WO2001072416A1 - Catalyseur destine a modifier les hydrocarbures et son procede de fabrication - Google Patents

Catalyseur destine a modifier les hydrocarbures et son procede de fabrication Download PDF

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Publication number
WO2001072416A1
WO2001072416A1 PCT/JP2001/002650 JP0102650W WO0172416A1 WO 2001072416 A1 WO2001072416 A1 WO 2001072416A1 JP 0102650 W JP0102650 W JP 0102650W WO 0172416 A1 WO0172416 A1 WO 0172416A1
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Prior art keywords
component
catalyst
ruthenium
carrier
reforming catalyst
Prior art date
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PCT/JP2001/002650
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English (en)
Japanese (ja)
Inventor
Hiroshi Ohashi
Tetsuya Fukunaga
Original Assignee
Idemitsu Kosan Co., Ltd.
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Priority claimed from JP2000214427A external-priority patent/JP2001340759A/ja
Application filed by Idemitsu Kosan Co., Ltd. filed Critical Idemitsu Kosan Co., Ltd.
Priority to AU2001244627A priority Critical patent/AU2001244627A1/en
Publication of WO2001072416A1 publication Critical patent/WO2001072416A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1064—Platinum group metal catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a hydrocarbon reforming catalyst, a method for producing the same, and a hydrocarbon steam reforming method using the reforming catalyst. More specifically, the present invention relates to a method for producing a steam containing hydrocarbon by using ruthenium as an active component. The present invention relates to a reforming catalyst for efficiently improving reforming activity, a method for producing the same, and a method for steam reforming hydrocarbons using the reforming catalyst.
  • Fuel cells convert chemical energy into electrical energy by electrochemically reacting hydrogen and oxygen, and have the characteristic of high energy use efficiency. Practical research is being actively conducted for industrial, industrial, and automotive applications.
  • the sources of hydrogen include methanol, liquefied natural gas mainly composed of methane, city gas mainly composed of natural gas, synthetic liquid fuel using natural gas as raw material, and petroleum-based fuel.
  • the use of petroleum hydrocarbon oils such as naphtha and kerosene has been studied.
  • ruthenium used in the ruthenium-based reforming catalyst is a noble metal
  • the catalyst used as a supporting component is generally expensive, so that a catalyst containing a ruthenium component is industrially used. To be useful, it is necessary to reduce not only the catalyst performance but also the catalyst price.
  • the conventional ruthenium-based reforming catalyst has a practically insufficient catalytic activity per supported ruthenium, and a more active reforming catalyst has been desired.
  • ruthenium-based reforming catalysts since ruthenium components are supported during the production of the catalyst, usually ruthenium chlorides and the like are used, and chlorine atoms remain in the catalyst, which causes peripheral equipment and piping. It may cause corrosion of metal members such as the system, and when used as a reforming catalyst for a molten carbonate fuel cell, it may react with carbonate to lower the cell characteristics. When such a ruthenium catalyst with chlorine atoms remaining is used for steam reforming, its reforming activity is not yet sufficient. Further, a reforming catalyst having higher activity has been desired.
  • the present invention has been made under such circumstances, in which the active components of the catalyst are uniformly supported, the catalyst activity per supported ruthenium is remarkably excellent, and the high activity is maintained even at a high temperature during the reaction. It is an object of the present invention to provide a catalyst for reforming hydrocarbons, a method for producing the same, and a method for steam reforming hydrocarbons that can efficiently obtain hydrogen for fuel cells using the catalyst for reforming. It is assumed that.
  • the present invention provides a reforming catalyst having extremely low catalytic activity per supported ruthenium without causing the corrosion of peripheral devices or the like and the deterioration of battery characteristics as a result.
  • An object of the present invention is to provide a production method and a method for steam reforming hydrocarbons, which can efficiently obtain hydrogen for fuel cells using the reforming catalyst.
  • the present inventors have conducted intensive research to achieve the above object.
  • the catalyst in the production of a ruthenium-based reforming catalyst, when the catalyst is dried at a constant temperature after impregnating the metal component with the carrier, the usual drying in a stationary state dissolves in the water simultaneously with the evaporation of the water.
  • the catalyst active component migrates, causing a phenomenon of non-uniform distribution on the catalyst.Therefore, to suppress such a phenomenon, the drying speed of the catalyst surface is reduced by placing the catalyst in a floating state during drying. It has been found that the catalyst becomes uniform and the movement of the catalytically active component is suppressed, and as a result, the active component can be uniformly supported on the carrier.
  • the present inventors carried out a heat treatment, an aqueous alkali solution treatment, and a water washing treatment, after supporting a metal component on an alumina carrier, alone or in an appropriate combination, so that almost all chlorine atoms remained. Was found to be removed without having to do so.
  • the reforming catalyst obtained by the above method has the same metal loading Even so, the catalyst activity is remarkably excellent, so that it can be used as a reforming catalyst for its purpose, and furthermore, by using this reforming catalyst for steam reforming, fuel It has been found that hydrogen for batteries can be obtained efficiently.
  • the present invention has been completed based on such findings. That is, the present invention
  • a reforming catalyst comprising a carrier carrying a metal component containing at least one selected from a ruthenium component and a zirconium component, wherein the chlorine atom content in the catalyst is 0.1% by weight.
  • a hydrocarbon reforming catalyst (first catalyst of the present invention) characterized by the following:
  • a reforming catalyst in which a support carries at least one metal component selected from a ruthenium component and a zirconium component, after the metal component is impregnated into the support, continuously or intermittently.
  • a reforming catalyst (second catalyst of the present invention) which is dried while being agitated, and
  • a method for producing a reforming catalyst (second method of the present invention), characterized in that the catalyst obtained is dried while moving continuously or intermittently.
  • the first catalyst according to the present invention is a reforming catalyst comprising a support carrying a metal component containing at least one selected from a ruthenium component and a zirconium component, wherein the chlorine atom content in the catalyst is Is less than 0.1% by weight.
  • a porous carrier is preferable, and a porous inorganic oxide is particularly preferable.
  • examples of such materials include silica, alumina, silica-alumina, titania, zirconia, magnesium, zinc oxide, clay, clay and diatomaceous earth. These may be used alone or in combination of two or more. Among these, alumina, especially ⁇ -alumina, is preferred from the viewpoint of catalyst strength and the like.
  • the carrier those whose composition and physical properties are adjusted or controlled by addition of additives, selection of pretreatment or preparation method, and the like can be appropriately used.
  • a chemical treatment such as an acid treatment, a base treatment, or an ion exchange treatment is performed to adjust the acidity, the moisture or 0% content is adjusted by heating or baking, and the fineness is adjusted by various means.
  • the carrier may contain or carry an appropriate metal component or the like in advance, be dried or calcined in advance, be unfired, undried, or be prepared by hydrolysis or the like. Or a slurry-like material.
  • the shape and size of the carrier are not particularly limited, and may be granulated or molded.
  • the carrier may be coated on a structure such as powder, beads, pellets, granules, and monolith. It is possible to appropriately use a prepared, fine particle, ultra fine particle, or the like.
  • a ruthenium component is indispensable as a metal component supported on the carrier.
  • it is preferable to support a ruthenium component and a Z or zirconium component it is preferable to support both a ruthenium component and a zirconium component. Is a supported amount, 0 ruthenium component ruthenium atom terms. 0 5-5 wt 0/0, the preferred properly 0.
  • further preferred properly is from 0.1 to 2 weight 0 / 0, 0. 0 5-2 0% by weight of zirconium components in Z r ⁇ 2 terms, the preferred properly is from 1.0 to 1 5% by weight. If the amount of the supported ruthenium component is less than 0.05% by weight, the catalytic activity may be insufficient, and a sufficient reforming effect may not be obtained. It is uneconomical to obtain the effect corresponding to the increase.
  • the chlorine atom content in the first catalyst of the present invention is less than 0.01% by weight.
  • chlorine atoms cause corrosion of metal members such as peripheral equipment and piping systems, and particularly, the catalytic activity per supported ruthenium is inferior, and reforming of molten carbonate fuel cells is difficult.
  • it reacts with carbonates to lower battery characteristics.
  • the carrier further supports a cobalt component and a Z or magnesium component, and the amount of the supported component is, in the case of the cobalt component, converted into cobalt atoms.
  • 0.05 to 5% by weight preferably 0.05 to 2% by weight, more preferably 0.1 to 2% by weight
  • the magnesium component is 0.5 to 20% in terms of Mgg. wt%, is preferred properly 0. 5 ⁇ gamma 5 wt%, rather further preferred is 1 to 1 0 weight 0/0.
  • Examples of the ruthenium compound which is a ruthenium component source used in the present invention include various types of ruthenium halides such as ruthenium nitrate and ruthenium trichloride, and various types of ruthenium halides such as hexacroporous ruthenium acid rim.
  • ruthenates such as phosphate, tetraxorthenate, and various amide complex salts, such as ruthenium tetroxide, hexaammonium ruthenium trichloride, and hexacyanoruthenate.
  • ruthenium oxides such as diruthenium trioxide, ruthenium hydroxide, or oxyhalides, which are insoluble or hardly soluble in water having a pH of around 7, can be dissolved by appropriately adding an acid such as hydrochloric acid. Can be used.
  • ruthenium chloride is particularly preferably used because it is widely used industrially and easily available. These ruthenium compounds may be used alone or in combination of two or more.
  • the zirconium compound which is the source of the zirconium component used in the present invention may be one which is soluble in a certain kind of solvent, or an acid such as hydrochloric acid or an acidic compound.
  • an acid such as hydrochloric acid or an acidic compound.
  • Various types can be used as long as they can be sufficiently dissolved by coexistence.
  • various halides such as zirconium tetrachloride or partial hydrolysis products thereof, various oxyhalogenated compounds such as zirconyl chloride (zirconium oxychloride), various halides such as zirconyl sulfate, zirconium nitrate, and zirconyl nitrate.
  • zirconates such as oxyacid salts, potassium tetrazirconate, sodium hexafluorosilodiconate,
  • organic acid salts or organic coordination compounds such as zirconium acetate, zirconyl acetate, zirconyl oxalate, tetrazolato zirconate acid spheres, etc., and alkoxides and hydroxides of zirconium, Various complex salts and the like can be mentioned.
  • Okishi chloride Jirukoyuu arm for example, represented by Z r OC l 2 ⁇ ⁇ ⁇ 2 0 and Z r 0 (OH) CI ⁇ n H 2 ⁇ Hydrates and those commercially available in the form of a solution are preferably used because they easily form a complex-like compound with ruthenium.
  • These zirconium compounds may be used alone or in combination of two or more.
  • the cobalt compound which is the cobalt source of the cobalt component used in the present invention is one which shows solubility in a certain solvent, or one which can be sufficiently dissolved by adding or coexisting an acid or an acidic compound such as hydrochloric acid.
  • Various compounds can be used as long as the compounds are highly soluble, such as nitrates and chlorides. Examples include cobalt nitrate, basic cobalt nitrate, cobalt dichloride, and various hydrates thereof. Among them, cobaltous nitrate and the like are particularly preferably used. In addition, these cobalt compounds may be used alone or in combination of two or more.
  • the magnesium compound which is a magnesium source of the magnesium component used in the present invention has solubility in a certain kind of solvent, and can be sufficiently dissolved by adding or coexisting an acid or an acidic compound such as hydrochloric acid.
  • various compounds can be used, and usually highly soluble compounds such as nitrates and chlorides are preferably used.
  • magnesium nitrate, magnesium chloride, and various hydrates thereof can be exemplified.
  • magnesium nitrate, each of these Seed hydrate salts are particularly preferably used.
  • These magnesium compounds may be used alone or in combination of two or more.
  • a method for supporting various metal components on a carrier is as follows.For example, at least one or two or more kinds of ruthenium compounds and zirconium compounds on an alumina carrier and, if necessary, one or more kinds
  • the carrier can be supported by contact impregnation with a solution containing a cobalt compound and a magnesium compound dissolved therein.
  • the above-mentioned various compounds can be supported in the vicinity of the surface of the carrier with good dispersibility and without unevenness. Even if pretreatment such as the above is performed, the highly dispersed state of each component can be maintained sufficiently stably, and the above-mentioned reforming catalyst can be easily obtained.
  • the solution used for this support contains a ruthenium compound, a zirconium compound and, if necessary, a cobalt compound and a magnesium compound, but is acidic, preferably has a pH of 3 or less, and preferably has a pH of 1. Adjust it to 5 or less. If the pH exceeds 3, the respective compounds tend to precipitate or agglomerate, making high-dispersion loading difficult. If the pH is 3 or less, it is considered that the ruthenium compound and the zirconium compound react with each other to form a complex-like compound, thereby exhibiting excellent properties.
  • Examples of the solvent of the solution used for this support include water or an aqueous solvent containing water as a main component, or an organic solvent such as alcohol or ether, which dissolves at least the above various compounds.
  • an organic solvent such as alcohol or ether
  • highly soluble water or water-based water A medium can be suitably used.
  • the impregnation-supporting operation by contacting the above-mentioned solution with the carrier can be carried out in accordance with a conventional method.
  • Method, pore filling method, or any combination of these methods dipping method, mild infiltration method, wet adsorption method, wet kneading method, spray method, coating method, etc. Any method may be used as long as it is brought into contact with and carried.
  • Drying a series of operations of sintering is a once also less takes place, if necessary, but it may also be repeated several times divided these operations into more than 2 times 0
  • the ratio between the carrier and the solution varies depending on the target loading ratio of the active metal component, the concentration of the metal compound in the aqueous solution used, the type of impregnation support method, the pore volume of the carrier used, and the specific surface area. Although it is not possible to determine, use at least an amount of solution that sufficiently wets the carrier to be supported, while the upper limit of the amount of solution used for the carrier is
  • the amount of the solution to be used is selected within the range of 100 m1 or less per 100 g of dry weight of the carrier to be used. Reduce to near water absorption, and more preferably use a volume of solution that matches the water absorption.
  • This contact operation can be suitably performed under atmospheric pressure or reduced pressure as in the conventional case, and the operation temperature at that time is not particularly limited, and can be performed at or near room temperature. It can be heated or heated as needed, and can be suitably carried out at a temperature of, for example, room temperature to about 80 ° C.
  • each component including ruthenium is transferred to the carrier. It can be uniformly supported. As can be seen from the characteristics of the impregnation-supporting method described above, all the components contained in the used solution may be supported depending on the case, and for example, extra components may be added at any time after the contact. Only a part of the components in the used solution may be supported by removing the solution.
  • Drying after the contact between the above solution and the carrier is not particularly limited, but usually,
  • Air drying at room temperature takes about 24 hours a day.
  • a dried state in which a large amount of water is evaporated can be obtained. In such a case, the drying operation is not necessarily performed.
  • the calcination can be performed according to a conventional method, usually in the air or in an air stream at 250 to 800 ° C., preferably 400 to 800 ° C. ° (: More preferably, it is carried out in a temperature range of 450 to 600 ° C.
  • oxygen-containing gas such as pure oxygen or oxygen-enriched air may be substituted or used in combination.
  • a firing time of about 1 to 24 hours is usually sufficient.
  • the supporting composition may be formed into a predetermined shape and size at an appropriate time before firing.
  • the molding can be performed according to a conventional method, and if necessary, an appropriate binder component may be added.
  • the ruthenium component and zirconium component, and the cobalt component and magnesium component added as necessary, in the carrier obtained by firing are usually supported in a highly dispersed state in the form of an oxide or a composite oxide. ing.
  • Washing is performed with warm water of 50 t or more, preferably at 60 ° C or more. If the temperature is lower than 50 ° C, chlorine atoms cannot be sufficiently removed and long-time washing is required, which is not economical.
  • Heat treatment should be performed at 180 to 800 ° C, preferably at 200 to 800 ° C (: more preferably at 210 to 500 ° C). If the heat treatment is less than 180 ° C, the supported components may be eluted when the heat treatment is performed later, and if it exceeds 800 ° C, the catalytic activity is reduced. Examples of such methods include firing in air, heat treatment in an inert gas atmosphere such as nitrogen, and heat treatment in an atmosphere containing a reactive gas such as hydrogen, carbon monoxide, and steam.
  • calcination at the above-mentioned temperature is a preferable method.
  • the removal of chlorine atoms is possible only by this heat treatment, but furthermore, calcination in air containing water vapor or Alternatively, heat treatment in steam flow is also possible.
  • aqueous alkaline solution used in the treatment with the aqueous alkaline solution there is no particular limitation on the aqueous alkaline solution used in the treatment with the aqueous alkaline solution, as long as it exhibits alkaline properties.
  • an aqueous ammonia solution, an alkaline metal or an alkaline earth An aqueous solution of metal and the like can be mentioned.
  • an aqueous solution of an alkali metal such as potassium hydroxide, sodium hydroxide, potassium carbonate, or sodium carbonate is preferably used. It is preferable to use a high-concentration aqueous solution for the treatment with the above aqueous solution. Good.
  • the reforming catalyst can be used.
  • the chlorine atom content is less than 0.1% by weight.
  • the catalyst thus obtained can be used as it is as a catalyst or a catalyst component for a predetermined catalytic reaction.However, if necessary, it is activated by performing various appropriate pretreatments. May be used for a catalytic reaction. For example, it may be appropriately reduced with a reducing agent such as hydrogen to convert a ruthenium component or the like into a highly dispersed metallic ruthenium for the reaction. In the dispersion metallization treatment by hydrogen reduction, reduction is preferably performed at 300 to 850 ° C. until H 2 consumption is no longer observed.
  • a reducing agent such as hydrogen
  • this catalyst can be applied to any reaction in which a ruthenium catalyst is generally effective, in addition to a steam reforming reaction of hydrocarbons or the like.
  • a ruthenium catalyst is generally effective, in addition to a steam reforming reaction of hydrocarbons or the like.
  • unsaturated compounds such as carbonyl compounds, aromatic compounds, and olefins
  • ammonia synthesis reaction FT synthesis reaction
  • selective oxidation reaction of CO, methane of CO and CO 2 reaction CO and C 0 2 of alcohol or other selective hydrogenation reaction to oxygenated compounds
  • homologation one sucrose in to the ethanol by CO and hydrogen of main evening Nord, Orefi down arsenide mud carbonylation reaction Selective hydrogenation of amines to amines, hydrogenolysis of hydrocarbons, selective hydrogenation of aromatic amines, reduction of NO.
  • a wide variety of reactions such as a purification reaction, a complete oxidation reaction at a low temperature, a partial oxidation reaction, and a photolysis reaction
  • the second catalyst according to the present invention is a reforming catalyst comprising a support carrying a metal component containing at least one selected from a ruthenium component and a zirconium component. Continuously Or, it relates to a reforming catalyst which is dried while intermittently floating.
  • the obtained supported catalyst is dried at a predetermined temperature, and
  • the catalyst is dried while moving it continuously or intermittently during the drying.
  • a floating drying method is a method that can dry the catalyst while moving the catalyst so that the drying speed of the catalyst surface is uniform and the active component can be uniformly supported.
  • rotary drying in which drying is performed while applying a constant or irregular rotation
  • vibration drying in which drying is performed while applying a constant or irregular vibration, a combination thereof, and the like are preferable. .
  • the above-mentioned floating drying can be performed by air drying at room temperature for about one day and night (24 hours), but it is usually in the range of 50 to 150 ° C, preferably in the range of 80 to 120 ° C. It is preferable to carry out at a temperature of 1 hour or more. Drying outside of the above temperature range may not provide sufficient effects of the present invention.
  • the carrier used in the second catalyst of the present invention include the same carriers as those used in the first catalyst.
  • the metal component supported on the carrier has a high activity.
  • at least one selected from the group consisting of an alkaline earth metal component and a rare earth component can be given from the viewpoint of improving heat resistance.
  • alkaline earth metal component and the rare earth component examples include Be, Mg, Ca, Sr, Ba, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu
  • a magnesium component is preferably used from the viewpoint of realizing a highly active catalyst and improving heat resistance.
  • the alkaline earth metal component and the rare earth component are preferably supported on a carrier in an amount of 0.5 to 20% by weight in terms of oxide.
  • the loading amount of the metal component on the carrier is 0.5 to 15% by weight, particularly 1 to 10% by weight in terms of oxide.
  • the reforming catalyst it is preferable to carry a cobalt component and / or a nickel component as a supported metal component in order to further enhance the catalytic activity.
  • the supported amount of these metal components is such that the atomic ratio (Co / Ru) of cobalt atom (Co) to ruthenium atom (Ru) becomes 0.01 to 30. It is preferable that If the above atomic ratio is smaller than 0.01, the effect of improving the activity may not be sufficiently obtained. When the atomic ratio exceeds 30, the amount of ruthenium relatively decreases, and it may be difficult to maintain high activity as a reforming catalyst. From this point, it is preferable that the above atomic ratio (C 0 / R u) is 0.1 to 30, particularly 0.1 to 10. When nickel is used, the same amount as the above-mentioned addition of cobalt can be added.
  • the supporting method for supporting the metal component on a carrier is not particularly limited.
  • the carrier may include at least one or two or more ruthenium compounds, A zirconium compound and one or more compounds selected from an alkaline earth metal compound and a rare earth element compound (preferably, one or more magnetic compounds)
  • the solution can be supported by contacting and impregnating a solution containing, if necessary, one or more cobalt compounds and / or a Nigel compound.
  • the ruthenium component and, if necessary, the zirconium component, the magnesium component, the cobalt component, and the like can be supported on the surface of the carrier and in the pores in a state having good dispersibility and no unevenness. After that, even if a pretreatment is performed at a high temperature, which is usually performed thereafter, the highly dispersed state of the ruthenium component and zirconium oxide or the like can be maintained sufficiently stably.
  • a system catalyst can be easily obtained.
  • Metallic compounds used as an alkaline earth metal source and a rare earth element source can be dissolved in a certain solvent or dissolved by adding an acid or acidic compound such as hydrochloric acid.
  • An aqueous solution can be used.
  • compounds such as nitrates and chlorides having high solubility can be suitably used.
  • Such materials include, for example, magnesium nitrate, magnesium chloride and the like.
  • magnesium nitrate and various hydrates thereof can be particularly preferably used.
  • these metal compounds may be used alone or in combination of two or more.
  • the pH of a cobalt compound used as a cobalt source and a nickel compound used as a Nigger source can be adjusted by adding a compound having solubility in a certain solvent or adding an acid or acidic compound such as hydrochloric acid.
  • a compound having solubility in a certain solvent or adding an acid or acidic compound such as hydrochloric acid Various substances that can be dissolved by adjustment can be used. Usually, highly soluble compounds such as nitrates and chlorides are preferred. Used. Specific examples include cobaltous nitrate, basic cobalt nitrate, cobalt dichloride, nickel nitrate, nickel chloride, and various hydrates thereof. Among them, 'cobaltous nitrate and the like are particularly preferable. These cobalt compounds may be used alone or in combination of two or more.
  • a solvent or an acid may be added in advance and a predetermined component may be added to and dissolved in the acidic solution at the same time, or may be added stepwise and dissolved.
  • a solution of each component may be separately prepared, and these solutions may be mixed.
  • a solution of some components may be prepared, and then the remaining components may be dissolved in the solution.
  • the liquid temperature is desirably about room temperature, but it may be heated to about 80 ° C. to promote dissolution.
  • acids such as inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid, and organic acids such as acetic acid and oxalic acid are appropriately added as needed to improve the solubility and adjust the pH. Select and use.
  • a solubility adjusting component and other components are added to a ruthenium compound as an essential compound and a zirconium compound added as necessary, as long as the object of the present invention is not impaired. It may be added as appropriate.
  • impregnation-supporting operation by contacting the above-prepared solution with the carrier can be performed in the same manner as in the first method described above.
  • the catalyst is dried while allowing the catalyst to float, as described above.
  • the active component is uniformly supported, the catalyst activity per supported ruthenium is remarkably excellent, and the high activity can be maintained even at a high temperature during the reaction.
  • baking can be performed under the same conditions as described above, but in this case, the ruthenium component, which is a catalytically active component, is scattered, oxidized, and further agglomerated due to the high temperature baking.
  • the ruthenium component which is a catalytically active component
  • the raw material hydrocarbon used in the present invention is not particularly limited, and examples thereof include methane, ethane, pronon, butane, pentane, hexane, heptane, octane, nona, and decane.
  • Linear or branched saturated aliphatic hydrocarbons having about 1 to 16 carbon atoms alicyclic saturated hydrocarbons such as cyclohexane, methylcyclohexane and cyclooctane, monocyclic and polycyclic aromatic hydrocarbons
  • Various hydrocarbons such as group hydrocarbons are used. These various hydrocarbons may be a mixture of two or more.
  • hydrocarbons such as city gas, LPG, naphtha, and kerosene having a boiling range of 300 ° C or less are also included.
  • kerosene it is particularly preferable to use kerosene as the hydrocarbon.
  • JIS No. 1 kerosene whose sulfur content is 150 ppm by weight or less.
  • This JIS No. 1 kerosene is obtained by desulfurizing crude kerosene obtained by distilling crude oil at normal pressure.
  • the crude kerosene usually has a high sulfur content, so it does not become JIS No. 1 kerosene as it is, and it is necessary to reduce the sulfur content.
  • desulfurization treatment by a hydrorefining method generally carried out industrially is preferable.
  • the desulfurization method is not particularly limited, hydrodesulfurization, adsorption desulfurization, and the like are performed.
  • the amount of hydrocarbons and steam are usually adjusted so that the steamnocarbon ratio is 1.5 to 10, preferably 1.5 to 5, and more preferably 2 to 4. It is preferable to decide. With such a steam / carbon ratio, a product gas having a high hydrogen content can be efficiently obtained. In the steam reforming method of the present invention, even if the steam / force-to-bon ratio is 4 or less, carbon precipitation can be suppressed, so that effective use of waste heat can be achieved.
  • the reaction temperature is usually from 200 to 900 ° C., preferably from 250 to 900 ° (:, more preferably from 400 to 900 t> more preferably from 600 to 900 ° C.). Particularly preferably from 65 to 800 ° C.
  • the reaction pressure is usually from 0 to 3.0 MPa, preferably from 0 to 1. OMPa.
  • the inlet temperature of the steam reforming catalyst layer at 63 (TC or lower, and more preferably at 600 ° C. or lower. If the temperature exceeds the limit, thermal decomposition of petroleum hydrocarbons is accelerated, and carbon is deposited on the catalyst or the reaction tube wall via generated radicals, which may make operation difficult.
  • the temperature is preferably in the range of 600 to 800 t. If the catalyst layer outlet temperature is lower than 65 0, the amount of hydrogen generated may not be sufficient, and if it exceeds 800 t, the reaction may occur. Equipment may require refractory materials and is not economically favorable.
  • the reaction system may be any system such as a continuous flow system and a batch system, but the continuous flow system is preferred.
  • the gas hourly space velocity (GHSV) of a mixed gas of hydrocarbon and steam is usually from 1,000 to 40, OOO h— 1 , preferably from 2,000 to 40,000. , 0 0 O h — 1 , more preferably 2, 0 0 0 to 20, 0 0 0 h — 1 .
  • the type of reaction is not particularly limited, and examples thereof include a fixed bed type, a moving bed type, and a fluidized bed type.
  • a mixture of hydrogen, methane, carbon monoxide and the like can be obtained.
  • the obtained mixture can be used for various applications as it is, or can be separated into gas components and provided for each application.
  • the steam reforming method of the present invention is particularly suitably used in a hydrogen production process of a fuel cell, and can generate hydrogen efficiently.
  • a catalyst useful as a reforming catalyst for a fuel cell a method for producing the same, and a steam reforming method, which do not react with carbonates and reduce cell characteristics when used in a salt type fuel cell. Can be.
  • a hydrocarbon reforming catalyst which has extremely excellent catalytic activity per supported ruthenium and can maintain its high activity even at a high temperature during calcination or reaction, a method for producing the same, and a method for producing the same It is possible to provide a hydrocarbon steam reforming method capable of efficiently obtaining hydrogen for a fuel cell using a reforming catalyst.
  • the active component of the catalyst is uniformly supported, the catalyst activity per supported ruthenium is remarkably excellent, and the catalyst is kept under high temperature during the reaction.
  • Catalyst for Reforming Hydrocarbons That Can Maintain High Activity Even Under High Pressure, a Method for Producing the Catalyst for Reforming, and Use of the Catalyst for Reforming Efficiently for Fuel Cell Hydrogen It is possible to provide a hydrocarbon steam reforming method that can be obtained.
  • the chlorine atom content and the activity of the reforming reaction (propane conversion rate, kerosene conversion rate) of the reforming catalysts obtained in Examples 1 to 6 and Comparative Examples 1 to 3 below were determined by the following methods. More measurement and evaluation.
  • each of the catalysts sized to 0.5 to 1 mm was filled into a stainless steel reaction tube having an inner diameter of 2 Omm.
  • the catalyst was heated at 600 ° C in a hydrogen stream in a reaction tube.
  • Kerosene conversion (Q / 6) (A / B) X 100
  • the impregnating liquid 100 g of the ⁇ -alumina molded body support was impregnated and supported by a pore-filling method. After loading, the support was dried at 120 for 5 hours and calcined at 500 ° C. for 2 hours in air. Next, using the remaining 20 cc of the impregnating liquid, the carrier calcined was again subjected to the same procedure.
  • the catalyst was obtained by carrying out impregnation, drying and calcination. The C 1 content of the catalyst was determined to be 190 O wtppm.
  • the catalyst obtained in Comparative Example 1 was washed with distilled water at 60 ° C. for 17 hours and 30 minutes until no C 1 ion was detected in the washing water, and dried at 120 t.
  • the C 1 content of the catalyst was 1 15 wtppm.
  • Example 4 The catalyst obtained in Comparative Example 1 was washed with 60 t of distilled water for 1 hour and dried at 110 ° C. The C 1 content of the catalyst was 365 wtppm.
  • Example 4 The catalyst obtained in Comparative Example 1 was washed with 60 t of distilled water for 1 hour and dried at 110 ° C. The C 1 content of the catalyst was 365 wtppm.
  • Comparative Example 2 The catalyst obtained in Comparative Example 1 was washed with distilled water at 60 ° C. for 4 hours and dried at 120 ° C. The C 1 content of the catalyst was 195 wtppm. Comparative Example 2
  • Comparative Example 2 The catalyst obtained in Comparative Example 2 was washed with distilled water at 60 ° C. for 4 hours and dried at 10 t. The C1 content of the catalyst was 17 Owtppm. Comparative Example 3
  • the impregnating liquid was impregnated and supported on 50 g of an ⁇ -alumina molded product carrier (spherical having a diameter of 3 mm) by a pore-filling method. After the loading, the catalyst was dried using a rotary evaporator under reduced pressure at a rotational speed of 45 rpm at a temperature of 85 ° C for 5 hours to obtain a catalyst.
  • the catalyst has a C 1 content of 8400 O w t p p m
  • Comparative Example 3 As shown in Table 1, the catalysts of Examples 1 to 6 which were subjected to cleaning and / or cleaning treatment had a C 1 value higher than those of Comparative Examples 1 to 3. The content is extremely low, and the propane conversion and kerosene conversion are high.
  • Kerosene conversion (%) (A / B) X 100
  • the solution was stirred with a stirrer for at least one hour to obtain an impregnating solution.
  • the pH at this time was 0.5 or less.
  • the impregnating liquid was impregnated and supported on 50 g of an ⁇ -alumina molded article carrier (spherical having a diameter of 3 mm) by a pore-filling method. After the loading, the loaded catalyst was put in a rotary evaporator and dried at a rotation speed of 45 rpm at a temperature of 85 ° C for 5 hours to obtain a reforming catalyst.
  • Example 7 a reforming catalyst was prepared in the same manner as in Example 7, except that after the drying in the mouth and the evaporator was completed, the mixture was further calcined at 500 ° C for 1 hour in air.
  • Example 8 is different from Example 8 in that drying is performed using a rotary evaporator. Instead, a catalyst was prepared in the same manner as in Example 8, except that the catalyst was dried at 120 ° C. for 5 hours using a commonly used stationary dryer.
  • the present invention provides a catalyst for reforming hydrocarbons in which the active component of the catalyst is uniformly supported, the catalyst activity per supported ruthenium is remarkably excellent, and the high activity can be maintained even at a high temperature during the reaction. , Provide its manufacturing method.
  • the present invention provides a reforming catalyst having extremely low catalytic activity per supported ruthenium without causing corrosion of peripheral devices and the like and deterioration of battery characteristics as a result of extremely few chlorine atoms remaining in the catalyst.
  • the present invention provides a method for producing a fuel cell, whereby hydrogen for a fuel cell can be efficiently obtained by a steam reforming method using the reforming catalyst.

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Abstract

L'invention concerne un catalyseur servant à modifier des hydrocarbures, qui comporte un support et sur ce dernier au moins un composant parmi le ruthénium et le zirconium. Le catalyseur contient une quantité inférieure ou égale à 0,1 % en pds d'un atome de chlore. L'invention concerne un catalyseur destiné à modifier des hydrocarbures, qui est produit selon un procédé consistant à imprégner un support avec un composant métallique contenant du ruthénium ou du zirconium, puis à sécher les particules du catalyseur obtenues tout en les déplaçant de manière continue ou intermittente. Le catalyseur contient du chlore résiduel en quantités négligeables et un composant actif placé de façon uniforme sur un support, ce qui n'entraîne pas la corrosion des dispositifs environnants ni la réduction de caractéristiques cellulaires, présente une activité très importante pour la quantité de ruthénium et peut garder cette même activité lors de la réaction à des températures élevées.
PCT/JP2001/002650 2000-03-29 2001-03-29 Catalyseur destine a modifier les hydrocarbures et son procede de fabrication WO2001072416A1 (fr)

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JP2000214427A JP2001340759A (ja) 2000-03-31 2000-07-14 炭化水素の改質用触媒、その製造方法及びそれを利用した水蒸気改質方法

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7500439B2 (en) 2006-06-15 2009-03-10 Ythan Environmental Services Ltd. Method and apparatus
CN112354518A (zh) * 2020-11-16 2021-02-12 湖南环达环保有限公司 一种锌铁复合氧化物负载活性炭脱硫剂的制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6142331A (ja) * 1984-08-01 1986-02-28 Jgc Corp ルテニウム触媒の調製法
JPH0615172A (ja) * 1992-06-30 1994-01-25 Tonen Corp 水蒸気改質触媒及びその製造方法
JPH08231204A (ja) * 1994-12-27 1996-09-10 Sekiyu Sangyo Kasseika Center 二酸化炭素改質反応による水素及び一酸化炭素の製造法
JPH0929098A (ja) * 1995-07-21 1997-02-04 Idemitsu Kosan Co Ltd 炭化水素の水蒸気改質用触媒
JP2000084410A (ja) * 1998-07-14 2000-03-28 Idemitsu Kosan Co Ltd オ―トサ―マルリフォ―ミング触媒および水素または合成ガスの製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6142331A (ja) * 1984-08-01 1986-02-28 Jgc Corp ルテニウム触媒の調製法
JPH0615172A (ja) * 1992-06-30 1994-01-25 Tonen Corp 水蒸気改質触媒及びその製造方法
JPH08231204A (ja) * 1994-12-27 1996-09-10 Sekiyu Sangyo Kasseika Center 二酸化炭素改質反応による水素及び一酸化炭素の製造法
JPH0929098A (ja) * 1995-07-21 1997-02-04 Idemitsu Kosan Co Ltd 炭化水素の水蒸気改質用触媒
JP2000084410A (ja) * 1998-07-14 2000-03-28 Idemitsu Kosan Co Ltd オ―トサ―マルリフォ―ミング触媒および水素または合成ガスの製造方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7500439B2 (en) 2006-06-15 2009-03-10 Ythan Environmental Services Ltd. Method and apparatus
CN112354518A (zh) * 2020-11-16 2021-02-12 湖南环达环保有限公司 一种锌铁复合氧化物负载活性炭脱硫剂的制备方法
CN112354518B (zh) * 2020-11-16 2023-07-25 湖南环达环保有限公司 一种锌铁复合氧化物负载活性炭脱硫剂的制备方法

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