JP4629886B2 - Catalyst for producing methacrolein and / or methacrylic acid, method for producing the same, and method for producing methacrolein and / or methacrylic acid - Google Patents

Description

表１から明らかなように、本発明の触媒は参考例の触媒と比べて高収率であり、触媒の複合化による顕著な効果が得られた。
【００６９】
【発明の効果】
本発明の触媒を用いることにより、イソブタンを気相接触酸化してメタクロレインおよび／またはメタクリル酸を高収率で製造することが可能である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a catalyst for producing methacrolein and / or methacrylic acid by vapor-phase catalytic oxidation of isobutane, a method for producing the catalyst, and a method for producing methacrolein and / or methacrylic acid using the catalyst. Is.
[0002]
[Prior art]
It has been heretofore known that heteropoly acid compounds represented by phosphomolybdic acid are effective as catalysts for producing methacrolein and / or methacrylic acid by gas phase catalytic oxidation of isobutane. JP-A-55-62041, JP-A-2-42032, JP-A-4-128247, JP-A-9-20700, and the like. Further, a catalyst in which a heteropolyacid compound is supported on tantalum oxide, niobium oxide or zirconium oxide treated with sulfate ions (JP-A-6-172250), a composite oxide catalyst of tantalum, niobium and molybdenum (JP-A-5-213799). And metal ion-exchanged phosphorus-vanadium catalyst (Japanese Patent Laid-Open No. 9-295802) have been proposed.
[0003]
However, all of the catalysts proposed so far do not always have a satisfactory reaction result, and further improvements are desired as industrial catalysts.
[0004]
[Problems to be solved by the invention]
The present invention relates to a catalyst capable of producing methacrolein and / or methacrylic acid in high yield by gas phase catalytic oxidation of isobutane, a method for producing the catalyst, and production of methacrolein and / or methacrylic acid using the catalyst. It aims to provide a method.
[0005]
[Means for Solving the Problems]
The above object of the present invention can be solved by the following present invention.
(I) A method for producing a catalyst for producing methacrolein and / or methacrylic acid by gas phase catalytic oxidation of isobutane, characterized in that the following component (A) and component (B) are mixed: A method for producing a catalyst for producing methacrolein and / or methacrylic acid.
Component (A): Solid acid represented by the following formula (1) P _a Mo _b A _c X _d Y _e Z _f O _g (1)
(In the formula (1), P, Mo and O represent phosphorus, molybdenum and oxygen, respectively, A represents at least one element selected from the group consisting of vanadium and copper, X represents antimony, bismuth, arsenic, Represents at least one element selected from the group consisting of germanium, tellurium, silver, selenium, silicon, tungsten and boron, Y represents iron, zinc, chromium, magnesium, tantalum, cobalt, manganese, barium, gallium, cerium and Z represents at least one element selected from the group consisting of potassium, rubidium, cesium and thallium, a, b, c, d, e, f and g represent the atomic ratio of each element, and when b = 12, a = 0.1-3, c = 0-3, d = 0-3 e = 0 to 3, a f = 0 to 3, g is the atomic ratio of oxygen required to satisfy the valence of each component.)
Component (B): Oxide represented by the following formula (2) Mo _h D _i O _j (2)
(In Formula (2), Mo and O represent molybdenum and oxygen, respectively, D represents at least one element selected from the group consisting of vanadium, nickel, and antimony. H, i, and j are atoms of each element. Represents a ratio, i = 0.01 to 3 when h = 1, and j is an atomic ratio of oxygen necessary to satisfy the valence of each component.)
(II) The method for producing a methacrolein and / or methacrylic acid production catalyst according to (I), wherein the amount of the component (B) is 1 to 60 parts by mass with respect to 100 parts by mass of the component (A). .
(III) The aqueous solution or slurry of the component (A) and the component (B) are mixed, and the mixture is dried and fired. The methacrolein and / or methacrylic acid production according to the above (I) or (II) For producing a catalyst for use.
(IV) a step of producing by Increment Takurorein and / or methacrylic acid catalyst for producing the method according to any one of (I) from (III), gas-phase catalytic oxidation of isobutane in the presence of the catalyst A process for producing methacrolein and / or methacrylic acid.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The catalyst for producing methacrolein and / or methacrylic acid of the present invention is a catalyst used for producing methacrolein and / or methacrylic acid by vapor-phase catalytic oxidation of isobutane with molecular oxygen, and the above-mentioned components ( A) and component (B) are included. When gas-phase catalytic oxidation of isobutane in the presence of such a catalyst of the present invention, methacrolein and / or methacrylic acid can be produced in a higher yield than conventional various catalysts.
[0008]
The reason why the catalyst for producing methacrolein and / or methacrylic acid of the present invention is superior to the conventional various catalysts is that the oxide having high oxidation activity of isobutane and the heteropolyacid having high selectivity of methacrolein and / or methacrylic acid. It is presumed that a synergistic effect was achieved as a result of compounding with the compound.
[0009]
Component (A) in the catalyst of the present invention is a solid acid represented by the following formula (1).
[0010]
_{P a Mo b A c X d} Y e Z f O g (1)
Here, in the formula (1), P, Mo and O represent phosphorus, molybdenum and oxygen, A represents at least one element selected from the group consisting of vanadium and copper, X represents antimony, bismuth, At least one element selected from the group consisting of arsenic, germanium, tellurium, silver, selenium, silicon, tungsten and boron; Y is iron, zinc, chromium, magnesium, tantalum, cobalt, manganese, barium, gallium, Z represents at least one element selected from the group consisting of potassium, rubidium, cesium and thallium, and represents at least one element selected from the group consisting of cerium and lanthanum. a, b, c, d, e, f and g represent the atomic ratio of each element, and when b = 12, a = 0.1-1, c = 0-3, d = 0-3, e = 0. -3, f = 0-3, and g is an atomic ratio of oxygen necessary to satisfy the valence of each component.
[0011]
Preparation of the solid acid of component (A) can be carried out using various methods such as precipitation methods and oxide mixing methods that are well known in the art. Specifically, a mixed solution or aqueous slurry obtained by using a raw material containing a constituent element of a solid acid and appropriately dissolving or suspending the required amount in a solvent such as water is evaporated to dryness, and further pulverized if necessary. An example is a method of heat treatment after molding. In addition, the component solution (B) may be added and mixed without evaporating and drying the mixed solution or the aqueous slurry.
[0012]
Various methods can be used as a method for drying the mixed solution or the aqueous slurry, and examples thereof include an evaporation to dryness method, a spray drying method, a drum drying method, and an airflow drying method.
[0013]
200-500 degreeC is preferable and the heat processing temperature of a component (A) has especially preferable 300-450 degreeC. The heat treatment of component (A) is preferably performed under an oxygen flow, an air flow or a nitrogen flow. The heat treatment time is not particularly limited, but usually about 1 to 40 hours is preferable. In addition, when heat-processing after mixing with a component (B), it does not need to heat-process before mixing.
[0014]
The raw materials used for the preparation of component (A) are not particularly limited, and nitrates, carbonates, acetates, ammonium salts, oxides, halides, and the like of each element can be used in combination. For example, ammonium paramolybdate, molybdenum trioxide, molybdic acid, or the like can be used as the molybdenum raw material. As the phosphorus raw material, orthophosphoric acid, metaphosphoric acid, phosphorus pentoxide, pyrophosphoric acid, ammonium phosphate and the like can be used. In addition, a heteropolyacid compound such as phosphomolybdic acid or ammonium phosphomolybdate can be used as a raw material for molybdenum and phosphorus.
[0015]
On the other hand, the component (B) in the catalyst of the present invention is an oxide represented by the following formula (2).
[0016]
Mo _h D _i O _j (2)
Here, in formula (2), Mo and O represent molybdenum and oxygen, respectively, and D represents at least one element selected from the group consisting of vanadium, nickel, antimony and zirconium. h, i, and j represent the atomic ratio of each element, i = 0.01 to 3 when h = 1, and j is the atomic ratio of oxygen necessary to satisfy the valence of each component. . i is particularly preferably 0.02 or more, and more preferably 2 or less.
[0017]
The preparation of the component (B) oxide can be carried out using various methods such as precipitation methods and oxide mixing methods that are well known in the art. Specifically, a raw material containing a molybdenum raw material and other constituent elements is used, and a mixed solution or aqueous slurry obtained by appropriately dissolving or suspending the required amount in a solvent such as water is dried and further required. The method of heat-treating after pulverizing and shaping by can be exemplified.
[0018]
Various methods can be used as a method for drying the mixed solution or the aqueous slurry, and examples thereof include an evaporation to dryness method, a spray drying method, a drum drying method, and an airflow drying method.
[0019]
The heat treatment temperature of component (B) is preferably 300 to 800 ° C, particularly preferably 350 to 700 ° C. The higher the heat treatment temperature, the more the control of the valence of the main component by electron transfer between the components proceeds, and the lower the heat treatment temperature, the less oxide melting, decomposition, sublimation and the like. As the atmosphere for the heat treatment, air, oxygen, nitrogen or the like is preferably used. The heat treatment time is not particularly limited, but usually about 1 to 40 hours is preferable. In addition, when heat-processing after mixing with a component (A), it does not need to heat-process before mixing.
[0020]
The raw material used for the preparation of component (B) is not particularly limited, and nitrates, carbonates, acetates, ammonium salts, oxides, halides, and the like of each element can be used in combination. Examples of the molybdenum raw material include ammonium paramolybdate, molybdenum trioxide, molybdenum dioxide, and molybdic acid. Among these, ammonium paramolybdate is preferably used.
[0021]
The catalyst for producing methacrolein and / or methacrylic acid of the present invention comprises the above component (A) and component (B). The amount of component (B) in the methacrolein and / or methacrylic acid production catalyst of the present invention is preferably 1 part by mass or more, particularly preferably 5 parts by mass or more, and 60 parts by mass with respect to 100 parts by mass of component (A). Hereinafter, 50 parts by mass or less is particularly preferable.
[0022]
In the production of the catalyst for producing methacrolein and / or methacrylic acid of the present invention, the method of mixing the component (A) and the component (B) is not particularly limited, and the types of the component (A) and the component (B) to be mixed, It can be appropriately selected depending on the properties and the addition ratio. Preferable mixing methods include a method of mixing an aqueous solution or slurry of component (A) and component (B), and a method of mixing component (A) and component (B). Even when the component (A) and the component (B) are mixed by any method, it is preferable to mix them as uniformly as possible.
[0023]
In the case of the method of mixing the aqueous solution or aqueous slurry of component (A) and component (B), the dried or fired product of component (B) is added to the aqueous solution or aqueous slurry of component (A) and mixed. The aqueous solution or aqueous slurry of component (A) may be prepared by dissolving or suspending the dried or fired product of component (A) in water, and drying the mixed solution or aqueous slurry at the time of preparing component (A). You may use as it is, without doing. Thereafter, even if the preparation of the component (A) proceeds, the amount and state of the component (B) do not change under normal preparation conditions. Moreover, even if it is the preparation method of the conditions that a component (B) changes, if a final catalyst satisfies the conditions of this invention, it does not interfere. The mixing is preferably carried out at 5 to 200 ° C. for 0.01 to 30 hours, although it varies depending on the composition of component (A) and component (B) and the mixing ratio thereof. The amount of the aqueous solution of component (A) or the water in the aqueous slurry is not particularly limited.
[0024]
As a drying method of the aqueous solution of the component (A) or the mixture of the aqueous slurry and the component (B) (mixed liquid material), various methods can be used depending on the state of the mixture. Spray drying, drum drying, airflow drying, and the like can be used. What is necessary is just to determine drying conditions suitably.
[0025]
The dried product thus obtained may be pulverized if necessary, and then subjected to the subsequent firing as it is, but it is usually preferable to form and then fire it.
[0026]
The molding method is not particularly limited, and various dry and wet molding methods such as tableting molding, press molding, extrusion molding, and granulation molding can be applied. There is no restriction | limiting in particular about the shape of a molded object, The optimal thing can be selected from shapes, such as a ball | bowl, a cylinder, a pellet, a ring, in consideration of the type | mold of a reactor, conditions, etc., for example.
[0027]
In molding, a small amount of known additives such as graphite and talc may be added.
[0028]
The firing method of the molded body thus obtained is not particularly limited, and known methods and conditions can be applied. The optimum conditions for firing differ depending on the raw materials used, composition, preparation method, etc., but usually the atmosphere is under the flow of an oxygen-containing gas such as air and / or under the flow of an inert gas, and the firing temperature is 200 to 500 ° C., preferably The baking can be performed at 300 ° C. or higher or 450 ° C. or lower and the baking time is 0.5 hour or longer, preferably 1 hour or longer or 40 hours or shorter.
[0029]
On the other hand, in the case of mixing the component (A) and the component (B), the dried product or fired product of the component (A) and the dried product or fired product of the component (B) may be mixed. After mixing a component (A) and a component (B), you may grind | pulverize, shape | mold, and heat-process as needed. Molding and heat treatment may be performed in the same manner as in the method of mixing the aqueous solution or slurry of component (A) and component (B). When component (A) and / or component (B) is not heat-treated before mixing, that is, when the dried product of component (A) and / or the dried product of component (B) are mixed, usually after mixing It is preferable to heat-treat.
[0030]
The catalyst of the present invention is for producing methacrolein and / or methacrylic acid by gas phase catalytic oxidation of isobutane. The reaction temperature of this reaction is preferably 230 to 450 ° C, particularly preferably 250 to 400 ° C. The reaction pressure can be from normal pressure to several atmospheres. The space velocity is preferably 200 to 3000 hr ⁻¹ .
[0031]
The concentration of isobutane in the raw material gas can be varied within a wide range, but it is preferably 1 to 40%, particularly 3 to 30% by volume.
[0032]
Air is economical as the molecular oxygen source used for the reaction, but if necessary, air enriched with pure oxygen can also be used. The molecular oxygen concentration in the raw material gas is preferably 0.4 to 4 mol, particularly 0.5 to 3 mol, with respect to 1 mol of isobutane.
[0033]
The source gas may be obtained by diluting isobutane and a molecular oxygen source with an inert gas such as nitrogen, water vapor, or carbon gas.
[0034]
The reaction source gas preferably contains water vapor. When the reaction is carried out in the presence of water, methacrolein and / or methacrylic acid is obtained in high yield. The concentration of water vapor in the raw material gas is preferably 1 to 30%, particularly 3 to 25% by volume.
[0035]
The reaction can be carried out in a fixed bed or a fluidized bed.
[0036]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to an Example.
[0037]
In the following Examples and Comparative Examples, “part” is part by mass, and analysis of the raw material gas and the product was performed using gas chromatography.
[0038]
The reaction rate of isobutane and the selectivity of produced methacrolein and / or methacrylic acid are defined as follows.
[0039]
Isobutane reaction rate (%) = (B / A) × 100
Selectivity of methacrolein (%) = (C / B) × 100
Methacrylic acid selectivity (%) = (D / B) × 100
Yield of methacrolein and methacrylic acid (%) = {(C + D) / A} × 100
Here, A is the number of moles of isobutane supplied, B is the number of moles of reacted isobutane, C is the number of moles of methacrolein produced, and D is the number of moles of methacrylic acid produced.
[0040]
[Reference Example 1]
P ₁ Mo ₁₂ heteropolyacid (manufactured by Nippon Inorganic Chemical Industry) was molded and crushed and then heat-treated at 380 ° C. for 5 hours under air flow as a catalyst.
[0041]
The catalyst was charged in a reaction tube, and a mixed gas of 25% isobutane, 25% oxygen, 15% water and 35% (volume%) was passed under normal pressure at a reaction temperature of 350 ° C. and a space velocity of 1200 hr ⁻¹ . When the product was collected and analyzed, the reaction rate of isobutane was 4.6%, the selectivity of methacrolein was 35.1%, the selectivity of methacrylic acid was 5.2%, and the yield of methacrolein and methacrylic acid was 1.9. %Met. The results are shown in Table 1.
[0042]
[Reference Example 2]
In a vessel equipped with a reflux condenser, 400 parts of pure water, 100 parts of molybdenum trioxide, 6.7 parts of 85% phosphoric acid, 2.6 parts of vanadium pentoxide and 4.2 parts of copper nitrate were dissolved in 5 parts of pure water. The solution was added, heated at 100 ° C. for 2 hours, cooled to 50 ° C., and a solution prepared by dissolving 14.6 parts of cesium bicarbonate in 20 parts of pure water was added thereto. The mixture was evaporated to dryness with heating and stirring, and the obtained solid was dried at 130 ° C. for 16 hours. The dried powder was molded and crushed and then heat-treated in the same manner as in Reference Example 1 as a catalyst. The composition of elements other than oxygen (hereinafter the same) of the obtained catalyst was P ₁ Mo ₁₂ V _0.5 Cu _0.3 Cs _1.3 .
[0043]
The catalyst was packed in a reaction tube and reacted in the same manner as in Reference Example 1. The results are shown in Table 1.
[0044]
[Reference Example 3]
100 parts of ammonium paramolybdate was dissolved in 200 parts of pure water. A solution obtained by dissolving 13.3 parts of ammonium metavanadate in 300 parts of pure water was added thereto, and the mixture was evaporated to dryness while heating. The obtained solid was dried at 130 ° C. for 16 hours. The dried powder was molded and crushed and then heat-treated at 300 ° C. for 8 hours under air flow and further at 500 ° C. for 2 hours under nitrogen flow was used as a catalyst. The composition of the obtained catalyst was Mo ₁ V _0.2 .
[0045]
The catalyst was packed in a reaction tube and reacted in the same manner as in Reference Example 1. The results are shown in Table 1.
[0046]
[Reference Example 4]
100 parts of ammonium paramolybdate was dissolved in 200 parts of pure water. To this was added a solution prepared by dissolving 49.4 parts of nickel nitrate in 200 parts of pure water, and further a solution prepared by dissolving 15 parts of urea in 50 parts of pure water. The mixture was evaporated to dryness with heating, and the obtained solid was dried at 130 ° C. for 16 hours. The dried powder was molded and crushed and then heat-treated at 500 ° C. for 8 hours under air flow as a catalyst. The composition of the obtained catalyst was Mo ₁ Ni _0.3 .
[0047]
The catalyst was packed in a reaction tube and reacted in the same manner as in Reference Example 1. The results are shown in Table 1.
[0048]
[Reference Example 5]
100 parts of ammonium paramolybdate was dissolved in 200 parts of pure water. To this was added 24.8 parts of antimony trioxide, this mixture was evaporated to dryness while heating, and the resulting solid was dried, molded, crushed and heat-treated as in Reference Example 4 as a catalyst. It was. The composition of the obtained catalyst was Mo ₁ Sb _0.3 .
[0049]
The catalyst was packed in a reaction tube and reacted in the same manner as in Reference Example 1. The results are shown in Table 1.
[0050]
[Reference Example 6]
100 parts of ammonium paramolybdate was dissolved in 200 parts of pure water. To this was added 8.3 parts of antimony trioxide and 7.0 parts of zirconium oxide, and this mixture was evaporated to dryness while heating, and the resulting solid was dried, molded and crushed in the same manner as in Reference Example 4. The heat-treated product was used as a catalyst. The composition of the obtained catalyst was Mo ₁ Sb _0.1 Zr _0.1 .
[0051]
The catalyst was packed in a reaction tube and reacted in the same manner as in Reference Example 1. The results are shown in Table 1.
[0052]
[Example 1]
The catalyst of Reference Example 1 (P ₁ Mo ₁₂ ) and the catalyst of Reference Example 3 (Mo ₁ V _0.2 ) were mixed and pulverized at a mass ratio of 7: 3, and then molded and crushed again as a catalyst.
[0053]
The catalyst was packed in a reaction tube and reacted in the same manner as in Reference Example 1. The results are shown in Table 1.
[0054]
[Example 2]
20 parts of the catalyst (Mo ₁ V _0.2 ) of Reference Example 3 was added to a solution obtained by dissolving 100 parts of the catalyst (P ₁ Mo ₁₂ ) of Reference Example 1 (heat treatment catalyst under air flow) in 100 parts of pure water, and this mixed liquid Was evaporated to dryness while heating. The obtained solid was dried, molded, crushed and heat-treated in the same manner as in Reference Example 2 and used as a catalyst.
[0055]
The catalyst was packed in a reaction tube and reacted in the same manner as in Reference Example 1. The results are shown in Table 1.
[0056]
[Example 3]
The catalyst of Reference Example 1 (P ₁ Mo ₁₂ ) and the catalyst of Reference Example 4 (Mo ₁ Ni _0.3 ) were mixed and pulverized at a mass ratio of 7 to 3, and then molded and crushed again.
[0057]
The catalyst was packed in a reaction tube and reacted in the same manner as in Reference Example 1. The results are shown in Table 1.
[0058]
[Example 4]
The catalyst of Reference Example 1 (P ₁ Mo ₁₂ ) and the catalyst of Reference Example 5 (Mo ₁ Sb _0.3 ) were mixed and pulverized at a mass ratio of 4: 1, and then molded and crushed again as a catalyst.
[0059]
The catalyst was packed in a reaction tube and reacted in the same manner as in Reference Example 1. The results are shown in Table 1.
[0060]
[Example 5]
The catalyst of Reference Example 1 (P ₁ Mo ₁₂ ) and the catalyst of Reference Example 6 (Mo ₁ Sb _0.1 Zr _0.1 ) were mixed and pulverized at a mass ratio of 4 to 1, and then molded and crushed again. It was.
[0061]
The catalyst was packed in a reaction tube and reacted in the same manner as in Reference Example 1. The results are shown in Table 1.
[0062]
[Example 6]
The catalyst of Reference Example 2 (P ₁ Mo ₁₂ V _0.5 Cu _0.3 Cs _1.3 ) and the catalyst of Reference Example 3 (Mo ₁ V _0.2 ) were mixed and pulverized at a mass ratio of 7: 3, and then molded and crushed again Was used as a catalyst.
[0063]
The catalyst was packed in a reaction tube and reacted in the same manner as in Reference Example 1. The results are shown in Table 1.
[0064]
[Example 7]
The catalyst (Mo ₁ V _0.2 ) 20 of Reference Example 20 was added to an aqueous slurry in which 100 parts of pure water was added to 100 parts (P ₁ Mo ₁₂ V _0.5 Cu _0.3 Cs _1.3 ) of the catalyst of Reference Example 2 (heat treatment catalyst under air flow). And the mixed liquid was evaporated to dryness while heating. The obtained solid was dried, molded, crushed and heat-treated in the same manner as in Reference Example 2 and used as a catalyst.
[0065]
The catalyst was packed in a reaction tube and reacted in the same manner as in Reference Example 1. The results are shown in Table 1.
[0066]
[Example 8]
In a vessel equipped with a reflux condenser, 400 parts of pure water, 100 parts of molybdenum trioxide, 6.7 parts of 85% phosphoric acid, 2.6 parts of vanadium pentoxide and 4.2 parts of copper nitrate were dissolved in 5 parts of pure water. The solution was added, heated at 100 ° C. for 2 hours, cooled to 50 ° C., and a solution prepared by dissolving 14.6 parts of cesium bicarbonate in 20 parts of pure water was added thereto. Further, 20 parts of the catalyst (Mo ₁ V _0.2 ) of Reference Example 3 was added to this mixed solution, and the mixed slurry was evaporated to dryness while stirring with heating. What was molded, crushed and heat-treated was used as a catalyst. In this example, the mixing ratio of the catalyst of Reference Example 2 (P ₁ Mo ₁₂ V _0.5 Cu _0.3 Cs _1.3 ) and the catalyst of Reference Example 3 (Mo ₁ V _0.2 ) corresponds to 6.2 to 1 in terms of mass ratio. To do.
[0067]
The catalyst was packed in a reaction tube and reacted in the same manner as in Reference Example 1. The results are shown in Table 1.
[0068]
[Table 1]

As is clear from Table 1, the catalyst of the present invention was higher in yield than the catalyst of the reference example, and a remarkable effect was obtained by combining the catalysts.
[0069]
【The invention's effect】
By using the catalyst of the present invention, it is possible to produce methacrolein and / or methacrylic acid in high yield by gas phase catalytic oxidation of isobutane.

Claims (4)

A process for producing a catalyst for producing methacrolein and / or methacrylic acid by gas phase catalytic oxidation of isobutane,
A method for producing a catalyst for producing methacrolein and / or methacrylic acid , comprising mixing the following component (A) and component (B).
Component (A): Solid acid represented by the following formula (1) P _a Mo _b A _c X _d Y _e Z _f O _g (1)
(In the formula (1), P, Mo and O represent phosphorus, molybdenum and oxygen, respectively, A represents at least one element selected from the group consisting of vanadium and copper, X represents antimony, bismuth, arsenic, Represents at least one element selected from the group consisting of germanium, tellurium, silver, selenium, silicon, tungsten and boron, Y represents iron, zinc, chromium, magnesium, tantalum, cobalt, manganese, barium, gallium, cerium and Z represents at least one element selected from the group consisting of potassium, rubidium, cesium and thallium, a, b, c, d, e, f and g represent the atomic ratio of each element, and when b = 12, a = 0.1-3, c = 0-3, d = 0-3 e = 0 to 3, a f = 0 to 3, g is the atomic ratio of oxygen required to satisfy the valence of each component.)
Component (B): Oxide represented by the following formula (2) Mo _h D _i O _j (2)
(In the formula (2), Mo and O each represents molybdenum and oxygen, D is vanadium, .h indicating at least one element selected from nickel and antimony or Ranaru group, i and j are the elements (When h = 1, i is from 0.01 to 1-3, and j is the atomic ratio of oxygen necessary to satisfy the valence of each component.) The method for producing a catalyst for producing methacrolein and / or methacrylic acid according to claim 1, wherein the amount of the component (B) is 1 to 60 parts by mass with respect to 100 parts by mass of the component (A). The method for producing a catalyst for producing methacrolein and / or methacrylic acid according to claim 1 or 2, wherein the aqueous solution or slurry of the component (A) is mixed with the component (B), and the mixture is dried and calcined. A step of producing by Increment Takurorein and / or methacrylic acid catalyst for producing the method according to any one of claims 1 to 3, a step of vapor-phase catalytic oxidation of isobutane in the presence of the catalyst, the A process for producing methacrolein and / or methacrylic acid, comprising: