JP6961358B2 - Oxide catalyst, method for producing oxide catalyst, and method for producing unsaturated aldehyde - Google Patents
Oxide catalyst, method for producing oxide catalyst, and method for producing unsaturated aldehyde Download PDFInfo
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- JP6961358B2 JP6961358B2 JP2017034626A JP2017034626A JP6961358B2 JP 6961358 B2 JP6961358 B2 JP 6961358B2 JP 2017034626 A JP2017034626 A JP 2017034626A JP 2017034626 A JP2017034626 A JP 2017034626A JP 6961358 B2 JP6961358 B2 JP 6961358B2
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Description
本発明は、酸化物触媒及びその製造方法、並びに該酸化物触媒を用いた不飽和アルデヒドの製造方法に関する。 The present invention relates to an oxide catalyst and a method for producing the same, and a method for producing an unsaturated aldehyde using the oxide catalyst.
アクリル酸メチル又はメタクリル酸メチル等の（メタ）アクリレートを製造する方法においては、中間体である不飽和アルデヒドの製造方法が必要となる。具体的には、プロピレン、イソブチレン、イソブタノール、及びｔ−ブチルアルコールからなる群より選ばれる少なくとも１種を原料とし、アクロレイン又はメタクロレイン等の不飽和アルデヒドを製造する方法である。該不飽和アルデヒドは、酸化的エステル化反応によって、アクリル酸メチル又はメタクリル酸メチル等の（メタ）アクリレートを製造する方法などに用いられる。
この（メタ）アクリレートを製造する方法としては、直メタ法と呼ばれる２つの反応工程からなる方法と、直酸法と呼ばれる３つの反応工程からなる方法と、が知られている。直酸法は、３つの工程で（メタ）アクリレートを製造するプロセスである（例えば、非特許文献１参照。）。直酸法の第１工程は、触媒の存在下で、プロピレン、イソブチレン、イソブタノール、及びｔ−ブチルアルコールからなる群より選ばれる少なくとも一つの出発物質と、分子状酸素と、を気相接触酸化反応させて、アクロレイン、又はメタクロレイン等の不飽和アルデヒドを製造する第１酸化工程である。また、第２工程は、触媒の存在下で、第１酸化工程で得られた不飽和アルデヒドと、分子状酸素と、を気相接触酸化反応させて、（メタ）アクリル酸を製造する第２酸化工程である。最後の工程は、第２酸化工程で得られた（メタ）アクリル酸をさらにエステル化して、（メタ）アクリレートを得るエステル化工程である。エステル化の際に、アルコールとしてメタノールなどを用いた場合には、アクリル酸メチル又はメタクリル酸メチルを得ることができる。
In the method for producing (meth) acrylate such as methyl acrylate or methyl methacrylate, a method for producing an unsaturated aldehyde as an intermediate is required. Specifically, it is a method for producing an unsaturated aldehyde such as acrolein or methacrolein using at least one selected from the group consisting of propylene, isobutylene, isobutanol, and t-butyl alcohol as a raw material. The unsaturated aldehyde is used in a method for producing (meth) acrylate such as methyl acrylate or methyl methacrylate by an oxidative esterification reaction.
As a method for producing this (meth) acrylate, a method consisting of two reaction steps called a direct meta method and a method consisting of three reaction steps called a direct acid method are known. The direct acid method is a process for producing (meth) acrylate in three steps (see, for example, Non-Patent Document 1). The first step of the direct acid method involves vapor-phase catalytic oxidation of molecular oxygen with at least one starting material selected from the group consisting of propylene, isobutylene, isobutanol, and t-butyl alcohol in the presence of a catalyst. This is the first oxidation step of reacting to produce an unsaturated aldehyde such as acrolein or methacrolein. In the second step, in the presence of a catalyst, the unsaturated aldehyde obtained in the first oxidation step and the molecular oxygen are subjected to a vapor-phase catalytic oxidation reaction to produce (meth) acrylic acid. It is an oxidation process. The final step is an esterification step of further esterifying the (meth) acrylic acid obtained in the second oxidation step to obtain a (meth) acrylate. When methanol or the like is used as the alcohol during esterification, methyl acrylate or methyl methacrylate can be obtained.
これに対し、直メタ法は、プロピレン、イソブチレン、イソブタノール、及びｔ−ブチルアルコールからなる群より選ばれる少なくとも１種の原料と、分子状酸素含有ガスと、を気相接触酸化反応させて、アクロレイン又はメタクロレイン等の不飽和アルデヒドを製造する第１反応工程と、得られた不飽和アルデヒドと、メタノール等のアルコールと、分子状酸素と、を反応させて、一挙にアクリル酸メチル又はメタクリル酸メチル等の（メタ）アクリレートを製造する第２反応工程の２つの触媒反応工程からなる。 On the other hand, in the direct methacrolein method, at least one raw material selected from the group consisting of propylene, isobutylene, isobutanol, and t-butyl alcohol and a molecular oxygen-containing gas are subjected to a gas-phase catalytic oxidation reaction. The first reaction step for producing an unsaturated aldehyde such as acrolein or methacrolein, the obtained unsaturated aldehyde, an alcohol such as methanol, and molecular oxygen are reacted to all at once methyl acrylate or methacrylic acid. It consists of two catalytic reaction steps, a second reaction step for producing a (meth) acrylate such as methyl.
上述の直酸法の第１酸化工程、及び直メタ法の第１反応工程において用いられる酸化物触媒としては、古くはソハイオ社によって見出され、必須成分としてＭｏ、Ｂｉ、Ｆｅを含む複合酸化物触媒が数多く報告されている。
これらの触媒中の各金属の機能については、例えば、非特許文献２に記載されている。具体的には、Ｍｏ−Ｂｉ−Ｆｅ系触媒では、モリブデンがイソブチレンの吸着サイトとしての機能を担って、ビスマスがイソブチレンの活性化サイトとして働き、α位水素を引き抜いてπアリル種を生成させ、鉄はＦｅ3+／Ｆｅ2+のレドックスにより気相から活性サイトへの酸素の授受に機能し、πアリル種に酸素が挿入され、メタクロレインが生成するとされている。
The oxide catalyst used in the first oxidation step of the direct acid method and the first reaction step of the direct meta method was found by Sohaio in ancient times and is a composite oxidation containing Mo, Bi and Fe as essential components. Many material catalysts have been reported.
The functions of each metal in these catalysts are described, for example, in Non-Patent Document 2. Specifically, in the Mo-Bi-Fe-based catalyst, molybdenum acts as an adsorption site for isobutylene, and bismuth acts as an activation site for isobutylene, abstracting α-position hydrogen to generate π-allyl species. It is said that iron functions to transfer oxygen from the gas phase to the active site by the redox of Fe 3+ / Fe 2+, and oxygen is inserted into the π-allyl species to produce methacrolein.
上記酸化物触媒が用いられる反応方式には、固定層、流動層及び移動層がある。これらのうち、固定層反応方式は、原料ガスの流動状態が押し出し流れに近く、反応収率を高くできるという利点を活かし、工業的に多く採用されている。
ところが、固定層反応方式は伝熱性が低く、除熱や加熱が必要な発熱反応や吸熱反応には本来不向きである。特に酸化反応のような激しい発熱反応では、温度が急激に上昇し制御困難に陥り反応が暴走することがないように、安定な運転管理を行う必要がある。
Reaction methods in which the oxide catalyst is used include a fixed layer, a fluidized bed and a moving layer. Of these, the fixed layer reaction method is widely used industrially, taking advantage of the fact that the flow state of the raw material gas is close to the extrusion flow and the reaction yield can be increased.
However, the fixed layer reaction method has low heat transfer properties and is originally unsuitable for exothermic reactions and endothermic reactions that require heat removal or heating. Especially in a violent exothermic reaction such as an oxidation reaction, it is necessary to perform stable operation management so that the temperature does not rise sharply and control becomes difficult and the reaction does not run out of control.
上記酸化物触媒に使用されるモリブデン、ビスマス、鉄等の遷移金属は、それぞれが単独で酸化された酸化物の他に、複数種の金属が固溶体となっているいわゆる複合酸化物になることが知られている。複合酸化物は、単独の金属の酸化物とは異なる特性を有し、その特性が金属種の選択や組成比等によっても大きく変化することから、顔料、電池の電極材料、触媒等、様々な分野で検討が進められている。 The transition metals such as molybdenum, bismuth, and iron used in the oxide catalyst may be so-called composite oxides in which a plurality of kinds of metals are solid solutions in addition to oxides each of which is oxidized independently. Are known. Composite oxides have properties different from those of single metal oxides, and the properties vary greatly depending on the selection of metal species, composition ratio, etc. Therefore, various pigments, battery electrode materials, catalysts, etc. Consideration is underway in the field.
モリブデン、ビスマス、及び鉄を含む酸化物触媒は、オレフィンやアルコールを酸化して、不飽和アルデヒドを製造する触媒としてこれまでに数多く報告されている。上述のように、組成比が異なれば酸化物触媒の特性も異なるので目的化合物の収率を向上させたりする目的で、様々な組成比を有する複合酸化物の触媒特性や調製条件が検討されている。
特許文献１には、長時間の運転においても触媒の還元劣化が抑制され、経時的な収率の低下が小さい触媒とすることを目的として、モリブデン、ビスマス、鉄及びイオン半径が０．９６Åよりも大きな元素Ａを含む結晶系からなるｄｉｓｏｒｄｅｒ相Ｂｉ3-xＡxＦｅ1Ｍｏ2Ｏ12を含む触媒が開示されている（ここで、特許文献１における「元素Ａ」は、後述する元素Ａとは異なるものである。）。
Oxide catalysts containing molybdenum, bismuth, and iron have been widely reported as catalysts for producing unsaturated aldehydes by oxidizing olefins and alcohols. As described above, since the characteristics of the oxide catalyst differ depending on the composition ratio, the catalyst characteristics and preparation conditions of the composite oxide having various composition ratios have been studied for the purpose of improving the yield of the target compound. There is.
Patent Document 1 describes molybdenum, bismuth, iron and an ionic radius of 0.96 Å for the purpose of suppressing reduction deterioration of the catalyst even during long-term operation and making the catalyst with a small decrease in yield over time. A catalyst containing a disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 composed of a crystal system containing a large element A is disclosed (here, “element A” in Patent Document 1 refers to element A described later. It is different from.).
本発明者らの研究によれば、特許文献１に記載の酸化物触媒は、固定層反応方式での気相接触酸化反応で運転中に活性が経時的に上がっていく傾向にあることが判明している。そのような酸化物触媒を用いて反応を長時間にわたって継続させると、触媒層の温度が徐々に上がっていき除熱律速となるため、固定層反応では安定運転が困難になると考えられる。すなわち、特許文献１及び非特許文献１〜２に記載の技術では、反応における経時的な活性上昇が少なく、且つ不飽和アルデヒドを高収率で生成させることのできる酸化物触媒を得ることができない。 According to the research by the present inventors, it has been found that the oxide catalyst described in Patent Document 1 tends to increase in activity with time during operation due to the vapor phase catalytic oxidation reaction in the fixed layer reaction method. doing. If the reaction is continued for a long time using such an oxide catalyst, the temperature of the catalyst layer gradually rises and the rate-determining of heat removal is achieved, so that stable operation is considered to be difficult in the fixed layer reaction. That is, with the techniques described in Patent Document 1 and Non-Patent Documents 1 and 2, it is not possible to obtain an oxide catalyst capable of producing unsaturated aldehyde in a high yield with little increase in activity over time in the reaction. ..
本発明は上記問題点に鑑みてなされたものであり、オレフィン及び／又はアルコールを原料とする不飽和アルデヒドの製造において、反応における経時的な活性上昇が少なく、且つ不飽和アルデヒドを高収率で生成させることのできる酸化物触媒及びその製造方法、並びに該酸化物触媒を用いた不飽和アルデヒドの製造方法を提供することを目的とする。 The present invention has been made in view of the above problems, and in the production of unsaturated aldehydes using olefins and / or alcohols as raw materials, there is little increase in activity over time in the reaction, and unsaturated aldehydes are produced in high yield. It is an object of the present invention to provide an oxide catalyst that can be produced, a method for producing the same, and a method for producing an unsaturated aldehyde using the oxide catalyst.
本発明者らは、所定の元素から構成される複合金属酸化物の結晶構造を調整することにより、上記課題を解決できることを見出し、本発明を完成するに至った。 The present inventors have found that the above problems can be solved by adjusting the crystal structure of a composite metal oxide composed of a predetermined element, and have completed the present invention.
すなわち、本発明は以下のとおりである。
［１］
プロピレン、イソブチレン、イソブタノール及びｔ−ブチルアルコールからなる群から選択される少なくとも１種を気相接触酸化することにより不飽和アルデヒドを製造する際に用いる酸化物触媒であって、
モリブデン、ビスマス、鉄、及びコバルトを含有し、
ＣｕＫα線をＸ線源として得られるＸ線回折パターンにおいて、２θ＝２６．４°±０．２°の位置に現れるＣｏＭｏＯ4相の回折ピーク（ｃ）の強度Ｐｃに対する、２θ＝２７．４°±０．２°に現れるＢｉ10Ｍｏ3Ｏ24相の回折ピーク（ａ）の強度Ｐａの比Ｒｉ＝Ｐａ／Ｐｃが０．２≦Ｒｉ≦１．０である、酸化物触媒。
［２］
ＣｕＫα線をＸ線源として得られるＸ線回折図における回折角（２θ）が、少なくとも２θ＝１０．３°±０．２°、２７．４°±０．２°、３１．０°±０．２°、及び５２．９°±０．２°の範囲に回折ピークを有する、［１］記載の酸化物触媒。
［３］
下記組成式（１）で表される組成を有する複合金属の酸化物を含む、［１］又は［２］に記載の酸化物触媒。
Ｍｏ12ＢｉaＦｅbＣｏcＣｅdＡeＢf （１）
（組成式（１）において、Ａはカリウム、セシウム及びルビジウムからなる群より選ばれる少なくとも１種の元素を示し、Ｂは、ニッケル、マンガン、銅、亜鉛、マグネシウム、カルシウム、ストロンチウム、バリウム、錫、鉛、ランタン、プラセオジウム、ネオジム、及びユウロピウムからなる群から選ばれる少なくとも１種の元素を示し、１≦ａ≦５、１≦ｂ≦５、２≦ｃ≦１０、０＜ｄ≦３、０＜ｅ≦２．０、０≦ｆ≦２である。）
［４］
［１］〜［３］のいずれかに記載の酸化物触媒の製造方法であって、
モリブデン元素を含む化合物、ビスマス元素を含む化合物、鉄元素を含む化合物、及びコバルト元素を含む化合物を液相で混合し、前駆体スラリーを調製する工程と、
前記前駆体スラリーを噴霧乾燥し、乾燥体を得る工程と、
前記乾燥体を、２００〜３００℃の範囲内で設定した第一の温度まで室温から昇温し、２００〜３００℃の範囲内の温度で１時間以上保持して第一焼成体を得る工程と、
前記第一焼成体と有機物とを混合成型して成型体を得る工程と、
前記成型体を、不活性ガス中で２００〜４００℃の範囲内で設定した第二の温度まで室温から１時間以上かけて昇温し、２００〜４００℃の範囲内の温度で１時間以上保持して第二焼成体を得る工程と、
前記第二焼成体を、不活性ガス中で４００〜６００℃の範囲内で設定した第三の温度まで、第二の温度から１時間以上かけて昇温し、４００〜６００℃の範囲内の温度で１時間以上保持して酸化物触媒を得る工程と、
を有する、酸化物触媒の製造方法。
［５］
［１］〜［３］のいずれかに記載の酸化物触媒を用いて、プロピレン、イソブチレン、イソブタノール及びｔ−ブチルアルコールからなる群から選ばれる少なくとも１種を酸化する工程を含む、不飽和アルデヒドの製造方法。
That is, the present invention is as follows.
[1]
An oxide catalyst used in the production of unsaturated aldehydes by vapor-phase catalytic oxidation of at least one selected from the group consisting of propylene, isobutylene, isobutanol and t-butyl alcohol.
Contains molybdenum, bismuth, iron, and cobalt,
In the X-ray diffraction pattern obtained by using CuKα ray as an X-ray source, 2θ = 27.4 ° with respect to the intensity Pc of the diffraction peak (c) of the CoMoO 4-phase appearing at the position of 2θ = 26.4 ° ± 0.2 °. An oxide catalyst in which the ratio Ri = Pa / Pc of the intensity Pa of the diffraction peak (a) of the Bi 10 Mo 3 O 24 phase appearing at ± 0.2 ° is 0.2 ≦ Ri ≦ 1.0.
[2]
The diffraction angle (2θ) in the X-ray diffraction diagram obtained by using CuKα ray as an X-ray source is at least 2θ = 10.3 ° ± 0.2 °, 27.4 ° ± 0.2 °, 31.0 ° ± 0. The oxide catalyst according to [1], which has a diffraction peak in the range of .2 ° and 52.9 ° ± 0.2 °.
[3]
The oxide catalyst according to [1] or [2], which comprises an oxide of a composite metal having a composition represented by the following composition formula (1).
Mo 12 Bi a Fe b Co c Ce d A e B f (1)
(In the composition formula (1), A represents at least one element selected from the group consisting of potassium, cesium and rubidium, and B represents nickel, manganese, copper, zinc, magnesium, calcium, strontium, barium, tin, Indicates at least one element selected from the group consisting of lead, lanthanum, placeodium, neodymium, and europium, 1 ≦ a ≦ 5, 1 ≦ b ≦ 5, 2 ≦ c ≦ 10, 0 <d ≦ 3, 0 < e ≦ 2.0, 0 ≦ f ≦ 2)
[4]
The method for producing an oxide catalyst according to any one of [1] to [3].
A step of preparing a precursor slurry by mixing a compound containing a molybdenum element, a compound containing a bismuth element, a compound containing an iron element, and a compound containing a cobalt element in a liquid phase.
The step of spray-drying the precursor slurry to obtain a dried product, and
A step of raising the temperature of the dried product from room temperature to a first temperature set in the range of 200 to 300 ° C. and holding the dried product at a temperature in the range of 200 to 300 ° C. for 1 hour or more to obtain a first fired product. ,
A step of mixing and molding the first fired body and an organic substance to obtain a molded body,
The molded product is heated in an inert gas to a second temperature set in the range of 200 to 400 ° C. over 1 hour from room temperature, and held at a temperature in the range of 200 to 400 ° C. for 1 hour or more. And the process of obtaining the second fired body
The second fired body is heated in an inert gas to a third temperature set in the range of 400 to 600 ° C. from the second temperature over an hour or more, and within the range of 400 to 600 ° C. The process of obtaining an oxide catalyst by holding it at temperature for 1 hour or more,
A method for producing an oxide catalyst.
[5]
An unsaturated aldehyde comprising the step of oxidizing at least one selected from the group consisting of propylene, isobutylene, isobutanol and t-butyl alcohol using the oxide catalyst according to any one of [1] to [3]. Manufacturing method.
本発明の酸化物触媒は、オレフィン及び／又はアルコールを原料とする不飽和アルデヒドの製造において、長時間の連続反応による経時的な活性上昇が少なく、且つ不飽和アルデヒドを高収率で生成させることができる。 The oxide catalyst of the present invention is capable of producing unsaturated aldehydes using olefins and / or alcohols as raw materials with little increase in activity over time due to a long-term continuous reaction and in high yield. Can be done.
以下、本発明を実施するための形態（以下、単に「本実施形態」という。）について説明するが、本発明は下記実施形態に限定されるものではない。本発明は、その要旨を逸脱しない範囲で様々な変形が可能である。 Hereinafter, embodiments for carrying out the present invention (hereinafter, simply referred to as “the present embodiment”) will be described, but the present invention is not limited to the following embodiments. The present invention can be modified in various ways without departing from the gist thereof.
本実施形態の酸化物触媒は、プロピレン、イソブチレン、イソブタノール及びｔ−ブチルアルコールからなる群から選択される少なくとも１種を気相接触酸化することにより不飽和アルデヒドを製造する際に用いる酸化物触媒であって、モリブデン、ビスマス、鉄、及びコバルトを含有し、ＣｕＫα線をＸ線源として得られるＸ線回折パターンにおいて、２θ＝２６．４°±０．２°の位置に現れるＣｏＭｏＯ4相の回折ピーク（ｃ）の強度Ｐｃに対する、２θ＝２７．４°±０．２°に現れるＢｉ10Ｍｏ3Ｏ24相の回折ピーク（ａ）の強度Ｐａの比Ｒｉ＝Ｐａ／Ｐｃが０．２≦Ｒｉ≦１．０である。このように構成されているため、本実施形態の酸化物触媒は、オレフィン及び／又はアルコールを原料とする不飽和アルデヒドの製造において、長時間の連続反応による経時的な活性上昇が少なく、且つ不飽和アルデヒドを高収率で生成させることができる。 The oxide catalyst of the present embodiment is an oxide catalyst used for producing an unsaturated aldehyde by vapor-phase catalytic oxidation of at least one selected from the group consisting of propylene, isobutylene, isobutanol and t-butyl alcohol. The CoMoO 4 phase that contains molybdenum, bismuth, iron, and cobalt and appears at the position of 2θ = 26.4 ° ± 0.2 ° in the X-ray diffraction pattern obtained by using CuKα ray as the X-ray source. The ratio Ri = Pa / Pc of the intensity Pa of the diffraction peak (a) of the Bi 10 Mo 3 O 24 phase appearing at 2θ = 27.4 ° ± 0.2 ° to the intensity Pc of the diffraction peak (c) is 0.2. ≦ Ri ≦ 1.0. Because of this configuration, the oxide catalyst of the present embodiment has little increase in activity over time due to a long-term continuous reaction in the production of unsaturated aldehydes using olefins and / or alcohols as raw materials, and is ineffective. Saturated aldehydes can be produced in high yield.
Ｍｏ−Ｂｉ−Ｆｅ系触媒では、前述のようにビスマスがイソブチレンの活性化サイトとして働く。この為、ビスマスを含む複合酸化物が活性種と推定される。本発明者らは、特許文献１では活性種は触媒に含まれるｄｉｓｏｒｄｅｒ相Ｂｉ3-xＡxＦｅ1Ｍｏ2Ｏ12を含む四成分複合酸化物であると推定し、反応における経時的な活性上昇の原因は、このｄｉｓｏｒｄｅｒ相Ｂｉ3-xＡxＦｅ1Ｍｏ2Ｏ12を含む四成分複合酸化物の還元に起因すると推定した。すなわち、金属の組成のみならず、上記結晶構造も複合酸化物の機能に影響していることを見出した。
さらに、本発明者らは、特許文献１の触媒に含まれるｄｉｓｏｒｄｅｒ相Ｂｉ3-xＡxＦｅ1Ｍｏ2Ｏ12を含む四成分複合酸化物は空気雰囲気下で製造しており、触媒が完全酸化状態である為に、反応雰囲気下で触媒が還元されて活性が上昇するのではないかと推測した。そこで、逆に反応雰囲気下で活性が上昇しない相がないかについて鋭意検討した結果、複合酸化物Ｂｉ10Ｍｏ3Ｏ24相を含む触媒が、反応における経時的な活性上昇を低減できることを見出した。
Ｂｉ10Ｍｏ3Ｏ24相が触媒中に含まれると反応における経時的な活性上昇を抑制できるメカニズムは明らかではないが、Ｂｉ10Ｍｏ3Ｏ24相が完全酸化状態ではなく、ある程度の酸素欠陥を有する部分的還元状態であるため、反応雰囲気における結晶構造が変化しにくい為であると推定している。なお、後述する比較例にて示すように、特許文献１に記載の技術では、Ｂｉ10Ｍｏ3Ｏ24相が形成された触媒が得られないことが判明している。
以上の観点より、本実施形態の酸化物触媒は、上記０．２≦Ｒｉ≦１．０で示唆される結晶構造を有するものとする。
In the Mo-Bi-Fe catalyst, bismuth acts as an activation site for isobutylene as described above. Therefore, the composite oxide containing bismuth is presumed to be an active species. In Patent Document 1, the present inventors presume that the active species is a four-component composite oxide containing disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 contained in the catalyst, and its activity over time in the reaction. It was presumed that the cause of the increase was the reduction of the four-component composite oxide containing the disorder phase Bi 3-x A x Fe 1 Mo 2 O 12. That is, it was found that not only the composition of the metal but also the crystal structure affects the function of the composite oxide.
Furthermore, the present inventors have produced a four-component composite oxide containing disorder phase Bi 3-x A x Fe 1 Mo 2 O 12 contained in the catalyst of Patent Document 1 in an air atmosphere, and the catalyst is completely complete. It was speculated that the catalyst might be reduced and the activity increased in the reaction atmosphere because of the oxidized state. Therefore, as a result of diligent studies on whether or not there is a phase in which the activity does not increase in the reaction atmosphere, it was found that the catalyst containing the composite oxide Bi 10 Mo 3 O 24 phase can reduce the increase in activity over time in the reaction. ..
Although the mechanism is not clear that can suppress the temporal increased activity in the reaction with Bi 10 Mo 3 O 24 phase is contained in the catalyst, Bi 10 Mo 3 O 24 phase is not a completely oxidized state, a certain degree of oxygen deficiency It is presumed that this is because the crystal structure in the reaction atmosphere is unlikely to change because it is in a partially reduced state. As shown in the comparative example described later, it has been found that the technique described in Patent Document 1 cannot obtain a catalyst in which the Bi 10 Mo 3 O 24 phase is formed.
From the above viewpoint, the oxide catalyst of the present embodiment has a crystal structure suggested by 0.2 ≦ Ri ≦ 1.0.
［酸化物触媒］
（１）組成
本実施形態の酸化物触媒は、モリブデン（Ｍｏ）、ビスマス（Ｂｉ）、鉄（Ｆｅ）、コバルト（Ｃｏ）を必須元素として含有する。
ＢｉとＭｏは、Ｂｉ2Ｍｏ3Ｏ12やＢｉ10Ｍｏ3Ｏ24等の複合酸化物を形成させるために必須であり、Ｍｏ１２原子に対するＢｉの原子比ａは、好ましくは１≦ａ≦５となるようにする。目的生成物の選択率をより高める観点で、原子比ａは、より好ましくは１≦ａ≦３であり、さらに好ましくは１．５≦ａ≦２．５である。
[Oxide catalyst]
(1) Composition The oxide catalyst of the present embodiment contains molybdenum (Mo), bismuth (Bi), iron (Fe), and cobalt (Co) as essential elements.
Bi and Mo are indispensable for forming a composite oxide such as Bi 2 Mo 3 O 12 and Bi 10 Mo 3 O 24 , and the atomic ratio a of Bi to the Mo 12 atom is preferably 1 ≦ a ≦ 5. To be. From the viewpoint of further increasing the selectivity of the target product, the atomic ratio a is more preferably 1 ≦ a ≦ 3, and even more preferably 1.5 ≦ a ≦ 2.5.
目的生成物の選択率を低下させることなく触媒活性を高める観点から、ＦｅはＭｏ、Ｂｉと同様に、工業的に目的生成物を合成する上で必須の元素である。Ｆｅは、Ｆｅ2Ｍｏ3Ｏ12やＦｅＭｏＯ4等の複合酸化物を形成し、気相から酸素を触媒の構造内に取り込み、反応で消費される格子酸素を補い、触媒が過還元されて劣化するのを抑制する働きがある。本実施形態の酸化物触媒のＭｏ１２原子に対するＦｅの原子比ｂは、Ｆｅ2Ｍｏ3Ｏ12の結晶を形成させる観点で、好ましくは１≦ｂ≦５であり、より好ましくは１．５≦ｂ≦４．０、さらに好ましくは２．０≦ｂ≦３．５である。 From the viewpoint of increasing the catalytic activity without lowering the selectivity of the target product, Fe is an essential element for industrially synthesizing the target product, like Mo and Bi. Fe forms a composite oxide such as Fe 2 Mo 3 O 12 or Fe Mo O 4 , takes oxygen from the gas phase into the structure of the catalyst, supplements the lattice oxygen consumed in the reaction, and the catalyst is overreduced and deteriorates. It has the function of suppressing the activity. The atomic ratio b of Fe to the Mo 12 atom of the oxide catalyst of the present embodiment is preferably 1 ≦ b ≦ 5, more preferably 1.5 ≦ b, from the viewpoint of forming crystals of Fe 2 Mo 3 O 12. ≦ 4.0, more preferably 2.0 ≦ b ≦ 3.5.
本実施形態の酸化物触媒において、Ｃｏは、Ｍｏ、Ｂｉ、Ｆｅと同様に工業的に目的生成物を合成する上で必須の元素である。Ｃｏは、複合酸化物ＣｏＭｏＯ4を形成し、Ｂｉ−Ｍｏ−Ｏ等の活性種を高分散させるための担体としての役割と、気相から酸素を取り込み、Ｂｉ−Ｍｏ−Ｏ等に供給する役割を果たしている。不飽和アルデヒドを高収率で得るには、ＣｏをＭｏと複合化させ、複合酸化物ＣｏＭｏＯ4を形成させる必要がある。Ｃｏ3Ｏ4やＣｏＯ等の単独酸化物の形成を少なくする観点から、Ｍｏ１２原子に対するＣｏの原子比ｃは、好ましくは２≦ｃ≦１０であり、より好ましくは４≦ｃ≦１０であり、さらに好ましくは６≦ｃ≦９である。 In the oxide catalyst of the present embodiment, Co is an essential element for industrially synthesizing the target product, like Mo, Bi, and Fe. Co forms a composite oxide CoMoO 4 and serves as a carrier for highly dispersing active species such as Bi-Mo-O and a role of taking in oxygen from the gas phase and supplying it to Bi-Mo-O and the like. Is playing. In order to obtain unsaturated aldehydes in high yield, it is necessary to combine Co with Mo to form the composite oxide CoMoO 4 . From the viewpoint of reducing the formation of a single oxide such as Co 3 O 4 or CoO, the atomic ratio c of Co to the Mo 12 atom is preferably 2 ≦ c ≦ 10, more preferably 4 ≦ c ≦ 10. More preferably, 6 ≦ c ≦ 9.
（２）結晶構造
本実施形態の酸化物触媒は、ＣｕＫα線をＸ線源としてＸ線回折（ＸＲＤ）で、Ｘ線回折角２θ＝５°〜６０°の範囲を測定するとき、２θ＝２６．４°±０．２°の位置に現れるＣｏＭｏＯ4相の回折ピーク（ｃ）の強度Ｐｃに対する、２θ＝２７．４°±０．２°に現れるＢｉ10Ｍｏ3Ｏ24相の回折ピーク（ａ）の強度Ｐａの比Ｒｉ＝Ｐａ／Ｐｃが０．２≦Ｒｉ≦１．０である。
ＣｕＫα線をＸ線源として得られるＸ線回折パターンにおいて、２θ＝２６．４°±０．２°の位置に現れる回折ピークはＣｏＭｏＯ4の（２２０）に相当し、２θ＝２７．４°±０．２°の位置に現れる回折ピークはＢｉ10Ｍｏ3Ｏ24の（５１１）に相当する。
(2) Crystal structure The oxide catalyst of the present embodiment measures the X-ray diffraction angle in the range of 2θ = 5 ° to 60 ° by X-ray diffraction (XRD) using CuKα ray as an X-ray source, and 2θ = 26. . The diffraction peak of the Bi 10 Mo 3 O 24 phase appearing at 2θ = 27.4 ° ± 0.2 ° with respect to the intensity Pc of the diffraction peak (c) of the CoMo O 4 phase appearing at the position of 4 ° ± 0.2 ° ( The ratio Ri = Pa / Pc of the intensity Pa of a) is 0.2 ≦ Ri ≦ 1.0.
In the X-ray diffraction pattern obtained by using CuKα ray as an X-ray source, the diffraction peak appearing at the position of 2θ = 26.4 ° ± 0.2 ° corresponds to (220) of CoMoO 4 , and 2θ = 27.4 ° ±. The diffraction peak appearing at the 0.2 ° position corresponds to (511) of the Bi 10 Mo 3 O 24.
上記のとおり、本実施形態の酸化物触媒が、Ｂｉ10Ｍｏ3Ｏ24の結晶を有することは、Ｘ線回折を測定することによって確認できる。Ｂｉ10Ｍｏ3Ｏ24の結晶相を有する触媒のＸ線回折で２θ＝５°〜６０°の範囲を測定すると、典型的には、２θ＝１０．３°±０．２°、２７．４°±０．２°、３１．０°±０．２°、５２．９°±０．２°の範囲に回折ピークを示す。しかしながら、酸化物触媒にはＢｉ10Ｍｏ3Ｏ24以外にも様々な結晶構造が含まれるため、ＸＲＤの回折ピークは極めて複雑になり、必ずしも全てのピークが検出されなくてもよい。なお、２θ＝２７．４°±０．２°の位置に検出される回折ピークは、Ｂｉ10Ｍｏ3Ｏ24に固有のものであり、Ｂｉ10Ｍｏ3Ｏ24の結晶構造の生成の指標とすることができる。したがって、本実施形態の酸化物触媒におけるＣｕＫα線をＸ線源として得られるＸ線回折図における回折角（２θ）は、少なくとも２θ＝２７．４°±０．２°の範囲に回折ピークが検出されることが好ましく、より好ましくは少なくとも２θ＝１０．３°±０．２°、２７．４°±０．２°、３１．０°±０．２°、及び５２．９°±０．２°の範囲に回折ピークが検出される。 As described above, it can be confirmed by measuring X-ray diffraction that the oxide catalyst of the present embodiment has crystals of Bi 10 Mo 3 O 24. When the range of 2θ = 5 ° to 60 ° is measured by X-ray diffraction of a catalyst having a crystal phase of Bi 10 Mo 3 O 24, typically 2θ = 10.3 ° ± 0.2 °, 27.4. Diffraction peaks are shown in the range of ° ± 0.2 °, 31.0 ° ± 0.2 °, and 52.9 ° ± 0.2 °. However, since the oxide catalyst contains various crystal structures other than Bi 10 Mo 3 O 24 , the diffraction peaks of the XRD become extremely complicated, and not all peaks need to be detected. The diffraction peak detected at the position of 2θ = 27.4 ° ± 0.2 ° is inherent to Bi 10 Mo 3 O 24, and the index of generation of the crystal structure of Bi 10 Mo 3 O 24 can do. Therefore, the diffraction angle (2θ) in the X-ray diffraction diagram obtained by using the CuKα ray in the oxide catalyst of the present embodiment as an X-ray source has a diffraction peak detected in the range of at least 2θ = 27.4 ° ± 0.2 °. More preferably, at least 2θ = 10.3 ° ± 0.2 °, 27.4 ° ± 0.2 °, 31.0 ° ± 0.2 °, and 52.9 ° ± 0. Diffraction peaks are detected in the 2 ° range.
本実施形態の酸化物触媒のＣｕＫα線をＸ線源として得られるＸ線回折パターンにおいて、２θ＝２６．４°±０．２°の位置に現れるＣｏＭｏＯ4の回折ピーク（ｃ）の強度Ｐｃに対する、２θ＝２７．４°±０．２°に現れるＢｉ10Ｍｏ3Ｏ24の回折ピーク（ａ）の強度Ｐａの比Ｒｉ＝Ｐａ／Ｐｃが０．２≦Ｒｉ≦１．０の範囲であれば、Ｂｉ10Ｍｏ3Ｏ24の結晶構造が充分に生成したと判断することができる。
Ｒｉの値が０．２以上であると、Ｂｉ10Ｍｏ3Ｏ24の結晶量が十分であり、触媒として使用した場合に反応中の活性上昇が抑制される。また、Ｒｉの値が１．０以下であると不飽和アルデヒドの収率に優れる。反応中の触媒の活性上昇を抑制する観点から、Ｒｉは、好ましくは０．２５≦Ｒｉ≦０．７５であり、より好ましくは０．３０≦Ｒｉ≦０．６０である。
In the X-ray diffraction pattern obtained by using the CuKα ray of the oxide catalyst of the present embodiment as an X-ray source, the intensity Pc of the diffraction peak (c) of CoMoO 4 appearing at the position of 2θ = 26.4 ° ± 0.2 °. The ratio of the intensity Pa of the diffraction peak (a) of the Bi 10 Mo 3 O 24 appearing at 2θ = 27.4 ° ± 0.2 ° Ri = Pa / Pc should be in the range of 0.2≤Ri≤1.0. For example, it can be determined that the crystal structure of Bi 10 Mo 3 O 24 is sufficiently formed.
When the Ri value is 0.2 or more, the amount of crystals of Bi 10 Mo 3 O 24 is sufficient, and the increase in activity during the reaction is suppressed when used as a catalyst. Further, when the Ri value is 1.0 or less, the yield of unsaturated aldehyde is excellent. From the viewpoint of suppressing an increase in the activity of the catalyst during the reaction, Ri is preferably 0.25 ≦ Ri ≦ 0.75, and more preferably 0.30 ≦ Ri ≦ 0.60.
本実施形態の酸化物触媒は、好ましくは、下記組成式（１）で表される組成を有する複合金属の酸化物を含む。
Ｍｏ12ＢｉaＦｅbＣｏcＣｅdＡeＢf （１）
（組成式（１）において、Ａはカリウム、セシウム及びルビジウムからなる群より選ばれる少なくとも１種の元素を示し、Ｂは、ニッケル、マンガン、銅、亜鉛、マグネシウム、カルシウム、ストロンチウム、バリウム、錫、鉛、ランタン、プラセオジウム、ネオジム、及びユウロピウムからなる群から選ばれる少なくとも１種の元素を示し、１≦ａ≦５、１≦ｂ≦５、２≦ｃ≦１０、０＜ｄ≦３、０＜ｅ≦２．０、０≦ｆ≦２である。）
The oxide catalyst of the present embodiment preferably contains an oxide of a composite metal having a composition represented by the following composition formula (1).
Mo 12 Bi a Fe b Co c Ce d A e B f (1)
(In the composition formula (1), A represents at least one element selected from the group consisting of potassium, cesium and rubidium, and B represents nickel, manganese, copper, zinc, magnesium, calcium, strontium, barium, tin, Indicates at least one element selected from the group consisting of lead, lanthanum, placeodium, neodymium, and europium, 1 ≦ a ≦ 5, 1 ≦ b ≦ 5, 2 ≦ c ≦ 10, 0 <d ≦ 3, 0 < e ≦ 2.0, 0 ≦ f ≦ 2)
上記組成式（１）において、Ｃｅは、上記ＭｏとＢｉの複合酸化物の構造安定化に寄与すると考えられている元素である。セリウムを含有するか否かは、後述するＢｉ10Ｍｏ3Ｏ24の結晶構造には影響しない。耐熱性を高める観点で、Ｍｏ１２原子に対するＣｅの原子比ｄは、好ましくは０＜ｄ≦３であり、より好ましくは０．２≦ｄ≦３、さらに好ましくは０．４≦ｄ≦２である。 In the composition formula (1), Ce is an element considered to contribute to the structural stabilization of the composite oxide of Mo and Bi. Whether or not it contains cerium does not affect the crystal structure of Bi 10 Mo 3 O 24, which will be described later. From the viewpoint of increasing heat resistance, the atomic ratio d of Ce to Mo12 atom is preferably 0 <d ≦ 3, more preferably 0.2 ≦ d ≦ 3, and further preferably 0.4 ≦ d ≦ 2. ..
上記組成式（１）において、Ａはカリウム、セシウム及びルビジウムからなる群より選ばれる少なくとも１種の元素を示し、酸化物触媒において、触媒で複合化されなかったＭｏＯ3等の酸点を中和する役割を示すと考えられる。カリウム、セシウム又はルビジウムを含有するか否かは、後述するＢｉ10Ｍｏ3Ｏ24の結晶構造には影響しない。Ｍｏ１２原子に対する元素Ａの原子比は、触媒活性の観点から、好ましくは０＜ｅ≦２．０である。Ａの原子比ｅをこの範囲に調整することにより、触媒が塩基性となるのを防ぎ、原料であるオレフィンやアルコールが触媒へ適度に吸着されるため、充分な触媒活性を発現する傾向にある。 In the above composition formula (1), A represents at least one element selected from the group consisting of potassium, cesium and rubidium, and in the oxide catalyst, neutralizes acid points such as MoO 3 which are not compounded by the catalyst. It is thought to show a role to play. Whether or not it contains potassium, cesium or rubidium does not affect the crystal structure of Bi 10 Mo 3 O 24, which will be described later. The atomic ratio of element A to Mo12 atom is preferably 0 <e ≦ 2.0 from the viewpoint of catalytic activity. By adjusting the atomic ratio e of A to this range, the catalyst is prevented from becoming basic, and the olefins and alcohols as raw materials are appropriately adsorbed on the catalyst, so that sufficient catalytic activity tends to be exhibited. ..
上記組成式（１）において、Ｂは、ニッケル、マンガン、銅、亜鉛、マグネシウム、カルシウム、ストロンチウム、バリウム、錫、鉛、ランタン、プラセオジウム、ネオジム、及びユウロピウムからなる群から選ばれる少なくとも１種の元素を示す。ニッケル、マンガン、銅、亜鉛、マグネシウム、カルシウム、ストロンチウム、バリウム、錫、鉛は酸化物中で一部のコバルトに置換し、触媒中のＣｏＭｏＯ4の結晶構造を安定化させる傾向があり、ランタン、プラセオジウム、ネオジム、ユウロピウムはモリブデンと複合酸化物を形成し、活性を向上させる傾向がある。触媒性能を示すＢｉ10Ｍｏ3Ｏ24結晶の生成とのバランスを保つ観点で、Ｂの原子比ｆの上限は、ｆ≦２であることがより好ましい。Ｂで示される元素は、触媒中のＣｏＭｏＯ4の結晶構造を安定化させるもの、又は触媒の活性を向上させるものであるため、Ｂｉ10Ｍｏ3Ｏ24の結晶構造には影響せず、含有量がゼロ（ｆ＝０）でもよい任意成分として位置づけられる。 In the composition formula (1), B is at least one element selected from the group consisting of nickel, manganese, copper, zinc, magnesium, calcium, strontium, barium, tin, lead, lanthanum, placeodium, neodymium, and europium. Is shown. Nickel, manganese, copper, zinc, magnesium, calcium, strontium, barium, tin and lead tend to replace some cobalt in the oxide and stabilize the crystal structure of CoMoO 4 in the catalyst, lanthanum, Placeodium, neodymium, and europium tend to form composite oxides with molybdenum to improve their activity. From the viewpoint of maintaining a balance with the formation of Bi 10 Mo 3 O 24 crystals showing catalytic performance, the upper limit of the atomic ratio f of B is more preferably f ≦ 2. Since the element represented by B stabilizes the crystal structure of CoMoO 4 in the catalyst or improves the activity of the catalyst, it does not affect the crystal structure of Bi 10 Mo 3 O 24 and contains it. Is positioned as an arbitrary component that may be zero (f = 0).
セリウム、Ａ及びＢで示される元素は、触媒中に含まれていても含まれていなくても、Ｂｉ10Ｍｏ3Ｏ24相の結晶構造とは別に結晶構造を形成するため、Ｂｉ10Ｍｏ3Ｏ24相の結晶構造には影響を及ぼさない。 The elements represented by cerium, A and B, whether contained in the catalyst or not, form a crystal structure separate from the crystal structure of the Bi 10 Mo 3 O 24 phase, and therefore Bi 10 Mo 3 It does not affect the crystal structure of the O 24 phase.
（３）金属酸化物以外の成分
本実施形態の酸化物触媒は、金属酸化物を担持するための担体を含有してもよい。担体を含む触媒は金属酸化物の高分散化及び担持された金属酸化物に、高い耐摩耗性を与えるという点で好ましいが、固定床反応器で不飽和アルデヒドを製造する際に、打錠成型した触媒を用いる場合には担体を含まなくてよい。押し出し成型法により触媒を成型する場合には、担体成分を含むことが好ましい。
担体としては、以下に限定されないが、例えば、シリカ、アルミナ、チタニア、ジルコニアが挙げられる。一般的にシリカは、他の担体に比べそれ自身不活性であり、目的生成物に対する選択性を低下させることなく、金属酸化物に対して良好なバインド作用を有する点で好ましい担体である。さらに、シリカ担体は、担持された金属酸化物に、高い耐摩耗性を与え易いという点でも好ましい。押し出し成型法により触媒を成型する場合、触媒全体に対する担体の含有量は５〜１０質量％であることが好ましい。
(3) Components other than metal oxide The oxide catalyst of the present embodiment may contain a carrier for supporting the metal oxide. A catalyst containing a carrier is preferable in that the metal oxide is highly dispersed and the supported metal oxide is provided with high abrasion resistance. However, when unsaturated aldehyde is produced in a fixed bed reactor, tableting molding is performed. It is not necessary to include a carrier when the catalyst is used. When the catalyst is molded by the extrusion molding method, it is preferable to include a carrier component.
Examples of the carrier include, but are not limited to, silica, alumina, titania, and zirconia. In general, silica is a preferred carrier in that it is itself inert compared to other carriers and has a good binding action on metal oxides without reducing selectivity for the target product. Further, the silica carrier is also preferable in that it easily imparts high wear resistance to the supported metal oxide. When the catalyst is molded by the extrusion molding method, the content of the carrier with respect to the entire catalyst is preferably 5 to 10% by mass.
触媒を流動床反応器で用いる場合も、上記と同様の観点から、シリカを担体として用いることが好ましい。Ｂｉ10Ｍｏ3Ｏ24の結晶構造への影響と、見掛け比重を適切にして流動性を良好にする観点から、触媒中の担体の含有量は、触媒の全質量に対して８０質量％以下であることが好ましく、７０質量％以下であることがより好ましく、６０質量％以下であることがさらに好ましい。流動床反応用触媒のように強度を要する触媒である場合には、実用上十分な耐破砕正や耐摩耗性等を有する観点から、担体の含有量は、触媒の全質量に対して２０質量％以上であることが好ましく、３０質量％以上であることがより好ましく、４０質量％以上であることがさらに好ましい。 When the catalyst is used in a fluidized bed reactor, it is preferable to use silica as a carrier from the same viewpoint as described above. From the viewpoint of affecting the crystal structure of Bi 10 Mo 3 O 24 and improving the fluidity by appropriately adjusting the apparent specific gravity, the content of the carrier in the catalyst is 80% by mass or less with respect to the total mass of the catalyst. It is preferably 70% by mass or less, and more preferably 60% by mass or less. In the case of a catalyst that requires strength, such as a catalyst for a fluidized bed reaction, the content of the carrier is 20 mass with respect to the total mass of the catalyst from the viewpoint of having practically sufficient crushing resistance and wear resistance. % Or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more.
［２］酸化物触媒の製造方法
本実施形態の酸化物触媒は、以下に限定されないが、元素組成比、調製方法、及び焼成方法を後述する好ましい範囲で制御することによって、Ｂｉ10Ｍｏ3Ｏ24の結晶構造が充分に含まれる酸化物触媒を得ることができる。
本実施形態に係る酸化物触媒の製造方法は、モリブデン元素を含む化合物、ビスマス元素を含む化合物、鉄元素を含む化合物、及びコバルト元素を含む化合物を液相で混合し、前駆体スラリーを調製する工程と、前記前駆体スラリーを噴霧乾燥し、乾燥体を得る工程と、前記乾燥体を、２００〜３００℃の範囲内で設定した第一の温度まで室温から昇温し、２００〜３００℃の範囲内の温度で１時間以上保持して第一焼成体を得る工程と、前記第一焼成体と有機物とを混合成型して成型体を得る工程と、前記成型体を、不活性ガス中で２００〜４００℃の範囲内で設定した第二の温度まで室温から１時間以上かけて昇温し、２００〜４００℃の範囲内の温度で１時間以上保持して第二焼成体を得る工程と、前記第二焼成体を、不活性ガス中で４００〜６００℃の範囲内で設定した第三の温度まで、第二の温度から１時間以上かけて昇温し、４００〜６００℃の範囲内の温度で１時間以上保持して酸化物触媒を得る工程と、を有することが好ましい。
[2] Method for Producing Oxide Catalyst The oxide catalyst of the present embodiment is not limited to the following, but by controlling the element composition ratio, the preparation method, and the firing method within a preferable range described later, Bi 10 Mo 3 O. An oxide catalyst sufficiently containing 24 crystal structures can be obtained.
In the method for producing an oxide catalyst according to the present embodiment, a compound containing a molybdenum element, a compound containing a bismuth element, a compound containing an iron element, and a compound containing a cobalt element are mixed in a liquid phase to prepare a precursor slurry. The step, the step of spray-drying the precursor slurry to obtain a dried compound, and the step of raising the temperature of the dried compound from room temperature to a first temperature set in the range of 200 to 300 ° C. to 200 to 300 ° C. A step of obtaining a first fired body by holding it at a temperature within the range for 1 hour or more, a step of mixing and molding the first fired body and an organic substance to obtain a molded body, and a step of obtaining the molded body in an inert gas. A step of raising the temperature from room temperature to a second temperature set in the range of 200 to 400 ° C. over 1 hour or more and holding the temperature in the range of 200 to 400 ° C. for 1 hour or more to obtain a second fired compound. The second fired compound is heated in an inert gas to a third temperature set in the range of 400 to 600 ° C. from the second temperature over an hour or more, and within the range of 400 to 600 ° C. It is preferable to have a step of obtaining an oxide catalyst by holding the compound at the same temperature for 1 hour or more.
本発明者らは、酸化物触媒の製造工程において、有機物を利用すること、及び還元焼成を利用することにより、Ｂｉ10Ｍｏ3Ｏ24相を十分に含む酸化物触媒を製造できることを見出し、これにより従来の酸化焼成では取りえない構造を有する酸化物触媒を実現した。 The present inventors have found that an oxide catalyst containing a sufficient amount of Bi 10 Mo 3 O 24 phase can be produced by using an organic substance and reduction calcination in the process of producing an oxide catalyst. As a result, an oxide catalyst having a structure that cannot be obtained by conventional oxidative firing has been realized.
Ｂｉ10Ｍｏ3Ｏ24相を選択的に合成する方法としては、例えば、特定の焼成雰囲気ないし焼成温度等の各種の焼成条件を調整する方法を採用することが挙げられ、この方法によって、ｄｉｓｏｒｄｅｒ相Ｂｉ3-xＡxＦｅ1Ｍｏ2Ｏ12相の生成を抑制し、Ｂｉ10Ｍｏ3Ｏ24の結晶を選択的に形成することができる。すなわち、そのような結晶構造を有する本実施形態の酸化物触媒を好ましく得ることができる。 As a method for selectively synthesizing the Bi 10 Mo 3 O 24 phase, for example, a method of adjusting various firing conditions such as a specific firing atmosphere or firing temperature can be adopted. By this method, the disorderer phase can be used. The formation of the Bi 3-x A x Fe 1 Mo 2 O 12 phase can be suppressed, and crystals of Bi 10 Mo 3 O 24 can be selectively formed. That is, the oxide catalyst of the present embodiment having such a crystal structure can be preferably obtained.
本実施態様の酸化物触媒は、例えば、原料スラリー（以下、「前駆体スラリー」ともいう）を調製する第１の工程、原料スラリーを噴霧乾燥して乾燥体を得る第２の工程、乾燥体を焼成する第３の工程を包含する方法によって得ることができる。以下、第１〜第３の工程を有する酸化物触媒の製造方法の好ましい態様について説明する。 The oxide catalyst of the present embodiment is, for example, a first step of preparing a raw material slurry (hereinafter, also referred to as “precursor slurry”), a second step of spray-drying the raw material slurry to obtain a dried product, and a dried product. Can be obtained by a method including a third step of firing. Hereinafter, a preferred embodiment of the method for producing an oxide catalyst having the first to third steps will be described.
（１）原料スラリーの調製
第１の工程では、触媒を構成する各金属元素を含む化合物からなる触媒原料を混合して原料スラリーを得る。
モリブデン、ビスマス、セリウム、鉄、コバルト、カリウム、ルビジウム、セシウム、ニッケル、マンガン、銅、亜鉛、マグネシウム、カルシウム、ストロンチウム、バリウム、錫、鉛、ランタン、プラセオジウム、ネオジム、ユウロピウムの各元素源としては、水又は硝酸に可溶なアンモニウム塩、硝酸塩、塩酸塩、有機酸塩を挙げることができ、酸化物や水酸化物、炭酸塩等でもよい。シリカ担体を含有する触媒を製造する場合は、原料スラリーにシリカ原料としてシリカゾルを添加するのが好ましい。
(1) Preparation of Raw Material Slurry In the first step, a catalyst raw material composed of a compound containing each metal element constituting the catalyst is mixed to obtain a raw material slurry.
Molybdenum, bismuth, cerium, iron, cobalt, potassium, rubidium, cesium, nickel, manganese, copper, zinc, magnesium, calcium, strontium, barium, tin, lead, lantern, placeodium, neodymium, and europium are the sources of each element. Examples thereof include ammonium salts, nitrates, hydrochlorides and organic acid salts which are soluble in water or nitrate, and oxides, hydroxides, carbonates and the like may be used. When producing a catalyst containing a silica carrier, it is preferable to add silica sol as a silica raw material to the raw material slurry.
原料スラリーの調製方法は、通常用いられる方法であれば特に限定されず、例えば、モリブデンのアンモニウム塩を温水に溶解させた溶液と、ビスマス、鉄、コバルト、アルカリ金属を硝酸塩として水又は硝酸水溶液に溶解させた溶液を混合することにより調製することができる。混合後の原料スラリー中の金属元素濃度は、均一性と生産量のバランスの観点から、通常１〜５０質量％であり、好ましくは１０〜４０質量％、より好ましくは２０〜４０質量％である。 The method for preparing the raw material slurry is not particularly limited as long as it is a commonly used method. It can be prepared by mixing the dissolved solutions. The concentration of metal elements in the raw material slurry after mixing is usually 1 to 50% by mass, preferably 10 to 40% by mass, and more preferably 20 to 40% by mass from the viewpoint of the balance between uniformity and production amount. ..
アンモニウム塩と硝酸塩を混合すると沈殿を生じ、スラリーとなる。
原料スラリーが均質でない場合、焼成後の触媒組成が不均質になり、均質に複合化された結晶構造は形成され難くなるため、得られた酸化物の複合化が十分でない場合に、スラリーの調製工程の適正化を試みるのは好ましい態様である。なお、上述の原料スラリーの調製工程は一例であって限定的なものではなく、各元素源の添加の順序を変えてもよい。硝酸を原料スラリー中に添加して硝酸濃度を調整してもよい。原料スラリーを均一にする観点から原料スラリーの温度（「スラリー温度」）と撹拌時間（「スラリー撹拌時間」）を調整することが好ましい。スラリー温度は２０〜８０℃、好ましくは３０〜７０℃、さらに好ましくは４０〜６０℃である。
スラリー攪拌時間は３０分以上１０時間以下が好ましく、より好ましくは１時間以上８時間以下、最も好ましくは２時間以上５時間以下である。
Mixing ammonium salt and nitrate produces a precipitate, which forms a slurry.
If the raw material slurry is not homogeneous, the catalyst composition after firing becomes inhomogeneous, and it becomes difficult to form a homogeneously composited crystal structure. Therefore, when the obtained oxide is not sufficiently composited, the slurry is prepared. Attempting to optimize the process is a preferred embodiment. The above-mentioned raw material slurry preparation step is an example and is not limited, and the order of addition of each element source may be changed. Nitric acid may be added to the raw material slurry to adjust the nitric acid concentration. From the viewpoint of making the raw material slurry uniform, it is preferable to adjust the temperature of the raw material slurry (“slurry temperature”) and the stirring time (“slurry stirring time”). The slurry temperature is 20 to 80 ° C., preferably 30 to 70 ° C., more preferably 40 to 60 ° C.
The slurry stirring time is preferably 30 minutes or more and 10 hours or less, more preferably 1 hour or more and 8 hours or less, and most preferably 2 hours or more and 5 hours or less.
（２）乾燥
第２の工程では、第１の工程で得られた原料スラリーを乾燥して乾燥体を得る。乾燥方法としては、特に制限はなく一般に用いられている方法によって行うことができ、蒸発乾涸法、噴霧乾燥法、減圧乾燥法などの任意の方法で行なうことができる。
噴霧乾燥法では、通常工業的に実施される遠心方式、二流体ノズル方式及び高圧ノズル方式等の方法によって行うことができ、乾燥熱源としては、スチーム、電気ヒーター等によって加熱された空気を用いることが好ましい。この際、噴霧乾燥装置の乾燥機入口の温度は、通常１５０〜４００℃、好ましくは１８０〜４００℃、より好ましくは２００〜３５０℃である。噴霧乾燥装置の乾燥機出口の温度は、通常１００〜２００℃、好ましくは１２０〜１８０℃、より好ましくは１３０〜１６０℃である。
(2) Drying In the second step, the raw material slurry obtained in the first step is dried to obtain a dried product. The drying method is not particularly limited and can be carried out by a generally used method, and can be carried out by any method such as an evaporation drying method, a spray drying method and a vacuum drying method.
The spray drying method can be performed by methods such as a centrifugal method, a two-fluid nozzle method, and a high-pressure nozzle method, which are usually industrially performed, and as the drying heat source, air heated by steam, an electric heater, or the like is used. Is preferable. At this time, the temperature at the inlet of the dryer of the spray dryer is usually 150 to 400 ° C, preferably 180 to 400 ° C, and more preferably 200 to 350 ° C. The temperature at the outlet of the dryer of the spray dryer is usually 100 to 200 ° C, preferably 120 to 180 ° C, and more preferably 130 to 160 ° C.
（３）焼成
第３の工程では、第２の工程で得られた乾燥体を焼成する。焼成は、回転炉、トンネル炉、マッフル炉等の焼成炉を用いて行うことができる。乾燥体の焼成方法は、用いる原料によっても異なる。例えば、原料に硝酸イオンを含む場合には、以下の第一〜第三の焼成による３段階焼成を行うことが好ましい。
(3) Firing In the third step, the dried product obtained in the second step is calcined. The firing can be performed using a firing furnace such as a rotary furnace, a tunnel furnace, or a muffle furnace. The method of firing the dried product also differs depending on the raw material used. For example, when the raw material contains nitrate ions, it is preferable to perform three-step firing by the following first to third firings.
［１］第一焼成工程
第一焼成工程においては、乾燥体を２００℃〜３００℃の範囲内で設定した第一の温度まで室温から昇温し、２００℃〜３００℃の範囲内の温度で１時間以上保持することにより第一焼成体を得る。第一の温度は、好ましくは２２０〜２８０℃、さらに好ましくは２４０℃〜２６０℃の温度範囲である。室温から第一の温度に到達するまでの昇温時間は１時間以上、好ましくは１〜１０時間、より好ましくは１〜５時間である。室温は、例えば０〜４０℃であり、２０〜３０℃であることが好ましい。
第一焼成工程は、乾燥体中に残存している硝酸アンモニウムや原料の金属硝酸塩由来の硝酸を徐々に燃焼させることを目的としており、２００℃〜３００℃の温度範囲で保持する時間は、好ましくは１〜１０時間であり、より好ましくは２〜５時間である。
第一焼成工程の温度が高すぎたり、時間が長すぎたりすると、第一焼成の段階で単純酸化物が成長し易くなる傾向にある。そのため、後述の第三焼成工程において、Ｂｉ10Ｍｏ3Ｏ24相の結晶構造を十分に生成する観点から、第一焼成工程における温度及び時間の上限を、単純酸化物の生成が起こらない程度に設定するのが好ましい。第一焼成温度を上記範囲にしたり、昇温時間及び保持時間にしたりすることにより、触媒粒子内での金属元素の移動が所望の領域となるため、後述の第三焼成工程において、Ｂｉ10Ｍｏ3Ｏ24相の結晶構造が生成しやすくなる。
[1] First firing step In the first firing step, the dried product is heated from room temperature to the first temperature set in the range of 200 ° C. to 300 ° C., and at a temperature in the range of 200 ° C. to 300 ° C. The first fired body is obtained by holding for 1 hour or more. The first temperature is preferably in the temperature range of 220 to 280 ° C, more preferably 240 ° C to 260 ° C. The temperature rising time from room temperature to reaching the first temperature is 1 hour or more, preferably 1 to 10 hours, and more preferably 1 to 5 hours. The room temperature is, for example, 0 to 40 ° C, preferably 20 to 30 ° C.
The purpose of the first firing step is to gradually burn the ammonium nitrate remaining in the dried body and the nitric acid derived from the raw material metal nitrate, and the time for holding in the temperature range of 200 ° C. to 300 ° C. is preferable. It is 1 to 10 hours, more preferably 2 to 5 hours.
If the temperature of the first firing step is too high or the time is too long, the simple oxide tends to grow easily at the first firing step. Therefore, from the viewpoint of sufficiently forming the crystal structure of the Bi 10 Mo 3 O 24 phase in the third firing step described later, the upper limit of the temperature and time in the first firing step is set to such that the formation of simple oxides does not occur. It is preferable to set it. By setting the first firing temperature to the above range, the temperature rising time, and the holding time, the movement of the metal element in the catalyst particles becomes a desired region. Therefore, in the third firing step described later, Bi 10 Mo 3 O 24 phase crystal structure is easily formed.
［２］成型工程
成型工程は、第一焼成体を成型して成型体を得る工程である。成型方法としては、特に限定されないが、例えば、公知の打錠成型法、押出成型法、転動造粒法等が挙げられる。このなかでも、成型触媒の生産性の観点から、打錠成型法又は押出成型法により、第一焼成体を成型して成型体を得ることが好ましい。成型形状は、特に限定されないが、例えば、球状、円柱状、リング（円筒状）、星型状等の形状が挙げられる。このなかでも、成型触媒の圧壊強度の高い観点で円柱状、リング状が好ましい。
[2] Molding step The molding step is a step of molding the first fired body to obtain a molded body. The molding method is not particularly limited, and examples thereof include a known tableting molding method, extrusion molding method, rolling granulation method, and the like. Among these, from the viewpoint of productivity of the molding catalyst, it is preferable to obtain a molded body by molding the first fired body by a tableting molding method or an extrusion molding method. The molding shape is not particularly limited, and examples thereof include a spherical shape, a cylindrical shape, a ring (cylindrical shape), and a star shape. Among these, a columnar shape and a ring shape are preferable from the viewpoint of high crushing strength of the molding catalyst.
成型工程では、成型しやすくする観点や成型収率を高める観点で第一焼成体に成型助剤を加えてもよい。成型助剤としては、特に限定されないが、例えば、ポリビニルアルコール、グラファイト、タルク、無機ケイ酸、炭素繊維などの無機ファイバー等が挙げられる。 In the molding step, a molding aid may be added to the first fired body from the viewpoint of facilitating molding and increasing the molding yield. The molding aid is not particularly limited, and examples thereof include inorganic fibers such as polyvinyl alcohol, graphite, talc, inorganic silicic acid, and carbon fibers.
本実施態様においては、第一焼成体を成型する際に、有機物を混合することが好ましい。有機物を添加する目的は、Ｂｉ10Ｍｏ3Ｏ24相の結晶構造を十分に生成する為である。成型時に添加する有機物は特に限定はないが、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、又は（メタ）アクリル酸イソブチルエステルの重合体やポリスチレン、セルロース、ポリビニルアルコールなど後述する第二焼成工程及び第三焼成工程によって容易に除去されるものが好ましい。ポリメタクリル酸メチル、ポリメタクリル酸イソブチル、ポリスチレン、セルロース、ポリビニルアルコールは比較的低い温度で単量体に分解し、気化蒸発するのでより好ましい。不飽和アルデヒドの収率を高める観点でセルロースがより好ましい。セルロースの中でも外形が球状である、すなわち、粒径が不均一なセルロースよりも、外形が棒状をした結晶セルロース（以下「棒状セルロース」ともいう。）を用いることが、均一なＢｉ10Ｍｏ3Ｏ24相の結晶構造を形成させる観点から特に好ましい。棒状をした結晶セルロースとは、短径と長径を持つ結晶セルロースからなる粒子において、短径に対し長径が１．２倍以上長いものを個数として５０％以上含有するものをいう。短径と長径は電子顕微鏡による観測で測定できる。具体的には、添加する結晶セルロースを一部採取し、電子顕微鏡を用いて粒子１００個の短径、長径を測定する。
有機物の添加量は、第一焼成体と該有機物との合計に対し、０．５〜１５ｗｔ％が好ましい。特に、棒状セルロースの添加量は、第一焼成体と該棒状セルロースとの合計に対し、０．５〜１０ｗｔ％が好ましく、より好ましくは１〜５ｗｔ％であり、特に好ましくは１．５〜３ｗｔ％である。球状セルロースやＰＶＡの場合は、棒状セルロースよりも多い添加量が好ましく、より好ましくは１〜５ｗｔ％であり、特に好ましくは１．５〜４ｗｔ％である。
第一焼成体と有機物を混合する方法としては、例えば、双腕式ニーダー、リボンミキサー、ヘンシェルミキサー等公知の装置を用いて行うことができる。
In this embodiment, it is preferable to mix an organic substance when molding the first fired body. The purpose of adding the organic matter is to sufficiently generate the crystal structure of the Bi 10 Mo 3 O 24 phase. The organic matter added at the time of molding is not particularly limited, but is a polymer of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, or isobutyl ester of (meth) acrylate, polystyrene, cellulose, polyvinyl. Acrylic acid or the like that is easily removed by the second firing step and the third firing step described later is preferable. Polymethylmethacrylate, isobutylpolymethacrylate, polystyrene, cellulose, and polyvinyl alcohol are more preferable because they decompose into monomers at a relatively low temperature and vaporize and evaporate. Cellulose is more preferable from the viewpoint of increasing the yield of unsaturated aldehyde. Contour among the cellulose is spherical, i.e., than the particle size uneven cellulose, outer shape (hereinafter also referred to as "rod-like cellulose".) Crystalline cellulose in which the rod-like be used, uniform Bi 10 Mo 3 O It is particularly preferable from the viewpoint of forming a 24-phase crystal structure. The rod-shaped crystalline cellulose refers to particles composed of crystalline cellulose having a minor axis and a major axis, which contain 50% or more of particles having a major axis 1.2 times or more longer than the minor axis. The minor axis and the major axis can be measured by observation with an electron microscope. Specifically, a part of the crystalline cellulose to be added is collected, and the minor axis and the major axis of 100 particles are measured using an electron microscope.
The amount of the organic substance added is preferably 0.5 to 15 wt% with respect to the total of the first fired product and the organic substance. In particular, the amount of rod-shaped cellulose added is preferably 0.5 to 10 wt%, more preferably 1 to 5 wt%, and particularly preferably 1.5 to 3 wt% with respect to the total of the first calcined product and the rod-shaped cellulose. %. In the case of spherical cellulose or PVA, the amount added is preferably larger than that of rod-shaped cellulose, more preferably 1 to 5 wt%, and particularly preferably 1.5 to 4 wt%.
As a method of mixing the first fired body and the organic substance, for example, a known device such as a double-armed kneader, a ribbon mixer, or a Henschel mixer can be used.
［３］第二焼成工程
第二焼成工程では、成型体を不活性ガス中で２００℃〜４００℃の範囲内で設定した第二の温度まで室温から１時間以上かけて昇温し、２００℃〜４００℃の範囲内の温度で１時間以上保持することにより第二焼成体を得る。この第二焼成工程は不活性ガス雰囲気で行われる。第二焼成工程において、焼成温度を上記範囲に調整し、かつ、不活性ガス雰囲気下での焼成とすることにより、成型体に含まれる有機物をよりおだやかに燃焼し、十分にＢｉ10Ｍｏ3Ｏ24相の前駆体が生成する傾向にある。なお、窒素等の不活性ガスではなく、窒素で希釈された酸素や空気でもＢｉ10Ｍｏ3Ｏ24相の前駆体を得ることは可能である。しかし、第二焼成工程の熱処理中に酸素が含まれていると有機物が分解するときに発熱が起きる恐れがあるだけでなく、第二焼成時間の正確なコントロールが困難となるため、結果として得られうるＢｉ10Ｍｏ3Ｏ24相の前駆体の量が減少する傾向にある。このような観点から、本実施形態に係る酸化物触媒の製造方法においては、第二焼成工程は不活性ガス雰囲気で行うことが好ましい。本実施形態で用いる不活性ガスとしては、特に限定されないが、例えば、ヘリウム、アルゴン、窒素が挙げられる。このなかでも、経済的な面から窒素が好ましい。
第二焼成工程の温度は、より好ましくは２３０℃〜３６０℃であり、さらに好ましくは２６０℃〜３３０℃である。このような温度とすることにより、成型体に含まれる有機物をよりおだやかに燃焼させることができる傾向にある。
[3] Second firing step In the second firing step, the molded body is heated from room temperature to a second temperature set in the range of 200 ° C. to 400 ° C. over 1 hour or more in an inert gas to 200 ° C. A second fired body is obtained by holding at a temperature in the range of ~ 400 ° C. for 1 hour or more. This second firing step is performed in an inert gas atmosphere. In the second firing step, by adjusting the firing temperature to the above range and firing in an inert gas atmosphere, the organic matter contained in the molded body is burned more gently, and Bi 10 Mo 3 O is sufficiently generated. 24- phase precursors tend to form. It is possible to obtain a precursor of the Bi 10 Mo 3 O 24 phase by using oxygen or air diluted with nitrogen instead of an inert gas such as nitrogen. However, if oxygen is contained during the heat treatment in the second firing step, not only may heat be generated when the organic matter decomposes, but also it becomes difficult to accurately control the second firing time, resulting in a result. The amount of possible Bi 10 Mo 3 O 24 phase precursors tends to decrease. From this point of view, in the method for producing an oxide catalyst according to the present embodiment, the second firing step is preferably performed in an inert gas atmosphere. The inert gas used in the present embodiment is not particularly limited, and examples thereof include helium, argon, and nitrogen. Of these, nitrogen is preferable from the economical point of view.
The temperature of the second firing step is more preferably 230 ° C. to 360 ° C., and even more preferably 260 ° C. to 330 ° C. By setting such a temperature, the organic matter contained in the molded body tends to be burned more gently.
第二焼成工程の保持時間は、好ましくは１時間以上、より好ましくは１．５〜１０時間、さらに好ましくは２〜５時間である。室温から第二の温度に到達するまでの昇温時間は１時間以上、好ましくは１．５〜１０時間、より好ましくは２〜５時間である。室温は、例えば０〜４０℃であり、２０〜３０℃であることが好ましい。
第二焼成工程の温度及び／又は時間が上記範囲内であることにより、第二焼成工程の段階でＣｏとＭｏとの２成分系酸化物の成長がより抑制される傾向にあり、後述の第三焼成工程においてＢｉ10Ｍｏ3Ｏ24相の結晶構造がより生成しやすくなる傾向にある。
The holding time of the second firing step is preferably 1 hour or more, more preferably 1.5 to 10 hours, still more preferably 2 to 5 hours. The temperature rising time from room temperature to reaching the second temperature is 1 hour or more, preferably 1.5 to 10 hours, and more preferably 2 to 5 hours. The room temperature is, for example, 0 to 40 ° C, preferably 20 to 30 ° C.
When the temperature and / or time of the second firing step is within the above range, the growth of the two-component oxides of Co and Mo tends to be further suppressed at the stage of the second firing step, which will be described later. (3) In the firing step, the crystal structure of the Bi 10 Mo 3 O 24 phase tends to be more easily formed.
［４］第三焼成工程
第三焼成工程においては、第二焼成体を、不活性ガス中で４００℃〜６００℃の範囲内で設定した第三の温度まで、第二の温度から１時間以上かけて昇温し、４００℃〜６００℃の範囲内の温度で１時間以上保持して酸化物触媒を得る。第三焼成工程においては、好ましくは１〜１０時間かけて設定温度まで昇温する。昇温レートは常に一定である必要はない。第二焼成の温度から第三の温度に到達するまでの昇温時間は、Ｂｉ10Ｍｏ3Ｏ24相を均一に形成し易くする観点で好ましくは１．５〜７時間、より好ましくは２〜４時間である。昇温時間が１時間未満であるとＢｉ10Ｍｏ3Ｏ24相の結晶が均一に形成せず、Ｂｉ2Ｏ3等の結晶が生成され易くなる傾向にある。
本発明者の知見によると、結晶構造は焼成温度と焼成時間の積の影響を受けるため、焼成温度と焼成時間を適切に設定することが好ましい。Ｂｉ10Ｍｏ3Ｏ24相を生成しやくする観点から、第三焼成工程における温度は、好ましくは４８０〜６００℃、より好ましくは５００℃〜５８０℃であり、さらに好ましくは５１０℃〜５６０℃である。第三焼成工程における保持時間は、好ましくは１〜２４時間、より好ましくは１．５〜２０時間、さらに好ましくは２〜１０時間である。第三焼成の保持時間が長すぎる場合、触媒の活性が下がる傾向にある。第三焼成の温度が４８０℃未満の低温では、Ｂｉ10Ｍｏ3Ｏ24相の結晶構造が形成しにくく、６００℃より高温の場合、表面積が小さくなり触媒の活性が下がる傾向にある。
以上の工程を行うことで、Ｂｉ10Ｍｏ3Ｏ24相の結晶構造を十分に含む酸化物触媒が得られる。
[4] Third firing step In the third firing step, the second fired body is placed in an inert gas up to a third temperature set within the range of 400 ° C. to 600 ° C. for 1 hour or more from the second temperature. The temperature is raised over 1 hour and held at a temperature in the range of 400 ° C. to 600 ° C. for 1 hour or more to obtain an oxide catalyst. In the third firing step, the temperature is preferably raised to a set temperature over 1 to 10 hours. The heating rate does not have to be constant at all times. The temperature rising time from the second firing temperature to the third temperature is preferably 1.5 to 7 hours, more preferably 2 to 7 hours from the viewpoint of facilitating uniform formation of the Bi 10 Mo 3 O 24 phase. 4 hours. If the temperature rising time is less than 1 hour , crystals of the Bi 10 Mo 3 O 24 phase are not uniformly formed, and crystals such as Bi 2 O 3 tend to be easily formed.
According to the findings of the present inventor, since the crystal structure is affected by the product of the firing temperature and the firing time, it is preferable to appropriately set the firing temperature and the firing time. From the viewpoint of facilitating the formation of the Bi 10 Mo 3 O 24 phase, the temperature in the third firing step is preferably 480 to 600 ° C, more preferably 500 ° C to 580 ° C, and further preferably 510 ° C to 560 ° C. be. The holding time in the third firing step is preferably 1 to 24 hours, more preferably 1.5 to 20 hours, still more preferably 2 to 10 hours. If the retention time of the third firing is too long, the activity of the catalyst tends to decrease. At a low temperature of less than 480 ° C., the crystal structure of the Bi 10 Mo 3 O 24 phase is difficult to form, and at a temperature higher than 600 ° C., the surface area tends to be small and the activity of the catalyst tends to decrease.
By performing the above steps, an oxide catalyst sufficiently containing the crystal structure of the Bi 10 Mo 3 O 24 phase can be obtained.
第三焼成工程後の酸化物触媒に、Ｂｉ10Ｍｏ3Ｏ24相の結晶構造が生成したことは、Ｘ線回折を測定することによって確認することができる。Ｂｉ10Ｍｏ3Ｏ24相の結晶構造が充分に成長していれば、０．２≦Ｒｉ≦１．０となる。 It can be confirmed by measuring X-ray diffraction that the crystal structure of the Bi 10 Mo 3 O 24 phase was formed in the oxide catalyst after the third firing step. If the crystal structure of the Bi 10 Mo 3 O 24 phase is sufficiently grown, 0.2 ≦ Ri ≦ 1.0.
［３］不飽和アルデヒドの製造方法
本実施形態の酸化物触媒を用い、プロピレン、イソブチレン、イソブタノール、及びｔ−ブチルアルコールからなる群から選ばれる少なくとも１種を酸化反応に供することにより、不飽和アルデヒドを製造することができる。以下、その具体例について説明するが、本実施形態に係る不飽和アルデヒドの製造方法は、以下の具体例に限定されるものではない。
[3] Method for Producing Unsaturated Aldehyde Unsaturated by using the oxide catalyst of the present embodiment and subjecting at least one selected from the group consisting of propylene, isobutylene, isobutanol, and t-butyl alcohol to an oxidation reaction. Aldehydes can be produced. Hereinafter, specific examples thereof will be described, but the method for producing an unsaturated aldehyde according to the present embodiment is not limited to the following specific examples.
（１）メタクロレインの製造方法
メタクロレインは、例えば、本実施形態の酸化物触媒を用いて、イソブチレン、イソブタノール、ｔ−ブチルアルコールの気相接触酸化反応を行うことにより得ることができる。気相接触酸化反応は、固定床反応器内の触媒層に、イソブチレン、イソブタノール若しくはｔ−ブチルアルコール単独か、又はこれらの混合ガスの濃度が１〜１０容量％になり、分子状酸素の濃度が１〜２０容量％になるように、分子状酸素含有ガスと希釈ガスを添加した混合ガスからなる原料ガスを導入する。イソブチレン、イソブタノール、ｔ−ブチルアルコール、又はこれらの混合ガスの濃度は、通常１〜１０容量％、好ましくは４〜９容量％、より好ましくは６〜９容量％である。反応温度は３００〜４８０℃、好ましくは３３０℃〜４５０℃、より好ましくは３５０℃〜４４０℃である。圧力は、常圧〜５気圧であり、空間速度４００〜４０００／時間［Ｎｏｒｍａｌ ｔｅｍｐｅｒａｔｕｒｅ ｐｒｅｓｓｕｒｅ （ＮＴＰ）条件下］で原料ガスを導入することで行うことができる。酸素と、イソブチレン、イソブタノール若しくはｔ−ブチルアルコール単独か、又はこれらの混合ガスとのモル比は、不飽和アルデヒドの収率を向上させるために反応器の出口酸素濃度を制御する観点から、通常１．０〜２．０であり、好ましくは１．１〜１．８、より好ましくは１．２〜１．８である。
(1) Method for Producing Methacrolein Methacrolein can be obtained, for example, by performing a gas phase catalytic oxidation reaction of isobutylene, isobutanol, and t-butyl alcohol using the oxide catalyst of the present embodiment. In the gas-phase catalytic oxidation reaction, the concentration of isobutylene, isobutanol or t-butyl alcohol alone or a mixed gas thereof becomes 1 to 10% by volume in the catalyst layer in the fixed bed reactor, and the concentration of molecular oxygen. A raw material gas composed of a mixed gas to which a molecular oxygen-containing gas and a diluting gas are added is introduced so that the concentration is 1 to 20% by volume. The concentration of isobutylene, isobutanol, t-butyl alcohol, or a mixed gas thereof is usually 1 to 10% by volume, preferably 4 to 9% by volume, and more preferably 6 to 9% by volume. The reaction temperature is 300 to 480 ° C, preferably 330 ° C to 450 ° C, more preferably 350 ° C to 440 ° C. The pressure is normal pressure to 5 atm, and can be performed by introducing the raw material gas at a space velocity of 400 to 4000 / hour [Normal temperature pressure (NTP) conditions]. The molar ratio of oxygen to isobutylene, isobutanol or t-butyl alcohol alone or a mixture thereof is usually from the viewpoint of controlling the outlet oxygen concentration of the reactor in order to improve the yield of unsaturated aldehyde. It is 1.0 to 2.0, preferably 1.1 to 1.8, and more preferably 1.2 to 1.8.
分子状酸素含有ガスとしては、特に限定されず、例えば、純酸素ガス、及び空気等の酸素を含むガス、またはＮ2Ｏ等の反応条件で分解して酸素を生成するガスが挙げられ、工業的観点から空気が好ましい。希釈ガスとしては、以下に限定されないが、例えば、窒素、二酸化炭素、水蒸気及びこれらの混合ガスが挙げられる。混合ガスにおける、分子状酸素含有ガスと希釈ガスの混合比は、体積比で０．０１＜分子状酸素含有ガス／（分子状酸素含有ガス＋希釈ガス）＜０．３の条件を満足することが好ましい。さらに、原料ガスにおける分子状酸素含有ガスの濃度は１〜２０容量％であることが好ましい。 The molecular oxygen-containing gas is not particularly limited, and examples thereof include pure oxygen gas, a gas containing oxygen such as air, and a gas that decomposes under reaction conditions such as N 2 O to generate oxygen. Air is preferable from the viewpoint of the viewpoint. Examples of the diluting gas include, but are not limited to, nitrogen, carbon dioxide, water vapor, and a mixed gas thereof. The mixing ratio of the molecular oxygen-containing gas and the diluted gas in the mixed gas satisfies the condition of 0.01 <molecular oxygen-containing gas / (molecular oxygen-containing gas + diluted gas) <0.3 in terms of volume ratio. Is preferable. Further, the concentration of the molecular oxygen-containing gas in the raw material gas is preferably 1 to 20% by volume.
原料ガス中の水蒸気は、触媒へのコーキングを防ぐ観点からは含まれることが好ましいが、メタクリル酸、酢酸等のカルボン酸の副生を抑制するために、できるだけ希釈ガス中の水蒸気濃度を下げることが好ましい。原料ガス中の水蒸気は、通常０〜３０容量％の範囲で使用される。同様に、アクロレインは、例えば、本実施形態の酸化物触媒を用いて、プロピレンの気相接触酸化反応を行うことにより得ることができる。 The water vapor in the raw material gas is preferably contained from the viewpoint of preventing caulking to the catalyst, but the water vapor concentration in the diluted gas should be reduced as much as possible in order to suppress the by-production of carboxylic acids such as methacrylic acid and acetic acid. Is preferable. The water vapor in the raw material gas is usually used in the range of 0 to 30% by volume. Similarly, acrolein can be obtained, for example, by carrying out a vapor phase catalytic oxidation reaction of propylene using the oxide catalyst of the present embodiment.
以下に実施例を示して、本実施形態をより詳細に説明するが、本実施形態は以下に記載の実施例によって限定されるものではない。なお、酸化物触媒における酸素原子の原子比は、他の元素の原子価条件により決定されるものであり、実施例及び比較例においては、触媒の組成を表す式中、酸素原子の原子比は省略する。また、酸化物触媒における各元素の組成比は、仕込みの組成比から算出した。 The present embodiment will be described in more detail with reference to the following examples, but the present embodiment is not limited to the examples described below. The atomic ratio of oxygen atoms in the oxide catalyst is determined by the valence conditions of other elements. In Examples and Comparative Examples, the atomic ratio of oxygen atoms is used in the formula representing the composition of the catalyst. Omit. The composition ratio of each element in the oxide catalyst was calculated from the composition ratio of the charged material.
＜Ｘ線回折角度の測定＞
ＸＲＤの測定は、Ｎａｔｉｏｎａｌ Ｉｎｓｔｉｔｕｔｅ ｏｆ Ｓｔａｎｄａｒｄｓ ＆ Ｔｅｃｈｎｏｌｏｇｙが標準参照物質６６０として定めるところのＬａＢ6化合物の（１１１）面、（２００）面を測定し、それぞれの値を３７．４４１°、４３．５０６°となるように規準化した。
ＸＲＤの装置としては、リガク製 Ｕｌｔｉｍａ−ＩＶを用いた。ＸＲＤの測定条件は、Ｘ線出力：４０ｋＶ−４０ｍＡ、Ｓｔｅｐ幅：０．０１°／ｓｔｅｐ、測定範囲：２θ＝５°〜６０°とした。
ＣｕＫα線をＸ線源として得られるＸ線回折パターンにおいて、現れたピークの位置及び強度に基づき、２θ＝２６．４°±０．２°の位置に現れるＣｏＭｏＯ4相の回折ピーク（ｃ）の強度Ｐｃに対する、２θ＝２７．４°±０．２°に現れるＢｉ10Ｍｏ3Ｏ24相の回折ピーク（ａ）の強度Ｐａの比Ｒｉ＝Ｐａ／Ｐｃを算出した。なお、２θ＝２６．４°±０．２°の位置に現れるＣｏＭｏＯ4相の回折ピーク（ｃ）の強度Ｐｃに対する、あるピークの強度Ｐの比Ｒ＝Ｐ／Ｐｃが０．００５未満の場合はノイズと判断し、ピークは検出されなかったものとした。
<Measurement of X-ray diffraction angle>
The XRD was measured by measuring the (111) plane and the (200) plane of the LaB 6 compound as defined by the National Institute of Standards & Technology as the standard reference substance 660, and the respective values were 37.441 ° and 43.506 °. It was standardized so that
As the XRD apparatus, Ultima-IV manufactured by Rigaku was used. The XRD measurement conditions were X-ray output: 40 kV-40 mA, Step width: 0.01 ° / step, and measurement range: 2θ = 5 ° to 60 °.
In the X-ray diffraction pattern obtained by using CuKα ray as an X-ray source, the diffraction peak (c) of the CoMoO 4- phase appearing at the position of 2θ = 26.4 ° ± 0.2 ° based on the position and intensity of the peak appearing. The ratio Ri = Pa / Pc of the intensity Pa of the diffraction peak (a) of the Bi 10 Mo 3 O 24 phase appearing at 2θ = 27.4 ° ± 0.2 ° with respect to the intensity Pc was calculated. When the ratio R = P / Pc of the intensity P of a certain peak to the intensity Pc of the diffraction peak (c) of the CoMoO 4- phase appearing at the position of 2θ = 26.4 ° ± 0.2 ° is less than 0.005. Was judged to be noise, and no peak was detected.
＜転化率と選択率＞
反応成績を表すため、次式で定義される転化率と選択率を算出した。なお、転化率と選択率を算出するための分析はガスクロマトグラフィーで行った。なお、下記実施例及び比較例においては、原料はイソブチレンであり、生成した化合物はメタクロレインであった。
この反応は１次反応であると仮定し、活性は転化率に１次に比例するものとした。
また、下記式で示される転化率の変化率を算出した。反応の経時的な転化率の変化率が大きい程、反応の経時的な活性上昇が大きいものと評価した。
転化率＝（反応した原料のモル数／供給した原料のモル数）×１００
選択率＝（生成した化合物のモル数／反応した原料のモル数）×１００
収率＝（生成した化合物のモル数／供給した原料のモル数）×１００
転化率の変化率＝（５００時間反応後の転化率―２時間反応後の転化率）／２時間反応後の転化率×１００
<Conversion rate and selectivity>
The conversion rate and selectivity defined by the following equations were calculated to represent the reaction results. The analysis for calculating the conversion rate and selectivity was performed by gas chromatography. In the following Examples and Comparative Examples, the raw material was isobutylene, and the produced compound was methacrolein.
This reaction was assumed to be a first-order reaction, and the activity was assumed to be first-order proportional to the conversion rate.
In addition, the rate of change of the conversion rate represented by the following formula was calculated. It was evaluated that the larger the rate of change in the conversion rate of the reaction over time, the greater the increase in activity of the reaction over time.
Conversion rate = (number of moles of raw material reacted / number of moles of raw material supplied) x 100
Selectivity = (number of moles of produced compound / number of moles of reacted raw material) x 100
Yield = (number of moles of produced compound / number of moles of supplied raw material) x 100
Rate of change in conversion rate = (conversion rate after 500-hour reaction-2 conversion rate after 2-hour reaction) / conversion rate after 2-hour reaction x 100
［実施例１］
約９０℃の温水２０８４．７４ｇにヘプタモリブデン酸アンモニウム［（ＮＨ4）6Ｍｏ7Ｏ24・４Ｈ2Ｏ］６９４．９１ｇを溶解させた（Ａ液）。また、硝酸ビスマス［Ｂｉ（ＮＯ3）3・５Ｈ2Ｏ］３４８．２７ｇ、硝酸セリウム［Ｃｅ（ＮＯ3）3・６Ｈ2Ｏ］１７２．６６ｇ、硝酸鉄［Ｆｅ（ＮＯ3）3・９Ｈ2Ｏ］３５７．７８ｇ、硝酸コバルト［Ｃｏ（ＮＯ3）2・６Ｈ2Ｏ］５１１．１０ｇ、硝酸カリウム［ＫＮＯ3］１．３２６ｇ、及び硝酸セシウム［ＣｓＮＯ3］１２．６７１ｇを、１８質量％の硝酸水溶液５８７．３１ｇに溶解させ、約９０℃の温水１３８９．８３ｇを添加した（Ｂ液）。Ａ液とＢ液の両液を混合し、約５０℃で約２時間程度撹拌混合して原料スラリーを得た。
この原料スラリーを、噴霧乾燥器に送り、入口温度２５０℃、出口温度約１４０℃で噴霧乾燥し、乾燥体を得た。
得られた乾燥体を、空気中で室温から２５０℃まで１時間かけて昇温し、４時間２５０℃を保持して第一焼成体を得た（第一焼成工程）。
室温まで冷却した第一焼成体に棒状の結晶セルロース（短径に対する長径が２倍以上のものを９０％以上含有）を、第一焼成体と結晶セルロースの合計に対し２．５ｗｔ％添加して混合し、直径５ｍｍ、高さ４ｍｍ、内径２ｍｍのリング状に打錠成形し、成型体を得た（成型工程）。
この成型体を窒素雰囲気中で室温から３００℃まで４時間かけて昇温し、２時間３００℃を保持して第二焼成体を得た（第二焼成工程）。
更に第二焼成体を窒素雰囲気中で３００℃から５３０℃まで２時間かけて昇温し、３時間５３０℃を保持して酸化物触媒を得た（第三焼成工程）。
得られた酸化物触媒の酸素以外の元素組成を表１に示し、粉末Ｘ線回折の測定結果を表２に示す。表２に示すとおり、実施例１の酸化物触媒は、２θ＝２６．３７°，１０．２７°，２７．４７°，３１．０２°，５２．８８°であり、Ｒｉ＝０．５５となった。この酸化物触媒について、反応開始から５００時間経過後にも同様の測定を行ったところ、２θ＝１０．２６°、２６．３６°、２７．４９°、３１．０４°、５２．８９°であり、Ｒｉ＝０．５５となった。すなわち、実施例１の酸化物触媒は反応開始前と反応開始から５００時間経過後でその結晶構造が維持されていることがわかった。
酸化物触媒の反応評価として、触媒５．５ｇを直径１４ｍｍのジャケット付ＳＵＳ製反応管に充填し、反応温度４３０℃でイソブチレン８容量％、酸素１２．８容量％、水蒸気３．０容量％及び窒素７６．２容量％からなる混合ガスを１２０ｍＬ／分（ＮＴＰ）の流量で通気し、メタクロレイン合成反応を行った。反応初期（反応開始２時間）の反応評価結果を表３に示し、転化率の経時変化を表４に示す。
また、図１に実施例１と後述する比較例１のＸＲＤ回折パターン（２θ＝２５°〜３５°の範囲）を対比する拡大図を示す。
[Example 1]
About 90 ° C. Ammonium heptamolybdate in hot water 2084.74g of dissolved [(NH 4) 6 Mo 7 O 24 · 4H 2 O] 694.91g (A solution). Further, bismuth nitrate [Bi (NO 3) 3 · 5H 2 O] 348.27g, cerium nitrate [Ce (NO 3) 3 · 6H 2 O] 172.66g, iron nitrate [Fe (NO 3) 3 · 9H 2 O] 357.78g, cobalt nitrate [Co (NO 3) 2 · 6H 2 O] 511.10g, potassium nitrate [KNO 3] 1.326g, and cesium nitrate [CsNO 3] 12.671g, 18 wt% nitric acid It was dissolved in 587.31 g of an aqueous solution, and 1389.83 g of warm water at about 90 ° C. was added (Liquid B). Both liquids A and B were mixed and stirred and mixed at about 50 ° C. for about 2 hours to obtain a raw material slurry.
This raw material slurry was sent to a spray dryer and spray-dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain a dried product.
The obtained dried product was heated in air from room temperature to 250 ° C. over 1 hour and kept at 250 ° C. for 4 hours to obtain a first calcined product (first calcining step).
To the first fired body cooled to room temperature, rod-shaped crystalline cellulose (containing 90% or more of those having a major axis twice or more the minor axis) was added in an amount of 2.5 wt% to the total of the first fired body and the crystalline cellulose. The mixture was mixed and compacted into a ring shape having a diameter of 5 mm, a height of 4 mm, and an inner diameter of 2 mm to obtain a molded body (molding step).
The temperature of this molded body was raised from room temperature to 300 ° C. over 4 hours in a nitrogen atmosphere, and the temperature was maintained at 300 ° C. for 2 hours to obtain a second fired body (second firing step).
Further, the temperature of the second calcined product was raised from 300 ° C. to 530 ° C. in a nitrogen atmosphere over 2 hours and maintained at 530 ° C. for 3 hours to obtain an oxide catalyst (third calcining step).
The composition of the elements other than oxygen of the obtained oxide catalyst is shown in Table 1, and the measurement results of powder X-ray diffraction are shown in Table 2. As shown in Table 2, the oxide catalyst of Example 1 was 2θ = 26.37 °, 10.27 °, 27.47 °, 31.02 °, 52.88 °, and Ri = 0.55. became. When the same measurement was performed on this
As a reaction evaluation of the oxide catalyst, 5.5 g of the catalyst was filled in a SUS reaction tube with a jacket having a diameter of 14 mm, and at a reaction temperature of 430 ° C, 8% by volume of isobutylene, 12.8% by volume of oxygen, 3.0% by volume of water vapor and A mixed gas consisting of 76.2% by volume of nitrogen was aerated at a flow rate of 120 mL / min (NTP) to carry out a methacrolein synthesis reaction. Table 3 shows the reaction evaluation results at the initial stage of the reaction (2 hours after the start of the reaction), and Table 4 shows the change over time in the conversion rate.
Further, FIG. 1 shows an enlarged view comparing the XRD diffraction patterns (range of 2θ = 25 ° to 35 °) of Example 1 and Comparative Example 1 described later.
［実施例２］
約９０℃の温水２１２０．２０ｇにヘプタモリブデン酸アンモニウム７０６．７３ｇを溶解させた（Ａ液）。また、硝酸ビスマス３２２．００ｇ、硝酸セリウム１３１．６９ｇ、硝酸鉄３０９．９６ｇ、硝酸コバルト５０９．９９ｇ、硝酸カリウム３．３７３ｇ、硝酸セシウム１９．３３ｇ及び硝酸ニッケル［Ｎｉ（ＮＯ3）2・６Ｈ2Ｏ］４８．９９７ｇ、硝酸マグネシウム［Ｍｇ（ＮＯ3）2・６Ｈ2Ｏ］４２．６８ｇ、及び硝酸ルビジウム［ＲｂＮＯ3］４．８７０ｇを、１８質量％の硝酸水溶液５９３．６５ｇに溶解させ、約９０℃の温水１４１３．４７ｇを添加した（Ｂ液）。Ａ液とＢ液の両液を混合し、約５０℃で約２時間程度撹拌混合して原料スラリーを得た。この原料スラリーを、噴霧乾燥器に送り、入口温度２５０℃、出口温度約１４０℃で噴霧乾燥し、乾燥体を得た。
得られた乾燥体を、空気中で室温から２５０℃まで２時間かけて昇温し、４時間２５０℃を保持して第一焼成体を得た。
室温まで冷却した第一焼成体に棒状の結晶セルロース（短径に対する長径が２倍以上のものを９０％以上含有）を、第一焼成体と結晶セルロースの合計に対し２．０ｗｔ％添加して混合し、直径５ｍｍ、高さ４ｍｍ、内径２ｍｍのリング状に打錠成形し、成型体を得た。
この成型体を窒素雰囲気中で室温から３３０℃まで３時間かけて昇温し、２時間３３０℃を保持して第二焼成体を得た。更に第二焼成体を窒素雰囲気中で３３０℃から５３０℃まで２時間かけて昇温し、３時間５３０℃を保持して酸化物触媒を得た。
得られた酸化物触媒の酸素以外の元素組成を表１に示し、粉末Ｘ線回折の測定結果を表２に示す。
酸化物触媒の反応評価として、酸化物触媒５．３ｇを反応管に充填し、実施例１と同様にメタクロレイン合成反応を行った。反応初期（反応開始２時間）の反応評価結果を表３に示し、転化率の経時変化を表４に示す。
[Example 2]
706.73 g of ammonium heptamolybdate was dissolved in 2120.20 g of warm water at about 90 ° C. (Liquid A). Further, bismuth nitrate 322.00G, cerium 131.69G, iron nitrate 309.96G, cobalt nitrate 509.99G, potassium nitrate 3.373G, cesium nitrate 19.33g and nickel nitrate [Ni (NO 3) 2 · 6H 2 O ] 48.997g, magnesium nitrate [Mg (NO 3) 2 · 6H 2 O] 42.68g, and rubidium nitrate [RbNO 3] 4.870g, were dissolved in 18 wt% aqueous solution of nitric acid 593.65g, approximately 90 1413.47 g of warm water at ° C. was added (Liquid B). Both liquids A and B were mixed and stirred and mixed at about 50 ° C. for about 2 hours to obtain a raw material slurry. This raw material slurry was sent to a spray dryer and spray-dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain a dried product.
The obtained dried product was heated in air from room temperature to 250 ° C. over 2 hours and maintained at 250 ° C. for 4 hours to obtain a first fired product.
To the first fired body cooled to room temperature, rod-shaped crystalline cellulose (containing 90% or more of those having a major axis twice or more the minor axis) was added in an amount of 2.0 wt% to the total of the first fired body and the crystalline cellulose. The mixture was mixed and compacted into a ring having a diameter of 5 mm, a height of 4 mm, and an inner diameter of 2 mm to obtain a molded product.
The temperature of this molded product was raised from room temperature to 330 ° C. over 3 hours in a nitrogen atmosphere, and the temperature was maintained at 330 ° C. for 2 hours to obtain a second fired product. Further, the temperature of the second calcined product was raised from 330 ° C. to 530 ° C. over 2 hours in a nitrogen atmosphere, and kept at 530 ° C. for 3 hours to obtain an oxide catalyst.
The composition of the elements other than oxygen of the obtained oxide catalyst is shown in Table 1, and the measurement results of powder X-ray diffraction are shown in Table 2.
As a reaction evaluation of the oxide catalyst, 5.3 g of the oxide catalyst was filled in the reaction tube, and the methacrolein synthesis reaction was carried out in the same manner as in Example 1. Table 3 shows the reaction evaluation results at the initial stage of the reaction (2 hours after the start of the reaction), and Table 4 shows the change over time in the conversion rate.
［実施例３］
棒状セルロース添加量を０．５ｗｔ％にしたこと以外は実施例１と同様の製造法で、酸化物触媒を得た。酸化物触媒の反応評価として、触媒５．３ｇを反応管に充填し、実施例１と同様にメタクロレイン合成反応を行った。反応初期（反応開始２時間）の反応評価結果を表３に示し、転化率の経時変化を表４に示す。
[Example 3]
An oxide catalyst was obtained by the same production method as in Example 1 except that the amount of rod-shaped cellulose added was 0.5 wt%. As a reaction evaluation of the oxide catalyst, 5.3 g of the catalyst was filled in a reaction tube, and a methacrolein synthesis reaction was carried out in the same manner as in Example 1. Table 3 shows the reaction evaluation results at the initial stage of the reaction (2 hours after the start of the reaction), and Table 4 shows the change over time in the conversion rate.
［実施例４］
棒状セルロース添加量を３．５ｗｔ％にしたこと以外は実施例１と同様の製造法で、酸化物触媒を得た。酸化物触媒の反応評価として、触媒５．３ｇを反応管に充填し、実施例１と同様にメタクロレイン合成反応を行った。反応初期（反応開始２時間）の反応評価結果を表３に示し、転化率の経時変化を表４に示す。
[Example 4]
An oxide catalyst was obtained by the same production method as in Example 1 except that the amount of rod-shaped cellulose added was 3.5 wt%. As a reaction evaluation of the oxide catalyst, 5.3 g of the catalyst was filled in a reaction tube, and a methacrolein synthesis reaction was carried out in the same manner as in Example 1. Table 3 shows the reaction evaluation results at the initial stage of the reaction (2 hours after the start of the reaction), and Table 4 shows the change over time in the conversion rate.
［実施例５］
第二焼成工程の設定温度（第二の温度）と保持温度とを３００℃から２００℃にしたこと以外は実施例１と同様の製造法で、酸化物触媒を得た。酸化物触媒の反応評価として、触媒５．４ｇを反応管に充填し、実施例１と同様にメタクロレイン合成反応を行った。反応初期（反応開始２時間）の反応評価結果を表３に示し、転化率の経時変化を表４に示す。
[Example 5]
An oxide catalyst was obtained by the same production method as in Example 1 except that the set temperature (second temperature) and the holding temperature in the second firing step were changed from 300 ° C. to 200 ° C. As a reaction evaluation of the oxide catalyst, 5.4 g of the catalyst was filled in a reaction tube, and a methacrolein synthesis reaction was carried out in the same manner as in Example 1. Table 3 shows the reaction evaluation results at the initial stage of the reaction (2 hours after the start of the reaction), and Table 4 shows the change over time in the conversion rate.
［実施例６］
第二焼成工程の設定温度（第二の温度）と保持温度とを３００℃から３６０℃にしたこと以外は実施例１と同様の製造法で、酸化物触媒を得た。酸化物触媒の反応評価として、触媒５．４ｇを反応管に充填し、実施例１と同様にメタクロレイン合成反応を行った。反応初期（反応開始２時間）の反応評価結果を表３に示し、転化率の経時変化を表４に示す。
[Example 6]
An oxide catalyst was obtained by the same production method as in Example 1 except that the set temperature (second temperature) and the holding temperature in the second firing step were changed from 300 ° C. to 360 ° C. As a reaction evaluation of the oxide catalyst, 5.4 g of the catalyst was filled in a reaction tube, and a methacrolein synthesis reaction was carried out in the same manner as in Example 1. Table 3 shows the reaction evaluation results at the initial stage of the reaction (2 hours after the start of the reaction), and Table 4 shows the change over time in the conversion rate.
［実施例７］
第二焼成工程の昇温時間を１時間にしたこと以外は実施例１と同様の製造法で、酸化物触媒を得た。酸化物触媒の反応評価として、触媒５．４ｇを反応管に充填し、実施例１と同様にメタクロレイン合成反応を行った。反応初期（反応開始２時間）の反応評価結果を表３に示し、転化率の経時変化を表４に示す。
[Example 7]
An oxide catalyst was obtained by the same production method as in Example 1 except that the temperature rising time in the second firing step was set to 1 hour. As a reaction evaluation of the oxide catalyst, 5.4 g of the catalyst was filled in a reaction tube, and a methacrolein synthesis reaction was carried out in the same manner as in Example 1. Table 3 shows the reaction evaluation results at the initial stage of the reaction (2 hours after the start of the reaction), and Table 4 shows the change over time in the conversion rate.
［実施例８］
第三焼成工程の設定温度（第三の温度）と保持温度とを５３０℃から４８０℃にしたこと以外は実施例１と同様の製造法で、酸化物触媒を得た。酸化物触媒の反応評価として、触媒５．４ｇを反応管に充填し、実施例１と同様にメタクロレイン合成反応を行った。反応初期（反応開始２時間）の反応評価結果を表３に示し、転化率の経時変化を表４に示す。
[Example 8]
An oxide catalyst was obtained by the same production method as in Example 1 except that the set temperature (third temperature) and the holding temperature in the third firing step were changed from 530 ° C. to 480 ° C. As a reaction evaluation of the oxide catalyst, 5.4 g of the catalyst was filled in a reaction tube, and a methacrolein synthesis reaction was carried out in the same manner as in Example 1. Table 3 shows the reaction evaluation results at the initial stage of the reaction (2 hours after the start of the reaction), and Table 4 shows the change over time in the conversion rate.
［実施例９］
第三焼成工程の設定温度（第三の温度）と保持温度とを５３０℃から５７０℃にしたこと以外は実施例１と同様の製造法で、酸化物触媒を得た。酸化物触媒の反応評価として、触媒５．４ｇを反応管に充填し、実施例１と同様にメタクロレイン合成反応を行った。反応初期（反応開始２時間）の反応評価結果を表３に示し、転化率の経時変化を表４に示す。
[Example 9]
An oxide catalyst was obtained by the same production method as in Example 1 except that the set temperature (third temperature) and the holding temperature in the third firing step were changed from 530 ° C. to 570 ° C. As a reaction evaluation of the oxide catalyst, 5.4 g of the catalyst was filled in a reaction tube, and a methacrolein synthesis reaction was carried out in the same manner as in Example 1. Table 3 shows the reaction evaluation results at the initial stage of the reaction (2 hours after the start of the reaction), and Table 4 shows the change over time in the conversion rate.
［実施例１０］
第三焼成工程の昇温時間を１時間にしたこと以外は実施例１と同様の製造法で、酸化物触媒を得た。酸化物触媒の反応評価として、触媒５．４ｇを反応管に充填し、実施例１と同様にメタクロレイン合成反応を行った。反応初期（反応開始２時間）の反応評価結果を表３に示し、転化率の経時変化を表４に示す。
[Example 10]
An oxide catalyst was obtained by the same production method as in Example 1 except that the temperature rising time in the third firing step was set to 1 hour. As a reaction evaluation of the oxide catalyst, 5.4 g of the catalyst was filled in a reaction tube, and a methacrolein synthesis reaction was carried out in the same manner as in Example 1. Table 3 shows the reaction evaluation results at the initial stage of the reaction (2 hours after the start of the reaction), and Table 4 shows the change over time in the conversion rate.
［実施例１１］
添加する有機物をポリビニルアルコール（和光純薬製、試薬特級）にし、添加量を３．５ｗｔ％にしたこと以外は、実施例１と同様の製造法で酸化物触媒を得た。酸化物触媒の反応評価として、触媒５．４ｇを反応管に充填し、実施例１と同様にメタクロレイン合成反応を行った。反応初期（反応開始２時間）の反応評価結果を表３に示し、転化率の経時変化を表４に示す。
[Example 11]
An oxide catalyst was obtained by the same production method as in Example 1 except that the organic substance to be added was polyvinyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent) and the addition amount was 3.5 wt%. As a reaction evaluation of the oxide catalyst, 5.4 g of the catalyst was filled in a reaction tube, and a methacrolein synthesis reaction was carried out in the same manner as in Example 1. Table 3 shows the reaction evaluation results at the initial stage of the reaction (2 hours after the start of the reaction), and Table 4 shows the change over time in the conversion rate.
［実施例１２］
添加する有機物を球状の結晶セルロース（短径に対する長径が１．１倍以下のものを９０％以上含有）にし、添加量を３．５ｗｔ％にしたこと以外は、実施例１と同様の製造法で酸化物触媒を得た。酸化物触媒の反応評価として、触媒５．４ｇを反応管に充填し、実施例１と同様にメタクロレイン合成反応を行った。反応初期（反応開始２時間）の反応評価結果を表３に示し、転化率の経時変化を表４に示す。
[Example 12]
The same production method as in Example 1 except that the organic substance to be added was spherical crystalline cellulose (containing 90% or more of those having a major axis of 1.1 times or less with respect to the minor axis) and the addition amount was 3.5 wt%. Obtained an oxide catalyst in. As a reaction evaluation of the oxide catalyst, 5.4 g of the catalyst was filled in a reaction tube, and a methacrolein synthesis reaction was carried out in the same manner as in Example 1. Table 3 shows the reaction evaluation results at the initial stage of the reaction (2 hours after the start of the reaction), and Table 4 shows the change over time in the conversion rate.
［比較例１］
棒状セルロースを添加しなかったこと以外は実施例１と同様の製造法で、酸化物触媒を得た。酸化物触媒の反応評価として、触媒５．３ｇを反応管に充填し、実施例１と同様にメタクロレイン合成反応を行った。反応初期（反応開始２時間）の反応評価結果を表３に示し、転化率の経時変化を表４に示す。
[Comparative Example 1]
An oxide catalyst was obtained by the same production method as in Example 1 except that rod-shaped cellulose was not added. As a reaction evaluation of the oxide catalyst, 5.3 g of the catalyst was filled in a reaction tube, and a methacrolein synthesis reaction was carried out in the same manner as in Example 1. Table 3 shows the reaction evaluation results at the initial stage of the reaction (2 hours after the start of the reaction), and Table 4 shows the change over time in the conversion rate.
［比較例２］
棒状セルロース添加量を０．３ｗｔ％にしたこと以外は実施例１と同様の製造法で、酸化物触媒を得た。酸化物触媒の反応評価として、触媒５．３ｇを反応管に充填し、実施例１と同様にメタクロレイン合成反応を行った。反応初期（反応開始２時間）の反応評価結果を表３に示し、転化率の経時変化を表４に示す。
[Comparative Example 2]
An oxide catalyst was obtained by the same production method as in Example 1 except that the amount of rod-shaped cellulose added was 0.3 wt%. As a reaction evaluation of the oxide catalyst, 5.3 g of the catalyst was filled in a reaction tube, and a methacrolein synthesis reaction was carried out in the same manner as in Example 1. Table 3 shows the reaction evaluation results at the initial stage of the reaction (2 hours after the start of the reaction), and Table 4 shows the change over time in the conversion rate.
［比較例３］
棒状セルロース添加量を１１．０ｗｔ％にしたこと以外は実施例１と同様の製造法で、酸化物触媒を得た。酸化物触媒の反応評価として、触媒５．３ｇを反応管に充填し、実施例１と同様にメタクロレイン合成反応を行った。反応初期（反応開始２時間）の反応評価結果を表３に示し、転化率の経時変化を表４に示す。
[Comparative Example 3]
An oxide catalyst was obtained by the same production method as in Example 1 except that the amount of rod-shaped cellulose added was 11.0 wt%. As a reaction evaluation of the oxide catalyst, 5.3 g of the catalyst was filled in a reaction tube, and a methacrolein synthesis reaction was carried out in the same manner as in Example 1. Table 3 shows the reaction evaluation results at the initial stage of the reaction (2 hours after the start of the reaction), and Table 4 shows the change over time in the conversion rate.
［比較例４］
第二焼成工程を空気雰囲気下で行ったこと以外は実施例１と同様の製造法で、酸化物触媒を得た。酸化物触媒の反応評価として、触媒５．４ｇを反応管に充填し、実施例１と同様にメタクロレイン合成反応を行った。反応初期（反応開始２時間）の反応評価結果を表３に示し、転化率の経時変化を表４に示す。
[Comparative Example 4]
An oxide catalyst was obtained by the same production method as in Example 1 except that the second firing step was performed in an air atmosphere. As a reaction evaluation of the oxide catalyst, 5.4 g of the catalyst was filled in a reaction tube, and a methacrolein synthesis reaction was carried out in the same manner as in Example 1. Table 3 shows the reaction evaluation results at the initial stage of the reaction (2 hours after the start of the reaction), and Table 4 shows the change over time in the conversion rate.
［比較例５］
第三焼成工程を空気雰囲気下で行ったこと以外は実施例１と同様の製造法で、酸化物触媒を得た。酸化物触媒の反応評価として、触媒５．４ｇを反応管に充填し、実施例１と同様にメタクロレイン合成反応を行った。反応初期（反応開始２時間）の反応評価結果を表３に示し、転化率の経時変化を表４に示す。
[Comparative Example 5]
An oxide catalyst was obtained by the same production method as in Example 1 except that the third firing step was performed in an air atmosphere. As a reaction evaluation of the oxide catalyst, 5.4 g of the catalyst was filled in a reaction tube, and a methacrolein synthesis reaction was carried out in the same manner as in Example 1. Table 3 shows the reaction evaluation results at the initial stage of the reaction (2 hours after the start of the reaction), and Table 4 shows the change over time in the conversion rate.
［比較例６］
第二焼成工程の設定温度（第二の温度）と保持温度とを３００℃から１８０℃にしたこと以外は実施例１と同様の製造法で、酸化物触媒を得た。酸化物触媒の反応評価として、触媒５．４ｇを反応管に充填し、実施例１と同様にメタクロレイン合成反応を行った。反応初期（反応開始２時間）の反応評価結果を表３に示し、転化率の経時変化を表４に示す。
[Comparative Example 6]
An oxide catalyst was obtained by the same production method as in Example 1 except that the set temperature (second temperature) and the holding temperature in the second firing step were changed from 300 ° C. to 180 ° C. As a reaction evaluation of the oxide catalyst, 5.4 g of the catalyst was filled in a reaction tube, and a methacrolein synthesis reaction was carried out in the same manner as in Example 1. Table 3 shows the reaction evaluation results at the initial stage of the reaction (2 hours after the start of the reaction), and Table 4 shows the change over time in the conversion rate.
［比較例７］
第三焼成工程の設定温度（第三の温度）と保持温度とを５３０℃から６２０℃にしたこと以外は実施例１と同様の製造法で、酸化物触媒を得た。酸化物触媒の反応評価として、触媒５．４ｇを反応管に充填し、実施例１と同様にメタクロレイン合成反応を行った。反応初期（反応開始２時間）の反応評価結果を表３に示し、転化率の経時変化を表４に示す。
[Comparative Example 7]
An oxide catalyst was obtained by the same production method as in Example 1 except that the set temperature (third temperature) and the holding temperature in the third firing step were changed from 530 ° C. to 620 ° C. As a reaction evaluation of the oxide catalyst, 5.4 g of the catalyst was filled in a reaction tube, and a methacrolein synthesis reaction was carried out in the same manner as in Example 1. Table 3 shows the reaction evaluation results at the initial stage of the reaction (2 hours after the start of the reaction), and Table 4 shows the change over time in the conversion rate.
［比較例８］
第二焼成工程の昇温時間を０．５時間にしたこと以外は実施例１と同様の製造法で、酸化物触媒を得た。酸化物触媒の反応評価として、触媒５．４ｇを反応管に充填し、実施例１と同様にメタクロレイン合成反応を行った。反応初期（反応開始２時間）の反応評価結果を表３に示し、転化率の経時変化を表４に示す。
[Comparative Example 8]
An oxide catalyst was obtained by the same production method as in Example 1 except that the temperature rising time in the second firing step was set to 0.5 hours. As a reaction evaluation of the oxide catalyst, 5.4 g of the catalyst was filled in a reaction tube, and a methacrolein synthesis reaction was carried out in the same manner as in Example 1. Table 3 shows the reaction evaluation results at the initial stage of the reaction (2 hours after the start of the reaction), and Table 4 shows the change over time in the conversion rate.
［比較例９］
第三焼成工程の昇温時間を０．５時間にしたこと以外は実施例１と同様の製造法で、酸化物触媒を得た。酸化物触媒の反応評価として、触媒５．４ｇを反応管に充填し、実施例１と同様にメタクロレイン合成反応を行った。反応初期（反応開始２時間）の反応評価結果を表３に示し、転化率の経時変化を表４に示す。
[Comparative Example 9]
An oxide catalyst was obtained by the same production method as in Example 1 except that the temperature rising time in the third firing step was set to 0.5 hours. As a reaction evaluation of the oxide catalyst, 5.4 g of the catalyst was filled in a reaction tube, and a methacrolein synthesis reaction was carried out in the same manner as in Example 1. Table 3 shows the reaction evaluation results at the initial stage of the reaction (2 hours after the start of the reaction), and Table 4 shows the change over time in the conversion rate.
［比較例１０］
添加する有機物をポリビニルアルコール（和光純薬製、試薬特級）２．５ｗｔ％にしたこと以外は、実施例１と同様の製造法で、酸化物触媒を得た。酸化物触媒の反応評価として、触媒５．４ｇを反応管に充填し、実施例１と同様にメタクロレイン合成反応を行った。反応初期（反応開始２時間）の反応評価結果を表３に示し、転化率の経時変化を表４に示す。
[Comparative Example 10]
An oxide catalyst was obtained by the same production method as in Example 1 except that the organic substance to be added was polyvinyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent) in an amount of 2.5 wt%. As a reaction evaluation of the oxide catalyst, 5.4 g of the catalyst was filled in a reaction tube, and a methacrolein synthesis reaction was carried out in the same manner as in Example 1. Table 3 shows the reaction evaluation results at the initial stage of the reaction (2 hours after the start of the reaction), and Table 4 shows the change over time in the conversion rate.
［比較例１１］
添加する有機物を球状の結晶セルロース（短径に対する長径が１．１倍以下のものを９０％以上含有）２．５ｗｔ％にしたこと以外は、実施例１と同様の製造法で、酸化物触媒を得た。酸化物触媒の反応評価として、触媒５．４ｇを反応管に充填し、実施例１と同様にメタクロレイン合成反応を行った。反応初期（反応開始２時間）の反応評価結果を表３に示し、転化率の経時変化を表４に示す。
[Comparative Example 11]
The oxide catalyst was produced by the same production method as in Example 1 except that the organic substance to be added was 2.5 wt% of spherical crystalline cellulose (containing 90% or more of those having a major axis of 1.1 times or less with respect to the minor axis). Got As a reaction evaluation of the oxide catalyst, 5.4 g of the catalyst was filled in a reaction tube, and a methacrolein synthesis reaction was carried out in the same manner as in Example 1. Table 3 shows the reaction evaluation results at the initial stage of the reaction (2 hours after the start of the reaction), and Table 4 shows the change over time in the conversion rate.
［比較例１２］
特許第０５９０８５９５号の実施例Ａ２記載の酸化物触媒を製造して、酸化物触媒の反応評価として、触媒５．４ｇを反応管に充填し、実施例１と同様にメタクロレイン合成反応を行った。反応初期（反応開始２時間）の反応評価結果を表３に示し、転化率の経時変化を表４に示す。
[Comparative Example 12]
The oxide catalyst described in Example A2 of Japanese Patent No. 05908595 was produced, and as a reaction evaluation of the oxide catalyst, 5.4 g of the catalyst was filled in a reaction tube, and a methacrolein synthesis reaction was carried out in the same manner as in Example 1. .. Table 3 shows the reaction evaluation results at the initial stage of the reaction (2 hours after the start of the reaction), and Table 4 shows the change over time in the conversion rate.
実施例１における転化率と比較例１における転化率との反応時間に対する変化を対比したグラフを図２に示す。実施例１の酸化物触媒を用いた反応は経時的に転化率が変化しないのに対し、比較例１の酸化物触媒を用いた反応は経時的に転化率が上昇していくことがわかる。実施例１の反応の転化率の変化率は０％であるのに対し、比較例１の反応の転化率の変化率は５．３％と大きいため、比較例１の酸化物触媒は実施例１の酸化物触媒よりも反応による経時的な活性上昇が大きいことが示唆される。
なお、実施例１の酸化物触媒は５００時間の反応で、転化率９４．７％、メタクロレイン選択率は８９．１％、メタクロレイン収率は８４．４％であり、初期と変化がなかった。
一方、比較例１の酸化物触媒は５００時間の反応で、転化率は９９．５％まで上昇し、メタクロレイン選択率は８０．１％まで低下し、メタクロレイン収率は７９．７％まで低下した。これは、実施例１では、反応開始から５００時間後において反応器内の温度は、４３０℃付近で変化が少ないのに対し、比較例1では、反応開始から５００時間後において反応器内の温度が４８０℃まで上昇し、触媒が劣化した為であると推測される。このように、比較例１において触媒の熱劣化及びそれに伴う収率低下を防止する上では温度を４３０℃程度に降下させる温度制御が必要となり、従来技術では長期にわたる安定運転が難しいことがわかる。これに対して、実施例１では大きな温度変化が生ずることなく高い収率を維持することができ、長期にわたる安定運転が可能となっていることがわかる。
FIG. 2 shows a graph comparing the changes in the conversion rate in Example 1 and the conversion rate in Comparative Example 1 with respect to the reaction time. It can be seen that the conversion rate of the reaction using the oxide catalyst of Example 1 does not change with time, whereas the conversion rate of the reaction using the oxide catalyst of Comparative Example 1 increases with time. The rate of change in the conversion rate of the reaction of Example 1 is 0%, whereas the rate of change of the conversion rate of the reaction of Comparative Example 1 is as large as 5.3%. Therefore, the oxide catalyst of Comparative Example 1 is an example. It is suggested that the activity increase with time due to the reaction is larger than that of the oxide catalyst of 1.
The oxide catalyst of Example 1 had a conversion rate of 94.7%, a methacrolein selectivity of 89.1%, and a methacrolein yield of 84.4% after a reaction of 500 hours, which were unchanged from the initial stage. rice field.
On the other hand, the oxide catalyst of Comparative Example 1 was reacted for 500 hours, the conversion rate increased to 99.5%, the methacrolein selectivity decreased to 80.1%, and the methacrolein yield decreased to 79.7%. It has decreased. This is because, in Example 1, the temperature inside the reactor changed little at around 430 ° C. 500 hours after the start of the reaction, whereas in Comparative Example 1, the temperature inside the
本発明の酸化物触媒は、不飽和アルデヒドの製造プロセスに使用でき、産業上の利用可能性を有する。 The oxide catalyst of the present invention can be used in the process of producing unsaturated aldehydes and has industrial applicability.
Claims (3)
モリブデン、ビスマス、鉄、及びコバルトを含有し、
ＣｕＫα線をＸ線源として得られるＸ線回折パターンにおいて、２θ＝２６．４°±０．２°の位置に現れるＣｏＭｏＯ4相の回折ピーク（ｃ）の強度Ｐｃに対する、２θ＝２７．４°±０．２°に現れるＢｉ10Ｍｏ3Ｏ24相の回折ピーク（ａ）の強度Ｐａの比Ｒｉ＝Ｐａ／Ｐｃが０．２≦Ｒｉ≦１．０であり、
ＣｕＫα線をＸ線源として得られるＸ線回折図における回折角（２θ）が、少なくとも２θ＝１０．３°±０．２°、２７．４°±０．２°、３１．０°±０．２°、及び５２．９°±０．２°の範囲に回折ピークを有し、
下記組成式（１）で表される組成を有する複合金属の酸化物を含む、酸化物触媒。
Ｍｏ 12 Ｂｉ a Ｆｅ b Ｃｏ c Ｃｅ d Ａ e Ｂ f （１）
（組成式（１）において、Ａはカリウム、セシウム及びルビジウムからなる群より選ばれる少なくとも１種の元素を示し、Ｂは、ニッケル、マンガン、銅、亜鉛、マグネシウム、カルシウム、ストロンチウム、バリウム、錫、鉛、ランタン、プラセオジウム、ネオジム、及びユウロピウムからなる群から選ばれる少なくとも１種の元素を示し、１≦ａ≦５、１≦ｂ≦５、２≦ｃ≦１０、０＜ｄ≦３、０＜ｅ≦２．０、０≦ｆ≦２である。） An oxide catalyst used in the production of unsaturated aldehydes by vapor-phase catalytic oxidation of at least one selected from the group consisting of propylene, isobutylene, isobutanol and t-butyl alcohol.
Contains molybdenum, bismuth, iron, and cobalt,
In the X-ray diffraction pattern obtained by using CuKα ray as an X-ray source, 2θ = 27.4 ° with respect to the intensity Pc of the diffraction peak (c) of the CoMoO 4-phase appearing at the position of 2θ = 26.4 ° ± 0.2 °. The ratio Ri = Pa / Pc of the intensity Pa of the diffraction peak (a) of the Bi 10 Mo 3 O 24 phase appearing at ± 0.2 ° is 0.2 ≦ Ri ≦ 1.0.
The diffraction angle (2θ) in the X-ray diffraction diagram obtained by using CuKα ray as an X-ray source is at least 2θ = 10.3 ° ± 0.2 °, 27.4 ° ± 0.2 °, 31.0 ° ± 0. .2 °, and the diffraction peaks possess a range of 52.9 ° ± 0.2 °,
An oxide catalyst containing an oxide of a composite metal having a composition represented by the following composition formula (1).
Mo 12 Bi a Fe b Co c Ce d A e B f (1)
(In the composition formula (1), A represents at least one element selected from the group consisting of potassium, cesium and rubidium, and B represents nickel, manganese, copper, zinc, magnesium, calcium, strontium, barium, tin, Indicates at least one element selected from the group consisting of lead, lanthanum, placeodium, neodymium, and europium, 1 ≦ a ≦ 5, 1 ≦ b ≦ 5, 2 ≦ c ≦ 10, 0 <d ≦ 3, 0 < e ≦ 2.0, 0 ≦ f ≦ 2)
モリブデン元素を含む化合物、ビスマス元素を含む化合物、鉄元素を含む化合物、及びコバルト元素を含む化合物を液相で混合し、前駆体スラリーを調製する工程と、
前記前駆体スラリーを噴霧乾燥し、乾燥体を得る工程と、
前記乾燥体を、２００〜３００℃の範囲内で設定した第一の温度まで室温から昇温し、２００〜３００℃の範囲内の温度で１時間以上保持して第一焼成体を得る工程と、
前記第一焼成体と有機物とを混合成型して成型体を得る工程と、
前記成型体を、不活性ガス中で２００〜４００℃の範囲内で設定した第二の温度まで室温から１時間以上かけて昇温し、２００〜４００℃の範囲内の温度で１時間以上保持して第二焼成体を得る工程と、
前記第二焼成体を、不活性ガス中で４００〜６００℃の範囲内で設定した第三の温度まで、第二の温度から１時間以上かけて昇温し、４００〜６００℃の範囲内の温度で１時間以上保持して酸化物触媒を得る工程と、
を有する、酸化物触媒の製造方法。 The method for producing an oxide catalyst according to claim 1.
A step of preparing a precursor slurry by mixing a compound containing a molybdenum element, a compound containing a bismuth element, a compound containing an iron element, and a compound containing a cobalt element in a liquid phase.
The step of spray-drying the precursor slurry to obtain a dried product, and
A step of raising the temperature of the dried product from room temperature to a first temperature set in the range of 200 to 300 ° C. and holding the dried product at a temperature in the range of 200 to 300 ° C. for 1 hour or more to obtain a first fired product. ,
A step of mixing and molding the first fired body and an organic substance to obtain a molded body,
The molded product is heated in an inert gas to a second temperature set in the range of 200 to 400 ° C. over 1 hour from room temperature, and held at a temperature in the range of 200 to 400 ° C. for 1 hour or more. And the process of obtaining the second fired body
The second fired body is heated in an inert gas to a third temperature set in the range of 400 to 600 ° C. from the second temperature over an hour or more, and within the range of 400 to 600 ° C. The process of obtaining an oxide catalyst by holding it at temperature for 1 hour or more,
A method for producing an oxide catalyst.
A method for producing an unsaturated aldehyde, which comprises a step of oxidizing at least one selected from the group consisting of propylene, isobutylene, isobutanol and t-butyl alcohol using the oxide catalyst according to claim 1.
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