JP4677194B2 - Method for converting lower hydrocarbons using catalysts - Google Patents

Method for converting lower hydrocarbons using catalysts Download PDF

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JP4677194B2
JP4677194B2 JP2004068439A JP2004068439A JP4677194B2 JP 4677194 B2 JP4677194 B2 JP 4677194B2 JP 2004068439 A JP2004068439 A JP 2004068439A JP 2004068439 A JP2004068439 A JP 2004068439A JP 4677194 B2 JP4677194 B2 JP 4677194B2
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molybdenum
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政道 倉元
綾一 小島
裕治 小川
勝 市川
康之 溝渕
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勝 市川
株式会社明電舎
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
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    • Y02P20/52Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals using catalysts, e.g. selective catalysts

Description

  The present invention relates to advanced utilization of natural gas, biogas, and methane hydrate mainly composed of methane.

  Natural gas, biogas, and methane hydrate are considered to be the most effective energy as a countermeasure against global warming, and there is an increasing interest in their utilization technologies. Taking advantage of its cleanliness, methane resources are attracting attention as new next-generation organic resources and hydrogen resources for fuel cells, but the present invention uses benzene and naphthalene, which are raw materials for chemical products such as plastics from methane. The present invention relates to a catalytic chemical conversion technology capable of efficiently producing an aromatic compound as a main component and high-purity hydrogen gas.

  As a method of co-producing an aromatic compound such as benzene and hydrogen from lower hydrocarbons, particularly methane, a method of reacting methane in the presence of a catalyst and in the absence of oxygen or an oxidizing agent is known. For example, according to Non-Patent Document 1 (JOURNAL OF CATALYSIS (1997)), a catalyst in which molybdenum is supported on ZSM-5 is effective as the catalyst. However, even when these catalysts are used, there are problems that carbon deposition is large and methane conversion is low.

Therefore, a catalyst in which molybdenum or the like is supported on a porous metallosilicate has been proposed (for example, Patent Document 1 (Japanese Patent Laid-Open No. 10-272366) and Patent Document 2 (Japanese Patent Laid-Open No. 11-60514)). According to these publications, a porous metallosilicate having a 7 Å strong pore diameter is adopted as a carrier, and a catalyst material is supported on the porous metallosilicate. According to experiments using this catalyst, it has been confirmed that lower hydrocarbons are efficiently aromatized, and accompanying this, high-purity hydrogen can be obtained. In particular, Patent Document 2 describes that the characteristics of the catalyst are improved by adding not only molybdenum but also metals other than molybdenum as the second component.
JOURNAL OF CATALYSIS, 1997, pp. 165, pp. 150-161 JP-A-10-272366 (paragraph numbers (0008) to (0013) and (0019)) JP 11-60514 A (paragraph numbers (0007) to (0011) and (0020))

  However, even today, in order to further increase the production efficiency of aromatic compounds and hydrogen, it is desired to develop even better catalysts. In particular, in the prior art, the production rate of hydrogen and aromatic compounds is not stable at present.

  The present invention has been made in view of such circumstances, and an object of the present invention is to use a catalyst that can stably and further improve the production rate of hydrogen and aromatic compounds when reforming and aromatizing lower hydrocarbons. The present invention provides a method for converting lower hydrocarbons.

The lower hydrocarbon conversion method of the present invention comprises a gas containing a lower hydrocarbon of any one of methane, ethane, ethylene, propane, propylene, n-butane, isobutane, n-butene and isobutene, and metallosilicate with molybdenum. lower hydrocarbon conversion lower hydrocarbon direct reforming catalyst supporting ruthenium, or the lower hydrocarbon is reacted with lower hydrocarbons directly reforming catalyst supporting molybdenum and rhodium metallosilicate the aromatic compound and hydrogen In the conversion method, when the gas is reacted with the lower hydrocarbon direct reforming catalyst, hydrogen is added to the gas. Hydrogen is preferably injected so as to have a constant concentration in the supply gas, for example, 6%.

  According to the lower hydrocarbon conversion method of the present invention, when hydrogen is added to the gas in the catalytic reaction of the lower hydrocarbon-containing gas with the lower hydrocarbon direct reforming catalyst, compared with the conventional conversion method in which no hydrogen is added. Thus, it has been found that stable aromatic compounds and hydrogen can be produced.

The lower hydrocarbon direct reforming catalyst is obtained by carbonizing a metallosilicate supporting ruthenium or rhodium in addition to molybdenum by supplying either a gas containing the lower hydrocarbon and hydrogen, hydrogen gas, or ammonia gas. To be generated . Examples of the method for supporting the metal element such as molybdenum, ruthenium, and rhodium include an impregnation method, an ion exchange method, and a method for depositing and supporting on a carrier using a sublimable compound. In addition, when the metallosilicate is subjected to carbonization, these metal elements or other metal elements such as iron group element components may be supported in appropriate combination .

  Further, as the metallosilicate, for example, in the case of aluminosilicate, it is a porous body having pores of 4.5 to 6.5 angstrom diameter made of silica and alumina, and includes molecular sieve 5A, faujasite (NaY and NaX). ), ZSM-5, MCM-22, and the like. Furthermore, a porous body composed of 6 to 13 angstrom micropores such as ALPO-5, VPI-5, etc. mainly composed of phosphoric acid, a zeolite carrier composed of channels, silica and a part of alumina as a component. Examples thereof include mesoporous porous carriers such as FSM-16 and MCM-41 having cylindrical pores (channels) having mesopores (10 to 1000 angstroms). In addition to the alumina silicate, a metallosilicate composed of silica and titania may be used.

  The lower hydrocarbon direct reforming catalyst to be used in the present invention is used in the form of a hollow cylinder, pellet, honeycomb, ring or other shapes in addition to powder or rod. In order to process the metallosilicate into the shape, an inorganic binder such as clay or an inorganic filler such as glass fiber may be added to the metallosilicate.

  According to the method for converting lower hydrocarbons of the present invention, since there is little reduction in efficiency due to deterioration of the catalyst over time, the aromatic compound and hydrogen can be produced more stably and efficiently. Therefore, in the method for producing hydrogen and aromatic compounds using the reforming catalyst supporting molybdenum, it greatly contributes to the construction of a system for controlling the mass productivity of hydrogen and aromatic compounds.

  DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments for carrying out a method for converting a lower hydrocarbon of the present invention will be described with reference to the drawings.

  The lower hydrocarbon direct reforming catalyst (hereinafter referred to as catalyst) provided in the present embodiment is formed by blending an inorganic component obtained by blending a metallosilicate with another inorganic filler together with an organic binder and moisture, It is obtained by drying and firing to obtain a fired body, and appropriately carrying a platinum group element as a second metal component on the molybdenum component on this fired body, followed by carbonization treatment by mixing a reducing gas. Examples of platinum group elements include ruthenium and rhodium.

  As the metallosilicate, for example, in the case of aluminosilicate, it is a porous body having pores having a diameter of 4.5 to 6.5 angstrom made of silica and alumina, molecular sieve 5A, faujasite (NaY and NaX), Examples include ZSM-5 and MCM-22. Furthermore, a porous body composed of 6 to 13 angstrom micropores such as ALPO-5 and VPI-5 mainly composed of phosphoric acid, a zeolite carrier composed of a channel, silica and a part of alumina as a component. Examples thereof include mesoporous porous carriers such as FSM-16 and MCM-41 having cylindrical pores (channels) having mesopores (10 to 1000 angstroms). In addition to the alumina silicate, a metallosilicate composed of silica and titania may be used.

  Examples of the inorganic filler include inorganic binders such as clay and reinforcing inorganic materials such as glass fibers, and are blended in an amount of 15 to 25% by weight based on the total inorganic components of the catalyst. The organic binder may be a known one as long as it can be molded by kneading the metallosilicate and the inorganic filler together with moisture.

A high-pressure molding method is employed for molding after blending the above materials. The catalyst support for reforming hydrocarbons is usually used in the form of a fluidized bed catalyst using particles having a particle size of several μm to several hundred μm. Conventionally, such a catalyst is obtained by mixing a catalyst carrier with an organic binder, an inorganic binder, and water to form a slurry and granulating it with a spray dryer, followed by firing. In this case, since the molding pressure is small, it is necessary to add about 40 to 60% by weight of clay added as a firing aid to ensure firing strength. In the molding process in the production process of the catalyst of the present invention, by using a high pressure molding method, the amount of inorganic binder such as clay is reduced to 15 to 25% by weight in the catalyst, that is, the metallosilicate component in the catalyst is 75 to 85%. The catalyst activity can be increased up to% by weight, and the substantial catalytic activity is higher than that of the catalyst obtained by granulation with a spray dryer. Specific examples of the high pressure molding method include a vacuum extrusion molding machine. Moreover, it is good to set the extrusion pressure at this time in the range of 70-100 kg / cm < 2 >. In addition, the shape of the molded body is formed into a hollow cylindrical shape, a pellet shape, a honeycomb shape, a ring shape, or other shapes in addition to a powder shape or a rod shape according to the usage form of the catalyst.

  What is necessary is just to dry the obtained molded object for a suitable temperature fixed time so that the water | moisture content added at the time of shaping | molding can be removed. In addition, the firing is performed at 30 to 50 ° C./hour for both temperature increase and temperature decrease rates. At this time, it is advisable to carry out temperature keeping for about 2 to 5 hours twice in a temperature range of 250 to 450 ° C. This is because when the temperature raising and lowering speed is equal to or higher than the above speed and the keep time for removing the binder is not secured, the binder burns instantaneously and the strength of the fired body is reduced. The firing temperature may be in the range of 725 to 800 ° C. This is because the strength of the carrier is lowered at 700 ° C. or lower, and the characteristics are lowered at 800 ° C. or higher.

  Next, in carrying the metal component on the obtained fired body, the inventors have also studied a method for carrying molybdenum, and filed an application relating to this in Japanese Patent Application No. 2002-260706. In the invention according to this application, an ammonium molybdate aqueous solution is used when impregnating molybdenum, but when the platinum group element is supported together with molybdenum, the ammonium molybdate aqueous solution is chlorinated in the ammonium molybdate aqueous solution at the time of impregnation. Products, nitrates, ammonium salts and the like may be used. At this time, the molybdenum loading may be, for example, 6% by weight with respect to the carrier. Moreover, the metal component of the platinum group element to be impregnated together may be a molar ratio of, for example, the above-described platinum group element: molybdenum = 0.2: 1. The molybdenum loading and the molar ratio of the platinum group component and molybdenum are not limited to this, and are adjusted as appropriate. Thus, the stability of the production rate of hydrogen and aromatic compounds by the catalyst is improved by simultaneously supporting not only molybdenum but also the platinum group metal element as the second component on the metallosilicate. The molybdenum and the metal component impregnated in the fired body are supported on the fired body as oxides by oxidation treatment at a constant temperature and time.

  In the carbonization treatment of the catalyst precursor obtained by the oxidation treatment of the impregnated fired body, a reducing gas is mixed instead of the atmosphere of methane gas and argon gas based on the conventional carbonization treatment, and the temperature is 350 to 750 ° C. Heat treatment is performed at a temperature for 2 to 24 hours. Examples of the reducing gas include a gas containing methane and hydrogen, hydrogen gas, or ammonia gas. The illustrated reducing gases may be used in appropriate combination. Furthermore, you may combine the methane gas and argon gas which are provided to the said conventional carbonization processing method.

  The catalyst produced as described above is tangible because the pressure molding method is adopted as described above, and is mainly packed in a fixed bed type reactor. Then, a gas containing lower hydrocarbon is supplied to the reaction apparatus to cause a catalytic reaction with the catalyst under a certain temperature, pressure, space velocity and residence time. At this time, by adding hydrogen to the gas containing the lower hydrocarbon, an aromatic compound and hydrogen can be produced at a stable production rate. Hydrogen is injected in the supply gas so as to have a constant concentration, for example, 6%. Examples of the lower hydrocarbon include methane, ethane, ethylene, propane, propylene, n-butane, isobutane, n-butene, and isobutene.

  The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples.

(Comparative Example 1)
In Comparative Example 1, hydrogen is not added to a gas containing lower hydrocarbons, but this gas is reacted with a lower hydrocarbon direct reforming catalyst to convert lower hydrocarbons. The lower hydrocarbon direct reforming catalyst carries ruthenium as a platinum group element component in addition to molybdenum.

1. Production of lower hydrocarbon reforming catalyst Ammonium type ZSM-5 (SiO 2 / Al 2 O 3 = 25-60) is adopted for the metallosilicate which is the main component of the catalyst, together with other inorganic components and organic binders. After kneading, shaping, drying, and further firing, the metal component was impregnated and then subjected to oxidation and carbonization treatment to obtain a lower hydrocarbon direct reforming catalyst (hereinafter referred to as catalyst). Below, each process of manufacture of the catalyst which concerns on a comparative example and an Example is demonstrated.

1) Compounding of catalyst component The components of the catalyst and the compounding ratio (wt%) are shown below.

Inorganic component: Organic binder: Moisture = 65.4: 13.6: 21.0
Moreover, it showed below the component of an inorganic component, and its mixture ratio (weight%).

ZSM-5: Clay: Glass fiber = 82.5: 10.5: 7.0
2) Molding An inorganic component, an organic binder, and moisture were blended in the above ratio and kneaded by a kneading means such as a kneader. Next, this mixture was formed into a rod shape (diameter 5 mm) by a vacuum extrusion molding machine. The molding pressure at this time was set to 70 to 100 kg / cm 2 . Then, a rod-shaped carrier having a diameter of 5 mm obtained by this extrusion molding was cut into a length of 6 mm to obtain a molded body.

  3) Drying and calcination In order to remove moisture added during molding, the molded body was dried at 100 ° C. for about 5 hours and then baked. The firing temperature was in the range of 725 to 800 ° C. The temperature increase and temperature decrease rates were both 30 to 50 ° C./hour. In order to prevent the organic binder from burning instantaneously during firing, the binder component was removed by carrying out a temperature keep of about 2 to 5 hours under a temperature range of 250 to 450 ° C. twice.

  4) Impregnation The obtained fired body was immersed in an aqueous ammonium molybdate solution to which ammonium ruthenate was added, and this sintered body was impregnated with a molybdenum component. The amount of molybdenum supported was 6% by weight with respect to the weight of the sintered body, and the amount of ruthenium supported was ruthenium: molybdenum = 0.2: 1 in molar ratio.

  5) Oxidation treatment In order to decompose and oxidize the metal salt impregnated in the sintered body to form molybdenum oxide, it was calcined at 550 ° C. for 10 hours to obtain a catalyst precursor.

6) Carbonization treatment 1 Based on the conventional carbonization treatment method of the catalyst precursor. The catalyst precursor impregnated with only molybdenum and oxidized was heated to 550 ° C. under an air atmosphere. After maintaining this state for 1 hour, the atmosphere was switched to a reaction gas of 9CH 4 + Ar and the temperature was raised to 650 ° C. This state was maintained for 1 hour. Then, it heated up to 750 degreeC. Thus, a catalyst according to Comparative Example 1 carrying only molybdenum was obtained.

2. Conversion of lower hydrocarbons Inconel 800H gas contact part calorizing treatment reaction tube (inner diameter: 18 mm) of a fixed bed flow reactor was charged with 14 g of the catalyst to be evaluated (zeolite ratio 82.50%). Then, a mixed gas containing methane (methane + 10% argon) was supplied thereto, and the reaction space velocity was 3000 ml / g-MFI / h (CH 4 gas flow base), the reaction temperature was 750 ° C., the reaction time was 10 hours, The catalyst and the mixed gas were reacted under a pressure of 0.3 MPa. At this time, the rate of formation of hydrogen and an aromatic compound (benzene) was examined over time.

(Comparative Example 2)
In Comparative Example 2, hydrogen is not added to the gas containing the lower hydrocarbon, but this gas is reacted with the lower hydrocarbon direct reforming catalyst to convert the lower hydrocarbon. The lower hydrocarbon direct reforming catalyst carries rhodium as a platinum group element component in addition to molybdenum. The conversion of the lower hydrocarbon was carried out in the same manner as in Comparative Example 1.

In addition, it manufactured by the same method as the manufacturing process of the catalyst which concerns on Example 1 except the impregnation process in manufacture of the said lower hydrocarbon direct reforming catalyst. That is, in the impregnation step, the sintered body obtained in steps 1) to 3) was immersed in an ammonium molybdate aqueous solution to which ammonium rhodate was added, and the sintered body was impregnated with a molybdenum component and an iron component. . The molybdenum loading was 6% by weight with respect to the weight of the sintered body, and the cobalt loading was rhodium: molybdenum = 0.2: 1 in molar ratio. The impregnated fired body was subjected to the carbonization treatment 1 to obtain a catalyst according to Comparative Example 2 carrying molybdenum and rhodium.
Example 1
In Example 1, while adding hydrogen to a gas containing lower hydrocarbons, this gas is reacted with a lower hydrocarbon direct reforming catalyst to convert lower hydrocarbons. The lower hydrocarbon direct reforming catalyst carries ruthenium as a platinum group element component in addition to molybdenum. The catalyst according to this example was manufactured by the same method as the manufacturing process of the catalyst according to Comparative Example 1.

  The method for converting lower hydrocarbons in this example will be described.

Inconel 800H gas contact part calorizing treatment reaction tube (inner diameter 18 mm) of a fixed bed flow type reactor was filled with 14 g of the catalyst to be evaluated (zeolite ratio 82.50%). Then, a mixed gas containing methane and hydrogen (methane + 10% argon + 6% hydrogen) is supplied thereto, and the reaction space velocity is 3000 ml / g-MFI / h (CH 4 gas flow base), the reaction temperature is 750 ° C., The catalyst and the mixed gas were reacted under the conditions of a reaction time of 10 hours and a reaction pressure of 0.3 MPa. At this time, the rate of formation of hydrogen and an aromatic compound (benzene) was examined over time.

(Example 2)
In Example 2, while adding hydrogen to a gas containing lower hydrocarbons, this gas is reacted with a lower hydrocarbon direct reforming catalyst to convert lower hydrocarbons. The lower hydrocarbon direct reforming catalyst carries ruthenium as a platinum group element component in addition to molybdenum. The catalyst according to the present example was manufactured by the same method as the catalyst manufacturing process according to Example 1, except for the following carbonization treatment 2.

Carbonization treatment 2 The catalyst precursor impregnated with molybdenum and oxidized is treated for 24 hours under an atmosphere of C 4 H 10 + 11H 2 mixed gas and 350 ° C., and then heated to 550 ° C., and the atmosphere is changed to 9CH 4 + Ar reaction gas. The temperature was raised to 750 ° C., and this state was maintained for 10 minutes. In this way, a catalyst according to Example 1 carrying molybdenum and ruthenium was obtained.

  The conversion of lower hydrocarbons in this example was performed in the same manner as the conversion method in Example 1.

(Example 3)
In Example 3, while adding hydrogen to a gas containing lower hydrocarbons, this gas is reacted with a lower hydrocarbon direct reforming catalyst to convert lower hydrocarbons. The lower hydrocarbon direct reforming catalyst carries rhodium as a platinum group element component in addition to molybdenum. The catalyst according to this example was manufactured by the same method as the manufacturing process of the catalyst according to Comparative Example 1.

  The conversion of lower hydrocarbons in this example was performed in the same manner as the conversion method in Example 1.

Example 4
In Example 3, while adding hydrogen to a gas containing lower hydrocarbons, this gas is reacted with a lower hydrocarbon direct reforming catalyst to convert lower hydrocarbons. The lower hydrocarbon direct reforming catalyst carries rhodium as a platinum group element component in addition to molybdenum. The catalyst according to this example is the same as the catalyst production process according to Comparative Example 1 except that the impregnation process is the same as the impregnation process in Comparative Example 2 and the carbonization process is the same method as the carbonization process 2 in Example 2. Produced by the method.

  The conversion of lower hydrocarbons in this example was performed in the same manner as the conversion method in Example 1.

  FIG. 1 shows the change over time in the hydrogen production rate during the 24-hour reforming time when the catalysts according to Comparative Example 1, Comparative Example 2, Example 1, Example 2, Example 3, and Example 4 were used. Is shown.

  FIG. 2 shows the change over time in the production rate of benzene during the reforming time of 24 hours when the catalysts according to Comparative Example 1, Comparative Example 2, Example 1, Example 2, Example 3, and Example 4 were used. Is shown.

  As is clear from the time-dependent changes in hydrogen, benzene, and production rate shown in FIGS. 1 and 2, when the catalysts according to Examples 1 to 4 are used, the catalysts according to Comparative Examples 1 and 2 are used. It can be confirmed that the stability of hydrogen and benzene production rates is improved.

  Although the lower hydrocarbon direct reforming catalyst of the present invention has been described in detail on the basis of the above-described examples, it will be understood by those skilled in the art that this example can be variously modified and modified within the scope of the technical idea of the present invention. Obviously, such variations and modifications should fall within the scope of the appended claims.

  For example, although the catalyst of this example employs molybdenum as the main supported metal, the effects as a lower hydrocarbon reforming catalyst have already been confirmed, and various catalysts introduced in the literature introduced in the above embodiment. It has been confirmed that similar effects can be obtained even when rhenium, tungsten, or a compound of these (including molybdenum) is used alone or in combination.

  Further, in this example, only the drying method of the support on which the catalyst metal is supported by the impregnation method is shown. However, when applied to the support on which the catalyst metal is supported by the ion exchange method, a sublimable compound is used. Thus, it has been confirmed that similar effects can be obtained even when vapor deposition is carried on a carrier.

  Furthermore, although the catalyst according to the example is formed in a rod shape, it is confirmed that the same effect can be obtained even in the case of forming a hollow cylindrical shape, honeycomb shape, powder shape, pellet shape, ring shape. Has been.

Changes over time in the hydrogen production rate during the 24-hour reforming time when the catalysts according to Comparative Example 1, Comparative Example 2, Example 1, Example 2, Example 3, and Example 4 were used. The time-dependent change of the production | generation rate of benzene in the reforming time of 24 hours at the time of using the catalyst which concerns on Comparative Example 1, Comparative Example 2, Example 1, Example 2, Example 3, and Example 4. FIG.

Claims (2)

  1. Lower hydrocarbon direct reforming catalyst in which molybdenum and ruthenium are supported on metallosilicate from gas containing lower hydrocarbon of any of methane, ethane, ethylene, propane, proprene, n-butane, isobutane, n-butene and isobutene or a process for the conversion lower hydrocarbon to convert the molybdenum and rhodium metallosilicate the lower hydrocarbon is reacted with loaded with lower hydrocarbons directly reforming catalyst to aromatic compound and hydrogen, the gas lower the A method for converting a lower hydrocarbon using a catalyst, wherein hydrogen is added to the gas when reacting with a hydrocarbon direct reforming catalyst.
  2. The lower hydrocarbon direct reforming catalyst is obtained by carbonizing a metallosilicate supporting ruthenium or rhodium in addition to molybdenum by supplying either a gas containing the lower hydrocarbon and hydrogen, hydrogen gas, or ammonia gas. The method for converting lower hydrocarbons using the catalyst according to claim 1, wherein the lower hydrocarbons are produced.
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JP4943671B2 (en) * 2004-07-08 2012-05-30 ズードケミー触媒株式会社 Lower hydrocarbon aromatization catalyst and method for producing aromatic hydrocarbon and hydrogen from lower hydrocarbon using the same
RU2349569C2 (en) 2004-07-28 2009-03-20 Мейденся Корпорейшн Method of producing aromatic hydrocarbon and hydrogen
JPWO2007037388A1 (en) * 2005-09-30 2009-04-16 株式会社明電舎 Method for producing aromatic compound
JP5540462B2 (en) 2007-06-07 2014-07-02 株式会社明電舎 Regeneration method for lower hydrocarbon aromatization catalyst
JP5266225B2 (en) * 2007-08-03 2013-08-21 三井化学株式会社 Process for producing aromatic hydrocarbons
WO2009091336A1 (en) 2008-01-16 2009-07-23 Agency For Science, Technology And Research Catalyst preparation and methods of using such catalysts
JP5736633B2 (en) * 2008-04-18 2015-06-17 株式会社明電舎 Catalyst and production method thereof

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US20010008949A1 (en) * 1997-09-30 2001-07-19 Phillips Petroleum Company Hydrocarbon conversion catalyst composition and processes therefor and therewith
JP2003026613A (en) * 2001-07-12 2003-01-29 National Institute Of Advanced Industrial & Technology Method for producing aromatic hydrocarbon and hydrogen from lower hydrocarbon
JP2004269398A (en) * 2003-03-07 2004-09-30 Hokkaido Soda Kk Method and apparatus for catalytically reacting lower hydrocarbon into aromatic compound, and method for producing aromatic compound and hydrogen

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010008949A1 (en) * 1997-09-30 2001-07-19 Phillips Petroleum Company Hydrocarbon conversion catalyst composition and processes therefor and therewith
JP2003026613A (en) * 2001-07-12 2003-01-29 National Institute Of Advanced Industrial & Technology Method for producing aromatic hydrocarbon and hydrogen from lower hydrocarbon
JP2004269398A (en) * 2003-03-07 2004-09-30 Hokkaido Soda Kk Method and apparatus for catalytically reacting lower hydrocarbon into aromatic compound, and method for producing aromatic compound and hydrogen

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