KR20070084220A - Reforming catalyst for oxygen-containing hydrocarbon, method for producing hydrogen or synthesis gas using same, and fuel cell system - Google Patents

Abstract

Disclosed is a reforming catalyst for oxygen-containing hydrocarbons which contains copper, a metal oxide having a spinel structure and a zeolite. Preferably, the reforming catalyst further contains alumina, a group VIII metal or a rare earth element. Also disclosed is a method for producing hydrogen or a synthesis gas by subjecting an oxygen-containing hydrocarbon to (1) steam reforming, (2) autothermal reforming, (3) partial oxidation reforming or (4) carbon dioxide reforming, while using the above-described reforming catalyst. Further disclosed is a fuel cell system using the reforming catalyst. The reforming catalyst has a high activity and excellent heat resistance. When the reforming catalyst further contains alumina, a group VIII metal or a rare earth element, the amount of coke generation is suppressed, thereby further improving durability of the catalyst. Consequently, hydrogen or a synthesis gas can be efficiently produced by subjecting an oxygen-containing hydrocarbon to various reforming using such a reforming catalyst, and thus the reforming catalyst is used in a fuel cell system or the like.

Description

Reforming catalyst for oxygen-containing hydrocarbons, method for producing hydrogen or synthesis gas and fuel cell system using the same.

The present invention relates to a reforming catalyst of an oxygen-containing hydrocarbon, a method for producing hydrogen or a synthesis gas using the same, and a fuel cell system. Specifically, a spinel structure-containing metal oxide and zeolite, or further various metals are contained. A reforming catalyst of an oxygen-containing hydrocarbon having excellent heat resistance, high activity, and improved durability, and a method for efficiently producing hydrogen or synthesis gas by performing various reforming on the oxygen-containing hydrocarbon using the reforming catalyst, and the reforming A fuel cell system using a catalyst is provided.

Synthetic gas contains carbon monoxide and hydrogen, and is not only used as a raw material gas for methanol synthesis, oxo synthesis, Fischer-Tropsch synthesis, but also widely used as raw material for ammonia synthesis and various chemical products.

The synthesis gas has conventionally been produced by a gasification method of coal, or by steam reforming or partial oxidation reforming of hydrocarbons using natural gas or the like as a raw material. However, in the gasification method of coal, not only complicated and expensive coal gasification furnaces are required, but there also existed a problem of becoming a large-scale plant. In addition, in the steam reforming method of hydrocarbons, since the reaction involves a large endotherm, a high temperature of about 700 to 1200 ° C is required for the progress of the reaction, and a special reforming furnace is required, and the catalyst used is high. There existed a problem of requiring heat resistance. In addition, since the high temperature is required even in the partial oxidation reforming of hydrocarbons, a special partial oxidation furnace is required, and a large amount of soot is generated by the reaction, and not only its treatment becomes a problem but also the catalyst deteriorates. There was a problem such as being easy.

Therefore, in order to solve such a problem, in recent years, it has been attempted to manufacture synthesis gas by using oxygen-containing hydrocarbons, such as dimethyl ether as a raw material, and performing various reforming to it.

On the other hand, in recent years, new energy technologies are in the spotlight due to environmental problems, and fuel cells are attracting attention as one of these new energy technologies. The fuel cell converts chemical energy into electrical energy by electrochemically reacting hydrogen and oxygen. The fuel cell is characterized by high energy use efficiency, and has been actively researched for practical use as a civil, industrial, or automobile.

Examples of the hydrogen source of the fuel cell include liquefied natural gas mainly composed of methanol and methane, city gas mainly composed of the natural gas, synthetic liquid fuel composed of natural gas, and petroleum hydrocarbons such as petroleum naphtha and kerosene. Research is being done.

In the case of producing hydrogen using these petroleum hydrocarbons, steam reforming treatment, partial oxidation reforming treatment, and the like are generally performed on the hydrocarbons in the presence of a catalyst, but in this case, such problems occur. Therefore, also in the production of hydrogen, various methods of using oxygen-containing hydrocarbons such as dimethyl ether as raw materials have been tried.

Although various types of catalysts have been disclosed so far using oxygen-containing hydrocarbons such as dimethyl ether as raw materials and various modifications are made therein to produce hydrogen or synthesis gas. Among them, oxygen-containing catalysts are used using Cu-based catalysts. As a technique for reforming a hydrocarbon, for example, a catalyst for producing a synthesis gas from an oxygen-containing hydrocarbon and carbon dioxide using a Cu-containing catalyst, a method for producing a synthesis gas using the same (see Patent Document 1, for example), and a Cu-containing catalyst A catalyst for producing hydrogen from an oxygen-containing hydrocarbon and water vapor using a method and a method for producing hydrogen using the same (see, for example, Patent Document 2), of the oxygen-containing hydrocarbon containing a metal containing Cu in a solid acid Reforming catalyst (see, for example, Patent Document 3, Patent Document 4), Cu-containing material and solid acidic material A catalyst for producing hydrogen from an oxygen-containing hydrocarbon and water vapor, including a mixture, and a method for producing hydrogen using the same (see Patent Document 5, for example), an oxygen-containing hydrocarbon comprising a mixture of a Cu-containing material and a solid acid product; A catalyst for producing a synthesis gas from water vapor and a method for producing a synthesis gas using the same (see Patent Document 6, for example) are disclosed.

However, all of the Cu-based catalysts used in these techniques have insufficient heat resistance, and therefore, there is a problem that deterioration of the catalyst cannot be avoided when the reaction temperature is raised to improve the reaction activity.

<Patent Document 1> Japanese Patent Application Laid-Open No. 10-174869

<Patent Document 2> Japanese Unexamined Patent Publication No. 10-174871

<Patent Document 3> Japanese Unexamined Patent Publication No. 2001-96159

<Patent Document 4> Japanese Patent Application Laid-Open No. 2001-96160

<Patent Document 5> Japanese Patent Application Laid-Open No. 2003-10684

<Patent Document 6> Japanese Unexamined Patent Publication No. 2003-33656

The present invention has been made under the above circumstances, and it is possible to carry out various reforming of an oxygen-containing hydrocarbon by using a reforming catalyst of an oxygen-containing hydrocarbon containing copper and having excellent heat resistance, high activity, and improved durability. It is an object of the present invention to provide a method for efficiently producing hydrogen or synthesis gas. It is also an object of the present invention to provide an excellent fuel cell system having a reformer having such an excellent reforming catalyst and a fuel cell fueled by hydrogen produced by the reformer.

As a result of intensive research to achieve the above object, the inventor has made the copper-containing catalyst a spinel structure, and by combining zeolite with the copper-containing spinel structure catalyst, the catalyst having high heat resistance and high activity and durability improved It was found that by further containing alumina, a Group 8 metal, and a rare earth element, the amount of coke produced can be further suppressed in the modification of the oxygen-containing hydrocarbon and its purpose can be achieved. The present invention has been completed based on these findings.

That is, the present invention provides the following reforming catalyst for an oxygen-containing hydrocarbon, a method for producing hydrogen or synthesis gas, and a fuel cell system.

(1) A reforming catalyst for an oxygen-containing hydrocarbon comprising copper and a metal oxide having a spinel structure and zeolite.

(2) The reforming catalyst for the oxygen-containing hydrocarbon of (1), wherein the content ratio of the metal oxide and zeolite containing copper and the spinel structure is 1: 1 to 100: 1 by mass.

(3) The reforming catalyst for the oxygen-containing hydrocarbon of (1) or (2), wherein the metal oxide containing copper and having a spinel structure is a Cu-Mn type spinel.

(4) The reforming catalyst for the oxygen-containing hydrocarbon according to any one of (1) to (3), wherein the zeolite is ZSM-5.

(5) The reforming catalyst for the oxygen-containing hydrocarbon according to any one of (1) to (4), which contains copper and contains a metal oxide, zeolite, and alumina having a spinel structure.

(6) The reforming catalyst for the oxygen-containing hydrocarbon according to any one of (1) to (5), wherein the zeolite contains a Group 8 metal and / or a rare earth element.

(7) The reforming catalyst for the oxygen-containing hydrocarbon of (6), wherein the Group 8 metal is at least one metal selected from Pt, Pd, Ir, Rh and Ru.

(8) The reforming catalyst for the oxygen-containing hydrocarbon of (6), wherein the Group 8 metal is at least one metal selected from Fe, Ni, and Co.

(9) A reforming catalyst of an oxygen-containing hydrocarbon obtained by reducing the reforming catalyst of any one of (1) to (8).

(10) The reforming catalyst for the oxygen-containing hydrocarbon according to any one of (1) to (9), wherein the oxygen-containing hydrocarbon is at least one selected from dimethyl ether and methyl ethyl ether.

(11) A method for producing hydrogen or synthesis gas, wherein the oxygen-containing hydrocarbon is steam reformed using the reforming catalyst of any one of (1) to (10).

(12) A method for producing hydrogen or synthesis gas, wherein the oxygen-containing hydrocarbon is self-heat reformed using the reforming catalyst of any one of (1) to (10).

(13) A method for producing hydrogen or synthesis gas, wherein the oxygen-containing hydrocarbon is partially oxidatively reformed using the reforming catalyst of any one of (1) to (10).

(14) A method for producing hydrogen or synthesis gas, wherein the oxygen-containing hydrocarbon is carbon dioxide reformed using the reforming catalyst of any one of (1) to (10).

(15) A fuel cell system comprising a reformer including the reforming catalyst of any one of (1) to (10), and a fuel cell using hydrogen produced by the reformer as a fuel.

1 is a schematic flowchart of a fuel cell system of the present invention.

Explanation of symbols for the main parts of the drawings

1: carburetor

11: water supply pipe

12: fuel introduction pipe

15: connector

21: fuel tank

23: desulfurizer

24: water pump

31: reformer

31A: Burner of the reformer

32: CO transformer

33: CO selective oxidizer

34: fuel cell

34A: fuel cell negative electrode

34B: Fuel Cell Positive Electrode

34C: fuel cell polymer electrolyte

35: air blower

36: rider separator

37: exhaust heat recovery device

37A: heat exchanger

37B: heat exchanger

37C: cooler

37D: Refrigerant Circulation Pump

Best Mode for Carrying Out the Invention

The reforming catalyst of the oxygen-containing hydrocarbon in the first invention of the present invention is a catalyst containing copper and a metal oxide having a spinel structure and a zeolite, preferably further alumina, a Group 8 metal and a rare earth element. It is a catalyst formed by containing.

As oxygen-containing hydrocarbon in this invention, ether, such as alcohol, such as methanol and ethanol, dimethyl ether, and methyl ethyl ether, is mentioned preferably. Among these, dimethyl ether and methyl ethyl ether are particularly preferable.

In the present invention, the metal oxide having a spinel structure has a cubic system as one of the typical crystal structure types seen in a metal double oxide of AB ₂ O ₄ type. In AB ₂ O ₄ , typically A is a divalent metal and B is a trivalent metal.

In the present invention, a metal oxide having a spinel structure containing copper is used, and examples of such metal oxides include Cu-Mn-type spinels, Cu-Fe-type spinels, Cu-Cr-type spinels, and the like. Cu-Mn type spinel is preferable. And the like for example, CuMn ₂ O ₄ as the CuMn type spinel, as the spinel type CuFe, for example, and the like CuFe ₂ O _4. As CuCr spinel type, for example, and the like CuCr ₂ O _4. Moreover, Cu (FeCr) ₂ O ₄ , Cu (FeAl) ₂ O ₄ , Cu (MnFe) ₂ O ₄ spinel of CuAl ₂ O ₄ or three component system can also be used. Cu (MnFe) As ₂ O ₄ spinel-type _{Cu (Mn 1.5 Fe 0.5) O} 4, Cu (Mn 1 .0 Fe 1 .0) O 4, Cu (Mn 2/3 Fe 4/3) O 4, Cu ( and the like _{Mn 0 .5 Fe 1 .5) O} 4.

The metal oxide of the spinel structure containing copper is excellent in heat resistance compared with the bispinel structure containing copper, and when used for reforming an oxygen-containing hydrocarbon, the catalytic activity per unit surface area is much higher.

On the other hand, in the reforming catalyst of the present invention, as long as the object of the present invention is not impaired, as the metal oxide containing copper, a compound containing copper having a bispinel structure can be used if desired.

Next, as an example of the production method of the metal oxide of spinel structure containing copper for use in a reforming catalyst of the present invention will be described for the case of producing the CuMn ₂ O ₄ spinel example.

First, water-soluble copper salts, such as copper nitrate, are used as a copper source, and water-soluble manganese salts, such as manganese nitrate, are used as a manganese source, and these are actually a stoichiometric ratio, ie, the molar ratio of Cu and Mn is 1: 1: Prepare an aqueous solution containing as much as possible. Subsequently, a chelating agent such as citric acid is added to the aqueous solution, followed by heating to evaporate water to form a gel. Next, the gel is subjected to heat treatment, and the oxide fine powder obtained by decomposing the nitrate, citric acid and the like in the gel is calcined in air at a temperature of about 300 to 500 ° C. for about 1 to 5 hours, and then about 500 to 1,000 ° C. By baking at the temperature of about 5 to 15 hours, CuMn ₂ O ₄ spinel is obtained. Further, when baked at a high temperature more than 700 ℃ is said to be a mixture of Mn ₂ O ₃ or Mn ₃ O ₄ and Cu _{1 .5} Mn _{1 .5} O ₄ spinel.

In this method, a copper source can be used so that Cu is excess than the stoichiometric ratio with respect to Mn. In this case, the obtained metal oxide becomes a mixture of copper oxide (Cu ₂ O or CuO, or a mixture thereof) and a spinel oxide.

In the case of preparing a CuFe ₂ O ₄ spinel, it is desirable to use a water-soluble iron salt, such as Cheorwon such as iron nitrate instead of the manganese source. In addition, by using a mixture of an iron source and a manganese source instead of the manganese source, a metal oxide containing Cu (FeMn) ₂ O ₄ spinel can be obtained.

The reforming catalyst of the oxygen-containing hydrocarbon of the present invention is one containing zeolite together with the metal oxide of the spinel structure containing copper. Examples of zeolites include ZSM-5, mordenite, X-type, Y-type, A-type, L-type, beta-type, ferriterite, etc., but mordenite and ZSM-5 are preferred in terms of catalytic activity and durability. Especially ZSM-5 is preferable.

As the mordenite and the ZSM-5, all or part of the proton exchange type is preferable than the cation exchange type in terms of catalytic activity.

The mixing ratio of Cu-Mn type spinel and zeolite is preferably 1: 1 to 100: 1 by mass ratio, more preferably 2: 1 to 50: 1. If the zeolite mixture ratio is smaller than this, the catalytic activity decreases, and if the zeolite mixture is large, the amount of coke generated which causes catalyst deterioration increases, which is not preferable.

The reforming catalyst of the oxygen containing hydrocarbon of this invention containing the metal oxide of a spinel structure containing copper, and a zeolite can be manufactured by the method shown below. That is, a method of forming a pellet of a suitable size after homogeneously mixing the metal oxide powder and the zeolite powder of the spinel structure containing copper, or a pellet of a suitable size containing the metal oxide of the spinel structure containing copper The reforming catalyst of the present invention can be prepared by, for example, mixing zeolite pellets of size.

As the alumina to be contained in the metal oxide and zeolite of the spinel structure containing copper, any of crystalline forms of commercially available α, β, γ, η, θ, κ and χ can be used. Moreover, what calcined alumina hydrates, such as boehmite, hyallite, and a gibbsite, can also be used. In addition, an alkali buffer having a pH of about 8 to 10 is added to aluminum nitrate to generate a precipitate of hydroxide, and a calcined product may be used, or aluminum chloride may be calcined. In addition, alkoxides such as aluminum isopropoxide are dissolved in alcohols such as 2-propanol, and inorganic acids such as hydrochloric acid are added as a catalyst for hydrolysis to prepare alumina gel, which is dried and calcined by a sol-gel method. You may use what was manufactured.

The alumina content is 5-50 mass%, preferably 8-40 mass%, More preferably, 10-30 mass% of alumina with respect to the whole mixture of the metal oxide, zeolite, and alumina of a spinel structure containing copper. By containing 5-50 mass% of alumina, the effect of suppressing coke production is obtained without significantly reducing the activity.

The addition of alumina may be simultaneously added at the time of mixing the spinel oxide containing zeolite and the zeolite, or may be added before or after mixing the spinel oxide containing zeolite and the zeolite.

Examples of Group 8 metals contained in the zeolite include precious metals such as platinum and palladium, and iron, cobalt and nickel.

Precious metals include platinum, palladium, ruthenium, rhodium and iridium, but platinum is particularly preferred.

Examples of the platinum compound which is a platinum component source include PtCl ₄ , H ₂ PtCl ₆ , Pt (NH ₃ ) ₄ Cl ₂ , (NH ₄ ) ₂ PtCl ₂ , H ₂ PtBr ₆ , NH ₄ [Pt (C ₂ H ₄ ) Cl ₃ ], Pt (NH ₃ ) ₄ (OH) ₂ , Pt (NH ₃ ) ₂ (NO ₂ ) ₂ , and the like.

These platinum compounds can be used individually by 1 type or in combination of 2 or more types. The same applies to the following palladium compounds, ruthenium compounds, rhodium compounds and iridium compounds.

As the palladium component cause the palladium compound, for example, (NH ₄₎ there may be mentioned _{2 PdCl 6, (NH 4)} 2 PdCl 4, Pd (NH 3) 4 Cl 2, PdCl 2, Pd (NO 3) 2 and the like.

As a ruthenium compound which is a ruthenium component source, for example, RuCl ₃ · nH ₂ O, Ru (NO ₃ ) ₃ , Ru ₂ (OH) ₂ Cl ₄ · 7NH ₃ · 3H ₂ O, K ₂ (RuCl ₅ (H ₂ O) ), (NH ₄ ) ₂ (RuCl ₅ (H ₂ O)), Ka (RuCl ₅ (NO)), RuBr ₃ nH ₂ O, Na ₂ RuO ₄ , Ru (NO) (NO ₃ ) ₃ , (Ru ₃ O (OAc) ₆ (H ₂ O) ₃ ) OAc nH ₂ O, K ₄ (Ru (CN) ₆ ) nH ₂ O, K ₂ (Ru (NO ₂ ) ₄ (OH) (NO)), (Ru (NH ₃ ) ₆ ) Cl ₃ , (Ru (NH ₃ ) ₆ ) Br ₃ , (Ru (NH ₃ ) ₆ ) Cl ₂ , (Ru (NH ₃ ) ₆ ) Br ₂ , (Ru ₃ O ₂ ( _{NH 3) 14) Cl 6 ·} H 2 O, (Ru (NO) (NH 3) 5) Cl 3, (Ru (OH) (NO) (NH 3) 4) (NO 3) 2, RuCl 2 (PPh ₃ ) ₃ , RuCl ₂ (PPh ₃ ) ₄ , (RuClH (PPh ₃ ) ₃ , C ₇ H ₈ , RuH ₂ (PPh ₃ ) ₄ , RuClH (CO) (PPh ₃ ) ₃ , RuH ₂ (CO) ( PPh ₃ ) ₃ , (RuCl ₂ (cod)) _n , Ru (CO) ₁₂ , Ru (acac) ₃ , (Ru (HCOO) (CO) ₂ ) _n , Ru ₂ I ₄ (p-cymene) _2, etc. Ruthenium salt Among these ruthenium compounds, RuCl ₃ · nH ₂ O, Ru (NO ₃ ) ₃ , Ru ₂ (OH) ₂ Cl ₄ · 7NH ₃ · 3H ₂ O are preferably used in terms of handling. do.

As rhodium component causes rhodium compound includes, for example, such as _{Na 3 RhCl 6, (NH 4} ) 2 RhCl 6, Rh (NH 3) 5 Cl 3, RhCl 3.

As the iridium component causes the iridium compounds, such as (NH _4), and the like _{2 IrCl 6, IrCl 3, H} 2 IrCl 6.

The loading amount of the noble metal component is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the zeolite in terms of balance between the effect of suppressing the formation of coke in the reforming reaction and economical efficiency.

The method of supporting the precious metal component in the zeolite is not particularly limited. When carrying two or more components, each component may be carried one by one and it may carry simultaneously. As the supporting operation of the precious metal component, various methods such as heating impregnation method, vacuum impregnation method, atmospheric impregnation method, evaporation drying method, pore filling method, incipient wetness method, etc., impregnation method, spray method, ion exchange method, etc. Although it can employ | adopt, the pore filling method, the impregnation method by an initial impregnation method, and the ion exchange method are preferable.

Fe, Ni, and Co components are mentioned as group 8 metal components other than the noble metal contained in the said zeolite. Although it does not specifically limit as a compound used as a raw material of Fe, Ni, and Co component, A water-soluble thing is preferable and nitrate is generally used.

There is no restriction | limiting in particular as a supporting method of Fe, Ni, Co to a zeolite. As the supporting operation, in addition to the method described in the above noble metal component, a method such as addition from the initial stage of zeolite synthesis can be adopted. In particular, it is preferable to carry | support by ion exchange method and the addition from the beginning of zeolite synthesis | combination by the method of following description.

Content of Fe, Ni, and Co component is 0.05-20 mass% with respect to zeolite, Preferably it is 0.1-10 mass%. The addition effect is obtained economically advantageously by containing 0.05-20 mass% of zeolite.

The addition effect is further improved by reducing the zeolite to which the Fe, Ni, and Co components are added, for example, by reducing at least 30 minutes at a temperature of 200 to 800 ° C, preferably 400 ° C, under a hydrogen-containing air stream.

Although there is no restriction | limiting in particular as a synthesis | combining method of a zeolite in the case of adding Fe, Ni, and Co from the beginning of zeolite synthesis, For example, the method of adding and carrying out organic compounds, such as tetrapropylammonium salt and alcohol, in a manufacturing raw material, and a manufacturing raw material The method of adding seed crystals, such as mordenite, etc. can be applied, without adding an organic compound in the inside.

Gels, sols or solutions before hydrothermal synthesis as raw materials for production include various silica sources, alumina sources, alkali metal sources, crystallization agents (templates), sulfuric acid, nitric acid, sodium hydroxide for adjusting pH, and sodium chloride, which is a crystallization promoter. Compounds may also be added.

Examples of the silica source at this time include sodium silicate, water glass, silica powder, silicic acid, aqueous colloidal silica, and the like. Particularly, in terms of gel particle control in an aqueous reaction mixture, supply of an alkali cation source, and raw material price, Water glass, colloidal silica, etc. are preferable. As water glass, what is prescribed | regulated as Japanese Industrial Standard No. 3 is suitable.

As the alumina source, sodium aluminate, aluminum sulfate, activated alumina, alumina hydrate and the like can be used, but sodium aluminate, aluminum sulfate and the like are particularly preferable.

As an alkali metal source, although it can supply with silica sources, such as water glass and colloidal silica, or an alumina source, such as sodium aluminate, alkali hydroxides, such as sodium hydroxide and potassium hydroxide, are mentioned. In particular, it is preferable to use sodium hydroxide.

The crystallizing agent (template) is an organic nitrogen compound, specifically, 1, 2, 3 amine, monoethanolamine, monopropanolamine, diglycolamine, tetrapropylammonium, tetraethylammonium and the like having 2 to 10 carbon atoms Ammonium salts, choline, pyrrolidine, ethylenediamine, diaminopropane and the like are used, and diglycolamine and tetrapropylammonium bromide are particularly preferable.

A mole ratio of each oxide is Si ₂ / Al ₂ O ₃ ratio is 10 to 300, preferably from 20 to 100. If it is smaller than this, crystallization does not progress or the crystallinity is bad, and if it is large, the activity is bad because there is little acid amount. The molar ratio of Al / M (M represents Fe.Ni.Co) is 0.5 to 20, preferably 1 to 10. When smaller than this, a part of M component precipitates out of a crystal | crystallization, or a crystallinity is bad, and when larger, an effect is small.

Examples of the rare earth element included in the zeolite include Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu. It does not specifically limit as a component source of these rare earth elements. Water solubility or methanol or ethanol solubility is preferable, and nitrate is generally used.

There is no restriction | limiting in particular as a supporting method of a rare earth element component. When supporting two or more components, the aqueous solution of each component, methanol, or ethanol solution may be carried one by one, and you may carry them simultaneously. As the supporting operation, various methods such as heating impregnation method, room temperature impregnation method, vacuum impregnation method, atmospheric impregnation method, evaporation drying method, pore filling method, initial impregnation method, impregnation method, spraying method, ion exchange method, etc. may be employed. Can be. In the impregnation with an aqueous solution, the pore peeling method and the initial impregnation method are effective, and in the impregnation with methanol and ethanol solutions, the evaporation drying method is also preferable.

The supported amount of the rare earth element component is 0.1 to 20 mass%, preferably 1 to 10 mass%. By setting it as 0.1-20 mass%, the rare earth element carrying effect is obtained economically advantageous.

In the present invention, the activity can be further improved by reducing the reforming catalyst. The reduction treatment includes a gas phase reduction method to be treated in an air stream containing hydrogen and a wet reduction method to be treated with a reducing agent. The reduction treatment of the former is usually carried out for 30 minutes to 24 hours, preferably 1 to 10 hours at a temperature of 150 to 500 ° C, preferably 200 to 300 ° C, under an air stream containing hydrogen. In addition to hydrogen gas, an inert gas such as nitrogen, helium or argon may coexist.

The latter wet reduction methods include liquid ammonia / alcohol / Na, Birch reduction using liquid ammonia / alcohol / Li, Bankeser reduction using methylamine / Li, Zn / HCl, Al / NaOH / H ₂ There is a method of treatment with a reducing agent such as O, NaH, LiAlH ₄ or a substituent thereof, hydrosilanes, sodium borohydride or a substituent thereof, diborane, formic acid, formalin, hydrazine and the like. In this case, the temperature is usually 10 minutes to 24 hours, preferably 30 minutes to 10 hours at room temperature to 100 ° C.

In addition, by flowing the reaction raw material, the catalyst is reduced even during the reaction by the generated hydrogen or CO.

In the present invention, the catalyst is reduced by the pre-reduction treatment or the product gas, so that Cu or other elements are separated from the spinel structure, and the spinel structure remains in a state where some or all of them are not retained. Use is an important point of the present invention.

In the method for producing hydrogen or syngas according to the second invention of the present application, oxygen-containing hydrocarbons such as dimethyl ether are subjected to (1) steam reforming, (2) self-heat reforming, and (3) moieties using the reforming catalyst of the present invention described above. Hydrogen or synthesis gas is produced by oxidation reforming or (4) carbon dioxide reforming.

Next, the case where dimethyl ether is used for each reforming method is demonstrated as an example.

[Steam Reforming]

In the case of using the reforming catalyst of the present invention, the steam reforming of dimethyl ether is considered to proceed with the reaction according to the reaction formula shown below.

CH ₃ OCH ₃ + H ₂ O → 2CH ₃ OH

2CH ₃ OH + 2H ₂ O → 2CO ₂ + 6H ₂

2CO ₂ + 2H ₂ → 2CO + 2H ₂ O

Therefore, when producing hydrogen, it is preferable to select reaction conditions so that reaction of said (3) may not progress easily, ie, reaction of the following Reaction Formula occurs.

CH ₃ OCH ₃ + 3H ₂ O → 2CO ₃ + 6H ₂

On the other hand, in the case of producing the synthesis gas, it is preferable to select the reaction conditions such that the reactions of the reaction formulas 1, 2 and 3 occur, that is, the reaction of the following reaction formula occurs.

CH ₃ OCH ₃ + H ₂ O → 2CO + 4H ₂

In the case of producing hydrogen, the molar ratio of water vapor / dimethyl ether is theoretically 3, but about 3 to 6 is preferred. On the other hand, in the case of producing synthesis gas, the molar ratio of water vapor / dimethyl ether is theoretically 1, but 1 to 1. 2 degree is preferable.

The reaction temperature is usually selected in the range of 200 to 500 ° C, preferably 250 to 450 ° C. When this temperature is less than 200 degreeC, the conversion rate of dimethyl ether may become low, and when it exceeds 500 degreeC, it will become the cause of active deterioration of a catalyst. GHSV (gas space-time velocity) preferably ranges from 100 to 10,000 h ⁻¹ on a dimethylether basis. If the GHSV is less than 100 h ^{−1, the} production efficiency is low and practically undesirable. If the GHSV is more than 10,000 h ⁻¹ , the conversion of dimethyl ether is too low, which is not practically desirable. In addition, the reaction pressure is usually about atmospheric pressure to about 1 MPa. When this pressure is too high, there exists a tendency for the conversion rate of a dimethyl ether to fall.

[Magnetic modification]

In the autothermal reforming reaction, the oxidation of dimethyl ether and the reaction of steam occur in the same reactor or in a continuous reactor. In this case, the reaction conditions are slightly different in hydrogen production and synthesis gas production, but in general, the oxygen / dimethyl ether molar ratio is preferably selected in the range of 0.1 to 1, and the water vapor / dimethyl ether molar ratio is preferably 0.5 to 3 Is selected from the range. When the oxygen / dimethyl ether molar ratio is less than 0.1, the supply of reaction heat by exotherm may not be sufficient. On the other hand, when the oxygen / dimethyl ether molar ratio exceeds 1, complete oxidation occurs and there is a fear that the hydrogen concentration is lowered. On the other hand, when the water vapor / dimethyl ether molar ratio is less than 0.5, the hydrogen concentration may decrease. On the other hand, when the water vapor / dimethyl ether molar ratio exceeds 3, there is a fear that the supply of exothermic heat is insufficient.

The reaction temperature is usually selected in the range of 200 to 800 ° C, preferably 250 to 500 ° C. In addition, about GHSV and reaction pressure, it is the same as that of the said steam reforming.

[Partial oxidation reforming]

In the partial oxidation reforming reaction, partial oxidation reaction of dimethyl ether occurs, and reaction conditions are slightly different in hydrogen production and synthesis gas production, but in general, the molar ratio of oxygen / dimethyl ether is preferably selected in the range of 0.3 to 1.5. If the molar ratio of oxygen / dimethyl ether is less than 0.3, the conversion rate of dimethyl ether may not be sufficiently high. On the other hand, if it exceeds 1.5, complete oxidation occurs, causing a decrease in hydrogen concentration. The reaction temperature is usually selected in the range of 200 to 900 ° C, preferably 250 to 600 ° C. In addition, about GHSV and reaction pressure, it is the same as that of the said steam reforming.

[CO2 Reform]

In the carbon dioxide reforming reaction, a reaction of dimethyl ether and carbon dioxide occurs, and reaction conditions are slightly different in hydrogen production and synthesis gas production, but in general, the molar ratio of CO ₂ / dimethyl ether is preferably 0.8 to 2, more preferably 0.9 To 1.5. If the molar ratio of CO ₂ / dimethyl ether is less than 0.8, the conversion of dimethyl ether may not increase sufficiently. On the other hand, if the molar ratio exceeds ₂ , a large amount of CO ₂ remains in the product, which may cause the partial pressure of hydrogen to decrease. In addition, the removal of CO ₂ may be necessary, which is undesirable. In this reaction, water vapor can be introduced, and the hydrogen concentration can be increased by this introduction. In addition, reaction temperature, GHSV, and reaction pressure are the same as that of the said steam reforming.

A third invention of the present application is a fuel cell system comprising a reformer having the above-described reforming catalyst and a fuel cell using hydrogen as a fuel produced by the reformer, which will be described with reference to FIG. 1.

The fuel in the fuel tank 21 is introduced into the desulfurizer 23. Usually, when using dimethyl ether etc. which are suitable as an oxygen containing hydrocarbon, sulfur is not contained but a desulfurization group is effective in the case of containing a sulfur containing compound as a complexing agent etc. The desulfurizer 23 may be filled with, for example, activated carbon, zeolite, or a metal adsorbent. The fuel desulfurized in the desulfurizer 23 is mixed with water passed through the water pump 24 from the water tank, introduced into the vaporizer 1, vaporized, and transferred to the reformer 31. The reformer 31 is filled with the above-described reforming catalyst, and hydrogen is produced by the above-described steam reforming reaction from the fuel mixture (oxygen-containing hydrocarbon and steam) transferred to the reformer 31.

The hydrogen thus produced is reduced to the extent that the CO concentration does not reach the characteristics of the fuel cell through the CO transformer 32 and the CO selective oxidizer 33. Examples of catalysts used in these reactors include iron-chromium catalysts, copper-zinc catalysts, or noble metal catalysts in the CO modifier 32, and ruthenium catalysts, platinum catalysts, or the like in the CO selective oxidizer 33. The mixed catalyst of the is mentioned. If the CO concentration in the hydrogen produced by the reforming reaction is low, the CO modifier 32 may not be attached.

The fuel cell 34 is an example of a solid polymer fuel cell having a polymer electrolyte 34C between the negative electrode 34A and the positive electrode 34B. The hydrogen-rich gas obtained by the above method on the negative electrode side is introduced into the positive electrode side after the appropriate humidification treatment (not shown in the humidifier), respectively, if necessary.

At this time, a reaction in which the hydrogen gas becomes a proton and releases electrons proceeds on the negative electrode side, and a reaction in which oxygen gas acquires electrons and protons into water proceeds on the positive electrode side, and a DC current is generated between the anodes 34A and 34B. do. In that case, a platinum black or activated carbon supported Pt catalyst or a Pt-Ru alloy catalyst is used as the negative electrode, and the positive electrode uses a platinum black or activated carbon supported Pt catalyst or the like.

The burner 31A of the reformer 31 is connected to the negative electrode 34A side, and the remaining hydrogen can be used as the fuel. In addition, the water separator 36 is connected to the positive electrode 34B side, water and exhaust gas generated by the combination of oxygen and hydrogen in the air supplied to the positive electrode 34B side are separated, and the water is used to generate water vapor. Can be. In the fuel cell 34, since heat is generated with power generation, an exhaust heat recovery device 37 is provided so that this heat can be recovered and used effectively. The exhaust heat recovery device 37 is a heat exchanger 37A attached to the fuel cell 34 to take heat generated during the reaction, a heat exchanger 37B for exchanging heat from the heat exchanger 37A with water, The cooler 37C and the pump 37D which circulates a refrigerant | coolant to these heat exchangers 37A and 37B and the cooler 37C are provided, and the hot water obtained by the heat exchanger 37B can be utilized effectively in other facilities.

Next, although an Example demonstrates this invention still in detail, this invention is not limited at all by these examples.

In each of the following Examples and Comparative Examples, Si, Al, Pt, Group 8 metals (Fe, Ni, Co) and rare earth metals (La, Ce, Sm) in the catalyst were prepared using an ICP emission spectrometer. It measured by the following method.

(Pretreatment of ICP)

1. Dissolution of Si and Al in ZSM-5

About 0.05 g of the sample is taken in a platinum dish, and about 0.5 g of a mixture of lithium tetraborate and lithium fluoride (mass ratio 9: 1) is added and mixed well. After melt | dissolving for 20 minutes in an 925 degreeC electric furnace, it is cooled to room temperature. To this, 40 mL of a mixed solution in which 5 g of tartaric acid and 40 mL of hydrochloric acid were dissolved was added to 1 L of distilled water, and dissolved by heating. After cooling to room temperature, the mixture was defined as 50 mL of distilled water. Si and Al in this solution are quantified by ICP.

2. Pt dissolution method in ZSM-5

About 1 g of a sample is taken in an alumina crucible, heat-processed at 900 degreeC for 60 minutes, 0.1 g of samples are taken to a Teflon (trademark) container, 1 mL of hydrofluoric acid and 4 mL of aqua regia are added, and it heat-drys. Next, 1 mL of hydrochloric acid is added, warmed with a lid on a watch plate, and allowed to cool, then 0.2 mL of 1000 ppm of Y standard solution is added as an internal standard solution, and the volume is 50 mL. Pt in this solution is quantified by ICP. It is measured by adding the same Y standard solution to the calibration curve solution of Pt.

3. Dissolution of Rare Earth Metals and Group 8 Metals (Fe, Ni, Co) in ZSM-5

About 0.04 g of sample is taken into a platinum dish, 3 mL of ion exchanged water, 0.5 mL of hydrofluoric acid, 0.5 mL of sulfuric acid, and 1 mL of hydrochloric acid are added, and heated until white smoke is produced. After cooling, 10 mL of ion-exchanged water is added to further heat. When the solution becomes clear, stop the heating, allow it to cool, and allow it to stand at 50 mL. Rare earth metals (La, Ce, Sm) and Group 8 metals (Fe, Ni, Co) in this solution are quantified by ICP.

(ICP measurement method)

1. Analytical Instruments

For analysis, the SPS-5100 type manufactured by Seiko Instruments Co., Ltd., a multi-element simultaneous ICP emission spectroscopic apparatus specified in ICP JIS K 0116, was used.

2. Measurement condition

Output: 1.3 kW

Argon gas flow rate: plasma gas... 16 L / min

                  Auxiliary gas… 0.2 L / min

                  Carrier gas… 0.4 to 0.5 L / min (pressure: 2.2 kg / cm 2)

Metering height: 12 mm (on work coil)

Measurement wavelength: 214.423 nm (Pt), 333.749 nm (La), 418.659 nm (Ce), 359.259 nm (Sm), 251.618 nm (Si), 396.152 nm (Al), 238.204 (Fe), 231.604 nm (Ni), 238.892 nm (Co)

(Evaluation of catalyst)

Evaluation of the catalyst obtained by each Example, a comparative example, etc. was performed by the steam reforming reaction of dimethyl ether (it describes as DME) as follows.

(1) The catalysts obtained in the examples, the comparative examples and the like are formed into 16 to 32 meshes and charged into the reactor.

(2) Reduction is carried out by heating to 250 ° C. for 1 hour in hydrogen gas (H ₂ : 100%) before the steam reforming reaction.

(3) In the activity evaluation, in Examples 1 to 9 and Comparative Examples 1 and 2, the steam / DME molar ratio of 5, the GHSV (gas space-time velocity) based on DME was 900 h ⁻¹ , and the GHSV based on total gas (DME + H ₂ O). The DME conversion (initial activity) at 5400 h ⁻¹ , reaction temperature 250 ° C. and coking rate after 18 hours were evaluated. In Examples 1, 3, 14 to 36 and Comparative Examples 3 to 4, GHSV (gas space time velocity) based on steam / DME molar ratio 5.0, DME was set to 333 h ⁻¹ and GHSV based on total gas (DME + H ₂ O). The DME conversion (initial activity) at 2000 h ⁻¹ , reaction temperature 280 ° C. and coking rate after 18 hours were evaluated.

The DME conversion was set to a value expressed by the following equation 1 from the reactor outlet gas composition.

DME conversion rate (%) = (A / B) × 100

A: CO molarity + CO ₂ molarity + CH ₄ molarity

B: CO molarity + CO ₂ molarity + CH ₄ molarity + (DME molarity x 2)

Caulking rate (%) was made into the numerical value represented by following formula (2).

Caulking rate (%) = (D / C) x 100

C: catalyst mass (g) including also the coke mass produced after 18 hours reaction at a reaction temperature of 250 ° C

D: Coke formation amount (coke mass: g) after reaction for 18 hours at 250 degreeC of reaction temperature.

(4) For durability evaluation, in Examples 1 to 9 and Comparative Examples 1 and 2, the steam / DME molar ratio of 5, the GHSV (gas space time velocity) based on the DME, 333 h ⁻¹ , and the GHSV based on the total gas (DME + H ₂ O) Was performed at 2000 h ⁻¹ and a reaction temperature of 250 ° C. for up to 250 hours, and the time required for the DME conversion to be less than 95% was defined as endurance time. Further, in Examples 3, 10 to 14, 17, 20, 21, 24, and Comparative Example 3, the GHSV (gas space-time velocity) based on steam / DME molar ratio 5.0, DME was set to 333 h ⁻¹ and the total gas (DME + H ₂ O). The GHSV of the reference was evaluated by the activity reduction rate ((initial DME conversion rate-DME conversion rate after 400 hours) / initial DME conversion rate) × 100 at 2000 h ⁻¹ and reaction temperature of 280 ° C. and the coking rate (%). It was.

Example 1 (mass ratio 2: 1 mixed catalyst of Cu-Mn spinel type oxide and H-ZSM-5)

13.28 g (55 mmol) of copper nitrate [manufactured by Nakarayesque Co., Ltd., 99.5% by mass Cu (NO ₃ ) ₂ .3H ₂ O] and manganese nitrate [manufactured by Sigma Aldrich Japan, 98.0% by mass Mn (NO ₃ ) in a 1-liter beaker ) ₂ .6H ₂ O] 300 milliliters of distilled water was added to 31.55 g (108 mmol), and the mixture was stirred at 60 ° C for 2 hours. Then, 34.65 g (165 mmol) of citric acid monohydrate (manufactured by Sigma Aldrich Japan) was added to this solution, and the mixture was stirred at 60 ° C for 1 hour, and then heated to 80 ° C to evaporate water.

The gel thus produced is heated at 140 ° C. for 7 hours, the nitric acid and citric acid are decomposed to obtain an oxide fine powder, and then calcined at 400 ° C. in air for 2 hours, and further calcined at 900 ° C. for 10 hours in air in a kiln. Was performed. After firing, Cu-Mn-spinel type oxide obtained (Cu _{1 .5 1 .5} Mn spinel as a mixture of Mn ₂ O ₃₎ 10 g and H-ZSM-5 (manufactured by Geo list, CBV3020E) mixing a mortar 5 g of This produced the mass ratio 2: 1 mixed catalyst of Cu-Mn spinel-type oxide and H-ZSM-5. Table 1 shows the results of activity evaluation and durability evaluation of the obtained catalyst.

Example 2 (mass ratio 2: 1 mixed catalyst of Cu-Mn spinel type oxide and H-mordenite)

H-mordenite (HSZ-640NAA manufactured by Tosoh Corporation) was ion-exchanged with 1 mol / liter of ammonium nitrate in a 60 DEG C. warm bath for 4 hours, dried overnight at 120 DEG C, and calcined at 500 DEG C in a kiln for 3 hours. Obtained mold mordenite. By mixing 10 g of the Cu-Mn spinel oxide prepared in the same manner as in Example 1 and 5 g of the obtained H-type mordenite by induction, a mixed catalyst of mass ratio 2: 1 of Cu-Mn spinel-type oxide and H-type mordenite was prepared. Prepared. Table 1 shows the results of the activity evaluation of the obtained catalyst.

Comparative Example 1 (mass ratio 2: 1 mixed catalyst of Cu-Mn spinel oxide and alumina)

10 g of Cu-Mn spinel oxide prepared in the same manner as in Example 1 and 5 g of alumina (AKP-G015, manufactured by Sumitomo Chemical Co., Ltd.) were mixed in a morbidity to give a mass ratio of Cu-Mn spinel oxide and alumina. A mixed catalyst was prepared. Table 1 shows the results of the activity evaluation of the obtained catalyst.

Comparative Example 2 (mass ratio 2: 1 mixed catalyst of Cu-Zn-Al catalyst and H-ZSM-5)

Cu-Zn-Al catalyst by mixing 10 g of a commercially available Cu-Zn-Al catalyst (manufactured by Sud Chemi Shokubai, MDC-3) and 5 g of H-ZSM-5 (manufactured by Geolist, CBV3020E) with a mortar. And a mass ratio of 2: 1 mixed catalyst of H-ZSM-5 were prepared. Table 1 shows the results of the activity evaluation of the obtained catalyst.

Example 3 (mass ratio 8: 1 mixed catalyst of Cu-Mn spinel type oxide and H-ZSM-5)

Cu-Mn spinel-type oxide and H-ZSM- were mixed by 20 g of Cu-Mn spinel-type oxide prepared in the same manner as in Example 1 and 2.5 g of H-ZSM-5 (CBV3020E manufactured by Geolist). A mass catalyst of 8: 1 mixed catalyst of 5 was prepared. Table 1 shows the results of the activity evaluation of the obtained catalyst.

Example 4 (mass ratio 32: 1 mixed catalyst of Cu-Mn spinel type oxide and H-ZSM-5)

Cu-Mn spinel-type oxide and H-ZSM- by mixing 32 g of Cu-Mn spinel oxide prepared in the same manner as in Example 1 and 1 g of H-ZSM-5 (CBV3020E manufactured by Geolist). A mass ratio 32: 1 mixed catalyst of 5 was prepared. The durability evaluation results of the obtained catalysts are shown in Table 1.

Example 5 (mass ratio 1: 2 mixed catalyst of Cu-Mn spinel type oxide and H-ZSM-5)

Cu-Mn spinel-type oxide and H-ZSM- were mixed by 5 g of Cu-Mn spinel-type oxide prepared in the same manner as in Example 1 and 10 g of H-ZSM-5 (CBV3020E manufactured by Geolist). A mass catalyst of 1: 2 mixed catalyst of 5 was prepared. The durability evaluation results of the obtained catalysts are shown in Table 1.

Example 6 (mass ratio 2: 1 mixed catalyst of Cu-Mn spinel type oxide and 0.1 mass% Pt / H-ZSM-5)

Chloroplatinic acid hexahydrate [Wako Pure Chemical Kogyo manufacture, 98.5 _{wt% H 2 PtCl 6 · 6 H} 2 O] 0.27 g (0.51 mmol) was dissolved in distilled water to 35 milliliters, H-ZSM-5 (Geo list manufactured, CBV3020E) was impregnated with 10 g, dried at 120 ° C for 3 hours, and calcined at 400 ° C for 3 hours to prepare 0.1% by mass of Pt / H-ZSM-5.

By mixing 10 g of Cu-Mn spinel oxide prepared in the same manner as in Example 1 and the above 0.1 mass% Pt / H-ZSM-5 with 5 g induction, the Cu-Mn spinel oxide and 0.1 mass% Pt / H A mass ratio 2: 1 mixed catalyst of -ZSM-5 was prepared. Table 1 shows the results of the activity evaluation of the obtained catalyst.

Example 7 (mass ratio 8: 1 mixed catalyst of Cu-Mn spinel type oxide and 0.1 mass% Pt / H-ZSM-5)

16 g of Cu-Mn spinel-type oxide prepared in the same manner as in Example 1 and 0.1 g of 0.1 mass% Pt / H-ZSM-5 were mixed with 2 g induction so that the Cu-Mn spinel-type oxide and 0.1 mass% Pt / H- A mass ratio 8: 1 mixed catalyst of ZSM-5 was prepared. Table 1 shows the results of activity evaluation and durability evaluation of the obtained catalyst.

Example 8 (mass ratio 2: 1 mixed catalyst of Cu-Mn spinel type oxide and 0.1 mass% Pt-ZSM-5)

0.086 g (0.26 mmol) of tetrachloramine platinum (manufactured by Kojima Chemical Co., Ltd., Pt (NH ₃ ) ₄ Cl ₂ ) was added to 300 milliliters of distilled water and stirred in an 80 ° C. warm bath. Subsequently, 50 g of H-ZSM-5 (Giolist Co., CBV3020E) was added to the solution, ion-exchanged for 9 hours in an 80 ° C hot bath, dried overnight at 120 ° C, and then calcined at 400 ° C in a firing furnace for 3 hours. 0.1 mass% Pt-ZSM-5 was obtained.

By mixing 10 g of Cu-Mn spinel oxide prepared in the same manner as in Example 1 and the above 0.1 mass% Pt-ZSM-5 with 5 g induction, the Cu-Mn spinel oxide and 0.1 mass% Pt-ZSM-5 A mixed catalyst having a mass ratio of 2: 1 was prepared. Table 1 shows the results of the activity evaluation of the obtained catalyst.

Example 9 (mass ratio 8: 1 mixed catalyst of Cu-Mn spinel type oxide and 0.1 mass% Pt-ZSM-5)

16 g of Cu-Mn spinel oxide prepared in the same manner as in Example 1 and 0.1 mass% Pt-ZSM-5 prepared in the same manner as in Example 8 were mixed with 2 g of Cu-Mn spinel oxide to A mass ratio 8: 1 mixed catalyst of 0.1 mass% Pt-ZSM-5 was prepared. Table 1 shows the results of activity evaluation and durability evaluation of the obtained catalyst.

From the results of the activity evaluation in Table 1, a catalyst in which zeolites such as H-ZSM-5 and H-mordenite were mixed with Cu-Mn spinel-type oxide was higher in DME steam reforming activity than a catalyst in which Cu-Mn spinel-type oxide and alumina were mixed. Even when compared with the conventional mixed catalyst of Cu-based catalyst and H-ZSM-5, it shows that the DME steam reforming activity is equal or more, and that the amount of coke generated after the reaction is small (Examples 1 to 2, comparison). Examples 1-2.

In Table 1, the durability of the catalyst was evaluated by changing the mixing ratio of Cu-Mn spinel-type oxide and H-ZSM-5 to 1: 2 to 32: 1. While it was 5 hours, in both 2: 1 and 32: 1, the durability is 250 hours or more, and it can be seen that it is preferable to set the mixing ratio of Cu-Mn spinel oxide to zeolite to 1 or more (Examples 3 to 3). 5).

In addition, from the activity evaluation results of Table 1, the catalyst in which the Cu-Mn spinel-type oxide and the zeolite containing the noble metal (Pt) was mixed further improved the activity compared to the case of the zeolite containing no noble metal, and the coking rate It can be seen that the degradation (comparison of Examples 6, 8 and Example 1, and Example 7, 9 and Example 3)

Example 10 (addition of 5% by mass of alumina to a mixed catalyst of mass ratio 8: 1 of Cu-Mn spinel oxide and H-ZSM-5)

16 g of Cu-Mn spinel oxide prepared in the same manner as in Example 1, 2 g of H-ZSM-5 (manufactured by Geolist, CBV3020E), and 0.95 g of alumina (manufactured by Sumitomo Chemical Co., Ltd., AKP-G015) The mixed catalyst (8: 1) of the Cu-Mn spinel type oxide and H-ZSM-5 which added 5 mass% of alumina was obtained by mixing by induction. Table 2 shows the results of evaluating the durability of the obtained catalyst.

Example 11 (addition of 8% by mass of alumina to a mixed catalyst of mass ratio 8: 1 of Cu-Mn spinel oxide and H-ZSM-5)

16 g of Cu-Mn spinel oxide prepared in the same manner as in Example 1, 2 g of H-ZSM-5 (Giolist, CBV3020E), and 1.6 g of alumina (AKP-G015 manufactured by Sumitomo Chemical Industries, Ltd.) By mixing by induction, a mixed catalyst (8: 1) of Cu-Mn spinel type oxide and H-ZSM-5 to which 8 mass% of alumina was added was obtained. Table 2 shows the results of evaluating the durability of the obtained catalyst.

Example 12 (20 mass% of alumina was added to the 8: 1 mixed catalyst of mass ratio of Cu-Mn spinel-type oxide and H-ZSM-5)

16 g of Cu-Mn spinel oxide prepared in the same manner as in Example 1, 2 g of H-ZSM-5 (manufactured by Geolist, CBV3020E), and 4.5 g of alumina (manufactured by Sumitomo Chemical Industries, Ltd., AKP-G015) The mixed catalyst (8: 1) of Cu-Mn spinel type oxide and H-ZSM-5 to which 20 mass% of alumina was added was obtained by mixing by induction. Table 2 shows the results of evaluating the durability of the obtained catalyst.

Example 13 (50% by mass of alumina was added to a 8: 1 mixed catalyst having a mass ratio of Cu-Mn spinel oxide and H-ZSM-5)

16 g of Cu-Mn spinel oxide prepared in the same manner as in Example 1, 2 g of H-ZSM-5 (manufactured by Geolist, CBV3020E), and 18 g of alumina (manufactured by Sumitomo Chemical Industries, Ltd., AKP-G015) The mixed catalyst (8: 1) of Cu-Mn spinel type oxide and H-ZSM-5 which added 50 mass% of alumina was obtained by mixing by induction. Table 2 shows the results of evaluating the durability of the obtained catalyst.

Comparative Example 3 (mass ratio 8: 1 mixed catalyst of Cu-Zn-Al catalyst and H-ZSM-5)

Cu-Zn-Al catalyst by mixing 16 g of a commercially available Cu-Zn-Al catalyst (manufactured by Sud Chemi Shokubai, MDC-3) and 2 g of H-ZSM-5 (manufactured by Geolist, CBV3020E) with a mortar. And a mass ratio 8: 1 mixed catalyst of H-ZSM-5 were prepared. Table 2 shows the results of evaluating the durability of the obtained catalyst.

On the other hand, Table 2 also shows the results when the durability evaluation by the same method as in Examples 10 to 13 was performed in Example 3. From the results of Examples 10 to 13 and Example 3, it was confirmed that the addition of alumina to the mixed catalyst of Cu-Mn spinel oxide and H-ZSM-5 reduced the activity and decreased the coking rate.

Example 14 (Cu-Mn spinel type oxide +1 mass% Fe / H-ZSM-5 (Si-Al, impregnated and supported) catalyst (mass ratio 8: 1))

1.47 g (3.6 mmol) of iron nitrate hydrate [manufactured by Wako Pure Chemical Industries, Ltd., 99 mass% Fe (NO ₃ ) ₃ .9H ₂ O] was dissolved in 11 milliliters of distilled water, and H-ZSM-5 (manufactured by Geolist) , CBV3020E) was impregnated with 20 g, dried at 120 ° C. for 3 hours, and then calcined at 400 ° C. for 3 hours to obtain 1% by mass of Fe / H-ZSM-5 (Si-Al). The obtained 1 mass% Fe / H-ZSM-5 (Si-Al) was hydrogen-reduced at 500 degreeC for 3 hours, before mixing with Cu-Mn spinel type oxide.

16 g of Cu-Mn spinel-type oxide prepared in the same manner as in Example 1 and 2 g of hydrogen reduction-treated 1 mass% Fe / H-ZSM-5 (Si-Al) obtained in the above procedure were mixed with a mortar. A -Mn spinel oxide + 1% by mass Fe / H-ZSM-5 (Si-Al, impregnated and supported) catalyst (mass ratio 8: 1) was obtained. Table 3 shows the results of activity evaluation and durability evaluation of the obtained catalyst.

Example 15 (Cu-Mn spinel type oxide + 1 mass% Ni / H-ZSM-5 (Si-Al, impregnated and supported) catalyst (mass ratio 8: 1))

1.02 g (3.4322 mmol) of nickel nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd., 98% Ni (NO ₃ ) ₂ .6H ₂ O) was dissolved in 11 milliliters of distilled water, and H-ZSM-5 (manufactured by Geolist Co., Ltd.) CBV3020E) was impregnated with 20 g, dried at 120 ° C for 3 hours, and calcined at 400 ° C for 3 hours to obtain 1% by mass of Ni / H-ZSM-5 (Si-Al). The obtained 1 mass% Ni / H-ZSM-5 (Si-Al) was hydrogen-reduced at 500 degreeC for 3 hours, before mixing with Cu-Mn spinel-type oxide.

16 g of Cu-Mn spinel oxide prepared in the same manner as in Example 1 and 2 g of 1 mass% Ni / H-ZSM-5 (Si-Al) that had been subjected to the hydrogen reduction treatment obtained in the above procedure were mixed with a mortar. -Mn spinel type oxide +1 mass% Ni / H-ZSM-5 (Si-Al, impregnation supported) catalyst (mass ratio 8: 1) was obtained. Table 3 shows the results of activity evaluation of the obtained catalyst.

Example 16 (Cu-Mn spinel type oxide +1 mass% Co / H-ZSM-5 (Si-Al, impregnation supported) catalyst (mass ratio 8: 1))

1.02 g (3.4 mmol) of cobalt nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd., 98% Co (NO ₃ ) ₂ .6H ₂ O) was dissolved in 11 milliliters of distilled water, and H-ZSM-5 (manufactured by Geolist Co., Ltd.) CBV3020E) was impregnated with 20 g, dried at 120 ° C for 3 hours, and calcined at 400 ° C for 3 hours to obtain 1% by mass of Co / H-ZSM-5 (Si-Al). The obtained 1 mass% Co / H-ZSM-5 (Si-Al) was subjected to hydrogen reduction treatment at 500 ° C. for 3 hours before mixing with Cu—Mn spinel oxide.

16 g of Cu-Mn spinel oxide prepared in the same manner as in Example 1 and 2 g of 1 mass% Ni / H-ZSM-5 (Si-Al) that had been subjected to the hydrogen reduction treatment obtained in the above procedure were mixed with a mortar. -Mn spinel oxide +1 mass% Co / H-ZSM-5 (Si-Al, impregnated and supported) catalyst (mass ratio 8: 1) was obtained. Table 3 shows the results of activity evaluation of the obtained catalyst.

Example 17 (Cu-Mn spinel type oxide +0.1 mass% Fe-H-ZSM-5 (Si-Al, ion exchange supported) catalyst (mass ratio 8: 1))

0.365 g (0.89 mmol) of iron nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd., 99 mass% Fe (NO ₃ ) ₃ .9H ₂ O) was added to 300 milliliters of distilled water and stirred in an 80 ° C. warm bath. Subsequently, 50 g of H-ZSM-5 (Giolist Co., CBV3020E) was added to this solution, ion-exchanged for 9 hours in an 80 degreeC warm bath, and after cooling, suction filtration was performed with 5 liters of distilled water. The ion exchange and suction filtration were further performed, and the resultant was dried overnight at 120 ° C., and then calcined at 400 ° C. for 3 hours in a calcination furnace to obtain 0.1 mass% Fe-H-ZSM-5 (Si-Al). The obtained 0.1 mass% Fe-H-ZSM-5 (Si-Al) was subjected to hydrogen reduction treatment at 500 ° C. for 3 hours before mixing with Cu—Mn spinel oxide.

16 g of Cu-Mn spinel oxide prepared in the same manner as in Example 1 and 2 g of 0.1 mass% Fe-H-ZSM-5 (Si-Al), which had been subjected to the hydrogen reduction treatment obtained in the above procedure, were mixed with a mortar. A -Mn spinel oxide and a 0.1 mass% Fe-H-ZSM-5 mixed catalyst (mass ratio 8: 1) were obtained. Table 3 shows the results of activity evaluation and durability evaluation of the obtained catalyst.

Example 18 (Cu-Mn spinel type oxide +0.1 mass% Ni-H-ZSM-5 (Si-Al, ion exchange supported) catalyst (mass ratio 8: 1))

0.253 g (0.85 mmol) of nickel nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd., 98 mass% Ni (NO ₃ ) ₂ .6H ₂ O) was added to 300 milliliters of distilled water, and stirred in an 80 ° C warm bath. Subsequently, 50 g of H-ZSM-5 (Giolist Co., CBV3020E) was added to this solution, ion-exchanged for 9 hours in an 80 degreeC warm bath, and after cooling, suction filtration was performed with 5 liters of distilled water. The ion exchange and suction filtration were further performed, and the resultant was dried overnight at 120 ° C., and then calcined at 400 ° C. for 3 hours in a calcination furnace to obtain 0.1 mass% Ni-H-ZSM-5 (Si-Al). The obtained 0.1 mass% Ni-H-ZSM-5 (Si-Al) was subjected to a hydrogen reduction treatment at 500 ° C for 3 hours before mixing with Cu-Mn spinel oxide.

16 g of Cu-Mn spinel oxide prepared in the same manner as in Example 1 and 2 g of 0.1 mass% Ni-H-ZSM-5 (Si-Al), which had been subjected to the hydrogen reduction treatment obtained in the above procedure, were mixed with a mortar. A -Mn spinel oxide and a 0.1 mass% Ni-H-ZSM-5 mixed catalyst (mass ratio 8: 1) were obtained. Table 3 shows the results of activity evaluation of the obtained catalyst.

Example 19 (Cu-Mn spinel type oxide +0.1 mass% Co-H-ZSM-5 (Si-Al, ion exchange supported) catalyst (mass ratio 8: 1))

0.252 g (0.85 mmol) of cobalt nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd., 98 mass% Co (NO ₃ ) ₂ .6H ₂ O) was added to 300 milliliters of distilled water and stirred in an 80 ° C warm bath. Subsequently, 50 g of H-ZSM-5 (Giolist Co., CBV3020E) was added to this solution, ion-exchanged for 9 hours in an 80 degreeC warm bath, and after cooling, suction filtration was performed with 5 liters of distilled water. The ion exchange and suction filtration were further performed, and the resultant was dried overnight at 120 ° C., and then calcined at 400 ° C. for 3 hours in a calcination furnace to obtain 0.1 mass% Co-H-ZSM-5 (Si-Al). The obtained 0.1 mass% Co-H-ZSM-5 (Si-Al) was subjected to a hydrogen reduction treatment at 500 ° C for 3 hours before mixing with Cu-Mn spinel oxide.

16 g of Cu-Mn spinel oxide prepared in the same manner as in Example 1 and 2 g of 0.1 mass% Co-H-ZSM-5 (Si-Al), which had been subjected to the hydrogen reduction treatment obtained in the above procedure, were mixed by induction. A -Mn spinel oxide and a 0.1 mass% Co-H-ZSM-5 mixed catalyst (mass ratio 8: 1) were obtained. Table 3 shows the results of activity evaluation of the obtained catalyst.

Example 20 (Cu-Mn spinel oxide + H-ZSM-5 (Si-Al-Fe, Al: Fe = 5: 5, Fe addition at the time of ZSM-5 synthesis) catalyst (mass ratio 8: 1))

Aluminum sulfate [Wako Pure Chemical Kogyo manufacture, 99.5 _{wt% Al 2 (SO 4) 3} · 18H 2 O] 9.15 g (13.7 mmol) of ferric nitrate nonahydrate [Wako Pure Chemical Kogyo prepared, 99 mass% Fe (NO ₃ ) ₃ .9H ₂ O] 11.2 g (27.4 mmol), sulfuric acid [manufactured by Wako Pure Chemical Industries, Ltd., 97% H ₂ SO ₄ ] 10 g (99.0 mmol), tetrapropylammonium bromide [manufactured by Wako Pure Chemical Industries, Ltd.) , 98 mass% (CH ₃ CH ₂ CH ₂ ) ₄ NBr] 26.8 g (98.9 mmol) and 250 milliliters of distilled water were mixed to prepare a homogeneous solution as an A solution. On the other hand, water glass (Nippon Kagaku and JIS 3 call the teacher prepared, SiO _2: 29 mass%, Na ₂ O: 9.4% by mass, water: 61.6% by mass), the homogeneous solution mixture of 215 g and distilled water 60 g, and the resulting Was made into B liquid. In addition, 40.2 g (684 mmol) of sodium chloride [Wakko Pure Chemical Industries, Ltd., 99.5 mass% NaCl] and 120 milliliters of distilled water were mixed, and the obtained homogeneous solution was used as C liquid.

While stirring this C liquid, the said A liquid and B liquid were dripped simultaneously, and mixed in C liquid. 2.0 g (19.8 mmol) of sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd., 97 mass% H ₂ SO ₄ ) was added to this raw material mixture to adjust the pH to 9.5. The reaction was carried out at 170 ° C. for 20 hours while stirring at 300 rpm. After the reaction, the mixture was cooled to room temperature, and then the solid product was filtered and washed by pressure filtration until the filtrate became pH9.5 or less. The solid thus recovered was dried at 120 ° C. for 6 hours, and then calcined at 550 ° C. for 6 hours in air.

Next, the calcined product was ion exchanged at 60 ° C. for 4 hours using 10 milliliters of 1 mol / L ammonium nitrate aqueous solution per 1 g of the calcined product, and cooled, followed by suction filtration with distilled water. The ion exchange and suction filtration were washed again, and the obtained ion exchanged product was dried at 120 ° C. for 6 hours, and then calcined at 400 ° C. for 3 hours to obtain H-ZSM-5 (Si-Al-Fe, Al: Fe = 5: 5. , Fe addition at the time of ZSM-5 synthesis). The fired product was confirmed to have a ZSM-5 structure by SiO ₂ / Al ₂ O ₃ = 57.7, Al / Fe = 1.11 by XCP, and XRD. The obtained H-ZSM-5 (Si-Al-Fe, Al: Fe = 5: 5) was subjected to hydrogen reduction treatment at 500 ° C. for 3 hours before mixing with Cu—Mn spinel oxide.

16 g of Cu-Mn spinel oxide prepared in the same manner as in Example 1 and 2 g of H-ZSM-5 (Si-Al-Fe, Al: Fe = 5: 5) which had been subjected to the hydrogen reduction treatment obtained in the above procedure were induced. By mixing with, a mixed catalyst (mass ratio 8: 1) of Cu-Mn spinel oxide and H-ZSM-5 (Si-Al-Fe, Al: Fe = 5: 5) was obtained. Table 3 shows the results of activity evaluation and durability evaluation of the obtained catalyst.

Example 21 (Cu-Mn spinel type oxide + H-ZSM-5 (Si-Al-Fe, Al: Fe = 9: 1, Fe addition at the time of ZSM-5 synthesis) catalyst (mass ratio 8: 1))

Aluminum sulfate [Wako Pure Chemical Kogyo manufacture, 99.5 _{wt% Al 2 (SO 4) 3} · 18H 2 O] 16.5 g (24.6 mmol) of ferric nitrate nonahydrate [Wako Pure Chemical Kogyo prepared, 99 mass% Fe (NO ₃ ) ₃ .9H ₂ O] 2.23 g (5.47 mmol), sulfuric acid [manufactured by Wako Pure Chemical Industries, Ltd., 97 mass% H ₂ SO ₄ ] 10 g (99.0 mmol), tetrapropylammonium bromide [Wako Pure Chemical Industries, Ltd.] prepared, 98 _{mass% (CH 3 CH 2 CH 2} ) 4 mixed NBr] 26.8 g (98.9 mmol) and 250 ml of distilled water, which was obtained as a homogeneous solution a solution. Liquid B and liquid C were prepared in the same manner as in Example 20.

While stirring this C liquid, the said A liquid and B liquid were dripped simultaneously, and mixed in C liquid. 1.4 g (13.9 mmol) of sulfuric acid (Wako Pure Chemical Industries, Ltd., 97 mass% H ₂ SO ₄ ) was added to the raw material mixture, and the pH was adjusted to 9.5. Hereinafter, it produced like Example 20 and obtained H-ZSM-5 (Si-Al-Fe, Al: Fe = 9: 1, Fe addition at the time of ZSM-5 synthesis | combination). The fired product was confirmed to have a ZSM-5 structure by SiO ₂ / Al ₂ O ₃ = 35.7, Al / Fe = 9.11 by XCP, and XRD. The obtained H-ZSM-5 (Si-Al-Fe, Al: Fe = 9: 1) was subjected to a hydrogen reduction treatment at 500 ° C for 3 hours before mixing with Cu-Mn spinel oxide.

Induced 16 g of Cu-Mn spinel oxide prepared in the same manner as in Example 1 and 2 g of H-ZSM-5 (Si-Al-Fe, Al: Fe = 9: 1) which had been subjected to the hydrogen reduction treatment obtained in the above procedure. By mixing with, a mixed catalyst (mass ratio 8: 1) of Cu-Mn spinel oxide and H-ZSM-5 (Si-Al-Fe, Al: Fe = 9: 1) was obtained. Table 3 shows the results of activity evaluation and durability evaluation of the obtained catalyst.

Example 22 (Cu-Mn spinel type oxide + H-ZSM-5 (Si-Al-Ni, Al: Ni = 9: 1, Ni added at the time of ZSM-5 synthesis) catalyst (mass ratio 8: 1))

Aluminum sulfate [Wako Pure Chemical Kogyo manufacture, 99.5 _{wt% Al 2 (SO 4) 3} · 18H 2 O] 16.5 g (24.6 mmol), nickel nitrate hexahydrate [Wako Pure Chemical Kogyo prepared, 98 mass% Ni (NO _{3) 2 · 6H 2 O]} 1.62 g (5.47 mmol), sulfuric acid [Wako Pure Chemical Kogyo _{produced, 97% H 2 SO 4]} 10 g (99.0 mmol), tetrapropylammonium bromide [Wako Pure Chemical Kogyo Preparation , 98 mass% (CH ₃ CH ₂ CH ₂ ) ₄ NBr] 26.8 g (98.9 mmol) and 250 milliliters of distilled water were mixed to prepare a homogeneous solution as an A solution. Liquid B and liquid C were prepared in the same manner as in Example 20.

While stirring the said C liquid, the said A liquid and B liquid were dripped simultaneously, and mixed in C liquid. 2.4 g (23.8 mmol) of sulfuric acid (Wako Pure Chemical Industries, Ltd., 97 mass% H ₂ SO ₄ ) was added to the raw material mixture, and the pH was adjusted to pH9.5. Hereinafter, it produced like Example 20 and obtained H-ZSM-5 (Si-Al-Ni, Al: Ni = 9: 1, Ni addition at the time of ZSM-5 synthesis | combination). The fired product was found to have SiO ₂ / Al ₂ O ₃ = 35.1 and Al / Ni = 9.06 by ICP. The obtained H-ZSM-5 (Si-Al-Ni, Al: Ni = 9: 1) was subjected to a hydrogen reduction treatment at 500 ° C. for 3 hours before mixing with Cu—Mn spinel oxide.

Induced 16 g of Cu-Mn spinel oxide prepared in the same manner as in Example 1 and 2 g of H-ZSM-5 (Si-Al-Ni, Al: Ni = 9: 1) which had been subjected to the hydrogen reduction treatment obtained in the above procedure. By mixing with, a mixed catalyst (mass ratio 8: 1) of Cu-Mn spinel oxide and H-ZSM-5 (Si-Al-Ni, Al: Ni = 9: 1) was obtained. Table 3 shows the results of activity evaluation of the obtained catalyst.

Example 23 (Cu-Mn spinel type oxide + H-ZSM-5 (Si-Al-Co, Al: Co = 9: 1, Co addition at the time of ZSM-5 synthesis) catalyst (mass ratio 8: 1))

Aluminum sulfate [Wako Pure Chemical Kogyo manufacture, 99.5 _{wt% Al 2 (SO 4) 3} · 18H 2 O] 16.5 g (24.6 mmol), cobalt nitrate hexahydrate [Wako Pure Chemical Kogyo prepared, 98 wt% Co (NO _{3) 2 · 6H 2 O]} 1.62 g (5.47 mmol), sulfuric acid [Wako Pure Chemical Kogyo _{produced, 97% H 2 SO 4]} 10 g (99.0 mmol), tetrapropylammonium bromide [Wako Pure Chemical Kogyo Preparation , 98 mass% (CH ₃ CH ₂ CH ₂ ) ₄ NBr] 26.8 g (98.9 mmol) and 250 milliliters of distilled water were mixed to prepare a homogeneous solution as an A solution. Liquid B and liquid C were prepared in the same manner as in Example 20.

While stirring the said C liquid, the said A liquid and B liquid were dripped simultaneously, and mixed in C liquid. 2.2 g (21.8 mmol) of sulfuric acid [Wako Pure Chemical Industries Ltd., 97 mass% H ₂ SO ₄ ] was added to this raw material mixture, and it adjusted to pH 9.5. Hereinafter, it manufactured like Example 20 and obtained H-ZSM-5 (Si-Al-Co, Al: Co = 9: 1, Co addition at the time of ZSM-5 synthesis | combination) was obtained. The calcined product was found to have SiO ₂ / Al ₂ O ₃ = 35.9 and Al / Co = 9.10 by ICP. The obtained H-ZSM-5 (Si-Al-Co, Al: Co = 9: 1) was subjected to a hydrogen reduction treatment at 500 ° C for 3 hours before mixing with Cu-Mn spinel oxide.

16 g of Cu-Mn spinel oxide prepared in the same manner as in Example 1 and 2 g of H-ZSM-5 (Si-Al-Co, Al: Co = 9: 1) obtained by the above-described hydrogen reduction treatment were induced. By mixing with, a mixed catalyst (mass ratio 8: 1) of Cu-Mn spinel oxide and H-ZSM-5 (Si-Al-Co, Al: Co = 9: 1) was obtained. Table 3 shows the results of the activity evaluation of the obtained catalyst.

On the other hand, the results of activity evaluation and durability evaluation in Example 3 are also shown in Table 3. From this result, it is confirmed that coke formation is suppressed by adding a Group 8 metal to the mixed catalyst of Cu-Mn spinel type oxide and H-ZSM-5, whereby durability is further improved.

Example 24 (Cu-Mn spinel type oxide +5 mass% La / H-ZSM-5 catalyst (mass ratio 8: 1))

1.64 g (3.380 mmol) of lanthanum nitrate hexahydrate [manufactured by Wako Pure Chemical Industries, Ltd., 99.9% La (NO ₃ ) ₃ .6H ₂ O] to ethanol [manufactured by Wako Pure Chemical Industries, Ltd., 99.5 mass% C ₂ H ₅ OH] It was dissolved in 75 milliliters, and 10 g of H-ZSM-5 (CBV3020E manufactured by Geolist) was added thereto, ethanol was removed by an evaporator in a 30 ° C warm bath, dried at 40 ° C overnight, and further at 120 ° C. It dried for 3 hours, baked at 500 degreeC for 10 hours, and obtained 5 mass% La / H-ZSM-5.

16 g of Cu-Mn spinel-type oxide prepared in the same manner as in Example 1 and 5 g of 5 mass% of Cu-Mn spinel-type oxide by mixing 2 g of 5 mass% La / H-ZSM-5 obtained in the above procedure. A mixed catalyst (8: 1) of La / H-ZSM-5 was obtained. Table 4 shows the results of activity evaluation and durability evaluation of the obtained catalyst.

Example 25 (Cu-Mn spinel type oxide +5 mass% Ce / H-ZSM-5 catalyst (mass ratio 8: 1))

1.66 g (3.91 mmol) of cerium nitrate hexahydrate [manufactured by Wako Pure Chemical Industries, Ltd., 98 mass% Ce (NO ₃ ) ₃ .6H ₂ O] was added to ethanol [manufactured by Wako Pure Chemical Industries, Ltd., 99.5 mass% C ₂ H ₅ OH ] Dissolved in 75 milliliters, 10 g of H-ZSM-5 (CBV3020E manufactured by Geolist) was added, ethanol was removed by an evaporator in a 30 ° C. warm bath, dried overnight at 40 ° C., and further 120 ° C. It dried for 3 hours, and baked at 500 degreeC for 10 hours, and obtained 5 mass% Ce / H-ZSM-5.

16 g of Cu-Mn spinel-type oxide prepared in the same manner as in Example 1 and 5 g of 5 mass% of Cu-Mn spinel-type oxide by mixing 2 g of 5 mass% Ce / H-ZSM-5 obtained in the above procedure. A mixed catalyst (8: 1) of Ce / H-ZSM-5 was obtained. Table 4 shows the results of the activity evaluation of the obtained catalyst.

Example 26 (Cu-Mn spinel type oxide +5 mass% Sm / H-ZSM-5 catalyst (mass ratio 8: 1))

1.56 g (3.54 mmol) of samarium nitrate hexahydrate [manufactured by Wako Pure Chemical Industries, Ltd., 99.5 mass% Sm (NO ₃ ) ₃ .6 H ₂ O] to ethanol [manufactured by Wako Pure Chemical Industries, Ltd., 99.5 mass% C ₂ H ₅ OH] was dissolved in 75 milliliters, and 10 g of H-ZSM-5 (Giolist Co., CBV3020E) was added thereto, ethanol was removed by an evaporator in a 30 ° C. warm bath, dried at 40 ° C. overnight, and further It dried at 120 degreeC for 3 hours, and baked at 500 degreeC for 10 hours, and obtained 5 mass% Sm / H-ZSM-5.

16 g of Cu-Mn spinel-type oxide prepared in the same manner as in Example 1 and 5 g of 5 mass% of Cu-Mn spinel-type oxide by mixing 2 g of 5 mass% Sm / H-ZSM-5 obtained in the above procedure. A mixed catalyst (8: 1) of Sm / H-ZSM-5 was obtained. Table 4 shows the results of the activity evaluation of the obtained catalyst.

Example 27 (Cu-Mn spinel type oxide +1 mass% La / H-ZSM-5 catalyst (mass ratio 2: 1))

0.32 g (0.73 mmol) of lanthanum nitrate hexahydrate [manufactured by Wako Pure Chemical Industries, Ltd., 99.9% La (NO ₃ ) ₃ .6H ₂ O] to ethanol [manufactured by Wako Pure Chemical Industries, Ltd., 99.5 mass% C ₂ H ₅ OH] It was dissolved in 75 milliliters, and 10 g of H-ZSM-5 (CBV3020E manufactured by Geolist) was added thereto, ethanol was removed by an evaporator in a 30 ° C warm bath, dried at 40 ° C overnight, and further at 120 ° C. It dried for 3 hours, baked at 500 degreeC for 10 hours, and obtained 1 mass% La / H-ZSM-5.

1 mass% of Cu-Mn spinel-type oxide by mixing 10 g of Cu-Mn spinel-type oxide prepared in the same manner as in Example 1 with 5 g of 1 mass% La / H-ZSM-5 obtained in the above procedure. A mixed catalyst (2: 1) of La / H-ZSM-5 was obtained. Table 4 shows the results of the activity evaluation of the obtained catalyst.

Example 28 (Cu-Mn spinel type oxide +10 mass% La / H-ZSM-5 catalyst (mass ratio 2: 1))

3.47 g (8.02 mmol) of lanthanum nitrate hexahydrate [manufactured by Wako Pure Chemical Industries, Ltd., 99.9% La (NO ₃ ) ₃ .6H ₂ O] to ethanol [manufactured by Wako Pure Chemical Industries, Ltd., 99.5 mass% C ₂ H ₅ OH] It was dissolved in 75 milliliters, and 10 g of H-ZSM-5 (CBV3020E manufactured by Geolist Co., Ltd.) was added thereto, and ethanol was removed by an evaporator in a 30 ° C warm bath, dried overnight at 40 ° C, and further at 120 ° C. It dried for 3 hours, baked at 500 degreeC for 10 hours, and obtained 10 mass% La / H-ZSM-5.

10 mass% of Cu-Mn spinel-type oxide by mixing 10 g of Cu-Mn spinel-type oxide prepared in the same manner as in Example 1 with 10 g of 10 mass% La / H-ZSM-5 obtained in the above procedure with 5 g induction. A mixed catalyst (2: 1) of La / H-ZSM-5 was obtained. Table 4 shows the results of the activity evaluation of the obtained catalyst.

Example 29 (Cu-Mn spinel type oxide +5 mass% La / H-ZSM-5 catalyst (mass ratio 2: 1))

Cu-Mn spinel type by mixing 10 g of Cu-Mn spinel oxide prepared in the same manner as in Example 1 and 5 mass% La / H-ZSM-5 prepared in the same manner as in Example 24 with 5 g induction A mixed catalyst (2: 1) of an oxide and 5 wt% La / H-ZSM-5 was obtained. Table 4 shows the results of the activity evaluation of the obtained catalyst.

Example 30 (Cu-Mn spinel type oxide +5 mass% La / H-ZSM-5 catalyst (mass ratio 2: 1 aqueous solution impregnation))

3.28 g (7.59 mmol) of lanthanum nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd., 99.9% La (NO ₃ ) ₃ .6H ₂ O) was dissolved in 11 milliliters of distilled water, and H-ZSM-5 (CBV3020E manufactured by Geolist) ) 20 g was dried, dried at 120 ° C. for 3 hours, and calcined at 500 ° C. for 10 hours to prepare 5% by weight of La / H-ZSM-5.

10 g of Cu-Mn spinel-type oxide prepared in the same manner as in Example 1 and 5 mass% La / ZSM-5 obtained in the above procedure were mixed with 5 g induction, thereby yielding 5 wt% La / A mixed catalyst (2: 1, aqueous solution impregnation) of H-ZSM-5 was obtained. Table 4 shows the results of the activity evaluation of the obtained catalyst.

Example 31 (Cu-Mn spinel type oxide +5 mass% Ce / H-ZSM-5 catalyst (mass ratio 2: 1))

Cu-Mn spinel type by mixing 10 g of Cu-Mn spinel oxide prepared in the same manner as in Example 1 and 5 mass% Ce / H-ZSM-5 prepared in the same manner as in Example 25 with 5 g induction A mixed catalyst (2: 1) of an oxide and 5 mass% Ce / H-ZSM-5 was obtained. Table 4 shows the results of the activity evaluation of the obtained catalyst.

Example 32 (Cu-Mn spinel type oxide +5 mass% Sm / H-ZSM-5 catalyst (mass ratio 2: 1))

Cu-Mn spinel type by mixing 10 g of Cu-Mn spinel oxide prepared in the same manner as in Example 1 with 5 mass% Sm / H-ZSM-5 prepared in the same manner as in Example 26 A mixed catalyst (2: 1) of an oxide and 5 mass% Sm / H-ZSM-5 was obtained. Table 4 shows the results of the activity evaluation of the obtained catalyst.

Example 33 (Cu-Mn spinel type oxide +5 mass% La / H-ZSM-5 catalyst (mass ratio 1: 1))

Cu-Mn spinel type by mixing 10 g of Cu-Mn spinel oxide prepared in the same manner as in Example 1 and 5 mass% La / H-ZSM-5 prepared in the same manner as in Example 24 with 10 g induction A mixed catalyst (1: 1) of an oxide and 5 mass% La / H-ZSM-5 was obtained. Table 5 shows the results of the activity evaluation of the obtained catalyst.

Example 34 (Cu-Mn spinel type oxide +5 mass% Ce / H-ZSM-5 catalyst (mass ratio 1: 1))

Cu-Mn spinel oxide prepared by mixing 10 g of Cu-Mn spinel oxide prepared in the same manner as in Example 1 with 5 mass% Ce / H-ZSM-5 prepared in the same manner as in Example 25 with 10 g induction. And 5 mass% Ce / H-ZSM-5 mixed catalyst (1: 1) were obtained. Table 5 shows the results of the activity evaluation of the obtained catalyst.

Example 35 (Cu-Mn spinel type oxide +5 mass% Sm / H-ZSM-5 catalyst (mass ratio 1: 1))

Cu-Mn spinel type by mixing 10 g of Cu-Mn spinel oxide prepared in the same manner as in Example 1 with 5 mass% Sm / H-ZSM-5 prepared in the same manner as in Example 26 A mixed catalyst (1: 1) of an oxide and 5 mass% Sm / H-ZSM-5 was obtained. Table 5 shows the results of the activity evaluation of the obtained catalyst.

Example 36 (Cu-Mn spinel type oxide + H-ZSM-5 catalyst (mass ratio 1: 1))

10 g of Cu-Mn spinel oxide prepared in the same manner as in Example 1 and 10 g of H-ZSM-5 (CBV3020E manufactured by Geolist Co., Ltd.) were mixed in a mortar to thereby suppress the Cu-Mn spinel oxide and H-ZSM-5. A mixed catalyst (1: 1) was obtained. Table 5 shows the results of the activity evaluation of the obtained catalyst.

Comparative Example 4 (Cu-Zn-Al + H-ZSM-5 Catalyst (Mass Ratio 8: 1))

By mixing 16 g of a commercially available Cu-Zn-Al catalyst (manufactured by Sud Chemi Corporation, MDC-3) and 2 g of H-ZSM-5 (manufactured by Geolist, CBV3020E), Cu-Zn-Al and H- A mixed catalyst (8: 1) of ZSM-5 was obtained. Table 5 shows the results of the activity evaluation of the obtained catalyst.

On the other hand, the results of activity evaluation in Example 1 and Example 3 are also shown in Table 4 and Table 5. From the results of Examples 24 to 26, Comparative Examples 4 and 3, the mixed catalyst of Cu-Mn spinel type oxide and H-ZSM-5 was compared with the mixed catalyst of Cu-Zn-Al and H-ZSM-5. It was confirmed that coking rate was lowered because the conversion rate of DME (dimethyl ether) was improved, and that the rare earth element was further added. In addition, from the comparison of Examples 27 to 32 with Examples 1, 33 and 35, and Example 36, coking was suppressed by adding a rare earth element to the mixed catalyst of Cu-Mn spinel oxide and H-ZSM-5. This was confirmed.

The catalyst containing the metal oxide and the zeolite of the present invention including copper and having a spinel structure has an oxygen-containing hydrocarbon such as dimethyl ether even when compared to a conventional catalyst containing copper and a metal oxide having a spinel structure. The activity of steam reforming is higher, and the amount of coke that causes catalyst deterioration is smaller than that of conventional mixed catalysts of copper catalysts and zeolites. In addition, by adding alumina, a Group 8 metal, and a rare earth element to the catalyst containing a metal oxide having a spinel structure and a zeolite and containing a copper, the amount of coke produced can be further suppressed in the modification of the oxygen-containing hydrocarbon. Can be.

Therefore, various reforming of the oxygen-containing hydrocarbon can be carried out using the reforming catalyst of the present invention to produce hydrogen or syngas efficiently stably for a long time. Further, an excellent fuel cell system can be constructed having a reformer having such an excellent reforming catalyst and a fuel cell fueled by hydrogen produced by the reformer.

Claims (15)

A reforming catalyst for an oxygen-containing hydrocarbon comprising copper and a metal oxide having a spinel structure and zeolite. The catalyst for reforming an oxygen-containing hydrocarbon according to claim 1, wherein the content ratio of the metal oxide and zeolite containing copper and the spinel structure is 1: 1 to 100: 1 by mass. 3. The reforming catalyst of an oxygen-containing hydrocarbon according to claim 1 or 2, wherein the metal oxide containing copper and having a spinel structure is Cu-Mn type spinel. The reforming catalyst of any one of claims 1 to 3, wherein the zeolite is ZSM-5. The oxygen-reforming hydrocarbon reforming catalyst according to any one of claims 1 to 4, comprising a metal oxide, zeolite, and alumina having a spinel structure while containing copper. The reforming catalyst for an oxygen-containing hydrocarbon according to any one of claims 1 to 5, wherein the zeolite contains a Group 8 metal and / or a rare earth element. 7. The reforming catalyst of an oxygen-containing hydrocarbon according to claim 6, wherein the Group 8 metal is at least one metal selected from Pt, Pd, lr, Rh and Ru. 7. The reforming catalyst of an oxygen-containing hydrocarbon as claimed in claim 6, wherein the Group 8 metal is at least one metal selected from Fe, Ni and Co. A reforming catalyst of an oxygen-containing hydrocarbon obtained by reducing the reforming catalyst according to any one of claims 1 to 8. The reforming catalyst of any one of claims 1 to 6, wherein the oxygen-containing hydrocarbon is at least one selected from dimethyl ether and methyl ethyl ether. The process for producing hydrogen or synthesis gas, wherein the oxygen-containing hydrocarbon is steam reformed using the reforming catalyst according to any one of claims 1 to 10. A method for producing hydrogen or synthesis gas, wherein the oxygen-containing hydrocarbon is subjected to autothermal reforming using the reforming catalyst according to any one of claims 1 to 10. A method for producing hydrogen or synthesis gas, wherein the oxygen-containing hydrocarbon is partially oxidized using the reforming catalyst according to any one of claims 1 to 10. A method for producing hydrogen or synthesis gas, wherein the oxygen-containing hydrocarbon is carbon dioxide reformed using the reforming catalyst according to any one of claims 1 to 10. A fuel cell system comprising a reformer comprising the reforming catalyst according to any one of claims 1 to 10, and a fuel cell using hydrogen produced by the reformer as a fuel.

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