JP2010058043A - Method for manufacturing steam reforming catalyst and hydrogen - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new steam reforming catalyst capable of eliminating the problems in a steam reformation of methanol, dimethyl ether or carbon monoxide, particularly a steam reforming catalyst that scarcely deteriorates an activity in catalyst and can keep a high hydrogen production velocity for a long period of time even if a reaction is performed at a high temperature, and to provide a method for manufacturing hydrogen using the catalyst. <P>SOLUTION: The steam reforming catalyst for methanol, dimethyl ether or carbon monoxide is provided, wherein each metal element of copper, zinc, and indium is contained as an oxide and further, an oxide of zirconium or aluminum or an oxide of yttrium is contained together with an oxide of zirconium. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a steam reforming catalyst for methanol, dimethyl ether or carbon monoxide and a method for producing hydrogen using the same.

  It is known that methanol is mainly converted into hydrogen and carbon dioxide by steam reforming and can be relatively easily converted into hydrogen having a low carbon monoxide content. For this reason, the methanol hydrogen reforming method is particularly expected as a means for supplying hydrogen to the polymer electrolyte fuel cell.

  Conventionally, many catalysts have been proposed as methanol steam reforming catalysts. In particular, in recent years, a catalyst composed of copper-zinc-alumina has been industrially used because it has high activity and low carbon monoxide selectivity. The reaction temperature in the steady state of such a catalyst is usually 300 ° C. or lower. This is because steam reforming is carried out at a reaction temperature of 300 ° C. or lower, so that it is not necessary to use an expensive apparatus, and a conventionally used catalyst has insufficient heat resistance (described below). (See Patent Document 1, Patent Document 2, etc.).

  For this reason, many of the catalysts that have been developed so far aim to have sufficient activity and durability at 300 ° C. or lower. Actually, the reaction activity of various catalysts is measured at 300 ° C. or less except for a special case where it is used for high-temperature steam reforming exceeding 300 ° C., and the reaction activity is measured at a higher reaction temperature. The purpose is to evaluate the durability of the catalyst.

  On the other hand, in Patent Document 3 below, as an advantage of performing methanol steam reforming under a high-temperature reaction condition exceeding 300 ° C., 300 ° C. or lower is industrially heated using a heat medium, whereas 300 It is stated that when the temperature is higher than 0 ° C., the combustion heat can be directly used and the reaction activity is improved, so that the apparatus can be made compact. Furthermore, palladium-based hydrogen separation membranes are often used in membrane reactors (membrane reactors) that simultaneously perform hydrogen separation and catalytic reaction, and a reaction temperature of 350 is used to maximize the performance of the hydrogen separation membrane. It is desirable that the temperature is higher than or equal to ° C. In addition, hydrogen production by steam reforming of dimethyl ether is known to be possible if a catalyst in which a solid acid catalyst such as alumina is mixed with a methanol steam reforming catalyst is used. A reaction temperature is usually required. In steam reforming from dimethyl ether, methanol is once formed by hydrolysis of dimethyl ether, and the formed methanol is converted to hydrogen by a steam reforming catalyst. However, a high reaction temperature is required for hydrolysis of dimethyl ether. It is because there is.

  However, it is generally known that the carbon monoxide selectivity increases as the reaction temperature increases (for example, Patent Document 2), and as a result, the amount of hydrogen produced decreases. For example, Patent Document 4 below shows the reaction temperature dependence of the hydrogen gas generation rate in methanol steam reforming, but the hydrogen gas generation rate reaches the peak when the reaction temperature exceeds 300 ° C. in any catalyst. On the other hand, the generation rate tends to decrease.

  Patent Document 5 listed below describes a catalyst obtained by adding manganese or yttrium to a compound mainly composed of copper, zinc and zirconium as a reforming catalyst for a hydrocarbon fuel. This catalyst is said to be usable for the steam reforming reaction of hydrocarbon fuels such as methanol, but there is a deterioration in activity even after the steam reforming test of methanol at 350 ° C. It is unsuitable as a catalyst.

  Thus, in steam reforming performed at a temperature exceeding 300 ° C., in addition to good heat resistance, the catalyst has low selectivity to carbon monoxide and is less likely to deteriorate in activity. Necessary. In particular, when the reaction temperature exceeds 400 ° C., the selectivity for carbon monoxide may be remarkably increased even at a catalyst having a low carbon monoxide selectivity below 300 ° C., and hydrogen supplied to the polymer electrolyte fuel cell As a result, it takes time to reduce carbon monoxide, which causes a loss of economic efficiency.

  Further, the low selectivity of carbon monoxide is important even when the reaction temperature is 300 ° C. or lower. Although it is said that the conventional catalyst has low carbon monoxide selectivity at 300 ° C. or lower, it is necessary to further reduce the carbon monoxide concentration to about 10 ppm or lower in order to supply hydrogen to the polymer electrolyte fuel cell. For this purpose, a carbon monoxide partial oxidation reactor and a PSA hydrogen purifier are installed after the methanol steam reformer to remove carbon monoxide. Therefore, if the selectivity of the carbon monoxide of the catalyst is lowered even at 300 ° C. or lower, the load on the carbon monoxide removal apparatus in the subsequent stage is reduced, leading to miniaturization of the apparatus, and a large economic advantage can be obtained.

  As described above, hydrogen can be produced by steam reforming of methanol or dimethyl ether, but it is also known that hydrogen can be produced by steam reforming of carbon monoxide. This reaction is generally referred to as a water gas shift reaction, and is used to reform a gas containing carbon monoxide at a high concentration obtained by steam reforming of hydrocarbons or the like.

The methanol steam reforming catalyst is usually also effective for steam reforming of carbon monoxide. This is understood as an elementary reaction of methanol steam reforming because there is a process in which carbon monoxide or carbon monoxide adsorbed species generated by methanol decomposition during the reaction reacts with steam to generate hydrogen. Therefore, the copper-zinc-alumina catalyst known as a catalyst for steam reforming of methanol exhibits high activity also in the water gas shift reaction. However, since the copper-zinc-alumina catalyst has low heat resistance, it is usually limited to use at 300 ° C. or lower, and an iron-chromium catalyst is used near 400 ° C. However, the iron-chromium catalyst has a drawback in that the activity is not sufficient and methane is by-produced. Furthermore, since the catalyst is different for high temperature and low temperature, there is a problem that a plurality of reactors are required.
JP-A-6-122501 Japanese Patent Laid-Open No. 7-24320 JP 2004-292202 A JP 7-265704 A JP 2001-259426 A

  The present invention has been made in view of the current state of the prior art described above, and its main purpose is for a novel steam reforming which can solve the above-mentioned problems in steam reforming of methanol, dimethyl ether or carbon monoxide. It is an object of the present invention to provide a catalyst, particularly a steam reforming catalyst that can maintain a high hydrogen production rate for a long period of time even when the reaction is carried out at a high temperature, and a method for producing hydrogen using the catalyst.

  The present inventor has intensively studied to achieve the above-described object. As a result, a catalyst containing copper, zinc and indium oxides as essential components, and further containing a zirconium or aluminum oxide in a specific amount, or a catalyst containing yttrium oxide together with a zirconium oxide, High activity for methanol or dimethyl ether steam reforming reaction, low carbon monoxide selectivity, and even when used for high temperature steam reforming for a long time, there is very little decrease in activity. It has been found that it has excellent performance as a reforming catalyst. Further, it has been found that this catalyst can produce hydrogen at a high temperature without producing methane as a by-product even when used as a steam reforming catalyst for carbon monoxide. The present invention has been completed based on these findings.

That is, the present invention provides the following steam reforming catalyst and hydrogen production method.
1. A catalyst for steam reforming of methanol, dimethyl ether or carbon monoxide containing each element of copper, zinc, indium and zirconium as an oxide.
2. When the oxide of each element of copper, zinc, indium and zirconium is copper oxide, zinc oxide, indium oxide and zirconium oxide, respectively, the content of copper oxide is 10 based on the total amount of these oxides. ~ 55 wt%, zinc oxide content 0.5-2 times copper oxide content, indium oxide content 0.5-15 wt% and zirconium oxide content 5-70 wt% Item 2. A catalyst for steam reforming of methanol, dimethyl ether or carbon monoxide according to Item 1 above.
3. A catalyst for steam reforming of methanol, dimethyl ether or carbon monoxide containing each element of copper, zinc, indium, zirconium and yttrium as an oxide.
4). When the oxide of each element of copper, zinc, indium, zirconium and yttrium is copper oxide, zinc oxide, indium oxide, zirconium oxide and yttrium oxide, respectively, based on the total amount of these oxides, copper oxide Content of 10 to 55% by weight, zinc oxide content of 0.5 to 2 times that of copper oxide, indium oxide content of 0.5 to 15% by weight, and zirconium oxide and yttrium oxide The water vapor of methanol, dimethyl ether or carbon monoxide according to item 3, wherein the total content is 5 to 70% by weight and Y / (Zr + Y) (molar fraction) is 0.01 to 0.9. Catalyst for reforming.
5). A catalyst for steam reforming of methanol, dimethyl ether or carbon monoxide containing each element of copper, zinc, indium and aluminum as an oxide.
6). When the oxide of each element of copper, zinc, indium and aluminum is copper oxide, zinc oxide, indium oxide and aluminum oxide, respectively, the content of copper oxide is 10 based on the total amount of these oxides. ~ 55 wt%, zinc oxide content 0.5-2 times copper oxide content, indium oxide content 0.5-15 wt%, and aluminum oxide content 5-70 wt% Item 6. The catalyst for steam reforming of methanol, dimethyl ether or carbon monoxide according to Item 5 above.
7). Item 3. The water vapor according to Item 1 or 2, wherein an alkaline precipitant is added to an aqueous solution containing a copper compound, a zinc compound, an indium compound, and a zirconium compound to precipitate the mixture, and then the formed precipitate is fired. A method for producing a reforming catalyst.
8). Item 3 or 4 above, wherein an alkaline precipitant is added to an aqueous solution containing a copper compound, a zinc compound, an indium compound, a zirconium compound and an yttrium compound to precipitate the mixture, and then the formed precipitate is baked. The manufacturing method of the catalyst for steam reforming of description.
9. Item 7. The water vapor according to Item 5 or 6, wherein an alkaline precipitant is added to an aqueous solution containing a copper compound, a zinc compound, an indium compound and an aluminum compound to precipitate the mixture, and then the formed precipitate is fired. A method for producing a reforming catalyst.
10. A method for producing hydrogen, comprising reacting a raw material gas containing methanol, dimethyl ether or carbon monoxide with water vapor in the presence of the catalyst according to any one of the above items 1 to 6.

  Hereinafter, the steam reforming catalyst of the present invention will be described in detail.

Steam reforming catalyst The steam reforming catalyst of the present invention contains each element of copper, zinc, and indium as an oxide, and further contains zirconium or aluminum as an oxide. Furthermore, an oxide of yttrium can be included together with an oxide of zirconium.

  Each oxide contained in the catalyst of the present invention may be an oxide containing only one kind of the above-described elements, or may be a complex oxide containing two or more kinds of elements. Good. In the case of a complex oxide, the combination of elements is arbitrary.

(1) Invention catalyst 1
Hereinafter, first, a catalyst containing each element of copper, zinc, indium and zirconium as an oxide (hereinafter referred to as “the catalyst 1 of the present invention”) will be described.

  Regarding copper and zinc oxides, it is known that catalysts containing these mixtures (copper-zinc catalysts) are active in methanol steam reforming and carbon monoxide steam reforming at 300 ° C. or lower. .

  It is known that the copper oxide functions as a main catalyst and is reduced during the reaction and is present in the catalyst as metallic copper or cuprous oxide.

  With respect to zinc oxide, it is recognized that there is a reaction promoting effect because high reaction activity cannot be obtained without it. Zinc is usually present primarily as zinc oxide.

In the catalyst 1 of the present invention, each element of copper, zinc, indium and zirconium can exist as an oxide containing only one kind of element or a composite oxide containing two or more kinds of elements. In the catalyst 1 of the present invention, the ratio of each oxide is determined based on the analysis result of the content of each metal element of copper, zinc, indium, and zirconium, and each metal element contains copper oxide (CuO), zinc oxide ( Included as ZnO), indium oxide (In ₂ O ₃ ) and zirconium oxide (ZrO ₂ ), copper oxide (CuO), zinc oxide (ZnO), indium oxide (In ₂ O ₃ ) and zirconium oxide (ZrO ₂ ) It is shown as the content ratio of each oxide when the total amount is 100% by weight.

  First, the content of copper is preferably about 10 to 55% by weight as the content of copper oxide (CuO), with the total amount of each oxide described above being 100% by weight, and about 15 to 50% by weight. It is more preferable that

  If the copper content is less than the above range, sufficient activity cannot be obtained for steam reforming, and if it is too much, it will cause a decrease in activity due to sintering, and it is long for steam reforming at high temperatures. Since it cannot be used for a period, neither is preferable. Copper in the present catalyst exists mainly as copper oxide, but when used as a steam reforming catalyst, copper oxide is mainly reduced to metallic copper during the reaction.

  The zinc content is preferably about 0.5 to 2 times the content of copper oxide (CuO), and about 0.7 to 1.5 times as the content of zinc oxide (ZnO). Is more preferable.

  In either case where the zinc content is too much or too little than the above range, it is not preferable because sufficient activity and selectivity cannot be obtained. In the present catalyst, zinc exists mainly as zinc oxide.

The content of indium is preferably about 0.5 to 15% by weight as the amount of indium oxide (In ₂ O ₃ ), with the total amount of each oxide described above being 100% by weight, and preferably 1 to 10% by weight. More preferably, it is about%.

  When the content of indium is less than the above range, the effect of sufficiently reducing carbon monoxide selectivity cannot be obtained, and the effect of stabilizing the catalytic activity is also impaired. When the content is too much above the above range, the catalytic activity is lowered.

  Indium is known to form a complex oxide with zinc, and is considered to exist as a complex oxide of indium oxide and / or indium / zinc in the catalyst. The abundance ratio of these oxides and composite oxides varies depending on the catalyst composition, catalyst preparation method, catalyst heat treatment temperature / time, etc., but usually exists mainly as indium oxide.

  Zirconium has an effect of stabilizing the form of the catalyst mainly by appropriately dispersing copper oxide and zinc oxide.

The content of zirconium is preferably about 5 to 70% by weight, and about 7 to 50% by weight as the amount of zirconium oxide (ZrO ₂ ), with the total amount of each oxide described above being 100% by weight. It is more preferable.

  If the zirconium content is low, the dispersing effect is lost, and if it is too high, the catalytic activity is lowered, which is not preferable.

  Zirconium is known to form a complex oxide with indium, and is considered to exist as a complex oxide of zirconium oxide and / or zirconium-indium in the catalyst. The abundance ratio of these oxides and composite oxides varies depending on the catalyst composition, catalyst preparation method, catalyst heat treatment temperature and time, etc., but usually exists mainly as zirconium oxide.

(2) Invention catalyst 2
The catalyst of the present invention can contain an yttrium oxide in addition to the oxides of the catalyst 1 of the present invention. Hereinafter, this catalyst is referred to as catalyst 2 of the present invention.

Also in the catalyst 2 of the present invention, each metal element can exist as an oxide containing only one kind of element or a complex oxide containing two or more kinds of elements. About the content rate of each oxide in this invention catalyst 2, based on the analysis result of content about each metal element of copper, zinc, indium, zirconium, and yttrium, each metal element is copper oxide (CuO), oxidation Included as zinc (ZnO), indium oxide (In ₂ O ₃ ), zirconium oxide (ZrO ₂ ) and yttrium oxide (Y ₂ O ₃ ), copper oxide (CuO), zinc oxide (ZnO), indium oxide (In ₂ O ₃ ), zirconium oxide (ZrO ₂ ) and yttrium oxide (Y ₂ O ₃ ) are shown as the content of each oxide when the total amount is 100% by weight.

  In the catalyst 2 of the present invention, as in the catalyst 1 of the present invention, the content of copper oxide is about 10 to 55% by weight, the content of zinc oxide is about 0.5 to 2 times the content of copper oxide, and indium oxide The content is preferably about 0.5 to 15% by weight.

Regarding zirconium and yttrium, the total content of zirconium oxide (ZrO ₂ ) and yttrium oxide (Y ₂ O ₃ ) is about 5 to 70% by weight, and Y / (Zr + Y) (molar fraction) is 0.00. The total amount of zirconium oxide (ZrO ₂ ) and yttrium oxide (Y ₂ O ₃ ) is preferably about 7 to 50% by weight, and Y / (Zr + Y) (molar fraction). Is more preferably about 0.02 to 0.7.

  When the total amount of zirconium and yttrium is small, the dispersing effect is lost, and when the total amount is too large, the catalytic activity is lowered. In addition, the catalytic activity tends to improve with an increase in the molar ratio of Y / (Zr + Y), but at the same time, the carbon monoxide selectivity increases. Therefore, if the molar ratio of Y / (Zr + Y) is too large, the carbon monoxide selectivity becomes too large, which is not preferable.

  Zirconium and yttrium are known to form complex oxides, and it is also known to form complex oxides with zirconium, yttrium, and indium. Accordingly, it is considered that zirconium and yttrium are present in the form of zirconium oxide, indium oxide, zirconium-yttrium composite oxide, zirconium-yttrium-indium composite oxide, and the like. The abundance ratio of these oxides and composite oxides varies depending on the catalyst composition, catalyst preparation method, catalyst heat treatment temperature and time, etc., but usually exists mainly as a composite oxide of zirconium and yttrium.

(3) Invention catalyst 3
Next, a catalyst containing each metal element of copper, zinc, indium and aluminum as an oxide (hereinafter referred to as “the catalyst 3 of the present invention”) will be described.

Also in the catalyst 3 of the present invention, each element can exist as an oxide containing only one kind of element or a composite oxide containing two or more kinds of elements. About the content rate of each oxide in this invention catalyst 3, based on the analysis result of content about each metal element of copper, zinc, indium, and aluminum, each metal element is copper oxide (CuO), zinc oxide ( As included as ZnO), indium oxide (In ₂ O ₃ ) and aluminum oxide (Al ₂ O ₃ ), copper oxide (CuO), zinc oxide (ZnO), indium oxide (In ₂ O ₃ ) and aluminum oxide (Al _It shows as a content rate of each oxide when the total amount of ₂ O ₃ ) is 100% by weight.

In the catalyst 3 of the present invention, the contents of copper oxide (CuO), zinc oxide (ZnO), and indium oxide (In ₂ O ₃ ) may be the same as those of the catalyst 1 of the present invention.

The content of aluminum is preferably about 5 to 70% by weight, and about 7 to 50% by weight as the amount of aluminum oxide (Al ₂ O ₃ ), with the total amount of the above oxides being 100% by weight. It is more preferable that

  When the aluminum content is less than the above range, the dispersing effect is lost, and when it is too much, the catalytic activity is lowered, which is not preferable.

  Aluminum is known to form a composite oxide with copper and / or zinc, and in the catalyst 3 of the present invention, it is considered to exist as aluminum oxide, a composite oxide of aluminum / copper, a composite oxide of aluminum / zinc, or the like. It is done. The abundance ratio of these oxides and composite oxides varies depending on the catalyst composition, catalyst preparation method, catalyst heat treatment temperature and time, etc., but usually exists mainly as aluminum oxide.

  The catalysts 1 to 3 of the present invention may be a mixture of the above-described oxides containing each metal element, and may contain other components as necessary as long as the performance of the catalyst of the present invention is not adversely affected. .

  The form of the catalyst of the present invention can be any form such as fine powder, powder, fragments, granules, pellets, and honeycombs. For example, a fine powder can be about 100 to 200 mesh, a powder can be about 20 to 100 mesh, and a fragment can be about 5 to 20 mesh. As the granular form, those having an average particle diameter of about 0.5 to 7 mm can be used, and as the pellet form, those having an average particle diameter of about 1 to 10 mm can be used.

  The catalysts 1 to 3 of the present invention may be used while being supported on an arbitrary carrier. In particular, when the inorganic fiber body is used with the catalyst of the present invention, the moldability of the catalyst, the gas diffusibility to the catalyst, and the like are improved. As an inorganic fiber body, what consists of glass fiber, a ceramic fiber, metal fiber, etc., and can be used for a nonwoven fabric, felt shape, and cotton shape can be used, and it is preferable that the porosity is 50% or more, 70% More preferably. The amount of the catalyst of the present invention held in the inorganic fiber body is preferably about 40 to 80% by weight based on the total amount of the inorganic fiber body and the catalyst of the present invention.

Method for Producing Steam Reforming Catalyst The catalyst of the present invention is not particularly limited as long as it contains an oxide containing each of the above elements as an active ingredient. For example, the coprecipitation method is not particularly limited. In addition, a catalyst production method such as an impregnation method, a precipitation method, or a sol-gel method can be used. In particular, in the case of producing by the coprecipitation method, it is possible to obtain a catalyst capable of exhibiting high catalytic activity while greatly dispersing the by-products of carbon monoxide while the components are uniformly dispersed to enhance the interaction. . Hereinafter, the manufacturing method by a coprecipitation method is demonstrated concretely.

  First, a raw material selected from a copper compound, a zinc compound, an indium compound, a zirconium compound, an yttrium compound and an aluminum compound is dissolved in water according to the type of metal element contained in the target catalyst, and a mixed aqueous solution is prepared. Prepare.

  Each raw material compound should just have sufficient solubility for producing the aqueous solution of a predetermined density | concentration. For example, copper nitrate, copper chloride, copper sulfate, copper acetate, etc. can be used as the copper compound. These can be used alone or in combination of two or more. As the zinc compound, for example, zinc nitrate, zinc chloride, zinc sulfate, zinc acetate and the like can be used. These can be used alone or in combination of two or more. As the indium compound, indium nitrate, indium chloride, indium sulfate, indium acetate, or the like can be used. These can be used alone or in combination of two or more. As the zirconium compound, for example, zirconyl nitrate, zirconium sulfate, zirconium oxychloride and the like can be used. These can be used alone or in combination of two or more. As the aluminum compound, aluminum acetate, aluminum chloride, aluminum sulfate, aluminum acetate or the like can be used. These can be used alone or in combination of two or more. As the yttrium compound, for example, yttrium nitrate, yttrium chloride, yttrium acetate, or the like can be used. These can be used alone or in combination of two or more.

  The concentration ratio of each raw material compound in the mixed aqueous solution may be a metal component ratio similar to the ratio of the metal component in the target catalyst. The total concentration of the raw material compounds is preferably about 0.1 to 5 mol / L, more preferably about 0.3 to 3 mol / L.

  Next, an alkali precipitant is added to the aqueous solution containing each of the raw material compounds described above to precipitate the mixed hydroxide that becomes the catalyst precursor. As the alkaline precipitant, for example, sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium carbonate, potassium hydrogen carbonate, potassium hydroxide, ammonium carbonate, ammonium hydrogen carbonate, ammonia and the like can be used. Usually, these alkali precipitants may be added as they are, but it is preferable to add them as an aqueous solution.

  The amount of the alkali precipitant relative to the raw material compound may be about 1 to 2 times, preferably about 1.05 to 1.6 times the chemical equivalent. The temperature during the preparation of the precipitate is preferably about 20 to 95 ° C, more preferably about 40 to 90 ° C.

  The catalyst precursor prepared as described above can be used as the target catalyst of the present invention by washing, drying, and calcining.

  The drying temperature may be about 50 to 150 ° C. The firing temperature may be about 300 to 900 ° C, preferably about 400 to 800 ° C.

  The firing time may be appropriately set according to the firing temperature and the like, and may usually be about 1 to 24 hours. The firing may be performed in an oxidizing atmosphere such as in the air.

  When the catalyst of the present invention is produced, the catalyst of any form can be obtained by performing pulverization, molding or the like as necessary.

  For example, as a method for processing into a fine powder form and a powder form, a method of pulverizing using a jet mill, a bead mill or the like and then sieving it can be mentioned.

  Examples of the method for processing into pieces include a method of crushing using a crusher.

  As a method for processing into granules, for example, various known methods such as spray drying, rolling granulation, fluidized bed granulation, etc. are applied to fine powder or powdery dry powder or calcined powder. Is mentioned.

  Examples of the method for processing into a pellet include a method of press-compressing a fine powder or a powdered dry powder or fired powder.

  Further, water or the like can be added to the precursor slurry, dried powder, or fired powder to form a slurry or paste, which can be supported on a carrier or a carrier structure, or applied and adhered. In this case, after carrying, it can be dried and used as it is or after firing. In particular, it is preferable to use an inorganic fiber as the carrier structure. In this case, the catalyst component is supported, and after drying or firing, compression molding may be performed by pressing, and then firing may be performed.

Method for producing a hydrogen following describes a method for producing hydrogen using steam reforming catalyst of the present invention.

(1) Steam reforming reaction of methanol or dimethyl ether First, a steam reforming method of methanol or dimethyl ether will be described. In this method, by reacting methanol or dimethyl ether with steam in the presence of the steam reforming catalyst of the present invention, hydrogen and carbon dioxide can be obtained while significantly suppressing carbon monoxide by-product. . In this method, the raw material is not limited to either methanol or dimethyl ether, and may contain methanol and dimethyl ether at the same time.

  The method of reacting methanol or dimethyl ether with steam is not particularly limited, and a method according to a known steam reforming method can be applied. For example, methanol or dimethyl ether and water vapor can be gas phase reacted with methanol or dimethyl ether and water vapor by continuously contacting the catalyst of the present invention.

  The catalyst of the present invention can be used alone. However, when dimethyl ether is contained in the reaction gas, the catalyst of the present invention is added to alumina in order to improve the efficiency of methanol production by hydrolysis of dimethyl ether. It is preferable to mix an acid catalyst such as zeolite or activated clay. The mixing amount of the acid catalyst is preferably about 0.5 to 10 times that of the catalyst of the present invention by weight.

  The ratio of each component in the mixed gas of methanol or dimethyl ether and water vapor is not particularly limited. For example, when methanol and water vapor are reacted, the molar ratio of methanol: water vapor is usually about 1: 1 to 3. Preferably, about 1: 1.1-2 is more preferable. In a conventional methanol steam reforming catalyst, a molar ratio of methanol and steam of 1.5 or more is usually employed. This is because when the molar ratio is 1.5 or less, the activity of the catalyst is significantly deteriorated and by-products are increased. In the case of the catalyst of the present invention, even a molar ratio of 1.5 or less can be used without any problem.

  Moreover, when making dimethyl ether and water vapor | steam react, it is preferable that the molar ratio of dimethyl ether: water vapor | steam is normally about 1: 3-9, and it is more preferable that it is about 1: 3.2-7.

  The gas mixture of methanol or dimethyl ether and steam may contain other gas components as long as the steam reforming of methanol and dimethyl ether is not disturbed. Examples of other gas components include oxygen, air, and nitrogen. In the method for producing hydrogen according to the present invention, water is one of the reactants, so the methanol used may contain water in advance.

  When the mixed gas contains oxygen and / or air, an oxidation reaction easily occurs simultaneously with the reforming of methanol or dimethyl ether, and the reaction heat necessary for the methanol reforming can be supplied by the oxidation reaction. The ratio of oxygen to methanol is usually preferably about 0.25 mol or less, more preferably about 0.05 to 0.15 mol, relative to 1 mol of methanol. In addition, the ratio of oxygen to dimethyl ether is usually preferably about 0.5 mol mol or less, more preferably about 0.1 to 0.2 mol, relative to 1 mol of dimethyl ether.

  The reaction between methanol and water vapor can be performed at a temperature of about 150 ° C. or higher, as in the case of using a conventional catalyst. Further, the reaction between dimethyl ether and water vapor can be carried out at a temperature of about 300 ° C. or higher as in the case of using a conventional catalyst. In these cases, an effect that carbon monoxide by-product is smaller than that of the conventional catalyst can be obtained.

  In particular, the catalyst of the present invention has excellent characteristics that it can maintain a high activity for a long period in a steam reforming reaction at a high temperature and has a low carbon monoxide selectivity. In order to advance the steam reforming at a high speed without impairing the hydrogen yield by utilizing such excellent characteristics, it is preferable to perform the steam reforming at a high temperature. For example, the temperature at which the reaction is constantly performed is preferably about 350 to 550 ° C. If the reaction temperature is below this range, a high hydrogen production rate that is an advantage of high-temperature steam reforming cannot be obtained, and if the reaction temperature is too high, the amount of carbon monoxide by-product tends to increase, which is preferable. Absent. Furthermore, by setting it as the said temperature range, when using dimethyl ether as a reaction gas, the methanol production | generation by hydrolysis of dimethyl ether can be accelerated | stimulated.

  About the pressure at the time of reaction, the partial pressure of the produced | generated hydrogen can be raised by setting it high. Usually, the reaction pressure is preferably about 0.05 MPa to 3 MPa, preferably about 0.1 MPa to 1 MPa.

  The supply rate of the mixed gas containing methanol or dimethyl ether and water vapor is not particularly limited, and can be appropriately selected according to the size, shape, shape of the catalyst, reaction temperature, reaction pressure, and the like of the reactor. Usually, when the reaction gas is methanol, the gas phase methanol supply rate in the standard state is preferably about 0.5 to 100 L / h, and about 1 to 70 L / h per 1 g of the catalyst. More preferred. When the reaction gas is dimethyl ether, the gas phase dimethyl ether supply rate is preferably about 0.5 to 20 L / h, more preferably about 1 to 10 L / h, per 1 g of catalyst.

(2) steam reforming of carbon monoxide reaction is then in the presence of a steam reforming catalyst of the present invention will be described hydrogen production method by reacting carbon monoxide with steam. In this method, by using the catalyst of the present invention, hydrogen and carbon dioxide can be obtained while significantly suppressing the by-product of methane even at high temperatures.

  A method for reacting carbon monoxide with steam is not particularly limited, and a method according to a known steam reforming method can be applied. For example, a mixed gas containing hydrocarbons such as carbon monoxide, water vapor, hydrogen, carbon dioxide, methane, etc. obtained by reforming hydrocarbons derived from coal, petroleum, natural gas, etc. is continuously added to the catalyst of the present invention. By contacting, carbon monoxide can be selectively converted into hydrogen and carbon dioxide.

  Although the ratio of each component in the mixed gas containing carbon monoxide and water vapor is not particularly limited, in order to efficiently convert carbon monoxide into hydrogen, for example, the molar ratio of carbon monoxide: water vapor is 1: About 1-50 is preferable and about 1: 2-10 is more preferable.

  The concentration of carbon monoxide when contacting the catalyst of the present invention is not particularly limited. For example, it is about 1 to 30 vol% for the purpose of hydrogen production, and about 10 ppm to 1 vol% for the purpose of removing carbon monoxide. Is preferable, and it is more preferable that it is about 10 ppm-1000 ppm. In this reaction, the flow rate of the gas containing carbon monoxide can be appropriately selected according to the concentration of carbon monoxide, and is preferably about 2 to 500 L / h, and about 5 to 100 L / h per gram of catalyst. More preferably.

  An inert gas such as nitrogen may be present as another gas component. Moreover, about 10 vol% or less of oxygen with respect to carbon monoxide and about 50 vol% or less of air with respect to carbon monoxide may exist.

  The reaction pressure in the steam reforming reaction of carbon monoxide is not particularly limited, and can be, for example, a pressure range of about normal pressure to 5 MPa.

  In the case of performing the steam reforming reaction using the catalyst of the present invention, it may be reduced with a reducing gas such as hydrogen in advance before the reaction, but the reduction before the reaction is not essential, and the catalyst is left as it is. Can be used. In this case, the catalyst is reduced during the reaction to be in a state suitable for the reaction. For this reason, even if a catalyst is placed in a reactor that frequently starts and stops, it is not necessary to always keep the catalyst in a reduced state, which is a great advantage.

  A hydrogen-containing gas containing less carbon monoxide is obtained by the steam reforming reaction of methanol or dimethyl ether or the steam reforming reaction of carbon monoxide.

  If necessary, carbon monoxide may be further removed from the product gas by using carbon monoxide removing means. As the carbon monoxide removal means, for example, a method in which carbon monoxide is separated from the product gas by a hydrogen PSA method, a method in which carbon monoxide is separated from the product gas by a hydrogen separation membrane, and carbon monoxide in the gas is selectively oxidized. And a method of converting carbon monoxide in the gas into methane.

  The steam reforming catalyst of the present invention can significantly suppress carbon monoxide by-product while exhibiting high catalytic activity in steam reforming of methanol and / or dimethyl ether. Further, even when the reaction is carried out at a high temperature of 300 ° C. or higher, there is little decrease in activity, and a high hydrogen production rate can be maintained for a long time. Therefore, by using the catalyst of the present invention and performing steam reforming at a high temperature in particular, hydrogen production can be performed at high speed without impairing the hydrogen yield, and the apparatus can be miniaturized.

  In addition, the catalyst of the present invention has little decrease in activity even in the case of steam reforming of carbon monoxide even when the reaction is performed at a high temperature of 300 ° C. or higher, and can suppress the by-product of methane. For this reason, hydrogen yield improves compared with the past, and reaction efficiency also improves.

  Examples and comparative examples will be shown below to further clarify the features of the present invention. However, the present invention is not limited to these examples and comparative examples.

  In addition, the methanol conversion rate and carbon monoxide selectivity described later are values determined by composition analysis of the reactor outlet gas by gas chromatography. The carbon monoxide selectivity is the number of moles of carbon monoxide produced divided by the sum of the number of moles of carbon dioxide produced and the number of moles of carbon monoxide.

  In the following examples and comparative examples, argon gas is included in the reaction gas, but it is merely for facilitating the experiment and is not necessarily required in actual implementation.

Example 1
Production of steam reforming catalyst Copper nitrate, zinc nitrate, indium nitrate and zirconyl nitrate were dissolved in distilled water so that the molar ratio was 1.0: 0.78: 0.05: 0.64, and the total The concentration was 0.5 mol / L.

  The obtained aqueous solution containing a metal salt is heated to 80 ° C., and a 1N sodium carbonate aqueous solution at 80 ° C. in an amount that is 1.2 times equivalent to the total number of equivalents of metal elements in the metal salt-containing aqueous solution. Was added and stirred to obtain a hydroxide precipitate.

  The obtained precipitate was washed with distilled water, dried at 120 ° C. for 15 hours, and subsequently heated in air at 500 ° C. for 12 hours to obtain a steam reforming catalyst. The obtained catalyst was crushed to obtain a 40-100 mesh powder.

  The obtained catalyst is based on the amount of each metal element of copper, zinc, indium and zirconium contained in the catalyst, converted to the weight when these are made into oxides, and based on the total amount, copper oxide 34.9% by weight, zinc oxide 27.9% by weight, indium oxide 2.8% by weight and zirconium oxide 34.4% by weight.

Production of hydrogen After the catalyst obtained by the above-described method was charged into a reactor of a fixed bed flow type reactor, a reaction gas composed of methanol, water vapor and argon (volume ratio: methanol: water vapor: argon = 1: 1.2: 0. The catalyst was reduced by feeding 51) to the reactor at 250 ° C. for 1 hour at a methanol feed rate of 52.5 L / g (catalyst) · h.

  After the reduction, the reactor was heated to 500 ° C. to start a steam reforming reaction of methanol, and the methanol was mainly converted into hydrogen and carbon dioxide. 1 hour after the start of the reaction, the methanol conversion was 85% and the carbon monoxide selectivity was 5.3%. After 6 hours from the start of the reaction, the methanol conversion was 85% and the carbon monoxide selectivity was 4.3%. In addition, it was confirmed that good activity could be maintained for a long time even at a high temperature and the carbon monoxide selectivity was low.

Example 2
Production of steam reforming catalyst Copper nitrate, zinc nitrate, indium nitrate, zirconyl nitrate and yttrium nitrate are distilled water at a molar ratio of 1.0: 0.78: 0.05: 0.62: 0.02. Except for being dissolved in, a steam reforming catalyst was obtained in the same manner as in Example 1 and then crushed to obtain a powder of 40 to 100 mesh.

  Based on the amount of each metal element of copper, zinc, indium, zirconium and yttrium contained in the catalyst, the obtained catalyst is converted to the weight when these are oxides, and based on the total amount, It contained 34.9% by weight of copper oxide, 27.9% by weight of zinc oxide, 2.8% by weight of indium oxide, 33.5% by weight of zirconium oxide, and 0.9% by weight of yttrium oxide.

Production of hydrogen After the catalyst obtained by the above-described method was charged into a reactor of a fixed bed flow type reactor, a mixed gas consisting of methanol, water vapor and argon was supplied under the same conditions as in Example 1, and the supplied methanol Was converted primarily to hydrogen and carbon dioxide. 1 hour after the start of the reaction, the methanol conversion was 89% and the carbon monoxide selectivity was 7.0%. After 6 hours from the start of the reaction, the methanol conversion was 88% and the carbon monoxide selectivity was 5.3%. In addition, it was confirmed that good activity could be maintained for a long time even at a high temperature and the carbon monoxide selectivity was low.

Example 3
Production of steam reforming catalyst Distilled water of copper nitrate, zinc nitrate, indium nitrate, zirconyl nitrate and yttrium nitrate in a molar ratio of 1.0: 1.04: 0.05: 0.43: 0.04 Except for being dissolved in, a steam reforming catalyst was obtained in the same manner as in Example 1 and then crushed to obtain a powder of 40 to 100 mesh.

  Based on the amount of each metal element of copper, zinc, indium, zirconium and yttrium contained in the catalyst, the obtained catalyst is converted to the weight when these are oxides, and based on the total amount, It contained 34.9% by weight of copper oxide, 37.2% by weight of zinc oxide, 2.8% by weight of indium oxide, 23.2% by weight of zirconium oxide, and 1.9% by weight of yttrium oxide.

Production of hydrogen After the catalyst obtained by the above-described method was charged into a reactor of a fixed bed flow type reactor, a mixed gas consisting of methanol, water vapor and argon was supplied under the same conditions as in Example 1, and the supplied methanol Was converted primarily to hydrogen and carbon dioxide. 1 hour after the start of the reaction, the methanol conversion was 89% and the carbon monoxide selectivity was 6.2%. After 6 hours from the start of the reaction, the methanol conversion was 89% and the carbon monoxide selectivity was 5.1%. In addition, it was confirmed that good activity could be maintained for a long time even at a high temperature and the carbon monoxide selectivity was low.

Example 4
Production of steam reforming catalyst Copper nitrate, zinc nitrate, indium nitrate, zirconyl nitrate and yttrium nitrate are distilled water so that the molar ratio is 1.0: 1.17: 0.07: 1.06: 0.17. Except for being dissolved in, a steam reforming catalyst was obtained in the same manner as in Example 1 and then crushed to obtain a powder of 40 to 100 mesh.

  Based on the amount of each metal element of copper, zinc, indium, zirconium and yttrium contained in the catalyst, the obtained catalyst is converted to the weight when these are oxides, and based on the total amount, It contained 23.8% by weight of copper oxide, 28.6% by weight of zinc oxide, 2.9% by weight of indium oxide, 39.0% by weight of zirconium oxide, and 5.7% by weight of yttrium oxide.

Production of hydrogen After the catalyst obtained by the above-described method was charged into a reactor of a fixed bed flow type reactor, a mixed gas consisting of methanol, water vapor and argon was supplied under the same conditions as in Example 1, and the supplied methanol Was converted primarily to hydrogen and carbon dioxide. One hour after the start of the reaction, the methanol conversion was 76% and the carbon monoxide selectivity was 7.9%. After 6 hours from the start of the reaction, the methanol conversion was 76% and the carbon monoxide selectivity was 6.5%. In addition, it was confirmed that good activity could be maintained for a long time even at a high temperature and the carbon monoxide selectivity was low.

Example 5
Manufacture of steam reforming catalyst Except for dissolving copper nitrate, zinc nitrate, indium nitrate, and zirconyl nitrate in distilled water so that the molar ratio is 1.0: 0.78: 0.03: 0.22. The steam reforming catalyst was obtained by operating in the same manner as in Example 1 and then crushed to obtain a 40-100 mesh powder.

  The obtained catalyst is based on the amount of each metal element of copper, zinc, indium and zirconium contained in the catalyst, converted to the weight when these are made into oxides, and based on the total amount, copper oxide 45.5 wt%, zinc oxide 36.3% wt, indium oxide 2.7 wt%, and zirconium oxide 15.5 wt%.

Production of hydrogen After the catalyst obtained by the above-described method was charged into a reactor of a fixed bed flow type reactor, a reaction gas composed of methanol, water vapor and argon (volume ratio methanol: water vapor: argon = 1: 1.2: 0). .9) was fed to the reactor at 250 ° C. for 1 hour at a methanol feed rate of 6.6 L / g (catalyst) · h.

  After the reduction, the reactor was heated to 300 ° C. to start a steam reforming reaction of methanol, and the methanol was mainly converted into hydrogen and carbon dioxide. One hour after the start of the reaction, the methanol conversion was 86% and the carbon monoxide selectivity was 1.5%. After 5 hours from the start of the reaction, the methanol conversion was 84% and the carbon monoxide selectivity was 1.3%. It was confirmed that good activity could be maintained for a long time and the carbon monoxide selectivity was low.

Example 6
Production of steam reforming catalyst Except for dissolving copper nitrate, zinc nitrate, indium nitrate and aluminum nitrate in distilled water so that the molar ratio is 1.0: 0.78: 0.08: 1.45, A steam reforming catalyst was obtained by operating in the same manner as in Example 1, and then crushed to obtain a powder of 40 to 100 mesh.

  The obtained catalyst is converted into the weight when these are converted into oxides based on the amount of each metal element of copper, zinc, indium and aluminum contained in the catalyst, and based on the total amount, copper oxide 34.9% by weight, zinc oxide 27.9% by weight, indium oxide 4.6% by weight, and aluminum oxide 32.6% by weight.

Production of hydrogen After the catalyst obtained by the above-described method was charged into a reactor of a fixed bed flow type reactor, a mixed gas consisting of methanol, water vapor and argon was supplied under the same conditions as in Example 5, and the supplied methanol Was converted primarily to hydrogen and carbon dioxide. 1 hour after the start of the reaction, the methanol conversion was 94%, and the carbon monoxide selectivity was 3.7%. After 5 hours from the start of the reaction, the methanol conversion was 96%, and the carbon monoxide selectivity was 3.1%. It was confirmed that good activity could be maintained for a long time and the carbon monoxide selectivity was low.

Example 7
Production of steam reforming catalyst Except for dissolving copper nitrate, zinc nitrate, indium nitrate and aluminum nitrate in distilled water so that the molar ratio is 1.0: 0.78: 0.03: 0.53, A steam reforming catalyst was obtained by operating in the same manner as in Example 1, and then crushed to obtain a powder of 40 to 100 mesh.

  The obtained catalyst is converted into the weight when these are converted into oxides based on the amount of each metal element of copper, zinc, indium and aluminum contained in the catalyst, and based on the total amount, copper oxide 45.5 wt%, zinc oxide 36.3% wt, indium oxide 2.7 wt%, and aluminum oxide 15.5 wt%.

Production of hydrogen After the catalyst obtained by the above-described method was charged into a reactor of a fixed bed flow type reactor, a mixed gas consisting of methanol, water vapor and argon was supplied under the same conditions as in Example 5, and the supplied methanol Was converted primarily to hydrogen and carbon dioxide. One hour after the start of the reaction, the methanol conversion was 100%, and the carbon monoxide selectivity was 5.0%. After 5 hours from the start of the reaction, the methanol conversion was 100%, and the carbon monoxide selectivity was 4.4%. It was confirmed that good activity could be maintained for a long time and the carbon monoxide selectivity was low.

Example 8
Production of steam reforming catalyst Except for dissolving copper nitrate, zinc nitrate, indium nitrate and aluminum nitrate in distilled water so that the molar ratio is 1.0: 0.78: 0.11: 0.31, A steam reforming catalyst was obtained by operating in the same manner as in Example 1, and then crushed to obtain a powder of 40 to 100 mesh.

  The obtained catalyst is converted into the weight when these are converted into oxides based on the amount of each metal element of copper, zinc, indium and aluminum contained in the catalyst, and based on the total amount, copper oxide 45.5% by weight, zinc oxide 36.3% by weight, indium oxide 9.1% by weight, and aluminum oxide 9.1% by weight.

Production of hydrogen After the catalyst obtained by the above-described method was charged into a reactor of a fixed bed flow type reactor, a mixed gas consisting of methanol, water vapor and argon was supplied under the same conditions as in Example 5, and the supplied methanol Was converted primarily to hydrogen and carbon dioxide. 1 hour after the start of the reaction, the methanol conversion was 98% and the carbon monoxide selectivity was 3.4%. After 5 hours from the start of the reaction, the methanol conversion was 96% and the carbon monoxide selectivity was 2.3%. It was confirmed that good activity could be maintained for a long time and the carbon monoxide selectivity was low.

Example 9
Manufacture of steam reforming catalyst Distilled water of copper nitrate, zinc nitrate, indium nitrate, zirconyl nitrate and yttrium nitrate in a molar ratio of 1.0: 1.04: 0.05: 0.36: 0.11 Except for being dissolved in, a steam reforming catalyst was obtained in the same manner as in Example 1 and then crushed to obtain a powder of 40 to 100 mesh.

  Based on the amount of each metal element of copper, zinc, indium, zirconium and yttrium contained in the catalyst, the obtained catalyst is converted to the weight when these are oxides, and based on the total amount, It contained 34.9% by weight of copper oxide, 37.2% by weight of zinc oxide, 2.8% by weight of indium oxide, 19.5% by weight of zirconium oxide and 5.6% by weight of yttrium oxide.

Production of hydrogen After crushing the catalyst obtained by the above-mentioned method, it is mixed with 2 times weight of γ-alumina (Sumitomo Chemical Co., Ltd., AKP-G015). The reactor was charged into a reactor of a fixed bed flow type reactor, and reduced by supplying a mixed gas of hydrogen and argon (hydrogen, 10 vol%) to the reactor at 250 ° C. for 1 hour.

  Subsequently, the temperature of the reactor was raised to 400 ° C. and a reaction gas composed of dimethyl ether, water vapor and argon (volume ratio, dimethyl ether: water vapor: argon = 1: 6.0: 1.7) was supplied at a dimethyl ether feed rate of 2.7 L / g ( Catalyst) dimethyl ether was converted to hydrogen and carbon dioxide by feeding at h. 1 hour after the start of the reaction, the dimethyl ether conversion was 100%, and the carbon monoxide selectivity was 14.3%. After 6 hours from the start of the reaction, the dimethyl ether conversion was 100%, and the carbon monoxide selectivity was 12.8%. It was confirmed that dimethyl ether could be stably converted to hydrogen even at high temperatures.

Example 10
Production of steam reforming catalyst Distilled water of copper nitrate, zinc nitrate, indium nitrate, zirconyl nitrate and yttrium nitrate in a molar ratio of 1.0: 0.78: 0.03: 0.33: 0.36 Except for being dissolved in, a steam reforming catalyst was obtained in the same manner as in Example 1 and then crushed to obtain a powder of 40 to 100 mesh.

  Based on the amount of each metal element of copper, zinc, indium, zirconium and yttrium contained in the catalyst, the obtained catalyst is converted to the weight when these are oxides, and based on the total amount, It contained 34.9% by weight of copper oxide, 27.8% by weight of zinc oxide, 1.9% by weight of indium oxide, 17.7% by weight of zirconium oxide, and 17.7% by weight of yttrium oxide.

Production of hydrogen After the catalyst obtained by the above-described method was charged into a reactor of a fixed bed flow type reactor, a mixed gas of hydrogen and argon (hydrogen, 10 vol%) was supplied to the reactor at 250 ° C. for 1 hour. Reduced.

  Then, while raising the temperature of the reactor to 400 ° C., the reaction gas supply rate of the reaction gas (volume ratio, carbon monoxide: water vapor: argon = 1: 3.1: 0.8) composed of carbon monoxide, water vapor and argon is used. Carbon monoxide was converted to hydrogen and carbon dioxide by feeding at 35.3 L / g (catalyst) · h.

  The carbon monoxide conversion rate after 1 hour from the start of the reaction was 94% and the carbon dioxide selectivity was 100%, the carbon monoxide conversion rate after 6 hours from the start of the reaction was 92%, and the carbon dioxide selectivity was 100%. It was confirmed that carbon monoxide could be converted to hydrogen without methane by-product even at high temperatures. The equilibrium conversion rate of carbon monoxide under the reaction conditions is 96%.

Comparative Example 1
Commercially available industrial copper-zinc-alumina methanol reforming catalyst (weight ratio copper: zinc: alumina = 1.0: 1.1: 0.3) was charged into a reactor of a fixed bed flow type reactor Under the same conditions as in Example 1, a mixed gas consisting of methanol, water vapor and argon was supplied, and the supplied methanol was mainly converted into hydrogen and carbon dioxide. The methanol conversion at 1 hour from the start of reaction was 73% and the carbon monoxide selectivity was 15.6%, the methanol conversion at 6 hours from the start of reaction was 64%, and the carbon monoxide selectivity was 13.2%. It was found that it exhibited significant activity degradation and high carbon monoxide selectivity at high temperatures.

Comparative Example 2
The steam reforming catalyst was operated in the same manner as in Example 1 except that copper nitrate, zinc nitrate and zirconyl nitrate were dissolved in distilled water so that the molar ratio was 1.0: 0.78: 0.69. After being obtained, the powder was crushed to obtain a powder of 40 to 100 mesh.

  The obtained catalyst was converted into the weight when each of these metal elements of copper, zinc and indium contained in the catalyst was converted into an oxide, and the total amount of the copper oxide was 34. 9.9% by weight, zinc oxide 27.9% by weight and indium oxide 37.2% by weight.

Production of hydrogen After the catalyst obtained by the above-described method was charged into a reactor of a fixed bed flow type reactor, a mixed gas consisting of methanol, water vapor and argon was supplied under the same conditions as in Example 1, and the supplied methanol Was converted primarily to hydrogen and carbon dioxide. 1 hour after the start of the reaction, the methanol conversion was 93%, and the carbon monoxide selectivity was 14.7%. After 6 hours from the start of the reaction, the methanol conversion was 90%, and the carbon monoxide selectivity was 13.3%. there were. From this result, when indium oxide was not contained in the catalyst, it was confirmed that some activity deterioration was observed at high temperature and the carbon monoxide selectivity was high.

Comparative Example 3
Commercially available industrial copper-zinc-alumina methanol reforming catalyst (weight ratio copper: zinc: alumina = 1.0: 1.1: 0.3) was charged into a reactor of a fixed bed flow type reactor Under the same conditions as in Example 5, a mixed gas consisting of methanol, water vapor and argon was supplied, and the supplied methanol was mainly converted into hydrogen and carbon dioxide. The methanol conversion at 1 hour from the start of the reaction was 87%, the carbon monoxide selectivity was 8.2%, the methanol conversion at 5 hours after the start of the reaction was 93%, and the carbon monoxide selectivity was 7.8%. It was confirmed that the carbon monoxide selectivity was high although the activity was relatively high and stable.

Claims (10)

A catalyst for steam reforming of methanol, dimethyl ether or carbon monoxide containing each element of copper, zinc, indium and zirconium as an oxide. When the oxide of each element of copper, zinc, indium and zirconium is copper oxide, zinc oxide, indium oxide and zirconium oxide, respectively, the content of copper oxide is 10 based on the total amount of these oxides. ~ 55 wt%, zinc oxide content 0.5-2 times copper oxide content, indium oxide content 0.5-15 wt% and zirconium oxide content 5-70 wt% The catalyst for steam reforming of methanol, dimethyl ether or carbon monoxide according to claim 1. A catalyst for steam reforming of methanol, dimethyl ether or carbon monoxide containing each element of copper, zinc, indium, zirconium and yttrium as an oxide. When the oxide of each element of copper, zinc, indium, zirconium and yttrium is copper oxide, zinc oxide, indium oxide, zirconium oxide and yttrium oxide, respectively, copper oxide based on the total amount of these oxides Content of 10 to 55% by weight, zinc oxide content of 0.5 to 2 times that of copper oxide, indium oxide content of 0.5 to 15% by weight, and zirconium oxide and yttrium oxide The methanol, dimethyl ether or carbon monoxide water vapor according to claim 3, wherein the total content is 5 to 70% by weight and Y / (Zr + Y) (molar fraction) is 0.01 to 0.9. Catalyst for reforming. A catalyst for steam reforming of methanol, dimethyl ether or carbon monoxide containing each element of copper, zinc, indium and aluminum as an oxide. When the oxide of each element of copper, zinc, indium and aluminum is copper oxide, zinc oxide, indium oxide and aluminum oxide, respectively, the content of copper oxide is 10 based on the total amount of these oxides. -55 wt%, zinc oxide content 0.5-2 times copper oxide content, indium oxide content 0.5-15 wt% and aluminum oxide content 5-70 wt% The catalyst for steam reforming of methanol, dimethyl ether or carbon monoxide according to claim 5. 3. The water vapor according to claim 1, wherein an alkaline precipitant is added to an aqueous solution containing a copper compound, a zinc compound, an indium compound, and a zirconium compound to precipitate the mixture, and then the formed precipitate is baked. A method for producing a reforming catalyst. 5. The precipitate formed is calcined after adding an alkaline precipitating agent to an aqueous solution containing a copper compound, a zinc compound, an indium compound, a zirconium compound and an yttrium compound, and then precipitating the formed precipitate. The manufacturing method of the catalyst for steam reforming of description. The water vapor according to claim 5 or 6, wherein an alkaline precipitant is added to an aqueous solution containing a copper compound, a zinc compound, an indium compound, and an aluminum compound to precipitate the mixture, and then the formed precipitate is baked. A method for producing a reforming catalyst. A method for producing hydrogen, comprising reacting a raw material gas containing methanol, dimethyl ether or carbon monoxide with water vapor in the presence of the catalyst according to claim 1.