JP3347263B2 - Preparation of catalysts for the production of unsaturated aldehydes and unsaturated carboxylic acids - Google Patents

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、プロピレン、イソ
ブチレン、三級ブタノールまたはメチルターシャリーブ
チルエーテルを気相接触酸化して、不飽和アルデヒドお
よび不飽和カルボン酸を製造する際に使用する触媒の調
製法に関する。[0001] The present invention relates to a process for preparing a catalyst used for producing unsaturated aldehydes and unsaturated carboxylic acids by subjecting propylene, isobutylene, tertiary butanol or methyl tert-butyl ether to gas phase catalytic oxidation. About.

【０００２】[0002]

【従来の技術】従来、不飽和アルデヒドおよび不飽和カ
ルボン酸を製造する際に用いられる触媒に関して、多数
の方法が提案されている。イソブチレンまたは三級ブタ
ノールを高温気相下で接触酸化してメタクロレインおよ
びメタクリル酸を製造する際に用いられる触媒につい
て、例えば、特公昭５３−４７０８８号公報、特公平５
−５０４８９号公報、特開昭５５−１７３０６号公報、
特開昭５７−１３０９４９号公報、特開昭５８−１２１
２３５号公報、特開昭５９−３１７２７号公報、特開昭
６０−２８８２４号公報等で多くの提案がなされてい
る。2. Description of the Related Art Heretofore, many methods have been proposed for catalysts used in producing unsaturated aldehydes and unsaturated carboxylic acids. Catalysts used for producing methacrolein and methacrylic acid by catalytically oxidizing isobutylene or tertiary butanol under a high-temperature gas phase are described in, for example, JP-B-53-47088 and JP-B-5
-50489, JP-A-55-17306,
JP-A-57-130949, JP-A-58-121
Many proposals have been made in JP-A-235-235, JP-A-59-31727, JP-A-60-28824 and the like.

【０００３】触媒の調製法については、ビスマス化合物
とタングステン化合物との混合物をあらかじめ６００〜
９００℃の温度で焼成処理して得られた酸化物を用いる
方法（特公平２−３２０１７号公報）、ビスマス、ナト
リウムおよびマグネシウム、カルシウム、亜鉛、セリウ
ムおよびサマリウムからなる群より選ばれた少なくとも
１種の元素の複合炭酸塩化合物を用いる方法（特公平６
−１３０９７号公報）、ビスマス成分、アンチモン成分
およびタングステン、ニッケル、コバルト、マグネシウ
ム、亜鉛、マンガン、カドミウム、鉛、バリウムおよび
クロムからなる群より選ばれた少なくとも１種の元素の
混合物をあらかじめ７００〜８５０℃の温度で熱処理し
て得られた化合物を用いる方法（特開平２−２２７１４
０号公報）、モリブデンおよびカリウム、ルビジウムお
よびセシウムからなる群より選ばれた少なくとも１種の
元素からなる混合物を用いる方法（特開平５−９７７６
１号公報）、ビスマス、テルル、アンチモン、スズおよ
び銅からなる群より選ばれた少なくとも１種の元素およ
びモリブデンおよびタングステンからなる群より選ばれ
た少なくとも１種の元素からなる混合物を用いる方法
（特開平６−７１１７７号公報）等、多くの提案がなさ
れている。[0003] With respect to the preparation method of the catalyst, a mixture of a bismuth compound and a tungsten compound is prepared in advance by 600-
A method using an oxide obtained by calcining at a temperature of 900 ° C. (Japanese Patent Publication No. 2-32017), at least one selected from the group consisting of bismuth, sodium and magnesium, calcium, zinc, cerium and samarium Using complex carbonate compounds of different elements (Japanese Patent Publication 6
JP-A-13097), a mixture of a bismuth component, an antimony component, and at least one element selected from the group consisting of tungsten, nickel, cobalt, magnesium, zinc, manganese, cadmium, lead, barium and chromium, is prepared in advance by 700 to 850. A method using a compound obtained by heat treatment at a temperature of 200 ° C. (JP-A-2-22714).
No. 0), a method using a mixture comprising at least one element selected from the group consisting of molybdenum and potassium, rubidium and cesium (JP-A-5-9776).
No. 1), a method using a mixture of at least one element selected from the group consisting of bismuth, tellurium, antimony, tin and copper and at least one element selected from the group consisting of molybdenum and tungsten (particularly, Many proposals have been made.

【０００４】[0004]

【発明が解決しようとする課題】しかしながら、上記公
報等に記載される触媒を用いて、プロピレン、イソブチ
レン、三級ブタノールまたはメチルターシャリーブチル
エーテルから不飽和アルデヒドおよび不飽和カルボン酸
を製造すると、いずれも収率が低く、工業的見地からさ
らに改良が望まれている。However, when unsaturated aldehydes and unsaturated carboxylic acids are produced from propylene, isobutylene, tertiary butanol or methyl tertiary butyl ether using the catalysts described in the above publications, etc. The yield is low and further improvement is desired from an industrial point of view.

【０００５】本発明は、プロピレン、イソブチレン、三
級ブタノールまたはメチルターシャリーブチルエーテル
を分子状酸素を用いて気相接触酸化して、不飽和アルデ
ヒドおよび不飽和カルボン酸を高い収率で製造する触媒
の新規な調製法を提供することを目的とする。The present invention provides a catalyst for producing unsaturated aldehydes and unsaturated carboxylic acids in high yield by subjecting propylene, isobutylene, tertiary butanol or methyl tertiary butyl ether to gas-phase catalytic oxidation using molecular oxygen. It is intended to provide a novel preparation method.

【０００６】[0006]

【課題を解決するための手段】本発明は、一般式 Ｍｏ_aＢｉ_bＦｅ_cＡ_dＢ_eＣ_fＤ_gＥ_hＳｉ_iＯ_j （式中、Ｍｏ、Ｂｉ、Ｆｅ、ＳｉおよびＯはそれぞれモ
リブデン、ビスマス、鉄、ケイ素および酸素を表し、Ａ
はタングステンおよびアンチモンからなる群より選ばれ
た少なくとも１種の元素、Ｂはニッケルおよびコバルト
からなる群より選ばれた少なくとも１種の元素、Ｃはマ
グネシウム、亜鉛、マンガン、クロム、スズおよび鉛か
らなる群より選ばれた少なくとも１種の元素、Ｄはリ
ン、ホウ素、イオウ、テルル、セレンおよびランタンか
らなる群より選ばれた少なくとも１種の元素、Ｅはカリ
ウム、ルビジウム、セシウムおよびタリウムからなる群
より選ばれた少なくとも１種の元素を示す。ただし、
ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈ、ｉおよびｊは各元素
の原子比を表し、ａ＝１２のとき、０．１≦ｂ≦５、
０．１≦ｃ≦５、０．０１≦ｄ≦５、１≦ｅ≦１２、０
≦ｆ≦１０、０≦ｇ≦５、０．０１≦ｈ≦２、０≦ｉ≦
２０であり、ｊは前記各成分の原子価を満足するのに必
要な酸素原子数である。）で表される組成を有する触媒
を調製するにあたり、ビスマスとＥ成分からなる混合物
または、ビスマス、Ｅ成分およびＡ成分からなる混合物
をあらかじめ２００〜６００℃の温度で熱処理して得ら
れる化合物を用いることを特徴とする、プロピレン、イ
ソブチレン、三級ブタノールまたはメチルターシャル−
ブチルエーテルを分子状酸素を用いて気相接触酸化して
不飽和アルデヒドおよび不飽和カルボン酸を製造するた
めの触媒の調製法である。The present invention SUMMARY OF] of the general formula _{Mo a Bi b Fe c A d} B e C f D g in E _h Si _i O _j (wherein, Mo, Bi, Fe, Si and O, respectively Stands for molybdenum, bismuth, iron, silicon and oxygen;
Is at least one element selected from the group consisting of tungsten and antimony, B is at least one element selected from the group consisting of nickel and cobalt, and C is magnesium, zinc, manganese, chromium, tin and lead At least one element selected from the group; D is at least one element selected from the group consisting of phosphorus, boron, sulfur, tellurium, selenium and lanthanum; and E is a group consisting of potassium, rubidium, cesium and thallium. Shows at least one selected element. However,
a, b, c, d, e, f, g, h, i and j represent the atomic ratio of each element, and when a = 12, 0.1 ≦ b ≦ 5;
0.1 ≦ c ≦ 5, 0.01 ≦ d ≦ 5, 1 ≦ e ≦ 12, 0
≦ f ≦ 10, 0 ≦ g ≦ 5, 0.01 ≦ h ≦ 2, 0 ≦ i ≦
20 and j is the number of oxygen atoms necessary to satisfy the valence of each component. In preparing the catalyst having the composition represented by the formula (1), a mixture obtained by previously heat-treating a mixture of bismuth and the E component or a mixture of bismuth, the E component, and the A component at a temperature of 200 to 600 ° C. is used. Propylene, isobutylene, tertiary butanol or methyl tert-
This is a method for preparing a catalyst for producing unsaturated aldehyde and unsaturated carboxylic acid by subjecting butyl ether to gas phase catalytic oxidation using molecular oxygen.

【０００７】[0007]

【発明の実施の形態】本発明で用いられる触媒は、一般
式 Ｍｏ_aＢｉ_bＦｅ_cＡ_dＢ_eＣ_fＤ_gＥ_hＳｉ_iＯ_j （式中のＭｏ、Ｂｉ、Ｆｅ、ＳｉおよびＯはそれぞれモ
リブデン、ビスマス、鉄、ケイ素および酸素を表し、Ａ
はタングステンおよびアンチモンからなる群より選ばれ
た少なくとも１種の元素、Ｂはニッケルおよびコバルト
からなる群より選ばれた少なくとも１種の元素、Ｃはマ
グネシウム、亜鉛、マンガン、クロム、スズおよび鉛か
らなる群より選ばれた少なくとも１種の元素、Ｄはリ
ン、ホウ素、イオウ、テルル、セレンおよびランタンか
らなる群より選ばれた少なくとも１種の元素、Ｅはカリ
ウム、ルビジウム、セシウムおよびタリウムからなる群
より選ばれた少なくとも１種の元素を示す。また、式中
のａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈ、ｉおよびｊは各元
素の原子比を表し、ａ＝１２のとき、０．１≦ｂ≦５、
０．１≦ｃ≦５、０．０１≦ｄ≦５、１≦ｅ≦１２、０
≦ｆ≦１０、０≦ｇ≦５、０．０１≦ｈ≦２、０≦ｉ≦
２０であり、ｊは前記各成分の原子価を満足するのに必
要な酸素原子数である。）で示される組成を有する。The catalyst used in the Detailed Description of the Invention The present invention relates to compounds of the general formula _{Mo a Bi b Fe c A d} B e C f D g E h Si i O j (Mo in the formula, Bi, Fe, Si and O Represents molybdenum, bismuth, iron, silicon and oxygen, respectively, A
Is at least one element selected from the group consisting of tungsten and antimony, B is at least one element selected from the group consisting of nickel and cobalt, and C is magnesium, zinc, manganese, chromium, tin and lead At least one element selected from the group; D is at least one element selected from the group consisting of phosphorus, boron, sulfur, tellurium, selenium and lanthanum; and E is a group consisting of potassium, rubidium, cesium and thallium. Shows at least one selected element. Further, a, b, c, d, e, f, g, h, i and j in the formula represent the atomic ratio of each element, and when a = 12, 0.1 ≦ b ≦ 5;
0.1 ≦ c ≦ 5, 0.01 ≦ d ≦ 5, 1 ≦ e ≦ 12, 0
≦ f ≦ 10, 0 ≦ g ≦ 5, 0.01 ≦ h ≦ 2, 0 ≦ i ≦
20 and j is the number of oxygen atoms necessary to satisfy the valence of each component. ).

【０００８】この触媒の調製に際して、各構成元素の原
料は特に限定されないが、構成元素の酸化物または強熱
すると酸化物になる化合物が好ましい。強熱すると酸化
物になる化合物の形態としては、例えば、水酸化物、硝
酸塩、アンモニウム塩、炭酸塩またはそれらの混合物等
が挙げられる。[0008] In preparing the catalyst, the raw material of each constituent element is not particularly limited, but an oxide of the constituent element or a compound which becomes an oxide when ignited is preferable. Examples of the form of the compound which becomes an oxide when ignited include a hydroxide, a nitrate, an ammonium salt, a carbonate or a mixture thereof.

【０００９】この触媒を調製するにあたり、ビスマスお
よびＥ成分、または、ビスマス、Ｅ成分およびＡ成分か
らなる化合物をあらかじめ調製する。この化合物におい
て、ビスマスおよびＥ成分、または、ビスマス、Ｅ成分
およびＡ成分の各原子比は０を除く任意の値である。In preparing this catalyst, a compound comprising bismuth and an E component or a compound comprising bismuth, an E component and an A component is prepared in advance. In this compound, the respective atomic ratios of bismuth and the E component, or bismuth, the E component and the A component are arbitrary values except 0.

【００１０】この化合物の原料は混合したのち乾燥す
る。この乾燥物の調製方法は特に制限されないが、例え
ば、蒸発乾固法、沈殿法等の公知の方法が挙げられる。
得られた乾燥物は、２００〜６００℃の温度で熱処理す
るのが好ましく、より好ましくは２５０〜５００℃であ
る。２００℃以下の温度では化合物の生成が不十分にな
ることがあり、６００℃以上の温度では生成した化合物
が溶融することがあり、良好な収率を示す触媒の調製が
困難な場合がある。熱処理を行う時間は特に限定されな
いが、好ましくは所定の温度に到達してから１０分間以
上である。The raw materials of this compound are dried after mixing. The method for preparing the dried product is not particularly limited, and examples thereof include known methods such as an evaporation to dryness method and a precipitation method.
The obtained dried product is preferably heat-treated at a temperature of 200 to 600 ° C, more preferably 250 to 500 ° C. At a temperature of 200 ° C. or lower, the formation of the compound may be insufficient. At a temperature of 600 ° C. or higher, the formed compound may be melted, and it may be difficult to prepare a catalyst having a good yield. The time for performing the heat treatment is not particularly limited, but is preferably 10 minutes or more after reaching a predetermined temperature.

【００１１】次いで、得られたビスマスおよびＥ成分、
または、ビスマス、Ｅ成分およびＡ成分からなる化合物
と他の触媒成分の原料を混合する。この際、ビスマス、
Ａ成分およびＥ成分の原料は個別に追加してもよい。各
原料は水に分散または溶解して混合することが好まし
い。Next, the obtained bismuth and E component,
Alternatively, a compound composed of bismuth, the E component and the A component is mixed with a raw material of another catalyst component. At this time, bismuth,
The raw materials of the component A and the component E may be separately added. Each raw material is preferably dispersed or dissolved in water and mixed.

【００１２】常法により、この混合物を乾燥し、焼成と
呼ばれる熱処理をすることで目的の触媒が得られる。熱
処理の温度は４００〜７００℃が好ましく、より好まし
くは４５０〜６５０℃である。この範囲外の温度で熱処
理を行うと良好な収率を示す触媒が得られないことがあ
る。また、所定の温度に到達してから熱処理を行う時間
については特に限定されないが、熱処理時間が短すぎた
り、長すぎたりすると高性能な触媒が得られないことが
あるため、０．５〜１５時間の範囲が好ましい。According to a conventional method, the mixture is dried and subjected to a heat treatment called calcination to obtain a desired catalyst. The temperature of the heat treatment is preferably from 400 to 700C, more preferably from 450 to 650C. If the heat treatment is performed at a temperature outside this range, a catalyst having a good yield may not be obtained. The time for performing the heat treatment after reaching the predetermined temperature is not particularly limited. However, if the heat treatment time is too short or too long, a high-performance catalyst may not be obtained. Time ranges are preferred.

【００１３】通常、触媒は成形して反応に使用される。
成形は、乾燥時、乾燥後または焼成後のいずれの段階で
行ってもよい。成形方法は特に限定されないが、例え
ば、打錠成形法、押し出し成形法、担持法、噴霧乾燥法
等の公知の方法が挙げられる。担持法の場合の担体とし
ては、例えば、シリカ、アルミナ、シリカ−アルミナ等
の不活性担体が挙げられる。また、成形性の向上、細孔
の発現等の目的に応じて、成形前の段階で助剤を適宜添
加することができる。成形触媒の形状は特に限定されな
いが、例えば、ペレット型、リング型、球形等が挙げら
れる。Usually, the catalyst is molded and used for the reaction.
The molding may be performed at any stage during drying, after drying, or after firing. The molding method is not particularly limited, and examples thereof include known methods such as a tableting method, an extrusion method, a supporting method, and a spray drying method. In the case of the supporting method, examples of the carrier include inert carriers such as silica, alumina, and silica-alumina. In addition, an auxiliary agent can be appropriately added at a stage before molding according to the purpose of improving moldability, developing pores, and the like. The shape of the molded catalyst is not particularly limited, and examples thereof include a pellet type, a ring type, and a spherical type.

【００１４】本発明により得られた触媒を用いて、プロ
ピレン、イソブチレン、三級ブタノールまたはメチルタ
ーシャリーブチルエーテルを分子状酸素により気相接触
酸化して、不飽和アルデヒドおよび不飽和カルボン酸を
製造する際、触媒層に供給する原料ガス中のプロピレ
ン、イソブチレン、三級ブタノールまたはメチルターシ
ャリーブチルエーテル対酸素のモル比は１：０.５〜３
が好ましい。酸素の供給源は純酸素ガスでもよいが、工
業的には空気の使用が有利である。原料ガスには、プロ
ピレン、イソブチレン、三級ブタノールまたはメチルタ
ーシャリーブチルエーテルおよび酸素以外に水蒸気や不
活性ガスを含んでもよい。不活性ガスは反応に関与しな
いものであれば特に制限されないが、工業的には窒素の
使用が有利である。反応圧力は常圧〜数気圧の範囲が好
ましく、反応温度は２５０〜４５０℃の範囲が好まし
い。反応方式に特に制限はないが、例えば、固定床、流
動床等の公知の方式が挙げられる。When propylene, isobutylene, tertiary butanol or methyl tertiary butyl ether is subjected to gas-phase catalytic oxidation with molecular oxygen using the catalyst obtained according to the present invention to produce unsaturated aldehydes and unsaturated carboxylic acids The molar ratio of propylene, isobutylene, tertiary butanol or methyl tertiary butyl ether to oxygen in the raw material gas supplied to the catalyst layer is 1: 0.5-3.
Is preferred. The source of oxygen may be pure oxygen gas, but the use of air is industrially advantageous. The raw material gas may contain water vapor or an inert gas in addition to propylene, isobutylene, tertiary butanol or methyl tertiary butyl ether and oxygen. The inert gas is not particularly limited as long as it does not participate in the reaction, but the use of nitrogen is industrially advantageous. The reaction pressure is preferably in the range of normal pressure to several atmospheres, and the reaction temperature is preferably in the range of 250 to 450 ° C. The reaction system is not particularly limited, and examples thereof include known systems such as a fixed bed and a fluidized bed.

【００１５】[0015]

【実施例】以下、本発明の実施例を示す。下記実施例お
よび比較例中の「部」は重量部を意味する。また、Ｗ、
Ｓｂ、Ｎｉ、Ｃｏ、Ｍｇ、Ｚｎ、Ｍｎ、Ｃｒ、Ｓｎ、Ｐ
ｂ、Ｐ、Ｂ、Ｓ、Ｔｅ、Ｓｅ、Ｌａ、Ｋ、Ｒｂ、Ｃｓお
よびＴｌは、それぞれタングステン、アンチモン、ニッ
ケル、コバルト、マグネシウム、亜鉛、マンガン、クロ
ム、スズ、鉛、リン、ホウ素、イオウ、テルル、セレ
ン、ランタン、カリウム、ルビジウム、セシウムおよび
タリウムを表す。分析はガスクロマトグラフィーにより
行った。原料の反応率、生成される不飽和アルデヒドお
よび不飽和カルボン酸の選択率、不飽和アルデヒドおよ
び不飽和カルボン酸を合わせた目的生成物の収率は以下
の定義に従って算出した。Embodiments of the present invention will be described below. "Parts" in the following Examples and Comparative Examples means parts by weight. Also, W,
Sb, Ni, Co, Mg, Zn, Mn, Cr, Sn, P
b, P, B, S, Te, Se, La, K, Rb, Cs and Tl are respectively tungsten, antimony, nickel, cobalt, magnesium, zinc, manganese, chromium, tin, lead, phosphorus, boron, sulfur, Represents tellurium, selenium, lanthanum, potassium, rubidium, cesium and thallium. The analysis was performed by gas chromatography. The conversion of the raw materials, the selectivity of the unsaturated aldehyde and unsaturated carboxylic acid to be produced, and the yield of the target product obtained by combining the unsaturated aldehyde and unsaturated carboxylic acid were calculated according to the following definitions.

【００１６】 原料の反応率（％） ＝ Ｂ／Ａ×１００ 不飽和アルデヒドの選択率（％） ＝ Ｃ／Ｂ×１００ 不飽和カルボン酸の選択率（％） ＝ Ｄ／Ｂ×１００ 目的生成物の収率（％） ＝ （Ｃ＋Ｄ）／Ａ
×１００ 式中のＡ，Ｂ，Ｃ，Ｄの意味は以下の通りである。Reaction rate of raw material (%) = B / A × 100 Selectivity of unsaturated aldehyde (%) = C / B × 100 Selectivity of unsaturated carboxylic acid (%) = D / B × 100 Target product Yield (%) = (C + D) / A
× 100 The meanings of A, B, C and D in the formula are as follows.

【００１７】Ａ：供給した原料のモル数 Ｂ：反応した原料のモル数 Ｃ：生成した不飽和アルデヒドのモル数 Ｄ：生成した不飽和カルボン酸のモル数 ［実施例１］純水５００部に６０重量％硝酸５０部を加
え、均一にしたのち、硝酸ビスマス５７．３部を加え溶
解した。これに硝酸セシウム２３．０部を溶解したの
ち、パラタングステン酸アンモニウム３０．８部を加え
加熱攪拌し、大部分の水分を蒸発させた。得られたケー
キ状物質を１２０℃で乾燥させたのち、４００℃で３時
間熱処理し、乳鉢で粉砕した（これを化合物Ａと呼
ぶ）。A: Number of moles of supplied raw material B: Number of moles of reacted raw material C: Number of moles of unsaturated aldehyde generated D: Number of moles of unsaturated carboxylic acid generated [Example 1] 500 parts of pure water After adding 50 parts by weight of 60% by weight nitric acid and making the mixture uniform, 57.3 parts of bismuth nitrate was added and dissolved. After dissolving 23.0 parts of cesium nitrate, 30.8 parts of ammonium paratungstate was added and heated with stirring to evaporate most of the water. After the obtained cake-like substance was dried at 120 ° C., it was heat-treated at 400 ° C. for 3 hours and pulverized in a mortar (this is referred to as compound A).

【００１８】純水１０００部にモリブデン酸アンモニウ
ム５００部、ホウ酸７．３部および硝酸セシウム９．２
部を加え加熱攪拌した（この溶液をＡ液と呼ぶ）。500 parts of ammonium molybdate, 7.3 parts of boric acid and 9.2 parts of cesium nitrate in 1000 parts of pure water.
The mixture was heated and stirred (this solution is referred to as solution A).

【００１９】別に、純水８５０部に６０重量％硝酸５０
部を加え、均一にしたのち、硝酸ビスマス３４．３部を
加え溶解した。これに硝酸第二鉄２８６．０部、硝酸ニ
ッケル３４３．２部、硝酸コバルト６８．７部、硝酸マ
グネシウム６０．５部および硝酸亜鉛７０．２部を順次
加え溶解した（この溶液をＢ液と呼ぶ）。Separately, 850 parts of pure water is mixed with 50% by weight of nitric acid 50%.
Then, 34.3 parts of bismuth nitrate was added and dissolved. 286.0 parts of ferric nitrate, 343.2 parts of nickel nitrate, 68.7 parts of cobalt nitrate, 60.5 parts of magnesium nitrate and 70.2 parts of zinc nitrate were sequentially added and dissolved. Call).

【００２０】Ａ液に化合物ＡおよびＢ液を加えスラリー
状としたのち、三酸化アンチモン５１．６部を加え加熱
攪拌し、大部分の水分を蒸発させた。Compounds A and B were added to Solution A to form a slurry, and then 51.6 parts of antimony trioxide was added and heated with stirring to evaporate most of the water.

【００２１】得られたケーキ状物質を１２０℃で乾燥さ
せたのち、５００℃で１０時間焼成し、プレス成型した
のち、破砕して１０〜２０メッシュ部分を分取した。After the obtained cake-like substance was dried at 120 ° C., it was baked at 500 ° C. for 10 hours, press-molded, and then crushed to collect 10 to 20 mesh portions.

【００２２】こうして得られた触媒の組成は次式に示す
とおりである。The composition of the catalyst thus obtained is as shown in the following formula.

【００２３】Ｍｏ₁₂Ｂｉ_0.8Ｆｅ₃Ｗ_0.5Ｓｂ_1.5Ｎｉ₅Ｃ
ｏ₁Ｍｇ₁Ｚｎ₁Ｂ_0.5Ｃｓ_0.7Ｏ_x （式中、酸素の原子比ｘは他の元素の原子価により自然
に決まる値であるので以下Ｏ_xの記載を省略する。） この触媒をステンレス製の固定床反応管に充填し、イソ
ブチレン５％、酸素１２％、水蒸気１０％および窒素７
３％（以上は全て容量％）の原料ガスを接触時間２秒で
触媒層を通過させ、３６５℃で反応させた。その結果、
イソブチレンの反応率９７．４％、メロクロレインの選
択率８８．３％、メタクリル酸の選択率３．４％、目的
生成物の収率８９．３％であった。Mo ₁₂ Bi _0.8 Fe ₃ W _0.5 Sb _1.5 Ni ₅ C
o ₁ Mg ₁ Zn ₁ B _0.5 Cs _0.7 O _x (In the formula, the atomic ratio x of oxygen is a value which is naturally determined by the valency of other elements, so the description of O _x is omitted below.) 5% isobutylene, 12% oxygen, 10% steam and 7% nitrogen
3% (all volume% above) of the raw material gas was passed through the catalyst layer for a contact time of 2 seconds and reacted at 365 ° C. as a result,
The conversion of isobutylene was 97.4%, the selectivity of merochlorein was 88.3%, the selectivity of methacrylic acid was 3.4%, and the yield of the target product was 89.3%.

【００２４】［比較例１］実施例１と同一組成を有する
触媒を以下の手順で調製した。Comparative Example 1 A catalyst having the same composition as in Example 1 was prepared by the following procedure.

【００２５】純水１０００部にモリブデン酸アンモニウ
ム５００部、パラタングステン酸アンモニウム３０．８
部、ホウ酸７．３部および硝酸セシウム３２．２部を加
え加熱攪拌した（この溶液をＡ液と呼ぶ）。500 parts of ammonium molybdate and 30.8 parts of ammonium paratungstate in 1000 parts of pure water
And 7.3 parts of boric acid and 32.2 parts of cesium nitrate were added and stirred with heating (this solution is referred to as solution A).

【００２６】別に、純水８５０部に６０重量％硝酸２５
０部を加え、均一にしたのち、硝酸ビスマス９１．６部
を加え溶解した。これに硝酸第二鉄２８６．０部、硝酸
ニッケル３４３．２部、硝酸コバルト６８．７部、硝酸
マグネシウム６０．５部および硝酸亜鉛７０．２部を順
次加え溶解した（この溶液をＢ液と呼ぶ）。Separately, 850 parts of pure water is mixed with 25% by weight of nitric acid 25%.
After 0 parts were added and the mixture was made uniform, 91.6 parts of bismuth nitrate was added and dissolved. 286.0 parts of ferric nitrate, 343.2 parts of nickel nitrate, 68.7 parts of cobalt nitrate, 60.5 parts of magnesium nitrate and 70.2 parts of zinc nitrate were sequentially added and dissolved. Call).

【００２７】Ａ液にＢ液を加えスラリー状としたのち、
三酸化アンチモン５１．６部を加え加熱攪拌し、大部分
の水分を蒸発させた。After adding liquid B to liquid A to form a slurry,
51.6 parts of antimony trioxide was added and heated and stirred to evaporate most of the water.

【００２８】得られたケーキ状物質を１２０℃で乾燥さ
せたのち、５００℃で１０時間焼成し、プレス成型した
のち、破砕して１０〜２０メッシュ部分を分取した。After the obtained cake-like substance was dried at 120 ° C., it was baked at 500 ° C. for 10 hours, press-molded, and then crushed to obtain 10 to 20 mesh portions.

【００２９】この触媒を用いて実施例１と同じ条件で反
応を行った。その結果、イソブチレンの反応率９６．０
％、メタクロレインの選択率８８．０％、メタクリル酸
の選択率３．５％、目的生成物の収率８７．８％であっ
た。化合物Ａを用いた実施例１に対して、化合物Ａを用
いないと、収率が低下した。Using this catalyst, a reaction was carried out under the same conditions as in Example 1. As a result, the conversion of isobutylene was 96.0.
%, The selectivity of methacrolein was 88.0%, the selectivity of methacrylic acid was 3.5%, and the yield of the target product was 87.8%. In contrast to Example 1 using compound A, the yield was reduced when compound A was not used.

【００３０】［比較例２］実施例１と同一組成を有する
触媒を実施例１に準じて調製した。ただし、化合物Ａは
１２０℃で乾燥させたのち、熱処理を行わずに用いた。Comparative Example 2 A catalyst having the same composition as in Example 1 was prepared according to Example 1. However, the compound A was used without drying after drying at 120 ° C.

【００３１】この触媒を用いて実施例１と同じ条件で反
応を行った。その結果、イソブチレンの反応率９６．２
％、メタクロレインの選択率８７．８％、メタクリル酸
の選択率３．５％、目的生成物の収率８７．８％であっ
た。化合物Ａを所定の温度範囲内で熱処理を行った実施
例１に対して、化合物Ａを熱処理しないで用いると、収
率が低下した。Using this catalyst, a reaction was carried out under the same conditions as in Example 1. As a result, the conversion of isobutylene was 96.2.
%, Selectivity for methacrolein was 87.8%, selectivity for methacrylic acid was 3.5%, and yield of the target product was 87.8%. When the compound A was used without heat treatment in Example 1 in which the compound A was heat-treated within a predetermined temperature range, the yield was reduced.

【００３２】［比較例３］実施例１と同一組成を有する
触媒を実施例１に準じて調製した。ただし、化合物Ａの
熱処理温度を７００℃とした。熱処理後の化合物は溶融
した形跡があり、ガラス状の固形物であった。Comparative Example 3 A catalyst having the same composition as in Example 1 was prepared according to Example 1. However, the heat treatment temperature of Compound A was 700 ° C. The compound after heat treatment had a trace of melting and was a glassy solid.

【００３３】この触媒を用いて実施例１と同じ条件で反
応を行った。その結果、イソブチレンの反応率９６．０
％、メタクロレインの選択率８８．１％、メタクリル酸
の選択率３．５％、目的生成物の収率８７．９％であっ
た。化合物Ａを所定の温度範囲内で熱処理を行った実施
例１に対して、化合物Ａの熱処理温度が６００℃を超え
ると、収率が低下した。Using this catalyst, a reaction was carried out under the same conditions as in Example 1. As a result, the conversion of isobutylene was 96.0.
%, The selectivity of methacrolein was 88.1%, the selectivity of methacrylic acid was 3.5%, and the yield of the target product was 87.9%. When the heat treatment temperature of Compound A exceeds 600 ° C. as compared with Example 1 in which Compound A was heat-treated within a predetermined temperature range, the yield was reduced.

【００３４】［実施例２］実施例１の触媒を用いて、反
応原料を三級ブタノールに変えた以外は実施例１と同じ
条件で反応を行った。その結果、三級ブタノールの反応
率１００％、メタクロレインの選択率８７．３％、メタ
クリル酸の選択率３．０％、目的生成物の収率９０．３
％であった。Example 2 Using the catalyst of Example 1, a reaction was carried out under the same conditions as in Example 1 except that the starting material for the reaction was changed to tertiary butanol. As a result, the conversion of tertiary butanol was 100%, the selectivity of methacrolein was 87.3%, the selectivity of methacrylic acid was 3.0%, and the yield of the target product was 90.3%.
%Met.

【００３５】［比較例４］比較例１の触媒を用いて、実
施例２と同じ条件で反応を行った。その結果、三級ブタ
ノールの反応率１００％、メタクロレインの選択率８
６．０％、メタクリル酸の選択率２．８％、目的生成物
の収率８８．８％であった。化合物Ａを用いた実施例２
に対して、化合物Ａを用いないと、収率が低下した。Comparative Example 4 Using the catalyst of Comparative Example 1, a reaction was carried out under the same conditions as in Example 2. As a result, the conversion of tertiary butanol was 100% and the selectivity of methacrolein was 8%.
The methacrylic acid selectivity was 6.0%, and the yield of the target product was 88.8%. Example 2 using compound A
In contrast, when compound A was not used, the yield decreased.

【００３６】［実施例３］純水５００部に６０重量％硝
酸５０部を加え、均一にしたのち、硝酸ビスマス９１．
６部を加え溶解した。これに硝酸カリウム２．４部およ
び硝酸セシウム３２．２部を溶解したのち加熱攪拌し、
大部分の水分を蒸発させた。得られたケーキ状物質を１
２０℃で乾燥させたのち、４００℃で３時間熱処理し、
乳鉢で粉砕した（これを化合物Ｂと呼ぶ）。Example 3 50 parts of 60% by weight nitric acid was added to 500 parts of pure water to make the mixture uniform.
6 parts were added and dissolved. After dissolving 2.4 parts of potassium nitrate and 32.2 parts of cesium nitrate, the mixture was heated and stirred.
Most of the water was evaporated. The cake-like substance obtained is 1
After drying at 20 ° C, heat-treating at 400 ° C for 3 hours,
Crushed in a mortar (this is called compound B).

【００３７】純水１０００部にモリブデン酸アンモニウ
ム５００部およびパラタングステン酸アンモニウム１
８．５部を加え加熱攪拌した（この溶液をＡ液と呼
ぶ）。In 1000 parts of pure water, 500 parts of ammonium molybdate and ammonium paratungstate 1
8.5 parts were added and heated and stirred (this solution is referred to as solution A).

【００３８】別に、純水１５００部に硝酸第二鉄２３
８．４部、硝酸ニッケル２０５．９部、硝酸コバルト２
７４．７部および硝酸鉛３９．１部を順次加え溶解した
（この溶液をＢ液と呼ぶ）。Separately, ferric nitrate 23 was added to 1500 parts of pure water.
8.4 parts, nickel nitrate 205.9 parts, cobalt nitrate 2
74.7 parts and 39.1 parts of lead nitrate were sequentially added and dissolved (this solution is called solution B).

【００３９】Ａ液に化合物ＢおよびＢ液を加えスラリー
状としたのち、三酸化アンチモン４４．７部および酸化
第一スズ３１．８部を加え加熱攪拌し、大部分の水分を
蒸発させた。Compound B and solution B were added to solution A to form a slurry, and then 44.7 parts of antimony trioxide and 31.8 parts of stannous oxide were added and heated with stirring to evaporate most of the water.

【００４０】得られたケーキ状物質を１２０℃で乾燥さ
せたのち、５００℃で１０時間焼成し、プレス成型した
のち、破砕して１０〜２０メッシュ部分を分取した。こ
うして得られた触媒の組成は次式に示すとおりである。The obtained cake-like substance was dried at 120 ° C., baked at 500 ° C. for 10 hours, press-molded, and then crushed to fractionate a 10 to 20 mesh portion. The composition of the catalyst thus obtained is as shown in the following formula.

【００４１】Ｍｏ₁₂Ｂｉ_0.8Ｆｅ_2.5Ｗ_0.3Ｓｂ_1.3Ｎｉ₃
Ｃｏ₄Ｓｎ₁Ｐｂ_0.5Ｋ_0.1Ｃｓ_0.7 この触媒を用いて実施例１と同じ条件で反応を行った。
その結果、イソブチレンの反応率９７．２％、メタクロ
レインの選択率８６．１％、メタクリル酸の選択率５．
１％、目的生成物の収率８８．６％であった。Mo ₁₂ Bi _0.8 Fe _2.5 W _0.3 Sb _1.3 Ni ₃
Co ₄ Sn ₁ Pb _0.5 K _0.1 Cs _{0.7 Using} this catalyst, a reaction was carried out under the same conditions as in Example 1.
As a result, the conversion of isobutylene was 97.2%, the selectivity of methacrolein was 86.1%, and the selectivity of methacrylic acid was 5.
The yield of the target product was 88.6%.

【００４２】［比較例５］実施例３と同一組成を有する
触媒を以下の手順で調製した。Comparative Example 5 A catalyst having the same composition as in Example 3 was prepared by the following procedure.

【００４３】純水１０００部にモリブデン酸アンモニウ
ム５００部、パラタングステン酸アンモニウム１８．５
部、硝酸カリウム２．４および硝酸セシウム３２．２部
を加え加熱攪拌した（この溶液をＡ液と呼ぶ）。500 parts of ammonium molybdate and 18.5 parts of ammonium paratungstate in 1000 parts of pure water
And 2.4 parts of potassium nitrate and 32.2 parts of cesium nitrate were added and stirred with heating (this solution is referred to as solution A).

【００４４】別に、純水１５００部に６０重量％硝酸２
５０部を加え、均一にしたのち、硝酸ビスマス９１．６
部を加え溶解した。これに硝酸第二鉄２３８．４部、硝
酸ニッケル２０５．９部、硝酸コバルト２７４．７部お
よび硝酸鉛３９．１部を順次加え溶解した（この溶液を
Ｂ液と呼ぶ）。Separately, 60 parts by weight of nitric acid 2
After adding 50 parts and making it uniform, bismuth nitrate 91.6
Was added and dissolved. 238.4 parts of ferric nitrate, 205.9 parts of nickel nitrate, 274.7 parts of cobalt nitrate and 39.1 parts of lead nitrate were sequentially added and dissolved (this solution is referred to as solution B).

【００４５】Ａ液にＢ液を加えスラリー状としたのち、
三酸化アンチモン４４．７部および酸化第一スズ３１．
８部を加え加熱攪拌し、大部分の水分を蒸発させた。After adding liquid B to liquid A to form a slurry,
44.7 parts of antimony trioxide and stannous oxide
8 parts were added and the mixture was heated and stirred to evaporate most of the water.

【００４６】得られたケーキ状物質を１２０℃で乾燥さ
せたのち、５００℃で１００時間焼成し、プレス成型し
たのち、破砕して１０〜２０メッシュ部分を分取した。After the obtained cake-like substance was dried at 120 ° C., it was baked at 500 ° C. for 100 hours, press-molded, and then crushed to obtain 10 to 20 mesh portions.

【００４７】この触媒を用いて実施例３と同じ条件で反
応を行った。その結果、イソブチレンの反応率９５．５
％、メタクロレインの選択率８６．０％、メタクリル酸
の選択率５．２％、目的生成物の収率８７．１％であっ
た。化合物Ｂを用いた実施例３に対して、化合物Ｂを用
いないと、収率が低下した。Using this catalyst, a reaction was carried out under the same conditions as in Example 3. As a result, the conversion of isobutylene was 95.5.
%, Methacrolein selectivity 86.0%, methacrylic acid selectivity 5.2%, and yield of the target product 87.1%. In contrast to Example 3 in which compound B was used, the yield was reduced when compound B was not used.

【００４８】［実施例４］純水５００部に６０重量％硝
酸５０部を加え、均一にしたのち、硝酸ビスマス１１
４．５部を加え溶解した。これに硝酸セシウム９．２部
および硝酸タリウム６．３部を溶解し、更にパラタング
ステン酸アンモニウム１８．５部を加えたのち加熱攪拌
し、大部分の水分を蒸発させた。得られたケーキ状物質
を１２０℃で乾燥させたのち、４００℃で３時間熱処理
し、乳鉢で粉砕した（これを化合物Ｃと呼ぶ）。Example 4 50 parts of 60% by weight nitric acid was added to 500 parts of pure water to make the mixture uniform, and then bismuth nitrate 11 was added.
4.5 parts were added and dissolved. 9.2 parts of cesium nitrate and 6.3 parts of thallium nitrate were dissolved therein, and 18.5 parts of ammonium paratungstate was further added, followed by heating and stirring to evaporate most of the water. After drying the obtained cake-like substance at 120 ° C., it was heat-treated at 400 ° C. for 3 hours and pulverized in a mortar (this is referred to as compound C).

【００４９】純水１０００部にモリブデン酸アンモニウ
ム５００部を加え加熱攪拌した（この溶液をＡ液と呼
ぶ）。500 parts of ammonium molybdate was added to 1000 parts of pure water, and the mixture was heated and stirred (this solution is called solution A).

【００５０】別に、純水１０００部に硝酸第二鉄２８
６．０部、硝酸コバルト４１２．０部、硝酸マグネシウ
ム３０．３部および硝酸亜鉛１０５．３部を順次加え溶
解した（この溶液をＢ液と呼ぶ）。Separately, ferric nitrate 28 was added to 1000 parts of pure water.
6.0 parts, 412.0 parts of cobalt nitrate, 30.3 parts of magnesium nitrate and 105.3 parts of zinc nitrate were sequentially added and dissolved (this solution is referred to as "solution B").

【００５１】Ａ液に化合物ＣおよびＢ液を加えスラリー
状としたのち、三酸化アンチモン３４．４部、酸化クロ
ム２．４部および３０重量％シリカゾル４７２．２部を
加え加熱攪拌し、大部分の水分を蒸発させた。Compound C and liquid B were added to liquid A to form a slurry, and then 34.4 parts of antimony trioxide, 2.4 parts of chromium oxide and 472.2 parts of 30% by weight silica sol were added, and the mixture was heated and stirred. Of water was evaporated.

【００５２】得られたケーキ状物質を１２０℃で乾燥さ
せたのち、５００℃で６時間焼成し、プレス成型したの
ち、破砕して１０〜２０メッシュ部分を分取した。The obtained cake-like substance was dried at 120 ° C., baked at 500 ° C. for 6 hours, press-molded, and then crushed to fractionate 10 to 20 mesh portions.

【００５３】こうして得られた触媒の組成は次式に示す
とおりである。The composition of the catalyst thus obtained is as shown in the following formula.

【００５４】 Ｍｏ₁₂Ｂｉ₁Ｆｅ₃Ｗ_0.3Ｓｂ₁ Ｃｏ₆Ｍｇ_0.5Ｚｎ_1.5Ｃｒ_0.1Ｃｓ_0.2Ｔｌ_0.1Ｓｉ₁₀ この触媒を用いて接触時間を３．６秒、反応温度を３６
０℃とした以外は実施例１と同じ条件で反応を行った。
その結果、イソブチレンの反応率９６．８％、メタクロ
レインの選択率８９．７％、メタクリル酸の選択率３．
３％、目的生成物の収率９０．０％であった。Mo ₁₂ Bi ₁ Fe ₃ W _0.3 Sb ₁ Co ₆ Mg _0.5 Zn _1.5 Cr _0.1 Cs _0.2 Tl _0.1 Si _{10 Using} this catalyst, the contact time was 3.6 seconds and the reaction temperature was 36.
The reaction was performed under the same conditions as in Example 1 except that the temperature was set to 0 ° C.
As a result, the conversion of isobutylene was 96.8%, the selectivity of methacrolein was 89.7%, and the selectivity of methacrylic acid was 3.
The yield of the target product was 30.0% and 90.0%.

【００５５】［比較例６］実施例４と同一組成を有する
触媒を以下の手順で調製した。Comparative Example 6 A catalyst having the same composition as in Example 4 was prepared by the following procedure.

【００５６】純水１０００部にモリブデン酸アンモニウ
ム５００部、パラタングステン酸アンモニウム１８．５
部、硝酸タリウム６．３部および硝酸セシウム９．２部
を加え加熱攪拌した（この溶液をＡ液と呼ぶ）。500 parts of ammonium molybdate and 18.5 parts of ammonium paratungstate in 1000 parts of pure water
6.3 parts of thallium nitrate and 9.2 parts of cesium nitrate were added and heated and stirred (this solution is referred to as solution A).

【００５７】別に、純水１０００部に６０重量％硝酸２
５０部を加え、均一にしたのち、硝酸ビスマス１１４．
５部を加え溶解した。これに硝酸第二鉄２８６．０部、
硝酸コバルト４１２．０部、硝酸マグネシウム３０．３
部および硝酸亜鉛１０５．３部を順次加え溶解した（こ
の溶液をＢ液と呼ぶ）。Separately, 60 parts by weight of nitric acid 2
After adding 50 parts and homogenizing, bismuth nitrate
5 parts were added and dissolved. 286.0 parts of ferric nitrate,
412.0 parts of cobalt nitrate, 30.3 of magnesium nitrate
And 105.3 parts of zinc nitrate were sequentially added and dissolved (this solution is referred to as solution B).

【００５８】Ａ液にＢ液を加えスラリー状としたのち、
三酸化アンチモン３４．４部、酸化クロム２．４部およ
び３０重量％シリカゾル４７２．２部を加え加熱攪拌
し、大部分の水分を蒸発させた。After adding the liquid B to the liquid A to form a slurry,
34.4 parts of antimony trioxide, 2.4 parts of chromium oxide and 472.2 parts of 30% by weight silica sol were added, and the mixture was stirred with heating to evaporate most of the water.

【００５９】得られたケーキ状物質を１２０℃で乾燥さ
せたのち、５００℃で６時間焼成し、プレス成型したの
ち、破砕して１０〜２０メッシュ部分を分取した。The obtained cake-like substance was dried at 120 ° C., baked at 500 ° C. for 6 hours, press-molded, and then crushed to obtain a 10 to 20 mesh portion.

【００６０】この触媒を用いて実施例４と同じ条件で反
応を行った。その結果、イソブチレンの反応率９６．０
％、メタクロレインの選択率８９．０％、メタクリル酸
の選択率３．０％、目的生成物の収率８８．３％であっ
た。化合物Ｃを用いた実施例４に対して、化合物Ｃを用
いないと、収率が低下した。Using this catalyst, a reaction was carried out under the same conditions as in Example 4. As a result, the conversion of isobutylene was 96.0.
%, Methacrolein selectivity was 89.0%, methacrylic acid selectivity was 3.0%, and the yield of the target product was 88.3%. In contrast to Example 4 using compound C, the yield was reduced when compound C was not used.

【００６１】［実施例５］純水５００部に６０重量％硝
酸５０部を加え、均一にしたのち、硝酸ビスマス１１
４．５部を加え溶解した。これに硝酸ルビジウム７．０
部を溶解したのち、三酸化アンチモン３４．４部を加え
加熱攪拌し、大部分の水分を蒸発させた。得られたケー
キ状物質を１２０℃で乾燥させたのち、４００℃で３時
間熱処理し、乳鉢で粉砕した（これを化合物Ｄと呼
ぶ）。Example 5 After adding 50 parts by weight of 60% by weight nitric acid to 500 parts of pure water to make the mixture uniform, bismuth nitrate 11 was added.
4.5 parts were added and dissolved. Rubidium nitrate 7.0
34.4 parts of antimony trioxide was added, and the mixture was heated and stirred to evaporate most of the water. After drying the obtained cake-like substance at 120 ° C., it was heat-treated at 400 ° C. for 3 hours and pulverized in a mortar (this is called compound D).

【００６２】純水１０００部にモリブデン酸アンモニウ
ム５００部、パラタングステン酸アンモニウム３０．８
部および硝酸セシウム１３．８部を加え加熱攪拌した
（この溶液をＡ液と呼ぶ）。In 1000 parts of pure water, 500 parts of ammonium molybdate, 30.8 parts of ammonium paratungstate
And 13.8 parts of cesium nitrate were added and stirred with heating (this solution is referred to as solution A).

【００６３】別に、純水１５００部に硝酸第二鉄２６
７．０部、硝酸第一鉄１３．１部、硝酸ニッケル４８
０．４部、硝酸マンガン６７．７部、硝酸マグネシウム
１２１．０部、硝酸亜鉛３５．１部およびテルル酸５．
４部を順次加え溶解した（この溶液をＢ液と呼ぶ）。Separately, ferric nitrate 26 was added to 1500 parts of pure water.
7.0 parts, ferrous nitrate 13.1 parts, nickel nitrate 48
0.4 parts, manganese nitrate 67.7 parts, magnesium nitrate 121.0 parts, zinc nitrate 35.1 parts and telluric acid 5.
Four parts were sequentially added and dissolved (this solution is referred to as solution B).

【００６４】Ａ液に化合物ＤおよびＢ液を加えスラリー
状としたのち加熱攪拌し、大部分の水分を蒸発させた。Compound D and liquid B were added to liquid A to form a slurry, which was then heated and stirred to evaporate most of the water.

【００６５】得られたケーキ状物質を１２０℃で乾燥さ
せたのち、５００℃で１０時間焼成し、プレス成型した
のち、破砕して１０〜２０メッシュ部分を分取した。After the obtained cake-like substance was dried at 120 ° C., it was baked at 500 ° C. for 10 hours, press-molded, and then crushed to fractionate 10 to 20 mesh portions.

【００６６】こうして得られた触媒の組成は次式に示す
とおりである。The composition of the catalyst thus obtained is as shown in the following formula.

【００６７】 Ｍｏ₁₂Ｂｉ₁Ｆｅ₃Ｗ_0.5Ｓｂ₁ Ｎｉ₇Ｍｇ₂Ｚｎ_0.5Ｍｎ₁Ｓ_0.2Ｔｅ_0.1Ｒｂ_0.2Ｃｓ_0.3 この触媒を用いて、反応温度を３７０℃とした以外は実
施例１と同じ条件で反応を行った。その結果、イソブチ
レンの反応率９４．８％、メタクロレインの選択率９
１．２％、メタクリル酸の選択率２．５％、目的生成物
の収率８８．８％であった。Mo ₁₂ Bi ₁ Fe ₃ W _0.5 Sb ₁ Ni ₇ Mg ₂ Zn _0.5 Mn ₁ S _0.2 Te _0.1 Rb _0.2 Cs _{0.3 Using} this catalyst, a reaction was carried out under the same conditions as in Example 1 except that the reaction temperature was changed to 370 ° C. As a result, the conversion of isobutylene was 94.8% and the selectivity of methacrolein was 9
The selectivity of methacrylic acid was 2.5%, and the yield of the target product was 88.8%.

【００６８】［比較例７］実施例５と同一組成を有する
触媒を以下の手順で調製した。Comparative Example 7 A catalyst having the same composition as in Example 5 was prepared by the following procedure.

【００６９】純水１０００部にモリブデン酸アンモニウ
ム５００部、パラタングステン酸アンモニウム３０．８
部、硝酸ルビジウム７．０部および硝酸セシウム１３．
８部を加え加熱攪拌した（この溶液をＡ液と呼ぶ）。In 1000 parts of pure water, 500 parts of ammonium molybdate, 30.8 parts of ammonium paratungstate
Parts, 7.0 parts of rubidium nitrate and cesium nitrate
8 parts were added and the mixture was heated and stirred (this solution is referred to as solution A).

【００７０】別に、純水１５００部に６０重量％硝酸２
５０部を加え、均一にしたのち、硝酸ビスマス１１４．
５部を加え溶解した。これに硝酸第二鉄２６７．０部、
硝酸第一鉄１３．１部、硝酸ニッケル４８０．４部、硝
酸マンガン６７．７部、硝酸マグネシウム１２１．０
部、硝酸亜鉛３５．１部およびテルル酸５．４部を順次
加え溶解した（この溶液をＢ液と呼ぶ）。Separately, 1500 parts of pure water was mixed with 60% by weight of nitric acid 2
After adding 50 parts and homogenizing, bismuth nitrate
5 parts were added and dissolved. 267.0 parts of ferric nitrate,
13.1 parts of ferrous nitrate, 480.4 parts of nickel nitrate, 67.7 parts of manganese nitrate, 121.0 parts of magnesium nitrate
, 35.1 parts of zinc nitrate and 5.4 parts of telluric acid were sequentially added and dissolved (this solution is referred to as solution B).

【００７１】Ａ液にＢ液を加えスラリー状としたのち、
三酸化アンチモン３４．４部を加え加熱攪拌し、大部分
の水分を蒸発させた。After adding the liquid B to the liquid A to form a slurry,
34.4 parts of antimony trioxide was added and heated and stirred to evaporate most of the water.

【００７２】得られたケーキ状物質を１２０℃で乾燥さ
せたのち、５００℃で１０時間焼成し、プレス成型した
のち、破砕して１０〜２０メッシュ部分を分取した。After the obtained cake-like substance was dried at 120 ° C., it was baked at 500 ° C. for 10 hours, press-molded, and then crushed to fractionate 10 to 20 mesh portions.

【００７３】この触媒を用いて実施例５と同じ条件で反
応を行った。その結果、イソブチレンの反応率９３．０
％、メタクロレインの選択率９１．０％、メタクリル酸
の選択率２．５％、目的生成物の収率８７．０％であっ
た。化合物Ｄを用いた実施例５に対して、化合物Ｄを用
いないと、収率が低下した。Using this catalyst, a reaction was carried out under the same conditions as in Example 5. As a result, the conversion of isobutylene was 93.0.
%, The selectivity of methacrolein was 91.0%, the selectivity of methacrylic acid was 2.5%, and the yield of the target product was 87.0%. As compared with Example 5 using Compound D, the yield was reduced when Compound D was not used.

【００７４】［実施例６］純水１０００部に６０重量％
硝酸５０部を加え均一にしたのち、硝酸ビスマス１０
３．０部を加え溶解した。これに硝酸セシウム３２．２
部を溶解したのち、パラタングステン酸アンモニウム３
０．８部および三酸化アンチモン５１．６部を加え加熱
攪拌し、大部分の水分を蒸発させた。得られたケーキ状
物質を１２０℃で乾燥させたのち、４００℃で３時間熱
処理し、乳鉢で粉砕した（これを化合物Ｅと呼ぶ）。[Example 6] 60% by weight in 1000 parts of pure water
After adding 50 parts of nitric acid and making it uniform, bismuth nitrate 10
3.0 parts were added and dissolved. Cesium nitrate 32.2
After dissolving the part, ammonium paratungstate 3
0.8 parts and 51.6 parts of antimony trioxide were added and heated and stirred to evaporate most of the water. After drying the obtained cake-like substance at 120 ° C., it was heat-treated at 400 ° C. for 3 hours and pulverized in a mortar (this is referred to as compound E).

【００７５】純水１０００部にモリブデン酸アンモニウ
ム５００部を加え加熱攪拌した（この溶液をＡ液と呼
ぶ）。[0075] 500 parts of ammonium molybdate was added to 1000 parts of pure water and heated and stirred (this solution is referred to as solution A).

【００７６】別に、純水１５００部に硝酸第二鉄２５
７．４部、硝酸ニッケル６８．６部、硝酸コバルト３４
３．３部、硝酸マグネシウム６０．５部および亜セレン
酸２４．４部を順次加え溶解した（この溶液をＢ液と呼
ぶ）。Separately, ferric nitrate 25 was added to 1500 parts of pure water.
7.4 parts, nickel nitrate 68.6 parts, cobalt nitrate 34
3.3 parts, 60.5 parts of magnesium nitrate and 24.4 parts of selenous acid were sequentially added and dissolved (this solution is called solution B).

【００７７】Ａ液に化合物ＥおよびＢ液を加えスラリー
状としたのち、３０重量％シリカゾル３７．８部を加え
加熱攪拌し、大部分の水分を蒸発させた。Compound E and liquid B were added to liquid A to form a slurry, and then 37.8 parts of a 30% by weight silica sol was added, and the mixture was heated and stirred to evaporate most of the water.

【００７８】得られたケーキ状物質を１２０℃で乾燥さ
せたのち、５００℃で１０時間焼成し、プレス成型した
のち、破砕して１０〜２０メッシュ部分を分取した。After the obtained cake-like substance was dried at 120 ° C., it was baked at 500 ° C. for 10 hours, press-molded, and then crushed to fractionate 10 to 20 mesh portions.

【００７９】こうして得られた触媒の組成は次式で示さ
れる。The composition of the catalyst thus obtained is shown by the following formula.

【００８０】Ｍｏ₁₂Ｂｉ_0.9Ｆｅ_2.7Ｗ_0.5Ｓｂ_1.5Ｎｉ₁
Ｃｏ₅Ｍｇ₁Ｓｅ_0.8Ｃｓ_0.7Ｓｉ_0.8 この触媒を用いて実施例１と同じ条件で反応を行った。
その結果、イソブチレンの反応率９７．３％、メタクロ
レインの選択率８７．４％、メタクリル酸の選択率４．
１％、目的生成物の収率８９．０％であった。Mo ₁₂ Bi _0.9 Fe _2.7 W _0.5 Sb _1.5 Ni ₁
Co ₅ Mg ₁ Se _0.8 Cs _0.7 Si _{0.8 Using} this catalyst, a reaction was carried out under the same conditions as in Example 1.
As a result, the conversion of isobutylene was 97.3%, the selectivity of methacrolein was 87.4%, and the selectivity of methacrylic acid was 4.
The yield of the target product was 89.0%.

【００８１】［比較例８］実施例６と同一組成を有する
触媒を以下の手順で調製した。Comparative Example 8 A catalyst having the same composition as in Example 6 was prepared by the following procedure.

【００８２】純水１０００部にモリブデン酸アンモニウ
ム５００部、硝酸セシウム３２．２部およびパラタング
ステン酸アンモニウム３０．８部を加え加熱攪拌した
（この溶液をＡ液と呼ぶ）。To 1000 parts of pure water were added 500 parts of ammonium molybdate, 32.2 parts of cesium nitrate, and 30.8 parts of ammonium paratungstate, and the mixture was heated and stirred (this solution is referred to as solution A).

【００８３】別に、純水１５００部に６０重量％硝酸２
５０部を加え、均一にしたのち、硝酸ビスマス１０３．
０部を加え溶解した。これに硝酸第二鉄２５７．４部、
硝酸ニッケル６８．６部、硝酸コバルト３４３．３部、
硝酸マグネシウム６０．５部および亜セレン酸２４．４
部を順次加え溶解した（この溶液をＢ液と呼ぶ）。Separately, 1500 parts of pure water was mixed with 60% by weight of nitric acid 2
After adding 50 parts and homogenizing, bismuth nitrate
0 parts were added and dissolved. 257.4 parts of ferric nitrate,
68.6 parts of nickel nitrate, 343.3 parts of cobalt nitrate,
60.5 parts of magnesium nitrate and 24.4 parts of selenous acid
Were added sequentially and dissolved (this solution is referred to as solution B).

【００８４】Ａ液にＢ液を加えスラリー状としたのち、
三酸化アンチモン５１．６部および３０重量％シリカゾ
ル３７．８部を加え加熱攪拌し、大部分の水分を蒸発さ
せた。After adding liquid B to liquid A to form a slurry,
51.6 parts of antimony trioxide and 37.8 parts of a 30% by weight silica sol were added, and the mixture was heated and stirred to evaporate most of the water.

【００８５】得られたケーキ状物質を１２０℃で乾燥さ
せたのち、５００℃で１０時間焼成し、プレス成型した
のち、破砕して１０〜２０メッシュ部分を分取した。After the obtained cake-like substance was dried at 120 ° C., it was baked at 500 ° C. for 10 hours, press-molded, and then crushed to fractionate 10 to 20 mesh portions.

【００８６】この触媒を用いて実施例６と同じ条件で反
応を行った。その結果、イソブチレンの反応率９６．０
％、メタクロレインの選択率８７．０％、メタクリル酸
の選択率４．０％、目的生成物の収率８７．４％であっ
た。化合物Ｅを用いた実施例６に対して、化合物Ｅを用
いないと、収率が低下した。Using this catalyst, a reaction was carried out under the same conditions as in Example 6. As a result, the conversion of isobutylene was 96.0.
%, The selectivity of methacrolein was 87.0%, the selectivity of methacrylic acid was 4.0%, and the yield of the target product was 87.4%. In contrast to Example 6 in which compound E was used, the yield was reduced when compound E was not used.

【００８７】［実施例７］純水５００部に６０重量％硝
酸５０部を加え、均一にしたのち、硝酸ビスマス１１
４．５部を加え溶解した。これに硝酸セシウム０．９部
を溶解したのち、ｐＨ＝９．０となるまで２８％アンモ
ニア水を添加し沈殿を生成させた。このスラリーを加熱
攪拌し、大部分の水分を蒸発させた。得られたケーキ状
物質を１２０℃で乾燥させたのち、４００℃で３時間熱
処理し、乳鉢で粉砕した（これを化合物Ｆと呼ぶ）。Example 7 50 parts of 60% by weight nitric acid was added to 500 parts of pure water to make the mixture uniform, and then bismuth nitrate 11 was added.
4.5 parts were added and dissolved. After dissolving 0.9 parts of cesium nitrate, 28% aqueous ammonia was added until pH = 9.0 to form a precipitate. The slurry was heated and stirred to evaporate most of the water. After the obtained cake-like substance was dried at 120 ° C., it was heat-treated at 400 ° C. for 3 hours and pulverized in a mortar (this is referred to as compound F).

【００８８】純水１０００部にモリブデン酸アンモニウ
ム５００部およびパラタングステン酸アンモニウム１
８．５部を加え加熱攪拌した（この溶液をＡ液と呼
ぶ）。In 1000 parts of pure water, 500 parts of ammonium molybdate and ammonium paratungstate 1
8.5 parts were added and heated and stirred (this solution is referred to as solution A).

【００８９】別に、純水１０００部に硝酸第二鉄１２
３．９部、硝酸コバルト３０９．０部、硝酸亜鉛７．０
部および硝酸マンガン５．４部を順次加え溶解した（こ
の溶液をＢ液と呼ぶ）。Separately, ferric nitrate 12 was added to 1000 parts of pure water.
3.9 parts, cobalt nitrate 309.0 parts, zinc nitrate 7.0
And 5.4 parts of manganese nitrate were sequentially added and dissolved (this solution is referred to as solution B).

【００９０】Ａ液に化合物ＦおよびＢ液を加えスラリー
状としたのち、三酸化アンチモン１０．３部および３０
重量％シリカゾル５６．７部を加え加熱攪拌し、大部分
の水分を蒸発させた。Compound F and liquid B were added to liquid A to form a slurry, and 10.3 parts of antimony trioxide and 30 parts of antimony trioxide were added.
56.7 parts by weight of a silica sol was added and stirred with heating to evaporate most of the water.

【００９１】得られたケーキ状物質を１２０℃で乾燥さ
せたのち、空気雰囲気下３００℃で１時間焼成し、プレ
ス成型したのち、破砕して１０〜２０メッシュ部分を分
取した。次に再び５００℃で６時間焼成した。After the obtained cake-like substance was dried at 120 ° C., it was baked at 300 ° C. for 1 hour in an air atmosphere, press-molded, and then crushed to collect 10 to 20 mesh portions. Next, it was fired again at 500 ° C. for 6 hours.

【００９２】こうして得られた触媒の組成は次式で示さ
れる。The composition of the catalyst thus obtained is shown by the following formula.

【００９３】Ｍｏ₁₂Ｂｉ₁Ｆｅ_1.3Ｗ_0.3Ｓｂ_0.3Ｃｏ_4.5
Ｚｎ_0.1Ｍｎ_0.08Ｃｓ_0.02Ｓｉ_1.2 この触媒を用いて反応原料をプロピレンに変え、反応温
度を３１０℃、接触時間を３．６秒とした以外は実施例
１と同じ条件で反応を行った。その結果、プロピレンの
反応率９９．６％、アクロレインの選択率８９．５％、
アクリル酸の選択率５．９％、目的生成物の収率９５．
０％であった。Mo ₁₂ Bi ₁ Fe _1.3 W _0.3 Sb _0.3 Co _4.5
Zn _0.1 Mn _0.08 Cs _0.02 Si _{1.2 Using} this catalyst, the reaction was carried out under the same conditions as in Example 1 except that the reaction raw material was changed to propylene, the reaction temperature was 310 ° C., and the contact time was 3.6 seconds. As a result, the conversion of propylene was 99.6%, the selectivity of acrolein was 89.5%,
95. Selectivity of acrylic acid 5.9%, yield of target product
It was 0%.

【００９４】［比較例９］実施例７と同一組成を有する
触媒を以下の手順で調製した。Comparative Example 9 A catalyst having the same composition as in Example 7 was prepared by the following procedure.

【００９５】純水１０００部にモリブデン酸アンモニウ
ム５００部、パラタングステン酸アンモニウム１８．５
部および硝酸セシウム０．９部を加え加熱攪拌した（こ
の溶液をＡ液と呼ぶ）。In 1,000 parts of pure water, 500 parts of ammonium molybdate and 18.5 parts of ammonium paratungstate
And 0.9 parts of cesium nitrate were added and heated and stirred (this solution is referred to as solution A).

【００９６】別に、純水６００部に６０重量％硝酸４
１．９部を加え、均一にしたのち、硝酸ビスマス１１
４．５部を加え溶解した。これに硝酸第二鉄１２３．９
部、硝酸コバルト３０９．０部、硝酸亜鉛７．０部およ
び硝酸マンガン５．４部を順次加え溶解した（この溶液
をＢ液と呼ぶ）。Separately, 60 parts by weight of nitric acid 4
After adding 1.9 parts and making it uniform, bismuth nitrate 11
4.5 parts were added and dissolved. Ferric nitrate 123.9
Parts, 309.0 parts of cobalt nitrate, 7.0 parts of zinc nitrate and 5.4 parts of manganese nitrate were sequentially added and dissolved (this solution is referred to as solution B).

【００９７】Ａ液にＢ液を加えスラリー状としたのち、
三酸化アンチモン１０．３部および３０重量％シリカゾ
ル５６．７部を加え加熱攪拌し、大部分の水分を蒸発さ
せた。After adding the liquid B to the liquid A to form a slurry,
10.3 parts of antimony trioxide and 56.7 parts of a 30% by weight silica sol were added and stirred with heating to evaporate most of the water.

【００９８】得られたケーキ状物質を１２０℃で乾燥さ
せたのち、空気雰囲気下３００℃で１時間焼成し、プレ
ス成型したのち、破砕して１０〜２０メッシュ部分を分
取した。次に再び５００℃で６時間焼成した。The obtained cake-like substance was dried at 120 ° C., baked at 300 ° C. for 1 hour in an air atmosphere, press-molded, and crushed to fractionate 10 to 20 mesh portions. Next, it was fired again at 500 ° C. for 6 hours.

【００９９】この触媒を用いて実施例７と同じ条件で反
応を行った。その結果、プロピレンの反応率９９．５
％、アクロレインの選択率８８．３％、アクリル酸の選
択率５．７％、目的生成物の収率９３．５％であった。
化合物Ｆを用いた実施例７に対して、化合物Ｆを用いな
いと、収率が低下した。Using this catalyst, a reaction was carried out under the same conditions as in Example 7. As a result, the conversion of propylene was 99.5.
%, Acrolein selectivity was 88.3%, acrylic acid selectivity was 5.7%, and the yield of the desired product was 93.5%.
In contrast to Example 7 using Compound F, the yield was reduced when Compound F was not used.

【０１００】［実施例８］純水５００部に６０重量％硝
酸５０部を加え、均一にしたのち、硝酸ビスマス１１
４．５部を加え溶解した。これに硝酸セシウム１．８部
を溶解したのち加熱攪拌し、大部分の水分を蒸発させ
た。得られたケーキ状物質を１２０℃で乾燥させたの
ち、４００℃で３時間熱処理し、乳鉢で粉砕した（これ
を化合物Ｇと呼ぶ）。Example 8 To 50 parts of pure water was added 50 parts of 60% by weight nitric acid, and the mixture was made uniform.
4.5 parts were added and dissolved. After dissolving 1.8 parts of cesium nitrate therein, the mixture was heated and stirred to evaporate most of the water. After drying the obtained cake-like substance at 120 ° C., it was heat-treated at 400 ° C. for 3 hours and pulverized in a mortar (this is referred to as compound G).

【０１０１】純水１０００部にモリブデン酸アンモニウ
ム５００部およびパラタングステン酸アンモニウム１
８．５部を加え加熱攪拌した（この溶液をＡ液と呼
ぶ）。In 1000 parts of pure water, 500 parts of ammonium molybdate and ammonium paratungstate 1
8.5 parts were added and heated and stirred (this solution is referred to as solution A).

【０１０２】別に、純水８５０部に硝酸第二鉄９５．３
部、硝酸ニッケル３４．３部、硝酸コバルト２７４．７
部、硝酸亜鉛７．０部、硝酸ランタン１０．２部および
８５重量％リン酸０．５部を順次加え溶解した（この溶
液をＢ液と呼ぶ）。Separately, 95.3 parts of ferric nitrate was added to 850 parts of pure water.
Parts, nickel nitrate 34.3 parts, cobalt nitrate 274.7
, 7.0 parts of zinc nitrate, 10.2 parts of lanthanum nitrate and 0.5 part of 85% by weight phosphoric acid were sequentially added and dissolved (this solution is referred to as solution B).

【０１０３】Ａ液に化合物ＧおよびＢ液を加えスラリー
状としたのち、３０重量％シリカゾル２３６．３部を加
え加熱攪拌し、大部分の水分を蒸発させた。Compounds A and B were added to Solution A to form a slurry, and 236.3 parts of a 30% by weight silica sol was added, followed by heating and stirring to evaporate most of the water.

【０１０４】得られたケーキ状物質を１２０℃で乾燥さ
せたのち、空気雰囲気下３００℃で１時間焼成し、プレ
ス成型したのち、破砕して１０〜２０メッシュ部分を分
取した。次に再び５００℃で６時間焼成した。After the obtained cake-like substance was dried at 120 ° C., it was baked at 300 ° C. for 1 hour in an air atmosphere, press-molded, and crushed to fractionate 10 to 20 mesh portions. Next, it was fired again at 500 ° C. for 6 hours.

【０１０５】こうして得られた触媒の組成は次式に示す
とおりである。The composition of the catalyst thus obtained is as shown in the following formula.

【０１０６】Ｍｏ₁₂Ｂｉ₁Ｆｅ₁Ｗ_0.3Ｎｉ_0.5Ｃｏ₄Ｚｎ
_0.1Ｐ_0.02Ｌａ_0.1Ｃｓ_0.04Ｓｉ₅ この触媒を用いて実施例７と同じ条件で反応を行った。
その結果、プロピレンの反応率９９．５％、アクロレイ
ンの選択率８９．６％、アクリル酸の選択率６．５％、
目的生成物の収率９５．６％であった。Mo ₁₂ Bi ₁ Fe ₁ W _0.3 Ni _0.5 Co ₄ Zn
_0.1 P _0.02 La _0.1 Cs _0.04 Si _{5 Using} this catalyst, a reaction was carried out under the same conditions as in Example 7.
As a result, the conversion of propylene was 99.5%, the selectivity of acrolein was 89.6%, the selectivity of acrylic acid was 6.5%,
The yield of the desired product was 95.6%.

【０１０７】［比較例１０］実施例８と同一組成を有す
る触媒を以下の手順で調製した。Comparative Example 10 A catalyst having the same composition as in Example 8 was prepared by the following procedure.

【０１０８】純水１０００部にモリブデン酸アンモニウ
ム５００部、パラタングステン酸アンモニウム１８．５
部および硝酸セシウム１．８部を加え加熱攪拌した（こ
の溶液をＡ液と呼ぶ）。In 1000 parts of pure water, 500 parts of ammonium molybdate and 18.5 parts of ammonium paratungstate
And 1.8 parts of cesium nitrate were added and stirred with heating (this solution is referred to as solution A).

【０１０９】別に、純水６００部に６０重量％硝酸４
１．９部を加え、均一にしたのち、硝酸ビスマス１１
４．５部を加え溶解した。これに硝酸第二鉄９５．３
部、硝酸ニッケル３４．３部、硝酸コバルト２７４．７
部、硝酸亜鉛７．０部、硝酸ランタン１０．２部および
８５重量％リン酸０．５部を順次加え溶解した（この溶
液をＢ液と呼ぶ）。Separately, 60 parts by weight of nitric acid 4
After adding 1.9 parts and making it uniform, bismuth nitrate 11
4.5 parts were added and dissolved. 95.3 Ferric nitrate
Parts, nickel nitrate 34.3 parts, cobalt nitrate 274.7
, 7.0 parts of zinc nitrate, 10.2 parts of lanthanum nitrate and 0.5 part of 85% by weight phosphoric acid were sequentially added and dissolved (this solution is referred to as solution B).

【０１１０】Ａ液にＢ液を加えスラリー状としたのち、
３０重量％シリカゾル２３６．３部を加え加熱攪拌し、
大部分の水分を蒸発させた。After adding the liquid B to the liquid A to form a slurry,
236.3 parts of 30% by weight silica sol was added, and the mixture was heated and stirred.
Most of the water was evaporated.

【０１１１】得られたケーキ状物質を１２０℃で乾燥さ
せたのち、空気雰囲気下３００℃で１時間焼成し、プレ
ス成型したのち、破砕して１０〜２０メッシュ部分を分
取した。次に再び５００℃で６時間焼成した。The obtained cake-like substance was dried at 120 ° C., calcined at 300 ° C. for 1 hour in an air atmosphere, press-molded, and crushed to fractionate a 10 to 20 mesh portion. Next, it was fired again at 500 ° C. for 6 hours.

【０１１２】この触媒を用いて実施例８と同じ条件で反
応を行った。その結果、プロピレンの反応率９９．２
％、アクロレインの選択率８８．４％、アクリル酸の選
択率６．５％、目的生成物の収率９４．１％であった。
化合物Ｇを用いた実施例８に対して、化合物Ｇを用いな
いと、収率が低下した。Using this catalyst, a reaction was carried out under the same conditions as in Example 8. As a result, the conversion of propylene was 99.2.
%, Acrolein selectivity 88.4%, acrylic acid selectivity 6.5%, and yield of the target product 94.1%.
In contrast to Example 8 in which compound G was used, the yield was reduced when compound G was not used.

【０１１３】[0113]

【発明の効果】新規な触媒調製法を用いることにより、
プロピレン、イソブチレン、三級ブタノールまたはメチ
ルターシャリーブチルエーテルから不飽和アルデヒドお
よび不飽和カルボン酸を高い収率で得ることができる。By using a novel catalyst preparation method,
Unsaturated aldehydes and unsaturated carboxylic acids can be obtained in high yields from propylene, isobutylene, tertiary butanol or methyl tertiary butyl ether.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.⁷ 識別記号 ＦＩ Ｃ０７Ｃ 27/14 Ｃ０７Ｃ 27/14 Ａ 45/35 45/35 45/37 45/37 47/22 47/22 Ａ Ｊ 51/235 51/235 51/25 51/25 57/05 57/05 // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ (58)調査した分野(Int.Cl.⁷，ＤＢ名) B01J 21/00 - 37/36 C07C 27/00 C07C 45/00 C07C 47/00 C07C 51/00 C07C 57/00 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C07C 27/14 C07C 27/14 A 45/35 45/35 45/37 45/37 47/22 47/22 A J 51/235 51/235 51/25 51/25 57/05 57/05 // C07B 61/00 300 C07B 61/00 300 (58) Field surveyed (Int.Cl. ⁷ , DB name) B01J 21/00-37 / 36 C07C 27/00 C07C 45/00 C07C 47/00 C07C 51/00 C07C 57/00

Claims (1)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】 一般式 Ｍｏ_aＢｉ_bＦｅ_cＡ_dＢ_eＣ_fＤ_gＥ_hＳｉ_iＯ_j （式中、Ｍｏ、Ｂｉ、Ｆｅ、ＳｉおよびＯはそれぞれモ
リブデン、ビスマス、鉄、ケイ素および酸素を表し、Ａ
はタングステンおよびアンチモンからなる群より選ばれ
た少なくとも１種の元素、Ｂはニッケルおよびコバルト
からなる群より選ばれた少なくとも１種の元素、Ｃはマ
グネシウム、亜鉛、マンガン、クロム、スズおよび鉛か
らなる群より選ばれた少なくとも１種の元素、Ｄはリ
ン、ホウ素、イオウ、テルル、セレンおよびランタンか
らなる群より選ばれた少なくとも１種の元素、Ｅはカリ
ウム、ルビジウム、セシウムおよびタリウムからなる群
より選ばれた少なくとも１種の元素を示す。ただし、
ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈ、ｉおよびｊは各元素
の原子比を表し、ａ＝１２のとき、０．１≦ｂ≦５、
０．１≦ｃ≦５、０．０１≦ｄ≦５、１≦ｅ≦１２、０
≦ｆ≦１０、０≦ｇ≦５、０．０１≦ｈ≦２、０≦ｉ≦
２０であり、ｊは前記各成分の原子価を満足するのに必
要な酸素原子数である。）で表される組成を有する触媒
を調製するにあたり、ビスマスとＥ成分からなる混合物
または、ビスマス、Ｅ成分およびＡ成分からなる混合物
をあらかじめ２００〜６００℃の温度で熱処理して得ら
れる化合物を用いることを特徴とする、プロピレン、イ
ソブチレン、三級ブタノールまたはメチルターシャリー
ブチルエーテルを分子状酸素を用いて気相接触酸化して
不飽和アルデヒドおよび不飽和カルボン酸を製造するた
めの触媒の調製法。1. A general formula _{Mo a Bi b Fe c A d} B e C f D g in E _h Si _i O _j (wherein, Mo, Bi, Fe, Si and O represent molybdenum, bismuth, iron, silicon and Represents oxygen, A
Is at least one element selected from the group consisting of tungsten and antimony, B is at least one element selected from the group consisting of nickel and cobalt, and C is composed of magnesium, zinc, manganese, chromium, tin and lead At least one element selected from the group; D is at least one element selected from the group consisting of phosphorus, boron, sulfur, tellurium, selenium and lanthanum; and E is a group consisting of potassium, rubidium, cesium and thallium. Shows at least one selected element. However,
a, b, c, d, e, f, g, h, i and j represent the atomic ratio of each element, and when a = 12, 0.1 ≦ b ≦ 5;
0.1 ≦ c ≦ 5, 0.01 ≦ d ≦ 5, 1 ≦ e ≦ 12, 0
≦ f ≦ 10, 0 ≦ g ≦ 5, 0.01 ≦ h ≦ 2, 0 ≦ i ≦
20 and j is the number of oxygen atoms necessary to satisfy the valence of each component. In preparing the catalyst having the composition represented by the formula (1), a compound obtained by previously heat-treating a mixture of bismuth and the E component or a mixture of bismuth, the E component and the A component at a temperature of 200 to 600 ° C. is used. A process for preparing a catalyst for producing unsaturated aldehydes and unsaturated carboxylic acids by subjecting propylene, isobutylene, tertiary butanol or methyl tertiary butyl ether to gas-phase catalytic oxidation using molecular oxygen.