raw materials contain about 10 ppm to 100 ppm or more of sulfur as a total sulfur content in the raw materials themselves, and LPG and city gas by post-addition.

  When reforming a hydrocarbon feedstock to a hydrogen-rich mixed gas, a large amount of sulfur in the hydrocarbon feedstock poisons the reformer catalyst in the fuel cell system and degrades the catalytic activity. A desulfurization catalyst and an expensive desulfurization system must be installed upstream of the fuel cell system. As a result, the cost of the entire system becomes high, which is one of the factors that obstruct the spread of fuel cell systems in the future.

  Therefore, studies are underway to reduce the cost by using a catalyst body with high sulfur poisoning resistance. Giving sulfur-resistant poisoning to the catalytically active metal itself is mainly carried out by improving the carrier for supporting the catalytically active metal (Patent Documents 1 to 4). Moreover, what contains magnesium and aluminum as a steam reforming catalyst of hydrocarbon is known (patent documents 5 and 6).

  On the other hand, a molded body having a size of several mm is generally used as the shape of the catalyst filled in the system. An advantage of using the molded body is that no major problem occurs even if the shape of the reformer of the system is experimentally changed or the model of the actual machine is changed. However, once the shape of the reformer is determined to some extent, the amount of catalyst to be used can be greatly reduced, leading to an increase in the honeycomb-shaped catalyst that can reduce the manufacturing cost.

  For the above reasons, a honeycomb catalyst body excellent in sulfur poisoning resistance is desired in the future.

JP-A-9-173842 JP 2001-340759 A JP 2004-900 A JP 2004-82034 A Japanese Patent Application Laid-Open No. 55-139836 Japanese Patent Application Laid-Open No. 2003-225566

  Although the techniques described in Patent Documents 1 to 4 improve sulfur poisoning resistance, they are still not sufficient. Patent Documents 5 and 6 do not consider sulfur poisoning resistance.

  In particular, since the steam reforming reaction for obtaining hydrogen is performed at a high reaction field temperature of 600 ° C. or more, the pores and surface area of the support itself are reduced, and the gas contact probability of the active species metal is easily impaired. Instead, since the sintering of the active species metal is promoted at the same time, the catalytic activity is accelerated and the durability of the catalyst body is greatly affected.

  Although there is a need for a porous material for a honeycomb carrier that imparts high-performance sulfur poisoning resistance to the catalyst and can maintain pores and surface area even at high temperatures, it has sufficient effect, performance, and durability. The current situation is not.

  The technical problem can be achieved by the present invention as follows.

The present invention is a compound composed of at least aluminum and magnesium, has a BET specific surface area of 10 to 300 m ² / g, an average pore diameter of 300 mm or less, and a pore volume of 0.1 cm ³ / g. It is a porous material for honeycombs characterized by being g or more (Invention 1).

  The present invention also includes the above porous material, silicon, aluminum, zirconium, cerium, titanium, cobalt, iron, copper, zinc, vanadium, manganese, platinum, gold, silver, iridium, rhodium, palladium, yttrium, It is a mixture of any one or more of scandium-containing rare earth elements, metals of Group Ia elements and Group IIa elements, oxides, hydroxides, carbonates, hydrous oxides, and clay minerals, and Mg in the mixture A porous material mixture for honeycombs, wherein the content is 10 to 55 wt% in terms of Mg (Invention 2).

  In the present invention, the porous material is selected from ruthenium, platinum, gold, silver, rhodium, iridium, palladium, cobalt, nickel, iron, copper, vanadium, and manganese having an average particle size of 50 nm or less. It is a porous catalyst material for honeycombs on which one or more active species metals are supported (Invention 3).

  In the present invention, the porous material mixture is selected from ruthenium, platinum, gold, silver, rhodium, iridium, palladium, cobalt, nickel, iron, copper, vanadium, and manganese having an average particle size of 50 nm or less. Or a porous catalyst material mixture for a honeycomb supporting one or more active species metals (Invention 4).

  In addition, the present invention provides the porous material of the present invention 1, the porous catalyst material of the present invention 3, the porous material mixture of the present invention 2, or the porous material catalyst material of the present invention 4 in a solvent. A suspension for supporting a honeycomb characterized by containing any of them (Invention 5).

  Further, the present invention is a honeycomb supporting suspension according to the present invention 5, wherein the suspension has a viscosity measured by an E-type viscometer of 1.5 to 150 mPa · sec. (Invention 6).

  Further, the present invention provides a honeycomb structure having a porous material according to the present invention 1, a porous material according to the present invention 3, a porous material mixture according to the present invention 2, or a porous material according to the present invention 4. A honeycomb catalyst body in which any of the body catalyst material mixture is present, wherein the abundance of the porous material or the porous material mixture is 0.0075 to 0.65 g in terms of 1 cc volume unit of the honeycomb structure. / Cc is a honeycomb catalyst body (Invention 7).

Further, in the present invention, when nitrogen gas corresponding to a gas space velocity of 10,000 h ⁻¹ is passed through the honeycomb catalyst body according to the present invention 7 for 30 minutes, the weight change of the catalyst body before and after the nitrogen gas flow is 20 wt% or less. This is a honeycomb catalyst body (Invention 8).

  The present invention also relates to the porous body material according to the present invention 1, the porous body catalyst material according to the present invention 3, the porous body material mixture according to the present invention 2, or the porous body catalyst material mixture according to the present invention 4. One of these is a honeycomb catalyst body structured in a honeycomb shape (Invention 9).

Further, according to the present invention, when nitrogen gas corresponding to a gas space velocity of 10,000 h ⁻¹ is circulated through the honeycomb catalyst body according to the present invention 9 for 30 minutes, the weight change of the catalyst body before and after the nitrogen gas circulation is 10 wt% or less. This is a honeycomb catalyst body (Invention 10).

  Further, the present invention is a method for producing a reaction mixed gas, characterized in that a mixed reaction gas of C1 component and hydrogen is obtained from a hydrocarbon raw material using any one of the honeycomb catalyst bodies of the present invention 7 to 10 (the present invention). 11).

  The honeycomb catalyst using the porous body material or the porous body catalyst material or the porous body material mixture or the porous body catalyst material mixture according to the present invention suppresses the sintering of the porous carrier and the active species metal, and has a high performance. In addition to excellent catalytic activity, excellent sulfur poisoning resistance can be maintained for a long time.

  The suspension for supporting a honeycomb according to the present invention is suitable as a suspension for application to a honeycomb because the viscosity measured with an E-type viscometer is controlled to 1.5 to 150 mPa · sec.

  Therefore, in this invention, even if it is a hydrocarbon raw material containing a trace amount sulfur, steam reforming can be performed efficiently and the mixed gas of C1 component and hydrogen can be manufactured.

  First, the porous material according to the present invention will be described.

  The porous material according to the present invention is a compound composed of at least aluminum and magnesium. Although it does not specifically limit besides aluminum and magnesium element, elements, such as sodium, calcium, silicon, iron, nickel, zinc, may be contained.

The BET specific surface area of the porous material according to the present invention 1 is 10 to 300 m ² / g. When the BET specific surface area is less than 10 m ² / g, the average pore diameter becomes large and sintering of the active species metal to be supported cannot be sufficiently suppressed. Those exceeding 300 m ² / g are not realistic because they cannot be industrially produced. Preferably it is 20-280 m < ² > / g, More preferably, it is 23-270 m < ² > / g.

  The average pore diameter of the porous material according to the present invention 1 is 300 mm or less. When the average pore diameter exceeds 300 mm, not only the sintering of the active species metal cannot be sufficiently suppressed but also the characteristics of sulfur poisoning resistance cannot be sufficiently exhibited. Preferably it is 290 mm or less, more preferably 280 mm or less.

The pore volume of the porous material according to the first aspect of the present invention is 0.1 cm ³ / g or more. When it is less than 0.1 cm ³ / g, not only a sufficient catalytic activity cannot be obtained, but also the characteristics of sulfur poisoning resistance cannot be exhibited sufficiently. Preferably it is 0.12 cm ³ / g.

  As for Mg content of the porous material which concerns on this invention 1, 15-60 wt% is preferable. If it is less than 15 wt%, not only a sufficient catalytic activity cannot be obtained, but also the characteristics of sulfur poisoning resistance cannot be fully exhibited. If it exceeds 60 wt%, the porous material according to the present invention cannot be obtained. Preferably it is 18-57 wt%, More preferably, it is 20-55 wt%.

  Next, a method for manufacturing a porous material according to the first aspect of the present invention will be described.

  The porous material according to the present invention is a hydrated double hydroxide obtained by mixing at least an aluminum raw material and a magnesium raw material and precipitating at a pH of 8 or higher, or the hydrated double hydroxide and an aluminum compound and / or magnesium. It can be obtained by heat-treating a mixed product comprising a compound at 350 to 1250 ° C.

  In the present invention, ruthenium, platinum, gold, silver, rhodium, iridium, palladium, cobalt, nickel, iron, copper, vanadium, or manganese selected from one or more active species metals in the present invention 3 described later. The raw material may be added during the reaction for obtaining the hydrated double hydroxide, or may be contained in the mixture before the heat treatment.

  As raw materials for aluminum raw materials, magnesium raw materials and various active species metals, sulfates, nitrates, chloride salts, hydroxides, oxides, oxyhydroxides, alkoxide compounds, complexes of citric acid, etc. can be used. .

  Since Mg content of the porous material which concerns on this invention 1 has preferable 15-60 wt%, various raw materials are mix | blended so that Mg content of the porous material obtained may become the said range.

  To make the pH of the reaction solution 8 or more, use ammonia, urea, hydroxides, carbonates or oxides of alkali metal elements or alkaline earth metal elements such as magnesium, potassium and sodium. Can do.

The temperature for precipitation is 10 to 300 ° C, preferably 15 to 280 ° C, more preferably 20 to 250 ° C. If it exceeds 300 ° C., industrial production becomes difficult. A temperature lower than 10 ° C. requires a cooling device, which causes a cost problem.
When the heat treatment temperature exceeds 1250 ° C., the pore diameter increases, the pore volume decreases, and the BET specific surface area also decreases, resulting in a decrease in the activity of the catalyst and a decrease in the effect of sulfur poisoning resistance. When it is lower than 350 ° C., it does not become a porous carrier. Preferably it is 370-1230 degreeC, More preferably, it is 400-1210 degreeC.

  The average pore diameter and pore volume of the porous material according to the present invention are greatly influenced by the three conditions of precipitation reaction, Mg content and heat treatment temperature in the reaction solution, and these conditions specified in the present invention. If any or all of these are deviated, the average pore diameter and pore volume of the resulting porous material are outside the scope of the present invention.

  In addition, when producing a molded body, it may be produced according to a conventional method. For example, it is applied to a cordierite honeycomb body, an alumina plate, a stainless steel metal plate, or a bead by a compression molding machine or an extrusion molding machine. A method for producing a shaped molded body may be used.

  The porous material mixture according to the present invention 2 includes the porous material according to the present invention 1 with silicon, aluminum, zirconium, cerium, titanium, cobalt, iron, copper, zinc, vanadium, manganese, platinum, gold, silver, A mixture of rare earth elements including iridium, rhodium, palladium, yttrium and scandium, metals of group Ia elements and group IIa elements, oxides, hydroxides, carbonates, hydrous oxides, and clay minerals. And the Mg content in the mixture is 10 to 55 wt% in terms of Mg. If the Mg content in the mixture is less than 10 wt%, not only a sufficient catalytic activity cannot be obtained, but also the characteristics of sulfur poisoning resistance cannot be exhibited sufficiently. If it exceeds 55 wt%, the porous material according to the present invention cannot be obtained. Preferably it is 15-52 wt%, More preferably, it is 20-50 wt%. The compound to be mixed is not particularly limited, and may be any of suspension, paste, powder, lump, and molded body.

  The mixture of the porous material of the present invention 2 may be prepared by mixing a porous material with, for example, silica or boehmite according to a conventional method. Further, it may be formed by mixing the porous carrier of the present invention with, for example, silica or boehmite.

The porous catalyst material according to the present invention 3 is ruthenium, platinum, gold, silver, rhodium, iridium, palladium, cobalt, nickel, iron, copper having an average particle size of 50 nm or less in the porous material according to the present invention 1. , One or more active species metals selected from vanadium and manganese are present. When the average particle size exceeds 50 nm, the catalytic activity is significantly reduced. Preferably it is 40 nm or less, More preferably, it is 30 nm or less.
The active species metal can be included at the same time as the production of the porous material of the first aspect of the present invention, or may be supported after the production of the porous material, and is not particularly limited. The supporting method is not particularly limited, and a generally performed method such as a spray drying method or an impregnation method may be used.

The porous catalyst material mixture according to the present invention includes ruthenium, platinum, gold, silver, rhodium, iridium, palladium, cobalt, nickel, iron, an average particle diameter of 50 nm or less in the porous material mixture according to the present invention 2, One or more active metals selected from copper, vanadium, and manganese are supported. When the average particle size exceeds 50 nm, the catalytic activity is significantly reduced. Preferably it is 40 nm or less, More preferably, it is 30 nm or less.
In addition, the active species metal may be included at the same time when the porous material according to the first aspect of the present invention is produced, or may be supported after the production of the porous material, and is not particularly limited. There is no particular limitation on the supporting method, and a generally used method such as a spray drying method or an impregnation method may be used.

  As the suspension used for supporting the honeycomb body according to the present invention, any one or more of the present inventions 1 to 4 can be used, and the viscosity of the suspension measured with an E-type viscometer is 1.5 to 150 mPa · sec. When the viscosity of the suspension is less than 1.5 mPa · sec, the amount of the suspension that comes out without being supported on the honeycomb carrier is too much, and it is not productive. If it exceeds 150 mPa · sec, the cells of the honeycomb carrier will be clogged. Preferably it is 2-125 mPa * sec, More preferably, it is 2.5-115 mPa. A suspension having an appropriate viscosity may be selected according to the number of cells of the honeycomb carrier.

  The concentration of the suspension for supporting a honeycomb according to the present invention can be arbitrarily set as long as it satisfies the above viscosity, but is preferably 10 to 65 wt%.

  The suspension for supporting a honeycomb according to the present invention uses, for example, water, ethanol, methanol, propanol, butanol, acetone, methyl ethyl ketone, benzene, diethyl ether, polyethylene glycol, glycerin, propylene glycol, ethylene glycol or the like as a solvent. And two or more of them may be used in combination.

  Although it is not particularly limited as an additive to the suspension, for example, stearate, oleate, PVA resin, cellulose resin, urethane resin, maleic acid, malic acid, acetic acid, succinic acid, maltose, starch, etc. You can select and use as needed. At this time, it is necessary to optimize the viscosity of the suspension of the present invention.

The honeycomb catalyst body according to the present invention 7 has an amount of the porous material, the porous catalyst material, the porous material mixture, or the porous catalyst material mixture supported on the honeycomb structure in an amount of 1 cc of the honeycomb structure. It is 0.0075 to 0.65 g / cc in terms of volume unit.
If the amount supported on the honeycomb structure is less than 0.0075 g / cc in terms of 1 cc volume unit of the honeycomb structure, the initial activity as a catalyst is insufficient. If it exceeds 0.65 g / cc, the cell is clogged and gas distribution is impossible. Preferably it is 0.03-0.63 g / cc, More preferably, it is 0.05-0.6 g / cc.
The material, shape, and size of the honeycomb structure to be the support are not particularly limited. For example, cordierite material, alumina material, or austenite, ferrite, martensite, or precipitation hardened metal The material may be a cylindrical shape or a quadrangular prism, the size in the gas flow section direction may be 20 mm or 150 mm, and the size in the gas flow direction may be 50 mm or 500 mm.

Further, the honeycomb catalyst body in which the porous body material, the porous body catalyst material, the porous body material mixture or the porous body catalyst material mixture is supported on the honeycomb structure described above has a gas space velocity relative to the volume of the honeycomb catalyst body. It is preferable that the weight change before and after flowing nitrogen gas corresponding to 10,000 h ⁻¹ for 30 minutes is 20 wt% or less. If it exceeds 20 wt%, not only will the catalyst activity be reduced, but it may cause powder damage to the subsequent process when used in an actual machine, causing the worst pipe to be blocked. Preferably it is 17 wt% or less, More preferably, it is 15 wt% or less.

  The honeycomb catalyst body according to the present invention 7 may be applied to the honeycomb structure serving as the support by using the suspension according to the present invention 5 so as to have a desired carrying amount according to a conventional method.

  When the substance to be supported is the above porous body material or porous body material mixture, the catalytically active species metal may be applied on the surface of the layer or in a mixed state with these substances. The amount of metal can be selected as appropriate.

  A honeycomb catalyst body structured in a honeycomb shape according to the present invention 9 is obtained by directly forming a porous material, a porous catalyst material, a porous material mixture or a porous catalyst material mixture into a honeycomb shape. is there. The forming method is not particularly limited, but generally, an organic / inorganic binder, water, an organic solution, or the like is added, mixed and kneaded with a mixer or kneader, and then formed into a honeycomb shape with an extruder or the like. When a porous material or a porous material mixture is used as the honeycomb material, a catalytically active seed metal may be further supported after forming the honeycomb shape.

In the honeycomb catalyst body according to the ninth aspect of the present invention, the weight change before and after the nitrogen gas corresponding to the gas space velocity of 10,000 h ⁻¹ is circulated for 30 minutes with respect to the volume of the honeycomb catalyst body is 10 wt% or less. preferable. If it exceeds 10 wt%, not only will the catalyst activity be reduced, but it may cause powder damage to the subsequent process when used in an actual machine, causing the worst pipe to be blocked. Preferably it is 7 wt% or less, More preferably, it is 5 wt% or less.

  Next, a method for producing a reaction gas mixture using the honeycomb catalyst body according to the present invention will be described.

  By bringing the honeycomb catalyst body according to the present invention into contact with a gaseous or liquid hydrocarbon raw material, a reaction mixed gas mainly composed of a C1 component and hydrogen can be obtained. Examples of the hydrocarbon raw material include methane, city gas, LPG, kerosene, isooctane, and gasoline. It is desirable to use a state in which these are gasified. For example, by utilizing a steam reforming reaction, an autothermal reforming reaction, or a partial reforming reaction not using steam, the C1 is brought into contact with the honeycomb catalyst body of the present invention. A reaction gas mixture mainly composed of components and hydrogen can be obtained.

  Since the honeycomb catalyst body according to the present invention is excellent in sulfur poisoning resistance, high activity can be maintained even if the hydrocarbon raw material contains a sulfur compound.

  In the present invention, sulfur may be contained in the hydrocarbon raw material. Examples of the compound containing sulfur contained in the hydrocarbon raw material include methyl mercaptan, ethyl mercaptan, isobutyl mercaptan, methyl ethyl sulfide, and dimethyl sulfide. , Tertiary butyl mercaptan, sec-butyl mercaptan, n-butyl mercaptan, isopropyl mercaptan, n-propyl mercaptan, isoamyl mercaptan, n-amyl mercaptan, α-methylbutyl mercaptan, α-ethylpropyl mercaptan, n-hexyl mercaptan, 2 -Methylcaptohexane, 3-mercaptohexane, tetrahydrothiophene and the like.

The step of obtaining a reaction mixed gas mainly composed of C1 component and hydrogen by decomposing a hydrocarbon raw material using the honeycomb catalyst body according to the present invention is a gaseous hydrocarbon raw material having a total sulfur content of 50 ppm or less. , GHSV is 100 to 1,000,000 h ⁻¹ , reaction temperature is 300 to 800 ° C., and S / C is 1.0 to 6.0.

  If the total sulfur content in the hydrocarbon feed exceeds 50 ppm, coking tends to occur.

  Gaseous hydrocarbon raw materials are a wide variety of hydrocarbon compounds such as methane, ethane, vaporized propane, isooctane, kerosene, and gasoline.

When GHSV is lower than 100 h ^{−1, the} obtained C1 component and hydrogen are too small, which is not practical. When GHSV exceeds 1,000,000 h ⁻¹ , a sufficient heat source cannot be provided for the endotherm caused by the reaction. Preferably it is 150-800,000h < ^-1 >, More preferably, it is 200-500,000h- ¹ .

  When the reaction temperature is below 300 ° C., the conversion to the C1 component and hydrogen hardly proceeds. If it exceeds 800 ° C., the material of the catalyst reactor becomes an expensive material such as Inconel, which is not realistic. Preferably it is 300-780 degreeC, More preferably, it is 320-750 degreeC.

  When S / C is lower than 1.0, the decomposition of the hydrocarbon itself proceeds and coking and carbon deposition progress greatly. If the S / C exceeds 6.0, the C1 component and hydrogen fraction obtained are low and not realistic.

The step of decomposing a hydrocarbon raw material using the honeycomb catalyst body according to the present invention to obtain a reaction mixed gas mainly composed of C1 component and hydrogen is a liquid hydrocarbon raw material having a total sulfur content of 50 ppm or less. LHSV is 5 h ⁻¹ or less, reaction temperature is 300 to 800 ° C., and S / C is 1.0 to 6.0.

  Liquid hydrocarbon raw materials are a wide variety of hydrocarbon compounds such as propane, isooctane, kerosene, and gasoline.

If the LHSV exceeds 5h- ¹ , the active species metal and the hydrocarbon raw material cannot be sufficiently contacted.

  When the reaction temperature is below 300 ° C., the conversion to the C1 component and hydrogen hardly proceeds. If it exceeds 800 ° C., the material of the catalyst reactor becomes an expensive material such as Inconel, which is not realistic. Preferably it is 310-800 degreeC, More preferably, it is 320-800 degreeC.

  When S / C is lower than 1.0, the decomposition of the hydrocarbon itself proceeds and coking and carbon deposition progress greatly. If the S / C exceeds 6.0, the C1 component and hydrogen fraction obtained are low and not realistic.

<Action>
The reason why the honeycomb structure or honeycomb catalyst body according to the present invention is excellent in sulfur poisoning resistance is not yet clear, but the present inventor estimates as follows.

  That is, a sufficient amount of magnesium contained in the honeycomb porous material or the honeycomb porous material mixture according to the present invention captures and adsorbs the sulfur compound to be bound to the active species metal first. Most remain adsorbed, but aluminum releases some sulfur compounds from the catalyst. Moreover, since the porous carrier has an appropriate BET specific surface area, average pore diameter, and pore volume, the inventor presumes that highly active catalytic activity can be maintained for a long time.

  By using the suspension according to the present invention, the solid component concentration and viscosity are optimized, not only can the amount of the solid component supported on the honeycomb be optimized, but also high space velocity gas can be circulated through the honeycomb. In addition, the catalyst activity is good without being peeled off, and the catalyst can have excellent resistance to catalyst deterioration due to the sulfur-containing compound contained in the hydrocarbon.

  A typical embodiment of the present invention is as follows.

  The BET specific surface area value is the B.R. E. T. T. et al. Measured by the method.

  The size of the supported active metal was measured using a transmission electron microscope (JEOL Ltd., JEM-1200EXII).

  The contents of Mg and active species metal were determined by dissolving a sample with an acid and analyzing it using a plasma emission spectroscopic analyzer (Seiko Electronics Co., Ltd., SPS4000).

  For the pore diameter and pore volume, an adsorption isotherm of nitrogen at 75K was prepared using a high-speed specific surface area / pore distribution measuring device (ASAP2010, manufactured by Micromeritics), and the adsorption isotherm was reduced by the BJH method. The pore distribution curve was obtained and obtained.

  The viscosity of the suspension was measured using an E-type viscometer (Toki Sangyo Co., Ltd., TV-30 viscometer) at a temperature of 25 ° C.

  For the steam reforming reaction, a laboratory-level single pipe fixed bed flow type was used. Although what is generally marketed may be sufficient, examination of this invention was implemented with the self-made apparatus. A gas chromatograph was used for component analysis after the modification.

Example 1 <Preparation of carrier>
68.4 g of Mg (NO ₃ ) ₂ · 6H ₂ O, 50.0 g of Al (NO ₃ ) ₃ · 9H ₂ O and 7.8 g of Ni (NO ₃ ) ₂ · 6H ₂ O were dissolved in water to make 600 ml. . Separately, a mixed solution of 400 ml of alkali was prepared by combining 71 ml of NaOH (concentration of 14 mol / L) and 14.1 g of Na ₂ CO ₃ . A mixed solution of the magnesium salt and aluminum salt was added to the alkali mixed solution, and aging was performed at 80 ° C. for 4.5 hours to obtain a hydrated double hydroxide. This was separated by filtration, dried, pulverized, and heat-treated at 580 ° C. for 4 hours. The obtained catalyst carrier (porous material for honeycomb) had a BET of 80.0 m ² / g, an average pore diameter of 234 mm, and a pore volume of 0.57 cm ³ / g.

<Preparation of catalyst>
Granular alumina and spray-dried silica were mixed with the honeycomb porous material. At this time, the Mg content was 26.9 wt% as a result of analysis. 35 g of ethylene glycol was added thereto and mixed and ground by a paint shaker to obtain a suspension having a viscosity of 5.3 mPa · sec.
This was supported at 0.370 g / cc on an austenitic SUS honeycomb structure having a diameter of 20 mm × height of 35 mm and 200 cpsi, dried at 103 ° C., heat-treated in air at 800 ° C. for 1.5 hours, and further heated to 800 ° C. Then, reduction treatment was performed in hydrogen for 0.5 h to obtain a honeycomb catalyst body supporting nickel metal. Further, this honeycomb catalyst body was immersed in a ruthenium nitrate solution, dried at 60 ° C., heat-treated in air at 500 ° C. for 1 h, and further reduced in hydrogen at 700 ° C. for 1 h.
The metal particle size of nickel and ruthenium in the obtained honeycomb catalyst body was 20 nm or less.
The change in the weight of the honeycomb catalyst body before and after flowing nitrogen corresponding to a gas space velocity of 10,000 h ⁻¹ for 30 minutes was 8 wt%.

<Catalyst activity evaluation>
The obtained honeycomb catalyst body was flowed at a flow rate fixed bed catalyst reactor using tertiary butyl mercaptan with a pure methane gas having a total sulfur content of 3 ppm at GHSV = 1,500 h ⁻¹ at a temperature of 700 ° C., S / C. The steam reforming activity of the catalyst was evaluated at = 2.8. Even at a reaction time of 24 h, only the C1 component and hydrogen were confirmed, and the deterioration was within 5% compared to the initial C1 conversion.

Example 2
In the same manner as in Example 1, 82.1 g of Mg (NO ₃ ) ₂ .6H ₂ O, 30.0 g of Al (NO ₃ ) ₃ .9H ₂ O, 63.0 ml of NaOH (14 mol / L concentration), and Na ₂ CO ₃ The reaction was performed at 90 ° C. for 10 hours using 8.48 g. Heat treatment was performed at 850 ° C. for 1 h. The obtained catalyst support (porous material for honeycomb) had a BET of 35 m ² / g, an average pore diameter of 250 mm, and a pore volume of 0.27 cm ³ / g.

Zirconia was mixed with the honeycomb porous material. At this time, the Mg content was 42.5 wt% as a result of analysis. 25 g of water was added to this and mixed and pulverized with a paint shaker to obtain a suspension having a viscosity of 112 mPa · sec.
0.182 g / cc was supported on a 400 cpsi ferritic SUS honeycomb structure 30 mm in diameter × 50 mm in height and heat-treated at 1000 ° C. for 3 h in advance, dried at 80 ° C., and then in air at 800 ° C. for 1.5 h. The honeycomb catalyst body carrying nickel metal was obtained by heat treatment and reduction treatment in hydrogen at 800 ° C. for 0.5 h.
The nickel metal particle size in the obtained honeycomb catalyst body was 8 nm or less. The change in weight of the honeycomb catalyst body before and after flowing nitrogen corresponding to a gas space velocity of 10,000 h ⁻¹ for 30 minutes was 12 wt%.
The obtained honeycomb catalyst body was flowed at a flow rate fixed bed catalyst reactor using a tertiary butyl mercaptan and a city gas having a total sulfur content of 5 ppm at GHSV = 700 h ⁻¹ at a temperature of 650 ° C. and S / C = 3. The steam reforming activity of the catalyst was evaluated at 0.0. Only the C1 component and hydrogen were confirmed even at the reaction time of 8 h, and the deterioration was within 5% compared to the initial C1 conversion.

Example 3
In the same manner as in Example 1, 76.3 g of Mg (NO ₃ ) ₂ .6H ₂ O, 38.5 g of Al (NO ₃ ) ₃ .9H ₂ O, 63.8 ml of NaOH (14 mol / L concentration), and Na ₂ CO ₃ The reaction was performed at 55 ° C. for 4 hours using 10.87 g. Heat treatment was performed at 630 ° C. for 1.5 hours. The obtained catalyst support (porous material for honeycomb) had a BET of 145 m ² / g, an average pore diameter of 280 mm, and a pore volume of 0.95 cm ³ / g.

Kaolinite was mixed into the honeycomb porous material. At this time, the Mg content was 31.9 wt% as a result of analysis. After adding 12.7 g of water, ethylene glycol, and ethanol (1: 1: 1) to this, kneader kneading, and drying at 140 ° C. as a honeycomb structure having a diameter of 30 mm × height of 50 mm and 400 cpsi in an extruder, It heat-processed in the air at 1000 degreeC for 5.5 hours. Further, this honeycomb body was immersed in a mixed solution of ruthenium nitrate and silver nitrate, dried at 60 ° C., heat-treated in air at 500 ° C. for 0.5 h, and further reduced in hydrogen at 700 ° C. for 1 h. The metal particle size of ruthenium and silver in the obtained honeycomb catalyst body was 9 nm or less. The change in the weight of the honeycomb catalyst body before and after flowing nitrogen corresponding to a gas space velocity of 10,000 h ⁻¹ for 30 minutes was 1.5 wt%.
The obtained honeycomb catalyst body was flowed at a flow rate fixed bed catalyst reactor using a tertiary butyl mercaptan with a pure propane gas having a total sulfur content of 5 ppm at GHSV = 1,000 h ⁻¹ at a temperature of 670 ° C., S / The steam reforming activity of the catalyst was evaluated at C = 3.5. Even at a reaction time of 15 hours, only the C1 component and hydrogen were confirmed, and the deterioration was within 5% compared to the initial C1 conversion.

Example 4
In the same manner as in Example 1, 77.6 g of Mg (NO ₃ ) ₂ .6H ₂ O, 36.6 g of Al (NO ₃ ) ₃ .9H ₂ O, 9.22 g of Ni (NO ₃ ) ₂ .6H ₂ O, NaOH Using 60.7 ml (14 mol / L concentration) and 8.27 g of NaCO _{3, a} reaction was performed at 40 ° C. for 4 h, and a heat treatment was performed at 640 ° C. for 1 h. The obtained catalyst carrier (porous material for honeycomb) had a BET of 204 m ² / g, an average pore diameter of 244 mm, and a pore volume of 1.22 cm ³ / g.

Lanthanum oxide and silica were mixed into the honeycomb porous material. At this time, the Mg content was 40.0 wt% as a result of analysis. 11.9 g of water, ethylene glycol, and ethanol (1.33: 1: 0.92) was added thereto, and after kneader kneading, a honeycomb structure of 20 mm square × height 50 mm, 500 cpsi was formed at 110 ° C. using an extruder. And dried at 1020 ° C. for 6.5 hours in air. Subsequently, reduction treatment was performed in hydrogen at 800 ° C. for 2 hours. The nickel metal particle size in the obtained honeycomb catalyst body was 15 nm or less. The change in weight of the honeycomb catalyst body before and after flowing nitrogen corresponding to a gas space velocity of 10,000 h ⁻¹ for 30 minutes was 1 wt%.
The resulting honeycomb catalyst body was flowed through a fixed bed catalytic reactor using methyl mercaptan and a city gas having a total sulfur content of 5 ppm was flowed at GHSV = 800 h ⁻¹ , temperature 680 ° C., S / C = 2.7. The steam reforming activity of the catalyst was evaluated. Only the C1 component and hydrogen were confirmed even at the reaction time of 11 h, and the deterioration was within 5% compared to the initial C1 conversion.

Comparative Example 1
55 g of water + 18 vol% ethanol was added to 30 g of γ-alumina having a BET of 175 m ² / g, an average pore diameter of 154 mm, and a pore volume of 0.883 cm ³ / g, and pulverized and mixed with a homogenizer, and the viscosity was 26 mPa · sec. A suspension was obtained. This was supported on 0.233 g / cc of an alumina silicate 300 cpsi honeycomb having a size of 15 mm × 25 mm × height 40 mm, dried at 100 ° C., and heat-treated in air at 1050 ° C. for 2 hours. This was immersed in a ruthenium nitrate solution, dried at 60 ° C., heat-treated at 500 ° C. for 1 h, and further subjected to reduction treatment in hydrogen at 500 ° C. for 1 h to obtain a honeycomb catalyst body carrying a ruthenium metal. The ruthenium metal particle size in the obtained honeycomb catalyst body was 17 nm or less. The change in weight of the honeycomb catalyst body before and after flowing nitrogen corresponding to a gas space velocity of 10,000 h ⁻¹ for 30 minutes was 11 wt%.
The obtained honeycomb catalyst body was flown at a fixed bed catalytic reactor using a methyl mercaptan, and pure methane gas having a total sulfur content of 3 ppm was flowed at GHSV = 1,000 h ^−1, at a temperature of 680 ° C. and S / C = 3. The steam reforming activity of the catalyst was evaluated at. Although only the C1 component and hydrogen were confirmed after the reaction time of 18 h, deterioration of 20% was confirmed as compared with the initial C1 conversion rate.

A honeycomb porous body material excellent in sulfur poisoning resistance that can be produced industrially in large quantities can be provided. Furthermore, by making a honeycomb catalyst body, a mixture reaction of C1 component and hydrogen from a hydrocarbon raw material containing sulfur It is very useful when producing gas.

Claims (11)

It is a compound composed of at least aluminum and magnesium, has a BET specific surface area of 10 to 300 m ² / g, an average pore diameter of 300 mm or less, and a pore volume of 0.1 cm ³ / g or more. A porous material for honeycombs, characterized by the above.   The porous material according to claim 1 and silicon, aluminum, zirconium, cerium, titanium, cobalt, iron, copper, zinc, vanadium, manganese, platinum, gold, silver, iridium, rhodium, palladium, yttrium and scandium. A rare earth element, a group Ia element and a metal of group IIa element, oxide, hydroxide, carbonate, hydrated oxide, a mixture with one or more of clay minerals, and the Mg content in the mixture Is a porous body material mixture for a honeycomb, characterized by being 10 to 55 wt% in terms of Mg.   The porous material according to claim 1, wherein one or two selected from ruthenium, platinum, gold, silver, rhodium, iridium, palladium, cobalt, nickel, iron, copper, vanadium, and manganese having an average particle diameter of 50 nm or less. A porous catalyst material for a honeycomb in which at least one kind of active species metal is present.   The porous material mixture according to claim 2, wherein the average particle size is selected from ruthenium, platinum, gold, silver, rhodium, iridium, palladium, cobalt, nickel, iron, copper, vanadium, and manganese having an average particle size of 50 nm or less A porous catalyst material mixture for honeycombs in which two or more kinds of active species metals are present.   Either the porous material according to claim 1, the porous catalyst material according to claim 3, the porous material mixture according to claim 2, or the porous catalyst material mixture according to claim 4 in a solvent. A suspension for supporting a honeycomb, comprising:   The suspension for supporting a honeycomb according to claim 5, wherein the suspension has a viscosity of 1.5 to 150 mPa · sec as measured by an E-type viscometer.   In the honeycomb structure, any one of the porous body material according to claim 1, the porous body catalyst material according to claim 3, the porous body material mixture according to claim 2, or the porous body catalyst material mixture according to claim 4. A honeycomb catalyst body in which the porous material or the porous material mixture is present in an amount of 0.0075 to 0.65 g / cc in terms of 1 cc volume unit of the honeycomb structure. A honeycomb catalyst body characterized. When nitrogen gas corresponding to a gas space velocity of 10,000 h- ¹ is passed through the honeycomb catalyst body according to claim 7 for 30 minutes, the weight change of the catalyst body before and after the nitrogen gas flow is 20 wt% or less. A honeycomb catalyst body.   Any one of the porous material according to claim 1, the porous catalyst material according to claim 3, the porous material mixture according to claim 2, or the porous catalyst material mixture according to claim 4 is formed in a honeycomb shape. Structured honeycomb catalyst body. When nitrogen gas corresponding to a gas space velocity of 10,000 h ^-1 is passed through the honeycomb catalyst body according to claim 9 for 30 minutes, the weight change of the catalyst body before and after the nitrogen gas flow is 10 wt% or less. A honeycomb catalyst body.   A method for producing a reaction mixed gas, wherein a mixed reaction gas of a C1 component and hydrogen is obtained from a hydrocarbon raw material using the honeycomb catalyst body according to any one of claims 7 to 10.