JPH08309192A - Manufacture of catalyst for synthesis of methacrolein and methacrylic acid - Google Patents
Manufacture of catalyst for synthesis of methacrolein and methacrylic acidInfo
- Publication number
- JPH08309192A JPH08309192A JP7121951A JP12195195A JPH08309192A JP H08309192 A JPH08309192 A JP H08309192A JP 7121951 A JP7121951 A JP 7121951A JP 12195195 A JP12195195 A JP 12195195A JP H08309192 A JPH08309192 A JP H08309192A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- stirring
- solution
- dispersion
- methacrolein
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、メタクロレイン及びメ
タクリル酸合成用触媒、即ちイソブチレン又は三級ブタ
ノールを分子状酸素により気相接触酸化して、メタクロ
レイン及びメタクリル酸を合成するのに使用する触媒の
製造法に関する。FIELD OF THE INVENTION The present invention is used to synthesize methacrolein and methacrylic acid by gas phase catalytic oxidation of methacrolein and methacrylic acid synthesis catalysts, ie, isobutylene or tertiary butanol with molecular oxygen. The present invention relates to a method for producing a catalyst.
【０００２】[0002]
【従来の技術】従来、イソブチレン又は三級ブタノール
を高温気相下で接触酸化してメタクロレイン及びメタク
リル酸を製造する際に用いられる触媒に関して、例えば
特開昭５５−１２７３２８号公報、特開昭５６−２９２
６号公報、特開昭５６−１６１３４１号公報、特開昭５
９−３１７２７号公報等に数多くの提案がなされてい
る。しかしながら、これらは主として触媒を構成する成
分及びその比率に関するものである。これらの中には触
媒そのものの調製法に関する記載はほとんどない。2. Description of the Related Art Conventionally, catalysts used for producing methacrolein and methacrylic acid by catalytically oxidizing isobutylene or tertiary butanol under a high temperature gas phase are disclosed, for example, in JP-A-55-127328 and JP-A-SHO. 56-292
6, JP-A-56-161341, JP-A-5
Many proposals have been made in Japanese Patent Publication No. 9-31727 and the like. However, these are mainly related to the components constituting the catalyst and the ratio thereof. Among these, there is almost no description about the preparation method of the catalyst itself.
【０００３】ところでＭｏ−Ｂｉ−Ｆｅ系複合酸化物触
媒はメタクロレイン及びメタクリル酸を合成する際の触
媒として多用されているが、その調製法としては、触媒
成分を含む二種類以上の溶液又は分散液を混合し、得ら
れた混合物を必要に応じて加熱処理し、その後乾燥し、
得られた乾燥物を焼成することにより調製されるのが通
常である。By the way, Mo-Bi-Fe-based composite oxide catalysts are often used as catalysts for synthesizing methacrolein and methacrylic acid. The method for preparing them is to prepare two or more kinds of solutions or dispersions containing catalyst components. The liquids are mixed, the resulting mixture is heat treated if necessary, then dried,
It is usually prepared by baking the obtained dried product.
【０００４】又、特開平４−１８２４４９号公報には、
アクロレイン又はメタクロレイン合成用触媒の調製法と
して、触媒成分を含む二種類以上の溶液又は分散液を可
能な限り短時間で混合し、その後得られた混合物を熟成
することなく直ちに噴霧乾燥し、得られた乾燥物を焼成
することにより調製する方法が開示されている。Further, Japanese Patent Laid-Open No. 4-182449 discloses that
As a method for preparing a catalyst for synthesizing acrolein or methacrolein, two or more kinds of solutions or dispersions containing a catalyst component are mixed in the shortest possible time, and then the resulting mixture is immediately spray-dried without aging to obtain a mixture. A method for preparing the dried product by baking is disclosed.
【０００５】しかしながら、かかる方法により得られる
触媒では、触媒活性及び目的生成物選択性等の点で工業
触媒として未だ不十分であり、一般に工業的見地から更
なる改良が望まれている。However, the catalyst obtained by such a method is still inadequate as an industrial catalyst in terms of catalytic activity and selectivity of a target product, and further improvement is generally desired from an industrial viewpoint.
【０００６】本発明者等は上述した如き現状に鑑み、イ
ソブチレン又は三級ブタノールを分子状酸素により気相
接触酸化して、メタクロレイン及びメタクリル酸を合成
するのに使用する触媒の製造法について鋭意検討した結
果、かかる触媒の性能を左右する触媒活性基本構造が、
触媒成分を含む二種類以上の溶液又は分散液を混合する
過程及び引き続いて行う加熱熟成過程でほぼ決定される
ことを見い出し本発明に到達した。即ち上記二種類又は
二種類以上の溶液又は分散液を混合した際に、触媒構造
の前駆体となる粒子が生成されるが、かかる粒子の微細
構造は混合方法及び引き続き行う加熱熟成方法、特に各
々の過程における液の攪拌方法に大きく依存することが
わかった。即ち、かかる混合過程を比較的強い攪拌状態
で行うことにより、望ましい構造を有する触媒前駆体粒
子が得られ、更に引き続いて、得られた触媒前駆体粒子
を比較的弱い攪拌状態で加熱熟成処理することにより、
触媒前駆体構造は更に成長し、より安定化されることが
わかった。In view of the current situation as described above, the inventors of the present invention are keenly aware of a method for producing a catalyst used for synthesizing methacrolein and methacrylic acid by gas phase catalytic oxidation of isobutylene or tertiary butanol with molecular oxygen. As a result of examination, the catalytically active basic structure that influences the performance of such a catalyst is
The present invention has been found out to be substantially determined by the process of mixing two or more kinds of solutions or dispersions containing catalyst components and the subsequent heat aging process. That is, when two or more kinds of solutions or dispersions are mixed, particles serving as a precursor of a catalyst structure are produced, and the fine structure of such particles is a mixing method and a subsequent heat aging method, particularly, respectively. It was found that it largely depends on the stirring method of the liquid in the process of. That is, by carrying out such a mixing process under a relatively strong stirring condition, catalyst precursor particles having a desired structure are obtained, and subsequently, the obtained catalyst precursor particles are heat-aged under a relatively weak stirring condition. By
The catalyst precursor structure was found to grow further and become more stable.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、メタクロレ
イン及びメタクリル酸合成用触媒、すなわちイソブチレ
ン又は三級ブタノールを分子状酸素により気相接触酸化
して、メタクロレイン及びメタクリル酸を合成する際に
使用する触媒の新規な製造法の提供を目的としている。DISCLOSURE OF THE INVENTION The present invention provides a catalyst for the synthesis of methacrolein and methacrylic acid, that is, isobutylene or tertiary butanol is subjected to a gas phase catalytic oxidation with molecular oxygen to synthesize methacrolein and methacrylic acid. It is intended to provide a new method for producing a catalyst to be used.
【０００８】[0008]
【課題を解決するための手段】本発明は、下記一般式 Ｍｏa Ｂｉb Ｆｅc Ａd Ｘe Ｙf Ｚg Ｏh （式中、Ｍｏ、Ｂｉ、Ｆｅ及びＯはそれぞれモリブデ
ン、ビスマス、鉄及び酸素を表し、Ａはニッケル及び／
又はコバルト、Ｘはマグネシウム、亜鉛、マンガン、ス
ズ及び鉛からなる群より選ばれた少なくとも１種の元
素、Ｙはリン、ホウ素、イオウ、テルル、ケイ素、ゲル
マニウム、セリウム、ニオブ、チタン、ジルコニウム、
タングステン及びアンチモンからなる群より選ばれた少
なくとも１種の元素、Ｚはカリウム、ナトリウム、ルビ
ジウム、セシウム及びタリウムからなる群より選ばれた
少なくとも１種の元素を表す。ただし、ａ、ｂ、ｃ、
ｄ、ｅ、ｆ、ｇ及びｈは各元素の原子比を表し、ａ＝１
２のとき、０．１≦ｂ≦５、０．１≦ｃ≦５、１≦ｄ≦
１２、０≦ｅ≦１０、０≦ｆ≦１０、０．０１≦ｇ≦３
であり、ｈは前記各成分の原子比を満足するのに必要な
酸素原子で数である。）で表される複合酸化物を触媒成
分として含有するメタクロレイン及びメタクリル酸合成
用触媒の製造法において、該複合酸化物を得るに際し、
触媒成分を二種類以上に分割し、その内の少なくとも二
種類を溶液又は分散液とした後、それぞれの溶液又は分
散液を攪拌しながら混合してスラリー状物とし、得られ
たスラリー状物を前記混合時の攪拌より弱い攪拌状態で
少なくとも３０分加熱熟成処理した後、乾燥し、得られ
た乾燥物を焼成することにより複合酸化物を得ることを
特徴とするメタクロレイン及びメタクリル酸合成用触媒
の製造法である。The present invention provides the following general formula: Mo a Bi b Fe c A d X e Y f Z g O h (wherein Mo, Bi, Fe and O are molybdenum, bismuth and iron, respectively). And oxygen, and A is nickel and / or
Or cobalt, X is at least one element selected from the group consisting of magnesium, zinc, manganese, tin and lead, Y is phosphorus, boron, sulfur, tellurium, silicon, germanium, cerium, niobium, titanium, zirconium,
At least one element selected from the group consisting of tungsten and antimony, and Z represents at least one element selected from the group consisting of potassium, sodium, rubidium, cesium and thallium. However, a, b, c,
d, e, f, g and h represent the atomic ratio of each element, and a = 1
When 2, 0.1 ≦ b ≦ 5, 0.1 ≦ c ≦ 5, 1 ≦ d ≦
12, 0 ≦ e ≦ 10, 0 ≦ f ≦ 10, 0.01 ≦ g ≦ 3
And h is the number of oxygen atoms required to satisfy the atomic ratio of each component. In the method for producing a methacrolein- and methacrylic acid-synthesizing catalyst containing a composite oxide represented by the formula (4) as a catalyst component, in obtaining the composite oxide,
The catalyst component is divided into two or more kinds, and at least two kinds of them are made into a solution or a dispersion, and then the respective solutions or dispersions are mixed with stirring to form a slurry, and the obtained slurry is obtained. A catalyst for the synthesis of methacrolein and methacrylic acid, which is characterized in that a composite oxide is obtained by heating and aging the mixture for at least 30 minutes under a stirring condition weaker than the agitation during the mixing, and drying the resulting dried product. Is a manufacturing method of.
【０００９】本発明において、触媒活性物質を構成する
元素の原料としては特に限定はないが、通常は酸化物又
は強熱することにより酸化物になり得る塩化物、水酸化
物、硫酸塩、硝酸塩、炭酸塩、アンモニウム塩又はそれ
らの混合物が用いられる。In the present invention, the raw materials for the elements constituting the catalytically active substance are not particularly limited, but are usually oxides, or chlorides, hydroxides, sulfates, nitrates which can be converted into oxides by igniting. , Carbonates, ammonium salts or mixtures thereof.
【００１０】本発明において、触媒成分を二種類以上に
分割する方法については特に限定はないが、触媒成分を
含む二種類の溶液又は分散液としては、第一の溶液又は
分散液にモリブデン化合物を含む溶液又は分散液を用
い、第二の溶液又は分散液にビスマス化合物を含む溶液
又は分散液を用いる方法が特に好ましい。In the present invention, the method of dividing the catalyst component into two or more kinds is not particularly limited, but as the two kinds of solutions or dispersions containing the catalyst component, a molybdenum compound is added to the first solution or dispersion. A method of using the solution or dispersion containing the bismuth compound and the solution or dispersion containing the bismuth compound in the second solution or dispersion is particularly preferable.
【００１１】これらの溶液又は分散液は以下のような方
法で調製することができる。即ち、適当なモリブデン化
合物、例えばモリブデン酸アンモニウムを水に溶解した
水溶液を第一の溶液とし、ビスマス、鉄、コバルト、セ
シウム等の化合物、例えば各々の硝酸塩を希硝酸に溶解
した水溶液を第二の溶液とする方法等が挙げられる。These solutions or dispersions can be prepared by the following method. That is, a suitable molybdenum compound, for example, an aqueous solution of ammonium molybdate dissolved in water is used as a first solution, and a compound of bismuth, iron, cobalt, cesium, etc., for example, an aqueous solution of each nitrate dissolved in dilute nitric acid is used as a second solution. Examples include a method of forming a solution.
【００１２】本発明において、触媒成分を含む溶液又は
分散液を調製するに際しては、それぞれの原料化合物が
溶液又は分散液調製時に沈殿生成反応、ゲル化等を起こ
さないような組み合わせを選べばよい。従って、触媒成
分を含む溶液又は分散液の数は通常二種類以上となる
が、その数には特に制限はない。又、全ての触媒成分を
溶液又は分散液として調製する必要はなく、触媒成分に
よっては例えば酸化物の粉末のまま用いてもよい。In the present invention, when preparing a solution or dispersion containing a catalyst component, a combination may be selected so that each raw material compound does not cause a precipitation-forming reaction, gelation or the like when preparing the solution or dispersion. Therefore, the number of solutions or dispersions containing the catalyst component is usually two or more, but the number is not particularly limited. Further, it is not necessary to prepare all the catalyst components as a solution or dispersion, and depending on the catalyst components, for example, the oxide powder may be used as it is.
【００１３】本発明において、上述した混合及び加熱熟
成を実施するには、回転式攪拌装置を有する同一の容器
内にて実施することが簡便で好ましいものである。しか
も更に、混合過程及び加熱熟成過程において、強い攪拌
状態及び弱い攪拌状態を実現する手段として、攪拌装置
の回転速度を調節する方法を用いると操作が簡便であ
り、好ましいものである。In the present invention, in order to carry out the above-mentioned mixing and heat aging, it is convenient and preferable to carry out in the same container having a rotary stirring device. Moreover, it is preferable that a method of adjusting the rotation speed of the stirring device is used as a means for realizing a strong stirring state and a weak stirring state in the mixing process and the heat aging process, since the operation is simple and convenient.
【００１４】本発明においては、混合過程における攪拌
強度の程度としては、強いほど好ましい。この攪拌強度
は、用いる装置、即ち容器、攪拌翼更には邪魔板の形
状、攪拌翼の回転速度、液量等により決定される。In the present invention, the stronger the stirring strength in the mixing process, the more preferable. The stirring strength is determined by the apparatus used, that is, the shape of the container, the stirring blade, the baffle plate, the rotation speed of the stirring blade, the liquid amount, and the like.
【００１５】本発明での混合過程における攪拌が弱すぎ
ると得られる沈殿粒子の微細構造、特に粒子表面及び内
部における元素分布、並びに粒子徑の制御が困難とな
り、目的とする高性能な触媒を再現性よく得ることがで
きない場合が多い。一方、攪拌があまりに強すぎると液
の飛散が生じるので、用いる容器、攪拌翼、邪魔板等の
形状及び液量に応じて適宜加減することが必要である。If the stirring in the mixing process in the present invention is too weak, it becomes difficult to control the fine structure of the precipitated particles, especially the element distribution on the surface and inside of the particles, and the particle size, and the desired high-performance catalyst is reproduced. In many cases, I can't get good results. On the other hand, if the stirring is too strong, the liquid will be scattered, so it is necessary to appropriately adjust the amount depending on the shape of the container, the stirring blade, the baffle plate and the like used and the amount of the liquid.
【００１６】混合の手順としては、モリブデン化合物を
含む溶液又は分散液にビスマスを含む溶液又は分散液を
緩やかに注入混合する方法が特に好ましい。As a mixing procedure, a method of gently injecting and mixing a solution or dispersion containing bismuth into a solution or dispersion containing a molybdenum compound is particularly preferable.
【００１７】このようにして得られた触媒前駆体微粒子
を含有するスラリー状物は直ちに乾燥するのではなく、
混合過程における攪拌より弱い攪拌状態で３０分以上加
熱熟成処理した後、乾燥する。この加熱熟成過程を経る
ことにより、触媒前駆体構造は更に成長し、より安定化
される。なお、この加熱熟成処理過程における攪拌強度
の程度としては弱いほど好ましく、回転式攪拌装置を用
いる場合、混合過程における回転速度の８０％以下にす
ることが好ましい。The slurry-like material containing the catalyst precursor fine particles thus obtained is not immediately dried, but
The mixture is heat-aged for 30 minutes or more in a stirring state weaker than the stirring in the mixing process, and then dried. Through this heat aging process, the catalyst precursor structure further grows and becomes more stable. The degree of stirring strength in this heating and aging process is preferably weaker, and when a rotary stirring device is used, it is preferably 80% or less of the rotation speed in the mixing process.
【００１８】加熱熟成過程における攪拌が強すぎると、
上述した触媒前駆体構造の成長反応が抑制されるため、
目的とする高性能な触媒を再現性よく得ることが難し
い。なお、攪拌があまり弱すぎると容器内の液に不均一
な温度分布が生じる場合があるので、用いる容器、攪拌
翼、邪魔板等の形状及び液量に応じて適宜加減すればよ
い。この加熱熟成処理温度としては８０〜１０３℃の範
囲が好ましい。If the stirring in the heat aging process is too strong,
Since the growth reaction of the catalyst precursor structure described above is suppressed,
It is difficult to obtain the desired high-performance catalyst with good reproducibility. If the stirring is too weak, a non-uniform temperature distribution may occur in the liquid in the container. Therefore, the amount may be appropriately adjusted depending on the shape of the container, the stirring blade, the baffle plate, and the like used and the amount of the liquid. The heat aging treatment temperature is preferably in the range of 80 to 103 ° C.
【００１９】本発明において、加熱熟成処理後のスラリ
ー状物を乾燥する方法としては特に限定はなく、汎用の
箱形乾燥機、噴霧乾燥機、ドラムドライヤー、スラリー
ドライヤー等を用いることができる。なお、本発明にお
ける乾燥とは、該スラリー状物からある程度の水分を除
去することにより、実質的に固形状物にすることであ
り、乾燥後の含水量等に関しては特に規定はない。又、
乾燥物の形状についても特に限定はなく、粉体状でもブ
ロック状でもよい。In the present invention, the method of drying the slurry-like material after the heat aging treatment is not particularly limited, and a general-purpose box dryer, spray dryer, drum dryer, slurry dryer or the like can be used. The term "drying" in the present invention means removing a certain amount of water from the slurry-like material to make it substantially solid, and there is no particular restriction on the water content after drying. or,
The shape of the dried product is not particularly limited, and may be powder or block.
【００２０】次に上述した方法により得られた乾燥物か
ら最終的な実用触媒を得る方法としては特に限定はない
が、通常は前記乾燥物を２００〜４００℃の範囲で１〜
５時間程度仮焼し、引き続き必要に応じて成型するか又
は不活性担体に担持し、その後４００〜６５０℃の温度
範囲で１〜２０時間程度焼成する方法が用いられる。There are no particular restrictions on the method for obtaining the final practical catalyst from the dried product obtained by the above-mentioned method, but the dried product is usually used in the range of 200 to 400 ° C.
A method is used in which it is calcined for about 5 hours, subsequently molded as required or supported on an inert carrier, and then calcined in the temperature range of 400 to 650 ° C. for about 1 to 20 hours.
【００２１】本発明の製造法で得られた触媒は成型体又
は担持体として固定床で使用することが好ましいが、更
に粒状として流動床で使用してもよい。The catalyst obtained by the production method of the present invention is preferably used in a fixed bed as a molded body or a supporting body, but it may be further used in the form of particles in a fluidized bed.
【００２２】本発明により得られた触媒を用いて、イソ
ブチレン又は三級ブタノールを分子状酸素により気相接
触酸化して、メタクロレイン及びメタクリル酸を製造す
るに際しては、イソブチレン又は三級ブタノール対酸素
のモル比は１：０．５〜３が好ましい。原料のイソブチ
レン又は三級ブタノールは不活性ガスで希釈して用いる
ことが好ましい。酸化に用いられる分子状酸素は純酸素
ガスでもよいが、工業的には空気が有利である。反応圧
力は常圧ないし数気圧まで用いられる。反応温度は３０
０〜４５０℃の範囲が好ましい。In producing methacrolein and methacrylic acid by vapor-phase catalytic oxidation of isobutylene or tertiary butanol with molecular oxygen using the catalyst obtained by the present invention, isobutylene or tertiary butanol and oxygen are used. The molar ratio is preferably 1: 0.5-3. The raw material isobutylene or tertiary butanol is preferably diluted with an inert gas before use. The molecular oxygen used for oxidation may be pure oxygen gas, but air is industrially advantageous. The reaction pressure is from normal pressure to several atmospheres. Reaction temperature is 30
The range of 0 to 450 ° C. is preferable.
【００２３】[0023]
【実施例】本発明を以下実施例により示す。なお、反応
用原料としてのイソブチレン又は三級ブタノールの反応
率、生成されるメタクロレイン及びメタクリル酸の選択
率は以下のように定義される。The present invention will be illustrated by the following examples. The reaction rate of isobutylene or tertiary butanol as a reaction raw material and the selectivity of methacrolein and methacrylic acid produced are defined as follows.
【００２４】[0024]
【数１】 [Equation 1]
【００２５】[0025]
【数２】 [Equation 2]
【００２６】[0026]
【数３】 (Equation 3)
【００２７】実施例１ 幅２０ｍｍ、長さ９０ｍｍの羽根を４枚備えたフラット
パドル型回転式攪拌翼及び幅２０ｍｍ、長さ３００ｍｍ
の邪魔板を４枚有する内径３４０ｍｍ、高さ４００ｍｍ
の丸底スレンレス製容器に水６０００ｇを投入し、加熱
した後、パラモリブデン酸アンモニウム３０００ｇを溶
解し、続いて三酸化アンチモン８２．６ｇを分散させ、
回転数１８０ｒｐｍで攪拌した（Ａ液）。別に水５５０
０ｇに６０％硝酸水溶液１００ｇ、硝酸ビスマス６８
６．９ｇ、硝酸第二鉄１１４４．１ｇ、硝酸ニッケル１
６４６．７ｇ、硝酸コバルト４１２．０ｇ、硝酸鉛４６
９．０ｇ、硝酸マグネシウム７２６．２ｇ、硝酸セリウ
ム６１．５ｇ及び硝酸セシウム１１０．４ｇを順次加え
溶解した（Ｂ液）。１８０ｒｐｍで攪拌した状態で、Ａ
液にＢ液を混合し、スラリー状物とした。Example 1 A flat paddle type rotary stirring blade equipped with four blades having a width of 20 mm and a length of 90 mm and a width of 20 mm and a length of 300 mm
With 4 baffles, inner diameter 340mm, height 400mm
6000 g of water was charged into a round bottom stainless steel container and heated, then 3000 g of ammonium paramolybdate was dissolved, and subsequently 82.6 g of antimony trioxide was dispersed,
The mixture was stirred at a rotation speed of 180 rpm (Liquid A). Separately water 550
60 g nitric acid aqueous solution 100 g, bismuth nitrate 68 to 0 g
6.9 g, ferric nitrate 1144.1 g, nickel nitrate 1
646.7 g, cobalt nitrate 412.0 g, lead nitrate 46
9.0 g, magnesium nitrate 726.2 g, cerium nitrate 61.5 g and cesium nitrate 110.4 g were sequentially added and dissolved (solution B). A with stirring at 180 rpm
Liquid B was mixed with the liquid to form a slurry.
【００２８】混合完了後、攪拌回転数を１００ｒｐｍに
減速した後、得られたスラリー状物を９０℃に加熱し、
１００ｒｐｍで攪拌した状態で１００分間熟成処理し、
続いて、噴霧乾燥した。After the mixing was completed, the stirring speed was reduced to 100 rpm, and the resulting slurry was heated to 90 ° C.
Aged for 100 minutes while stirring at 100 rpm,
Subsequently, it was spray dried.
【００２９】得られた乾燥物を３００℃で１時間仮焼し
た後、直径及び高さがそれぞれ３ｍｍの円柱状に成型
し、５１０℃で３時間焼成した。The dried material thus obtained was calcined at 300 ° C. for 1 hour, then molded into a cylindrical shape having a diameter and a height of 3 mm, respectively, and calcined at 510 ° C. for 3 hours.
【００３０】こうして得られた触媒の組成は次式で示さ
れる。 Ｍｏ12Ｂｉ1 Ｆｅ2 Ｎｉ4 Ｃｏ1 Ｐｂ1Ｍｇ2Ｓｂ0.4 Ｃ
ｅ0.1Ｃｓ0.4Ｏx （式中、Ｍｏ、Ｂｉ、Ｆｅ、Ｎｉ、Ｃｏ、Ｐｂ、Ｍｇ、
Ｓｂ、Ｃｅ、Ｃｓ及びＯはそれぞれモリブデン、ビスマ
ス、鉄、ニッケル、コバルト、鉛、マグネシウム、アン
チモン、セリウム、セシウム及び酸素を表す。又、元素
記号右併記の数字は各元素の原子比であり、ｘは前記各
成分の原子価を満足するのに必要な酸素原子数であ
る。）The composition of the catalyst thus obtained is shown by the following equation. Mo 12 Bi 1 Fe 2 Ni 4 Co 1 Pb 1 Mg 2 Sb 0.4 C
e 0.1 Cs 0.4 O x (in the formula, Mo, Bi, Fe, Ni, Co, Pb, Mg,
Sb, Ce, Cs and O represent molybdenum, bismuth, iron, nickel, cobalt, lead, magnesium, antimony, cerium, cesium and oxygen, respectively. The numbers on the right side of the element symbols are the atomic ratios of the respective elements, and x is the number of oxygen atoms required to satisfy the valences of the respective components. )
【００３１】こうして得られた触媒をステンレス製反応
管に充填し、イソブチレン５％、酸素１２％、水蒸気１
０％及び窒素７３％の原料混合ガスを接触時間４．５秒
で触媒層を通過させ、３５０℃で反応させた。その結果
は表１に示す如く、イソブチレンの反応率９７．４％、
メタクロレインの選択率８８．２％、メタクリル酸の選
択率５．４％であった。The catalyst thus obtained was filled in a stainless steel reaction tube, and isobutylene 5%, oxygen 12%, water vapor 1
A raw material mixed gas of 0% and 73% nitrogen was passed through the catalyst layer at a contact time of 4.5 seconds, and reacted at 350 ° C. As a result, as shown in Table 1, the reaction rate of isobutylene is 97.4%,
The selectivity of methacrolein was 88.2% and the selectivity of methacrylic acid was 5.4%.
【００３２】実施例２ 実施例１において、熟成過程における攪拌回転数を１３
０ｒｐｍに変更する以外は実施例１と同じ操作で触媒を
得た。得られた触媒を用いて、実施例１と同様の方法に
より反応を行った。得られた結果を表１に示す。得られ
た触媒の性能は実施例１と同等であった。Example 2 In Example 1, the stirring speed was set to 13 during the aging process.
A catalyst was obtained by the same operation as in Example 1 except that the speed was changed to 0 rpm. A reaction was carried out in the same manner as in Example 1 using the obtained catalyst. The results obtained are shown in Table 1. The performance of the obtained catalyst was equivalent to that of Example 1.
【００３３】比較例１ 実施例１において、熟成過程における攪拌回転数を混合
過程における回転数と同じ１８０ｒｐｍとし、その他は
実施例１と同様の方法により反応を行った。得られた結
果を表１に示す。得られた触媒の性能は実施例１に比べ
劣るものであった。Comparative Example 1 The reaction was carried out in the same manner as in Example 1 except that the stirring rotation speed in the aging process was 180 rpm, which was the same as the rotation speed in the mixing process. The results obtained are shown in Table 1. The performance of the obtained catalyst was inferior to that of Example 1.
【００３４】実施例３ 実施例１で用いたものと同じような丸底ステンレス製容
器内に、水６０００ｇを投入し、加熱した後、パラモリ
ブデン酸アンモニウム３０００ｇを溶解し、続いて二酸
化テルル２２．６ｇを分散させ、回転数２００ｒｐｍで
攪拌した（Ｃ液）。別に水５５００ｇに６０％硝酸水溶
液１００ｇ、８５％リン酸水溶液３２．６ｇ、硝酸ビス
マス１０３０．３ｇ、硝酸第二鉄１０２９．７ｇ、硝酸
ニッケル８２３．３ｇ、硝酸コバルト１２３５．９ｇ、
硝酸亜鉛８４２．４ｇ、硝酸マンガン８１．３ｇ、硝酸
タリウム３７．７ｇ及び硝酸ルビジウム６２．６ｇを順
次加え溶解した（Ｄ液）。２００ｒｐｍで攪拌した状態
で、Ｃ液にＤ液を混合し、スラリー状物とした。Example 3 In a container made of stainless steel with a round bottom similar to that used in Example 1, 6000 g of water was charged, and after heating, 3000 g of ammonium paramolybdate was dissolved, followed by tellurium dioxide 22. 6 g was dispersed and stirred at a rotation speed of 200 rpm (C liquid). Separately, to 5500 g of water, 100 g of 60% nitric acid aqueous solution, 32.6 g of 85% phosphoric acid aqueous solution, 1030.3 g of bismuth nitrate, 1029.7 g of ferric nitrate, 823.3 g of nickel nitrate, and 1235.9 g of cobalt nitrate,
842.4 g of zinc nitrate, 81.3 g of manganese nitrate, 37.7 g of thallium nitrate and 62.6 g of rubidium nitrate were sequentially added and dissolved (solution D). The liquid C was mixed with the liquid D under stirring at 200 rpm to form a slurry.
【００３５】混合完了後、攪拌回転数を８０ｒｐｍに減
速した後、得られたスラリー状物を１００℃に加熱し、
８０ｒｐｍで攪拌した状態で６０分間熟成処理し、続い
て、噴霧乾燥した。After the mixing was completed, the stirring speed was reduced to 80 rpm, and the obtained slurry was heated to 100 ° C.
The mixture was aged for 60 minutes while being stirred at 80 rpm, and then spray-dried.
【００３６】得られた乾燥物を３００℃で１時間仮焼し
た後、直径及び高さがそれぞれ３ｍｍの円柱状に成型
し、５１０℃で３時間焼成した。The dried material thus obtained was calcined at 300 ° C. for 1 hour, then molded into a cylindrical shape having a diameter and a height of 3 mm, respectively, and calcined at 510 ° C. for 3 hours.
【００３７】こうして得られた触媒の組成は次式で示さ
れる。 Ｍｏ12Ｂｉ1.5 Ｆｅ1.8 Ｎｉ2Ｃｏ3Ｚｎ2Ｍｎ0.2Ｐ0.2
Ｔｅ0.1Ｔｌ0.1Ｒｂ0.3Ｏx （式中、Ｍｏ、Ｂｉ、Ｆｅ、Ｎｉ、Ｃｏ、Ｚｎ、Ｍｎ、
Ｐ、Ｔｅ、Ｔl、Ｒｂ及びＯはそれぞれモリブデン、ビ
スマス、鉄、ニッケル、コバルト、亜鉛、マンガン、リ
ン、テルル、タリウム、ルビジウム及び酸素を表す。
又、元素記号右併記の数字は各元素の原子比であり、ｘ
は前記各成分の原子価を満足するのに必要な酸素原子数
である。）The composition of the catalyst thus obtained is shown by the following formula. Mo 12 Bi 1.5 Fe 1.8 Ni 2 Co 3 Zn 2 Mn 0.2 P 0.2
Te 0.1 Tl 0.1 Rb 0.3 O x (in the formula, Mo, Bi, Fe, Ni, Co, Zn, Mn,
P, Te, Tl, Rb and O represent molybdenum, bismuth, iron, nickel, cobalt, zinc, manganese, phosphorus, tellurium, thallium, rubidium and oxygen, respectively.
The numbers on the right side of the element symbols are the atomic ratios of each element, x
Is the number of oxygen atoms necessary to satisfy the valence of each component. )
【００３８】こうして得られた触媒を用いて、実施例１
と同様の反応を行った。その結果を表１に示す。Using the catalyst thus obtained, Example 1
The same reaction was carried out. Table 1 shows the results.
【００３９】実施例４ 実施例３において、熟成処理時間を４０分に変更する以
外は実施例３と同じ操作で触媒を得た。得られた触媒を
用いて、実施例３と同様の方法により反応を行った。得
られた結果を表１に示す。得られた触媒の性能は実施例
３と同等であった。Example 4 A catalyst was obtained in the same manner as in Example 3, except that the aging treatment time was changed to 40 minutes. A reaction was carried out in the same manner as in Example 3 using the obtained catalyst. The results obtained are shown in Table 1. The performance of the obtained catalyst was equivalent to that of Example 3.
【００４０】比較例２ 実施例３において、熟成処理時間を１０分に変更する以
外は実施例３と同じ操作で触媒を得た。得られた触媒を
用いて、実施例３と同様の方法により反応を行った。得
られた結果を表１に示す。得られた触媒の性能は実施例
３及び４に比べ劣るものであった。Comparative Example 2 A catalyst was obtained in the same manner as in Example 3, except that the aging treatment time was changed to 10 minutes. A reaction was carried out in the same manner as in Example 3 using the obtained catalyst. The results obtained are shown in Table 1. The performance of the obtained catalyst was inferior to that of Examples 3 and 4.
【００４１】[0041]
【表１】 [Table 1]
【００４２】実施例５ 実施例１で用いたものと同じような丸底ステンレス製容
器内に、水６０００ｇを投入し、加熱した後、パラモリ
ブデン酸アンモニウム３０００ｇ及びタングステン酸ア
ンモニウム１８４．８ｇを溶解し、回転数１６０ｒｐｍ
で攪拌した（Ｅ液）。別に水５５００ｇに６０％硝酸水
溶液１００ｇ、硝酸ビスマス６８６．９ｇ、硝酸第二鉄
１０２９．７ｇ、硝酸ニッケル１２３５．０ｇ、硝酸コ
バルト１２３５．９ｇ、硝酸マグネシウム３６３．１
ｇ、硝酸セシウム８２．８ｇ及び硝酸カリウム１４．３
ｇを順次加え溶解した（Ｆ液）。１６０ｒｐｍで攪拌し
た状態で、Ｅ液にＦＤ液を混合し、スラリー状物とし
た。Example 5 6000 g of water was placed in a round-bottom stainless steel container similar to that used in Example 1 and heated, and then 3000 g of ammonium paramolybdate and 184.8 g of ammonium tungstate were dissolved. , Rpm 160rpm
The mixture was stirred (solution E). Separately, in 5500 g of water, 100 g of 60% nitric acid aqueous solution, 686.9 g of bismuth nitrate, 1029.7 g of ferric nitrate, 1235.0 g of nickel nitrate, 1235.9 g of cobalt nitrate, and 363.1 of magnesium nitrate.
g, cesium nitrate 82.8 g and potassium nitrate 14.3
g was sequentially added and dissolved (solution F). The FD liquid was mixed with the E liquid in a state of stirring at 160 rpm to form a slurry.
【００４３】混合完了後、攪拌回転数を７０ｒｐｍに減
速した後、得られたスラリー状物を８５℃に加熱し、７
０ｒｐｍで攪拌した状態で１２０分間熟成処理し、続い
て、噴霧乾燥した。After the completion of mixing, the stirring speed was reduced to 70 rpm, and the obtained slurry was heated to 85 ° C.
The mixture was aged for 120 minutes while being stirred at 0 rpm, and then spray-dried.
【００４４】得られた乾燥物を３００℃で１時間仮焼し
た後、直径及び高さがそれぞれ３ｍｍの円柱状に成型
し、５１０℃で３時間焼成した。The dried product thus obtained was calcined at 300 ° C. for 1 hour, then molded into a cylindrical shape having a diameter and a height of 3 mm, respectively, and calcined at 510 ° C. for 3 hours.
【００４５】こうして得られた触媒の組成は次式で示さ
れる。 Ｍｏ12Ｂｉ1 Ｆｅ1.8 Ｎｉ3Ｃｏ3Ｍｇ1Ｗｏ0.5Ｓｉ1Ｃ
ｓ0.3Ｋ0.1Ｏx （式中、Ｍｏ、Ｂｉ、Ｆｅ、Ｎｉ、Ｃｏ、Ｍｇ、Ｗ、Ｓ
ｉ、Ｃｓ、Ｋ及びＯはそれぞれモリブデン、ビスマス、
鉄、ニッケル、コバルト、マグネシウム、タングステ
ン、ケイ素、セシウム、カリウム及び酸素を表す。又、
元素記号右併記の数字は各元素の原子比であり、ｘは前
記各成分の原子価を満足するのに必要な酸素原子数であ
る。）The composition of the catalyst thus obtained is shown by the following formula. Mo 12 Bi 1 Fe 1.8 Ni 3 Co 3 Mg 1 Wo 0.5 Si 1 C
s 0.3 K 0.1 O x (in the formula, Mo, Bi, Fe, Ni, Co, Mg, W, S
i, Cs, K and O are molybdenum, bismuth,
Represents iron, nickel, cobalt, magnesium, tungsten, silicon, cesium, potassium and oxygen. or,
The number on the right side of the element symbol is the atomic ratio of each element, and x is the number of oxygen atoms required to satisfy the valence of each component. )
【００４６】こうして得られた触媒を用いて、反応用原
料をイソブチレンの代わりに三級ブタノールに変更する
以外は実施例１と同様の反応を行った。その結果を表２
に示す。Using the catalyst thus obtained, the same reaction as in Example 1 was carried out except that the reaction raw material was changed to tertiary butanol instead of isobutylene. The results are shown in Table 2.
Shown in
【００４７】比較例３ 実施例５において、混合過程における攪拌回転数を７０
ｒｐｍに変更し、且つ熟成過程における攪拌回転数を１
６０ｒｐｍに変更する以外は実施例５と同じ操作で触媒
を得た。得られた触媒を用いて、実施例５と同様の方法
により反応を行った。得られた結果を表２に示す。得ら
れた触媒の性能は実施例５に比べ劣るものであった。Comparative Example 3 In Example 5, the stirring rotation speed in the mixing process was 70.
Change to rpm and stirrer speed in the aging process is 1
A catalyst was obtained by the same operation as in Example 5 except that the speed was changed to 60 rpm. A reaction was carried out in the same manner as in Example 5 using the obtained catalyst. The obtained results are shown in Table 2. The performance of the obtained catalyst was inferior to that of Example 5.
【００４８】[0048]
【表２】 [Table 2]
【００４９】[0049]
【発明の効果】本発明のメタクロレインおよびメタクリ
ル酸合成用触媒の製造法によると、触媒活性及び目的生
成物選択性に優れた触媒を容易に再現性よく製造するこ
とができる。EFFECTS OF THE INVENTION According to the method for producing a catalyst for methacrolein and methacrylic acid synthesis of the present invention, a catalyst excellent in catalytic activity and selectivity of a target product can be easily and reproducibly produced.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display location // C07B 61/00 300 C07B 61/00 300
Claims (4)
ン、ビスマス、鉄及び酸素を表し、Ａはニッケル及び／
又はコバルト、Ｘはマグネシウム、亜鉛、マンガン、ス
ズ及び鉛からなる群より選ばれた少なくとも１種の元
素、Ｙはリン、ホウ素、イオウ、テルル、ケイ素、ゲル
マニウム、セリウム、ニオブ、チタン、ジルコニウム、
タングステン及びアンチモンからなる群より選ばれた少
なくとも１種の元素、Ｚはカリウム、ナトリウム、ルビ
ジウム、セシウム及びタリウムからなる群より選ばれた
少なくとも１種の元素を表す。ただし、ａ、ｂ、ｃ、
ｄ、ｅ、ｆ、ｇ及びｈは各元素の原子比を表し、ａ＝１
２のとき、０．１≦ｂ≦５、０．１≦ｃ≦５、１≦ｄ≦
１２、０≦ｅ≦１０、０≦ｆ≦１０、０．０１≦ｇ≦３
であり、ｈは前記各成分の原子比を満足するのに必要な
酸素原子で数である。）で表される複合酸化物を触媒成
分として含有するメタクロレイン及びメタクリル酸合成
用触媒の製造法において、該複合酸化物を得るに際し、
触媒成分を二種類以上に分割し、その内の少なくとも二
種類を溶液又は分散液とした後、それぞれの溶液又は分
散液を攪拌しながら混合してスラリー状物とし、得られ
たスラリー状物を前記混合時の攪拌より弱い攪拌状態で
少なくとも３０分加熱熟成処理した後、乾燥し、得られ
た乾燥物を焼成することにより複合酸化物を得ることを
特徴とするメタクロレイン及びメタクリル酸合成用触媒
の製造法。1. The following general formula Mo a Bi b Fe c A d X e Y f Z g O h (wherein Mo, Bi, Fe and O represent molybdenum, bismuth, iron and oxygen, respectively, and A is nickel). as well as/
Or cobalt, X is at least one element selected from the group consisting of magnesium, zinc, manganese, tin and lead, Y is phosphorus, boron, sulfur, tellurium, silicon, germanium, cerium, niobium, titanium, zirconium,
At least one element selected from the group consisting of tungsten and antimony, and Z represents at least one element selected from the group consisting of potassium, sodium, rubidium, cesium and thallium. However, a, b, c,
d, e, f, g and h represent the atomic ratio of each element, and a = 1
When 2, 0.1 ≦ b ≦ 5, 0.1 ≦ c ≦ 5, 1 ≦ d ≦
12, 0 ≦ e ≦ 10, 0 ≦ f ≦ 10, 0.01 ≦ g ≦ 3
And h is the number of oxygen atoms required to satisfy the atomic ratio of each component. In the method for producing a methacrolein- and methacrylic acid-synthesizing catalyst containing a composite oxide represented by the formula (4) as a catalyst component, in obtaining the composite oxide,
The catalyst component is divided into two or more kinds, and at least two kinds of them are made into a solution or a dispersion, and then the respective solutions or dispersions are mixed with stirring to form a slurry, and the obtained slurry is obtained. A catalyst for the synthesis of methacrolein and methacrylic acid, which is characterized in that a composite oxide is obtained by heating and aging the mixture for at least 30 minutes under a stirring condition weaker than the agitation during the mixing, and drying the resulting dried product. Manufacturing method.
散液を混合する過程及び加熱熟成過程を回転式攪拌装置
を有する同一の容器内にて実施し、加熱熟成過程におい
て、混合過程における攪拌より弱い攪拌状態を実現する
手段として攪拌装置の回転を減速させる方法を用いるこ
とを特徴とする請求項１記載の製造法。2. A process of mixing two or more kinds of solutions or dispersions containing a catalyst component and a heat aging process are carried out in the same container having a rotary stirring device, and stirring in the mixing process is performed in the heat aging process. 2. The manufacturing method according to claim 1, wherein a method of slowing down the rotation of the stirring device is used as a means for realizing a weaker stirring state.
混合過程における回転速度の８０％以下であることを特
徴とする請求項２記載の製造法。3. The method according to claim 2, wherein the rotation speed of the stirrer in the aging process is 80% or less of the rotation speed in the mixing process.
として、第一の溶液又は分散液にモリブデン化合物を含
む溶液又は分散液を用い、第二の溶液又は分散液にビス
マス化合物を含む溶液又は分散液を用いる請求項１、２
又は３記載の製造法。4. A solution or dispersion containing a molybdenum compound in a first solution or dispersion and a solution containing a bismuth compound in a second solution or dispersion as the solution or dispersion containing two types of catalyst components. Alternatively, a dispersion is used.
Or the production method described in 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12195195A JP3288197B2 (en) | 1995-05-19 | 1995-05-19 | Method for producing catalyst for synthesizing methacrolein and methacrylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12195195A JP3288197B2 (en) | 1995-05-19 | 1995-05-19 | Method for producing catalyst for synthesizing methacrolein and methacrylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08309192A true JPH08309192A (en) | 1996-11-26 |
| JP3288197B2 JP3288197B2 (en) | 2002-06-04 |
Family
ID=14823962
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12195195A Expired - Lifetime JP3288197B2 (en) | 1995-05-19 | 1995-05-19 | Method for producing catalyst for synthesizing methacrolein and methacrylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3288197B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003053570A1 (en) | 2001-12-21 | 2003-07-03 | Asahi Kasei Chemicals Corporation | Oxide catalyst composition |
| CN1314487C (en) * | 2004-11-26 | 2007-05-09 | 上海华谊丙烯酸有限公司 | Catalyst for selectively oxidizing tertiary butanol or isobutene to synthesize methyl acrylic aldehyde and its use |
| JP2007222855A (en) * | 2006-02-27 | 2007-09-06 | Mitsubishi Rayon Co Ltd | Manufacturing method of unsaturated aldehyde and catalysts for unsaturated carboxylic acid composition |
| JP2009523609A (en) * | 2006-01-17 | 2009-06-25 | サウディ ベーシック インダストリーズ コーポレイション | Process for producing mixed metal oxide catalysts for producing unsaturated aldehydes from olefins |
| JP2012250237A (en) * | 2009-04-30 | 2012-12-20 | Shin-Etsu Chemical Co Ltd | Dispersion liquid of photocatalyst particle and method of producing the same |
| US8470730B2 (en) | 2005-07-05 | 2013-06-25 | Mitsubishi Rayon Co., Ltd. | Process for producing catalyst |
| WO2015037611A1 (en) * | 2013-09-11 | 2015-03-19 | 三菱レイヨン株式会社 | Method of preparing catalyst for production of methacrylic acid |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150020541A (en) | 2012-05-18 | 2015-02-26 | 닛뽄 가야쿠 가부시키가이샤 | Catalyst for use in production of methacrylic acid, method for producing said catalyst, and method for producing methacrylic acid using said catalyst |
-
1995
- 1995-05-19 JP JP12195195A patent/JP3288197B2/en not_active Expired - Lifetime
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003053570A1 (en) | 2001-12-21 | 2003-07-03 | Asahi Kasei Chemicals Corporation | Oxide catalyst composition |
| US7012039B2 (en) | 2001-12-21 | 2006-03-14 | Asahi Kasei Chemicals Corporation | Oxide catalyst composition |
| CN1308074C (en) * | 2001-12-21 | 2007-04-04 | 旭化成化学株式会社 | Oxide catalyst composition |
| CN1314487C (en) * | 2004-11-26 | 2007-05-09 | 上海华谊丙烯酸有限公司 | Catalyst for selectively oxidizing tertiary butanol or isobutene to synthesize methyl acrylic aldehyde and its use |
| US8470730B2 (en) | 2005-07-05 | 2013-06-25 | Mitsubishi Rayon Co., Ltd. | Process for producing catalyst |
| US8563774B2 (en) | 2005-07-05 | 2013-10-22 | Mitsubishi Rayon Co., Ltd. | Method for producing catalyst |
| JP2009523609A (en) * | 2006-01-17 | 2009-06-25 | サウディ ベーシック インダストリーズ コーポレイション | Process for producing mixed metal oxide catalysts for producing unsaturated aldehydes from olefins |
| JP2007222855A (en) * | 2006-02-27 | 2007-09-06 | Mitsubishi Rayon Co Ltd | Manufacturing method of unsaturated aldehyde and catalysts for unsaturated carboxylic acid composition |
| JP2012250237A (en) * | 2009-04-30 | 2012-12-20 | Shin-Etsu Chemical Co Ltd | Dispersion liquid of photocatalyst particle and method of producing the same |
| WO2015037611A1 (en) * | 2013-09-11 | 2015-03-19 | 三菱レイヨン株式会社 | Method of preparing catalyst for production of methacrylic acid |
| JPWO2015037611A1 (en) * | 2013-09-11 | 2017-03-02 | 三菱レイヨン株式会社 | Method for producing a catalyst for methacrylic acid production |
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|---|---|
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