JPH1133403A - Production of catalyst for synthesis of methacrylic acid and production of methacrylic acid - Google Patents
Production of catalyst for synthesis of methacrylic acid and production of methacrylic acidInfo
- Publication number
- JPH1133403A JPH1133403A JP19571897A JP19571897A JPH1133403A JP H1133403 A JPH1133403 A JP H1133403A JP 19571897 A JP19571897 A JP 19571897A JP 19571897 A JP19571897 A JP 19571897A JP H1133403 A JPH1133403 A JP H1133403A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- solution
- methacrylic acid
- stirring
- mixing
- 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.)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、メタクロレイン、
イソブタン、イソ酪酸またはイソブチルアルデヒド等を
気相接触酸化してメタクリル酸を合成する際に使用する
触媒の製造方法、およびメタクリル酸の製造方法に関す
る。The present invention relates to methacrolein,
The present invention relates to a method for producing a catalyst used for synthesizing methacrylic acid by subjecting isobutane, isobutyric acid or isobutyraldehyde to gas phase catalytic oxidation, and a method for producing methacrylic acid.
【０００２】[0002]
【従来の技術】従来、メタクロレイン等を高温気相下で
接触酸化して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５５−３１００７号公報、特
開昭５８−７４１４２号公報、特開昭５８−１６６９３
８号公報、特開昭６１−５０４３号公報等数多くの提案
がなされている。しかし、これらは主として触媒を構成
する成分およびその比率に関するものであって、製造法
の詳細に関する記載はほとんどない。2. Description of the Related Art Conventionally, a catalyst used for producing methacrylic acid by subjecting methacrolein or the like to catalytic oxidation in a high-temperature gas phase is disclosed in, for example, JP-A-55-31007 and JP-A-58-74142. JP-A-58-16693
No. 8, Japanese Patent Application Laid-Open No. 61-5043, and many other proposals have been made. However, these mainly relate to the components constituting the catalyst and the ratio thereof, and there is almost no description on the details of the production method.
【０００３】メタクリル酸製造用触媒として多用される
Ｍｏ−Ｐ系固体触媒は、通常、触媒成分を含む二種類以
上の溶液または分散液を混合し、得られた混合物を必要
に応じて加熱処理した後、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。[0003] Mo-P-based solid catalysts, which are frequently used as catalysts for producing methacrylic acid, are usually prepared by mixing two or more kinds of solutions or dispersions containing a catalyst component and subjecting the resulting mixture to heat treatment as required. Thereafter, it is dried, and is prepared by baking the obtained dried product.
【０００４】特開平４−１８２４５０号公報には、触媒
成分を含む二種類以上の溶液または分散液を可能な限り
短時間に混合し、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っ
て触媒を製造する方法が記載されている。また、特開平
７−１８５３５４号公報には、触媒成分を含む二種類以
上の溶液または分散液を高速で撹拌混合し、かつ高速撹
拌下で加熱熟成処理した後乾燥し、得られた乾燥物を焼
成することにより製造する方法が記載されている。[0004] JP-A-4-182450 discloses that two or more kinds of solutions or dispersions containing a catalyst component are mixed in the shortest possible time and the resulting mixture is immediately spray-dried without aging. A method for producing a catalyst by calcining the obtained dried product is described. Also, JP-A-7-185354 discloses that two or more kinds of solutions or dispersions containing a catalyst component are stirred and mixed at a high speed, heated and aged under high-speed stirring, and then dried. A method of manufacturing by firing is described.
【０００５】しかし、これらの方法で得られる触媒で
は、触媒活性、選択性などの点で工業触媒としてまだ不
十分であり、さらに改良が望まれている。However, catalysts obtained by these methods are still insufficient as industrial catalysts in terms of catalytic activity, selectivity, etc., and further improvements are desired.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、メタクロレ
イン、イソブタン、イソ酪酸またはイソブチルアルデヒ
ド等を分子状酸素により気相接触酸化してメタクリル酸
を高収率、高選択率で製造しうる触媒の製造方法、およ
びメタクリル酸を高収率、高選択率で製造する製造方法
を提供することを目的とする。SUMMARY OF THE INVENTION The present invention relates to a catalyst capable of producing methacrylic acid in a high yield and a high selectivity by subjecting gaseous catalytic oxidation of methacrolein, isobutane, isobutyric acid or isobutyraldehyde with molecular oxygen. And a method for producing methacrylic acid with high yield and high selectivity.
【０００７】[0007]
【課題を解決するための手段】本発明は、下記一般式
（Ｉ）で表されるメタクリル酸合成用触媒の製造方法に
おいて、触媒成分の中の少なくともモリブデン成分を含
む溶液または分散液（Ａ液）と、少なくともリン成分を
含む溶液または分散液（Ｂ液）とを撹拌装置を用いて撹
拌しながら混合し、Ａ液とＢ液の混合後のスラリー分散
液を、混合時の装置と同じ装置を用いて混合時の０．８
５倍以下の回転数または振動数で撹拌しながら３０分以
上熟成することを含むメタクリル酸合成用触媒の製造方
法に関する。The present invention relates to a method for producing a methacrylic acid synthesis catalyst represented by the following general formula (I), wherein a solution or dispersion containing at least a molybdenum component (A solution) ) And a solution or dispersion containing at least a phosphorus component (solution B) are mixed with stirring using a stirrer, and the slurry dispersion obtained after mixing solution A and solution B is mixed with the same device as the device used for mixing. 0.8 when mixed with
The present invention relates to a method for producing a catalyst for synthesizing methacrylic acid, which comprises aging for 30 minutes or more while stirring at a rotation frequency or frequency of 5 times or less.
【０００８】 ＭｏaＰbＶcＣｕdＸeＹfＺgＯh （Ｉ） （式中、Ｍｏ、Ｐ、Ｖ、ＣｕおよびＯはそれぞれモリブ
デン、リン、バナジウム、銅および酸素を表し、Ｘはヒ
素、ホウ素、ゲルマニウム、アンチモン、テルル、ビス
マス、セレンおよびケイ素からなる群より選ばれた少な
くとも１種の元素を表し、Ｙはカリウム、ナトリウム、
ルビジウム、セシウムおよびタリウムからなる群より選
ばれた少なくとも１種の元素を表し、Ｚはマグネシウ
ム、イオウ、カルシウム、チタン、クロム、マンガン、
鉄、ニッケル、コバルト、亜鉛、ニオブ、銀、スズ、バ
リウム、タンタル、タングステン、鉛、ランタンおよび
セリウムからなる群より選ばれた少なくとも１種の元素
を表し、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇおよびｈは各元素
の原子比を表し、ａ＝１２のとき、０．１≦ｂ≦３、
０．０１≦ｃ≦３、０．０１≦ｄ≦２、０≦ｅ≦３、
０．０１≦ｆ≦３、０≦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の原子比である。）
前記撹拌装置としては、回転翼撹拌機またはホモジナイ
ザーを用いることが好ましい。[0008] Mo a P b V c Cu d X e Y f Z g O h (I) ( wherein, represents Mo, P, V, Cu and O represent molybdenum, phosphorus, vanadium, copper and oxygen, X Represents at least one element selected from the group consisting of arsenic, boron, germanium, antimony, tellurium, bismuth, selenium and silicon, and Y is potassium, sodium,
Represents at least one element selected from the group consisting of rubidium, cesium and thallium, and Z is magnesium, sulfur, calcium, titanium, chromium, manganese,
Represents at least one element selected from the group consisting of iron, nickel, cobalt, zinc, niobium, silver, tin, barium, tantalum, tungsten, lead, lanthanum and cerium, a, b, c, d, e, f, g and h represent the atomic ratio of each element, and when a = 12, 0.1 ≦ b ≦ 3;
0.01 ≦ c ≦ 3, 0.01 ≦ d ≦ 2, 0 ≦ e ≦ 3,
0.01 ≦ f ≦ 3 and 0 ≦ g ≦ 3, and h is an atomic ratio of oxygen necessary to satisfy the atomic ratio of each component. )
It is preferable to use a rotary blade stirrer or a homogenizer as the stirring device.
【０００９】また、本発明では、混合時の撹拌にホモジ
ナイザーを用いて、熟成時に回転翼撹拌機を用いてもよ
い。In the present invention, a homogenizer may be used for stirring at the time of mixing, and a rotary blade stirrer may be used at the time of ripening.
【００１０】[0010]
【発明の実施の形態】触媒の調製に用いる触媒成分元素
の原料としては、特に限定はないが、通常は酸化物また
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、炭酸塩およびアンモニウム塩、ま
たはそれらの混合物が用いられる。DETAILED DESCRIPTION OF THE INVENTION The raw material of the catalyst component element used in the preparation of the catalyst is not particularly limited, but is usually an oxide or a chloride, a hydroxide, or a sulfate which can be turned into an oxide by heating. , Nitrates, carbonates and ammonium salts, or mixtures thereof.
【００１１】本発明において各触媒成分を混合するに
は、少なくともモリブデン成分を含む溶液または分散液
（Ａ液）と、少なくともリンを含む溶液または分散液
（Ｂ液）を予め調製し、Ａ液とＢ液を混合する。モリブ
デンおよびリン以外の成分は、Ａ液またはＢ液のどちら
かに溶解させるか、あるいは成分によっては例えば酸化
物等の粉末のまま分散させる。さらに、Ａ液またはＢ液
以外に別途溶液または分散液を調製し、Ａ液とＢ液の混
合後の液にさらに添加して混合したり、粉末のまま混合
してもよい。この場合の添加時期はＡ液とＢ液の混合後
直後でも、熟成後でもよい。In the present invention, in order to mix the respective catalyst components, a solution or dispersion containing at least a molybdenum component (solution A) and a solution or dispersion containing at least phosphorus (solution B) are prepared in advance. Mix liquid B. Components other than molybdenum and phosphorus are dissolved in either solution A or solution B, or, depending on the components, are dispersed as powders such as oxides. Furthermore, a solution or a dispersion liquid may be separately prepared in addition to the liquid A or the liquid B, and may be further added to and mixed with the liquid after mixing the liquid A and the liquid B, or may be mixed as it is as a powder. In this case, the addition may be performed immediately after the mixing of the solution A and the solution B or after aging.
【００１２】Ａ液およびＢ液を調製するに際しては、そ
れぞれの液に含ませる原料化合物を混合したときに、新
たな沈殿生成反応、ゲル化等を起こさないような組み合
わせを選ぶ。尚、沈殿生成反応、ゲル化等を起こさない
範囲であれば、Ａ液中に少量のリン成分が含まれていた
り、同様にＢ液中にモリブデン成分が含まれていたりし
ても触媒性能に対して特に悪影響はない。In preparing the solution A and the solution B, a combination is selected so as not to cause a new precipitation reaction, gelation, etc. when the raw material compounds contained in the respective solutions are mixed. In addition, as long as the precipitate formation reaction, gelation, etc. do not occur, even if the solution A contains a small amount of the phosphorus component or the solution B also contains the molybdenum component, the catalyst performance is not improved. There is no adverse effect on this.
【００１３】例えば、適当なモリブデン化合物、例えば
パラモリブデン酸アンモニウムを水に溶解した水溶液を
Ａ液とし、リン、銅、セシウム等の化合物、例えばリン
酸、硝酸銅、硝酸セシウム等を水に溶解した水溶液をＢ
液とする方法が挙げられる。For example, an aqueous solution prepared by dissolving a suitable molybdenum compound, for example, ammonium paramolybdate in water is used as solution A, and a compound such as phosphorus, copper, cesium, etc., for example, phosphoric acid, copper nitrate, cesium nitrate, etc. is dissolved in water. Aqueous solution to B
A method of making a liquid is used.
【００１４】本発明において、Ａ液とＢ液の混合時の撹
拌強度の程度としては、後述する熟成時の撹拌より強
く、できるだけ強いほど好ましい。生成する沈殿粒子の
粒径が微細でかつ均一になり、高性能な触媒を再現性よ
く得られるからである。In the present invention, the degree of stirring intensity at the time of mixing the liquid A and the liquid B is stronger than the stirring at the time of ripening described later, and the stronger the stirring, the better. This is because the size of the generated precipitated particles is fine and uniform, and a high-performance catalyst can be obtained with good reproducibility.
【００１５】撹拌に用いる装置としては、回転翼撹拌
機、ホモジナイザー等の回転式撹拌装置、振り子式の直
線運動型撹拌機、容器ごと振とうする振とう機、超音波
などを用いた振動式撹拌機等の常用される撹拌装置を用
いることができる。中でも、回転翼撹拌機、ホモジナイ
ザー等の回転式撹拌装置を用いると撹拌の強度を容易に
調節することが可能で工業上簡便であるので好ましい。
特に、より高活性な触媒が得られる点でホモジナイザー
の使用が好ましい。As the apparatus used for the stirring, a rotary stirring apparatus such as a rotary blade stirrer, a homogenizer, a pendulum type linear motion type stirrer, a shaker for shaking the whole container, a vibrating stirrer using an ultrasonic wave or the like. A commonly used stirring device such as a mixer can be used. Among them, it is preferable to use a rotary stirrer such as a rotary blade stirrer or a homogenizer since the intensity of stirring can be easily adjusted and industrially simple.
In particular, it is preferable to use a homogenizer in that a more highly active catalyst can be obtained.
【００１６】回転翼撹拌機としては、翼の形状が、フラ
ットパドル形、ピッチパドル形、プロペラ形、ラジアル
フローファンタービン形、ラジアルフローディスクター
ビン形、アキシャルフローファンタービン形、アキシャ
ルフローディスクタービン形、エッジタービン形、アン
カー形、パドル翼付きアンカー形、ゲート形、シングル
リボン形、ダブルリボン形およびトリプルリボン形であ
るもの等を用いることができる。また、ホモジナイザー
は、スリットを持つ外筒の内部を回転刃が回転して撹拌
するものであり、ホモミクサーという名称でも知られて
いる。例えば、特殊機加工業社製のＴ．Ｋ．ホモミクサ
ー、ＩＫＡ社製のウルトラターラックス等を挙げること
ができる。The rotary blade agitator has a flat paddle type, a pitch paddle type, a propeller type, a radial flow fan turbine type, a radial flow disk turbine type, an axial flow fan turbine type, an axial flow disk turbine type, An edge turbine type, an anchor type, an anchor type with paddle blades, a gate type, a single ribbon type, a double ribbon type and a triple ribbon type can be used. Further, the homogenizer is such that a rotary blade rotates and stirs the inside of an outer cylinder having a slit, and is also known as a homomixer. For example, T.M. K. Homomixer and Ultra Turrax manufactured by IKA can be used.
【００１７】回転翼撹拌機またはホモジナイザー等の回
転式撹拌装置を用いたときの撹拌翼または回転刃の回転
速度は、液の飛散などの不都合が起きない程度に容器、
撹拌翼、邪魔板等の形状、液量等を勘案して適宜調整す
ることができる。When a rotary stirring device such as a rotary blade stirrer or a homogenizer is used, the rotation speed of the stirring blade or the rotary blade is set to such a degree that no inconvenience such as scattering of a liquid occurs.
It can be appropriately adjusted in consideration of the shape of the stirring blade, the baffle plate and the like, the liquid amount, and the like.
【００１８】Ａ液とＢ液の混合の際、Ａ液にＢ液を添加
しても、またＢ液にＡ液を添加してもいずれでもよい。
Ａ液およびＢ液の混合・撹拌時の温度は、後述する熟成
時の温度より低く、通常４０〜８０℃、好ましくは５０
〜７０℃である。When mixing the A liquid and the B liquid, either the B liquid may be added to the A liquid, or the A liquid may be added to the B liquid.
The temperature at the time of mixing and stirring the A liquid and the B liquid is lower than the temperature at the time of aging described later, and is usually 40 to 80 ° C, preferably
７０70 ° C.
【００１９】本発明では、Ａ液とＢ液の混合によって得
られたスラリー分散液を直ちに乾燥するのではなく、少
なくとも３０分以上加熱熟成する。本発明者らは、この
熟成過程において、触媒前駆体がより好ましい構造に変
化または成長すると推定している。In the present invention, the slurry dispersion obtained by mixing the solution A and the solution B is not immediately dried but is aged by heating for at least 30 minutes. The present inventors presume that during this aging process, the catalyst precursor changes or grows to a more favorable structure.
【００２０】熟成時の撹拌強度の程度としては、弱いほ
ど好ましい。触媒前駆体の構造変化または成長反応が進
み、高性能な触媒を再現性よく得られるからである。The strength of the stirring during aging is preferably as low as possible. This is because the structural change or growth reaction of the catalyst precursor proceeds, and a high-performance catalyst can be obtained with good reproducibility.
【００２１】このときの撹拌装置としては、混合時と同
じ装置、あるいは混合時にホモジナイザーを用いた場合
には回転翼撹拌機も用いることができるが、より高性能
な触媒を得るためには、混合時にホモジナイザーを用い
熟成時に回転翼撹拌機を用いることが好ましい。回転式
撹拌装置を用いる場合、用いる容器、撹拌翼、邪魔板等
の形状および液量を勘案しながら、容器内の液に不均一
な温度分布を生じない範囲で十分弱い撹拌を行う。As a stirring device at this time, the same device as used for mixing, or a rotary blade stirrer when a homogenizer is used for mixing can be used. It is preferable to use a homogenizer in some cases and to use a rotary blade stirrer in aging. When a rotary stirrer is used, sufficiently weak stirring is performed within a range that does not cause uneven temperature distribution in the liquid in the container, while taking into consideration the shape and liquid volume of the container, stirring blade, baffle plate, and the like to be used.
【００２２】混合時の装置と同じ装置を用いて撹拌する
場合の撹拌条件は、混合時の回転数または振動数の少な
くとも０．８５倍以下であり、好ましくは０．８倍以下
である。撹拌条件のパラメータは、撹拌装置が回転式の
ときは回転数を、振り子式、振とう式および超音波式の
ときは振動数を（周波数）を指す。The stirring conditions when stirring using the same apparatus as the mixing apparatus are at least 0.85 times, preferably 0.8 times or less the rotation speed or the vibration frequency during mixing. The parameters of the stirring conditions indicate the number of rotations when the stirrer is of a rotary type, and the frequency (frequency) when the stirrer is of the pendulum type, the shaking type and the ultrasonic type.
【００２３】熟成時の温度は、８０〜１０５℃であり、
熟成時間は３０分以上、好ましくは６０分以上である。The ripening temperature is 80 to 105 ° C.,
The aging time is 30 minutes or more, preferably 60 minutes or more.
【００２４】本発明では、熟成して得られたスラリー状
物を次に乾燥する。乾燥方法は特に限定はなく、汎用の
箱型乾燥機、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、乾燥後少量の水を含有していても何ら問題がない。
また、乾燥して得られた乾燥触媒前駆体の形状について
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 slurry obtained by aging is then dried. The drying method is not particularly limited, and a general-purpose box-type dryer, spray dryer, drum dryer, slurry dryer, or the like can be used. Incidentally, the drying in the present invention is to remove a certain amount of water from the slurry to make it substantially a solid, and there is no problem even if it contains a small amount of water after drying. .
The shape of the dried catalyst precursor obtained by drying is not particularly limited, and may be a powder or a block.
【００２５】その後の処理は特に限定されるものではな
く、公知の方法によって処理することができるが、通
常、乾燥触媒前駆体を必要に応じて成形するか、あるい
は不活性担体に担持し、その後空気流通下や窒素流通下
で２００〜５００℃好ましくは３００〜４５０℃の範囲
で焼成して触媒を得る。The subsequent treatment is not particularly limited and can be carried out by a known method. Usually, the dried catalyst precursor is molded as required, or supported on an inert carrier, and then dried. The catalyst is obtained by calcination in the range of 200 to 500 ° C, preferably 300 to 450 ° C under flowing air or flowing nitrogen.
【００２６】このようにして得られた触媒は、成形体ま
たは担持体として固定床で使用することが好ましいが、
粒状として流動床で使用してもよい。The catalyst thus obtained is preferably used in a fixed bed as a compact or a carrier.
It may be used in a fluidized bed as granules.
【００２７】本発明においてメタクリル酸を製造するに
は、メタクロレイン、イソブタン、イソ酪酸またはイソ
ブチルアルデヒド等を原料として使用できるが、以下に
メタクロレインの場合を例にとって反応条件を説明す
る。メタクロレインと分子状酸素を含む原料ガスを、上
記のようにして得られた触媒に接触させ、メタクロレイ
ンを分子状酸素により気相接触酸化して行う。このとき
のメタクロレイン原料としては必ずしも純粋なメタクロ
レインである必要はなく、イソブチレンまたは三級ブタ
ノールを気相接触酸化して得られたメタクロレイン含有
ガスでも良い。原料ガス中のメタクロレインの濃度は１
〜２０容量％、特に３〜１０容量％が好ましい。メタク
ロレイン対酸素のモル比は１：０．３〜１：４が好まし
く、特に１：０．４〜１：２．５が好ましい。In producing methacrylic acid in the present invention, methacrolein, isobutane, isobutyric acid, isobutyraldehyde and the like can be used as raw materials. The reaction conditions will be described below by taking methacrolein as an example. A raw material gas containing methacrolein and molecular oxygen is brought into contact with the catalyst obtained as described above, and methacrolein is subjected to gas-phase catalytic oxidation with molecular oxygen. The methacrolein raw material at this time does not necessarily need to be pure methacrolein, but may be a methacrolein-containing gas obtained by gas-phase catalytic oxidation of isobutylene or tertiary butanol. The concentration of methacrolein in the source gas is 1
-20% by volume, especially 3-10% by volume is preferred. The molar ratio of methacrolein to oxygen is preferably from 1: 0.3 to 1: 4, particularly preferably from 1: 0.4 to 1: 2.5.
【００２８】酸化に用いられる分子状酸素は純酸素ガス
でも良いが、工業的には空気が経済的で有利である。原
料ガスは窒素、水蒸気、二酸化炭素等で希釈して用いる
ことが好ましい。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２３０〜４５０℃の範囲が好まし
い。The molecular oxygen used for the oxidation may be pure oxygen gas, but industrially, air is economical and advantageous. The source gas is preferably diluted with nitrogen, steam, carbon dioxide or the like before use. The reaction pressure is from normal pressure to several atmospheres. The reaction temperature is preferably in the range of 230 to 450 ° C.
【００２９】[0029]
【実施例】以下に実施例を示して本発明をさらに詳細に
説明する。分析はガスクロマトグラフィーにより行っ
た。また、触媒の組成は触媒成分の原料仕込み量から求
めた。なお、実施例および比較例中のメタクロレインの
反応率、生成される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 described in more detail with reference to the following examples. The analysis was performed by gas chromatography. Further, the composition of the catalyst was determined from the amount of raw materials used for the catalyst components. The conversion of methacrolein and the selectivity of methacrylic acid to be produced in the examples and comparative examples are defined as follows.
【００３０】 メタクロレインの反応率（％）＝（Ｂ／Ａ）×１００ メタクリル酸の選択率（％）＝（Ｃ／Ｂ）×１００ ここで、Ａは供給したメタクロレインのモル数、Ｂは反
応したメタクロレインのモル数、Ｃは生成したメタクリ
ル酸のモル数である。Reaction rate of methacrolein (%) = (B / A) × 100 Selectivity of methacrylic acid (%) = (C / B) × 100 where A is the number of moles of supplied methacrolein, and B is The number of moles of reacted methacrolein, and C is the number of moles of methacrylic acid generated.
【００３１】［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撹拌翼および
幅２０ｍｍ、長さ３００ｍｍの邪魔板を４枚有する内径
３４０ｍｍ、高さ４００ｍｍの丸底ステンレス製容器中
で、水７５００ｇにパラモリブデン酸アンモニウム５０
００ｇを溶解しＡ−１液を用意した。Example 1 A flat paddle type rotary stirring blade provided with four blades having a width of 20 mm and a length of 90 mm, and a round plate having an inner diameter of 340 mm and a height of 400 mm having four baffles 20 mm wide and 300 mm long. In a bottom stainless steel container, add ammonium paramolybdate 50 to 7500 g of water.
00g was dissolved to prepare solution A-1.
【００３２】これとは別に水２０００ｇに８５重量％リ
ン酸５４４．２ｇ、硝酸銅１１４．０ｇ、硝酸第二鉄１
９０．７ｇおよび硝酸セシウム４６０．０ｇを順次加え
溶解し、Ｂ−１液を用意した。Separately, 544.2 g of 85% by weight phosphoric acid, 114.0 g of copper nitrate and 1 part of ferric nitrate were added to 2000 g of water.
90.7 g and 460.0 g of cesium nitrate were sequentially added and dissolved to prepare a B-1 solution.
【００３３】上記のステンレス製容器中のＡ−１液を１
８０ｒｐｍで撹拌しながら、６５℃に加温したＡ−１液
にＢ−１液を注いで１分で混合し、スラリー分散液を得
た。続いて、このスラリー分散液にメタバナジン酸アン
モニウム１３８．０ｇを投入して混合した。The solution A-1 in the above stainless steel container was
While stirring at 80 rpm, the B-1 solution was poured into the A-1 solution heated to 65 ° C and mixed for 1 minute to obtain a slurry dispersion. Subsequently, 138.0 g of ammonium metavanadate was added to the slurry dispersion and mixed.
【００３４】混合完了後、撹拌回転数を１５０ｒｐｍに
減速した後、得られたスラリー分散液を９０℃に加熱
し、１５０ｒｐｍで撹拌した状態で１００分間熟成処理
した。続いて、ドラムドライヤーを用いて乾燥した。After the mixing was completed, the stirring rotation speed was reduced to 150 rpm, and the obtained slurry dispersion was heated to 90 ° C. and aged for 100 minutes with stirring at 150 rpm. Subsequently, it was dried using a drum dryer.
【００３５】得られた乾燥触媒前駆体を直径および高さ
が共に３ｍｍの円柱状に成形し、３８０℃で４時間焼成
して触媒を得た。得られた触媒の酸素以外の組成（以下
同じ。）は次式で示される。The obtained dried catalyst precursor was formed into a column having a diameter and a height of 3 mm, and calcined at 380 ° C. for 4 hours to obtain a catalyst. The composition of the obtained catalyst other than oxygen (hereinafter the same) is represented by the following formula.
【００３６】Ｍｏ12Ｐ2Ｖ0.5Ｃｕ0.2Ｃｓ1Ｆｅ0.2 こうして得られた触媒をステンレス製反応管に充填し、
メタクロレイン５％、酸素１０％、水蒸気３０％および
窒素５５％（容量％）の原料混合ガスを反応温度２９０
℃、接触時間３．６秒で通じた。その結果、メタクロレ
インの反応率８６．７％、メタクリル酸の選択率８４．
８％であった。Mo 12 P 2 V 0.5 Cu 0.2 Cs 1 Fe 0.2 The thus obtained catalyst was filled in a stainless steel reaction tube,
A raw material mixed gas of methacrolein 5%, oxygen 10%, steam 30% and nitrogen 55% (volume%) was reacted at a reaction temperature of 290.
C. and a contact time of 3.6 seconds. As a result, the conversion of methacrolein was 86.7% and the selectivity of methacrylic acid was 84.
8%.
【００３７】［実施例２］実施例１において、熟成時の
撹拌回転数を１００ｒｐｍに変更した以外は実施例１を
繰り返して触媒を調製した。この触媒を用いて実施例１
と同じ反応条件で反応を行い、表１に示す結果を得た。Example 2 A catalyst was prepared by repeating Example 1 except that the stirring rotation speed during aging was changed to 100 rpm. Example 1 using this catalyst
The reaction was carried out under the same reaction conditions as described above, and the results shown in Table 1 were obtained.
【００３８】［比較例１］実施例１において、熟成時の
撹拌回転数を混合時の回転数と同じ１８０ｒｐｍとした
以外は実施例１を繰り返して触媒を調製した。この触媒
を用いて実施例１と同じ反応条件で反応を行い、表１に
示す結果を得た。Comparative Example 1 A catalyst was prepared by repeating Example 1 except that the stirring rotation speed during aging was changed to 180 rpm, which was the same as the mixing rotation speed. Using this catalyst, the reaction was carried out under the same reaction conditions as in Example 1, and the results shown in Table 1 were obtained.
【００３９】［実施例３］幅２０ｍｍ、長さ３００ｍｍ
の邪魔板を４枚有する内径３４０ｍｍ、高さ４００ｍｍ
の丸底ステンレス製容器に、ホモジナイザー（外筒（外
刃）の外径５０ｍｍ、内径４６ｍｍ、特殊機化工業社製
Ｔ．Ｋ．ホモミクサーＭＡＲＫ ＩＩ １０型）を取り
付けた容器を用いて、この容器中で、水７５００ｇにパ
ラモリブデン酸アンモニウム５０００ｇを溶解しＡ−３
液を用意した。Example 3 20 mm wide and 300 mm long
340mm inside diameter, height 400mm with four baffles
Using a homogenizer (outer diameter 50 mm, inner diameter 46 mm, TK homomixer MARK II type 10 manufactured by Tokushu Kika Kogyo Co., Ltd.) In water, 5000 g of ammonium paramolybdate was dissolved in 7500 g of water, and A-3
A liquid was prepared.
【００４０】これとは別に水２０００ｇに８５重量％リ
ン酸４０８．１ｇ、６０重量％ヒ酸１１１．６ｇ、硝酸
銅１７１．０ｇ、硝酸亜鉛１４０．４ｇおよび硝酸ルビ
ジウム４１７．６ｇを順次加え溶解し、Ｂ−３液を用意
した。Separately, 408.1 g of 85% by weight phosphoric acid, 111.6 g of 60% by weight arsenic acid, 171.0 g of copper nitrate, 140.4 g of zinc nitrate and 417.6 g of rubidium nitrate were sequentially added to 2000 g of water and dissolved. , B-3 solution were prepared.
【００４１】上記ステンレス容器中のＡ−３液を７００
０ｒｐｍで撹拌しながら、７０℃に加温したＡ−３液に
Ｂ−３液を注いで３０秒で混合し、スラリー分散液を得
た。続いて、このスラリー分散液にメタバナジン酸アン
モニウム１６５．６ｇを投入して混合した。The solution A-3 in the stainless steel container was
While stirring at 0 rpm, the B-3 solution was poured into the A-3 solution heated to 70 ° C and mixed for 30 seconds to obtain a slurry dispersion. Subsequently, 165.6 g of ammonium metavanadate was added to the slurry dispersion and mixed.
【００４２】混合完了後、ホモジナイザーをはずし、代
わりに幅２０ｍｍ、長さ９０ｍｍの羽根を４枚備えたフ
ラットパドル型回転式撹拌機を取り付け、撹拌回転数を
８０ｒｐｍに設定し、スラリー分散液の温度を１００℃
に加熱し、８０ｒｐｍで撹拌した状態で６０分間熟成処
理した。続いて、ドラムドライヤーを用いて乾燥した。
得られた乾燥触媒前駆体を実施例１と同様に成形、焼成
して次式で示される組成の触媒を得た。After the mixing was completed, the homogenizer was removed, and instead, a flat paddle type rotary stirrer equipped with four blades having a width of 20 mm and a length of 90 mm was attached, the stirring rotation speed was set to 80 rpm, and the temperature of the slurry dispersion was changed. At 100 ° C
And aged for 60 minutes with stirring at 80 rpm. Subsequently, it was dried using a drum dryer.
The obtained dried catalyst precursor was molded and fired in the same manner as in Example 1 to obtain a catalyst having a composition represented by the following formula.
【００４３】 Ｍｏ12Ｐ1.5Ｖ0.6Ｃｕ0.3Ａｓ0.2Ｒｂ1.2Ｚｎ0.2 こうして得られた触媒を用いて、実施例１と同様にして
反応を行い、表１の結果を得た。Mo 12 P 1.5 V 0.6 Cu 0.3 As 0.2 Rb 1.2 Zn 0.2 Using the catalyst thus obtained, a reaction was carried out in the same manner as in Example 1, and the results shown in Table 1 were obtained.
【００４４】［実施例４］実施例３において、熟成処理
時間を４０分に変更した以外は実施例３を繰り返して触
媒を調製した。この触媒を用いて実施例１と同じ反応条
件で反応を行い、表１に示す結果を得た。Example 4 A catalyst was prepared by repeating Example 3 except that the aging time was changed to 40 minutes. Using this catalyst, the reaction was carried out under the same reaction conditions as in Example 1, and the results shown in Table 1 were obtained.
【００４５】［比較例２］実施例３において、熟成処理
時間を１０分に変更した以外は実施例３を繰り返して触
媒を調製した。この触媒を用いて実施例１と同じ反応条
件で反応を行い、表１に示す結果を得た。Comparative Example 2 A catalyst was prepared by repeating Example 3 except that the aging time was changed to 10 minutes. Using this catalyst, the reaction was carried out under the same reaction conditions as in Example 1, and the results shown in Table 1 were obtained.
【００４６】［実施例５］実施例１と同じ容器から邪魔
板を取り外し、回転式撹拌翼の代わりに実施例３で用い
たホモジナイザーを取り付けた容器を用いて、この容器
内で水７５００ｇにパラモリブデン酸アンモニウム５０
００ｇおよびパラタングステン酸アンモニウム６１．６
ｇを溶解し、さらに二酸化ゲルマニウム９８．７ｇを分
散させ回転数８０００ｒｐｍで撹拌しＡ−５液を用意し
た。Example 5 The baffle was removed from the same container as in Example 1, and the container equipped with the homogenizer used in Example 3 was used instead of the rotary stirring blade. Ammonium molybdate 50
00g and ammonium paratungstate 61.6
g) was dissolved, and 98.7 g of germanium dioxide was further dispersed and stirred at a rotation speed of 8000 rpm to prepare a liquid A-5.
【００４７】これとは別に水２０００ｇに８５重量％リ
ン酸２７２．１ｇ、硝酸銅１１４．０ｇ、硝酸ニッケル
２０５．８ｇ、硝酸セシウム２３０．０ｇおよび硝酸カ
リウム１１９．３ｇを順次加え溶解しＢ−５液を用意し
た。Separately, 272.1 g of 85% by weight phosphoric acid, 114.0 g of copper nitrate, 205.8 g of nickel nitrate, 230.0 g of cesium nitrate and 119.3 g of potassium nitrate were successively added to 2000 g of water and dissolved, and dissolved. Was prepared.
【００４８】上記ステンレス容器中のＡ−５液を８００
０ｒｐｍで撹拌しながら、６０℃に加温したＡ−５液に
Ｂ−５液を注いで２分で混合し、スラリー分散液を得
た。続いて、このスラリー分散液にメタバナジン酸アン
モニウム１６５．６ｇを投入して混合した。The solution A-5 in the stainless steel container was
While stirring at 0 rpm, Solution B-5 was poured into Solution A-5 heated to 60 ° C and mixed for 2 minutes to obtain a slurry dispersion. Subsequently, 165.6 g of ammonium metavanadate was added to the slurry dispersion and mixed.
【００４９】混合完了後、ホモジナイザー回転数を５０
００ｒｐｍに減速した後、得られたスラリー分散液を８
５℃に加熱し、５０００ｒｐｍで撹拌した状態で１２０
分間熟成処理した。続いて、噴霧乾燥した。得られた乾
燥触媒前駆体を実施例１と同様に成形、焼成して次式で
示される組成の触媒を得た。After completion of the mixing, the homogenizer was rotated at 50 rpm.
After decelerating to 00 rpm, the resulting slurry dispersion was
Heat to 5 ° C. and stir at 5000 rpm for 120
It was aged for minutes. Subsequently, it was spray-dried. The obtained dried catalyst precursor was molded and fired in the same manner as in Example 1 to obtain a catalyst having a composition represented by the following formula.
【００５０】Ｍｏ12Ｐ1Ｖ0.6Ｃｕ0.2Ｇｅ0.4Ｃｓ0.5Ｋ
0.5Ｎｉ0.3Ｗ0.1 こうして得られた触媒を用いて、実施例１と同様にして
反応を行い、表１の結果を得た。Mo 12 P 1 V 0.6 Cu 0.2 Ge 0.4 Cs 0.5 K
0.5 Ni 0.3 W 0.1 Using the catalyst thus obtained, a reaction was carried out in the same manner as in Example 1, and the results shown in Table 1 were obtained.
【００５１】［比較例３］実施例５において、混合時の
ホモジナイザー回転数を５０００ｒｐｍに変更し、か
つ、熟成時の回転数を８０００ｒｐｍに変更した以外は
実施例５を繰り返して触媒を調製した。この触媒を用い
て実施例１と同じ反応条件で反応を行い、表１に示す結
果を得た。Comparative Example 3 A catalyst was prepared by repeating Example 5 except that the rotation speed of the homogenizer during mixing was changed to 5000 rpm, and the rotation speed during aging was changed to 8000 rpm. Using this catalyst, the reaction was carried out under the same reaction conditions as in Example 1, and the results shown in Table 1 were obtained.
【００５２】[0052]
【表１】 注：実施例３、実施例４および比較例２の混合時の撹
拌、並びに実施例５および比較例３の混合時および熟成
時の撹拌はホモジナイザーを使用した。[Table 1] Note: A homogenizer was used for stirring when mixing Example 3, Example 4, and Comparative Example 2 and for mixing and aging of Example 5 and Comparative Example 3.
【００５３】[0053]
【発明の効果】本発明の製造方法によって製造された触
媒を、メタクロレイン、イソブタン、イソ酪酸またはイ
ソブチルアルデヒド等の分子状酸素による気相接触酸化
に用いると、高収率、高選択率でメタクリル酸を製造す
ることができる。When the catalyst produced by the production method of the present invention is used for gas phase catalytic oxidation with molecular oxygen such as methacrolein, isobutane, isobutyric acid or isobutyraldehyde, methacrylic acid can be obtained with high yield and high selectivity. Acids can be produced.
Claims (4)
酸合成用触媒の製造方法において、 触媒成分の中の少なくともモリブデン成分を含む溶液ま
たは分散液（Ａ液）と、少なくともリン成分を含む溶液
または分散液（Ｂ液）とを撹拌装置を用いて撹拌しなが
ら混合し、Ａ液とＢ液の混合後のスラリー分散液を、混
合時の装置と同じ装置を用いて混合時の０．８５倍以下
の回転数または振動数で撹拌しながら３０分以上熟成す
ることを含むメタクリル酸合成用触媒の製造方法。 ＭｏaＰbＶcＣｕdＸeＹfＺgＯh （Ｉ） （式中、Ｍｏ、Ｐ、Ｖ、ＣｕおよびＯはそれぞれモリブ
デン、リン、バナジウム、銅および酸素を表し、Ｘはヒ
素、ホウ素、ゲルマニウム、アンチモン、テルル、ビス
マス、セレンおよびケイ素からなる群より選ばれた少な
くとも１種の元素を表し、Ｙはカリウム、ナトリウム、
ルビジウム、セシウムおよびタリウムからなる群より選
ばれた少なくとも１種の元素を表し、Ｚはマグネシウ
ム、イオウ、カルシウム、チタン、クロム、マンガン、
鉄、ニッケル、コバルト、亜鉛、ニオブ、銀、スズ、バ
リウム、タンタル、タングステン、鉛、ランタンおよび
セリウムからなる群より選ばれた少なくとも１種の元素
を表し、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇおよびｈは各元素
の原子比を表し、ａ＝１２のとき、０．１≦ｂ≦３、
０．０１≦ｃ≦３、０．０１≦ｄ≦２、０≦ｅ≦３、
０．０１≦ｆ≦３、０≦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の原子比である。）1. A method for producing a methacrylic acid synthesis catalyst represented by the following general formula (I), comprising: a solution or dispersion (solution A) containing at least a molybdenum component in a catalyst component; and at least a phosphorus component. The solution or the dispersion (solution B) is mixed with stirring using a stirrer, and the slurry dispersion obtained after mixing the solution A and the solution B is mixed with the slurry dispersion at the time of mixing using the same apparatus as used for mixing. A method for producing a catalyst for methacrylic acid synthesis, comprising aging for at least 30 minutes while stirring at a rotation frequency or frequency of 85 times or less. Mo a P b V c Cu d X e Y f Z g O h (I) ( wherein, represents Mo, P, V, Cu and O represent molybdenum, phosphorus, vanadium, copper and oxygen, X is arsenic, Represents at least one element selected from the group consisting of boron, germanium, antimony, tellurium, bismuth, selenium and silicon, wherein Y is potassium, sodium,
Represents at least one element selected from the group consisting of rubidium, cesium and thallium, and Z is magnesium, sulfur, calcium, titanium, chromium, manganese,
Represents at least one element selected from the group consisting of iron, nickel, cobalt, zinc, niobium, silver, tin, barium, tantalum, tungsten, lead, lanthanum and cerium, a, b, c, d, e, f, g and h represent the atomic ratio of each element, and when a = 12, 0.1 ≦ b ≦ 3;
0.01 ≦ c ≦ 3, 0.01 ≦ d ≦ 2, 0 ≦ e ≦ 3,
0.01 ≦ f ≦ 3 and 0 ≦ g ≦ 3, and h is an atomic ratio of oxygen necessary to satisfy the atomic ratio of each component. )
酸合成用触媒の製造方法において、 触媒成分の中の少なくともモリブデン成分を含む溶液ま
たは分散液（Ａ液）と、少なくともリン成分を含む溶液
または分散液（Ｂ液）とをホモジナイザーを用いて撹拌
しながら混合し、Ａ液とＢ液の混合後のスラリー分散液
を、回転翼撹拌機を用いて撹拌しながら３０分以上熟成
することを含むメタクリル酸合成用触媒の製造方法。2. The method for producing a methacrylic acid synthesis catalyst represented by the general formula (I), wherein a solution or a dispersion containing at least a molybdenum component (Solution A) among the catalyst components and at least a phosphorus component are included. Mixing the solution or dispersion liquid (liquid B) with stirring using a homogenizer, and aging the slurry dispersion liquid after mixing liquid A and liquid B with stirring using a rotary blade stirrer for 30 minutes or more. A method for producing a catalyst for methacrylic acid synthesis, comprising:
って製造されたメタクリル酸合成用触媒。3. A catalyst for synthesizing methacrylic acid produced by the production method according to claim 1 or 2.
ン、イソブタン、イソ酪酸またはイソブチルアルデヒド
を分子状酸素で気相接触酸化することを特徴とするメタ
クリル酸の製造方法。4. A method for producing methacrylic acid, comprising subjecting methacrolein, isobutane, isobutyric acid or isobutyraldehyde to gas-phase catalytic oxidation with molecular oxygen using the catalyst of claim 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19571897A JPH1133403A (en) | 1997-07-22 | 1997-07-22 | Production of catalyst for synthesis of methacrylic acid and production of methacrylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19571897A JPH1133403A (en) | 1997-07-22 | 1997-07-22 | Production of catalyst for synthesis of methacrylic acid and production of methacrylic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1133403A true JPH1133403A (en) | 1999-02-09 |
Family
ID=16345819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19571897A Pending JPH1133403A (en) | 1997-07-22 | 1997-07-22 | Production of catalyst for synthesis of methacrylic acid and production of methacrylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1133403A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11114418A (en) * | 1997-09-30 | 1999-04-27 | Sumitomo Chem Co Ltd | Catalyst for gas-phase catalytic oxidation reaction of isobutane and manufacturing of alkene and/or oxygen-containing compound using this catalyst |
| WO2006001360A1 (en) * | 2004-06-28 | 2006-01-05 | Mitsubishi Rayon Co., Ltd. | Process for producing catalyst for methacrylic acid synthesis |
| JP2007044668A (en) * | 2005-08-12 | 2007-02-22 | Nippon Kayaku Co Ltd | Method for producing composite metal oxide catalyst and application of the catalyst |
| JP2007222855A (en) * | 2006-02-27 | 2007-09-06 | Mitsubishi Rayon Co Ltd | Manufacturing method of unsaturated aldehyde and catalysts for unsaturated carboxylic acid composition |
| JP2008150231A (en) * | 2006-12-15 | 2008-07-03 | Toyota Central R&D Labs Inc | Composite oxide powder and method for producing the same |
| JP2011173114A (en) * | 2010-01-28 | 2011-09-08 | Mitsubishi Rayon Co Ltd | Catalyst for manufacturing methacrylic acid, manufacturing method of the same, and manufacturing method of methacrylic acid |
-
1997
- 1997-07-22 JP JP19571897A patent/JPH1133403A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11114418A (en) * | 1997-09-30 | 1999-04-27 | Sumitomo Chem Co Ltd | Catalyst for gas-phase catalytic oxidation reaction of isobutane and manufacturing of alkene and/or oxygen-containing compound using this catalyst |
| WO2006001360A1 (en) * | 2004-06-28 | 2006-01-05 | Mitsubishi Rayon Co., Ltd. | Process for producing catalyst for methacrylic acid synthesis |
| JPWO2006001360A1 (en) * | 2004-06-28 | 2008-04-17 | 三菱レイヨン株式会社 | Method for producing catalyst for synthesis of methacrylic acid |
| US7557061B2 (en) | 2004-06-28 | 2009-07-07 | Mitsubishi Rayon Co., Ltd. | Process for producing catalyst for methacrylic acid synthesis |
| JP2007044668A (en) * | 2005-08-12 | 2007-02-22 | Nippon Kayaku Co Ltd | Method for producing composite metal oxide catalyst and application of the catalyst |
| JP2007222855A (en) * | 2006-02-27 | 2007-09-06 | Mitsubishi Rayon Co Ltd | Manufacturing method of unsaturated aldehyde and catalysts for unsaturated carboxylic acid composition |
| JP2008150231A (en) * | 2006-12-15 | 2008-07-03 | Toyota Central R&D Labs Inc | Composite oxide powder and method for producing the same |
| JP2011173114A (en) * | 2010-01-28 | 2011-09-08 | Mitsubishi Rayon Co Ltd | Catalyst for manufacturing methacrylic acid, manufacturing method of the same, and manufacturing method of methacrylic acid |
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