JPH05253480A - Production of catalyst for synthesis of unsaturated aldehyde and unsaturated carboxylic acid - Google Patents
Production of catalyst for synthesis of unsaturated aldehyde and unsaturated carboxylic acidInfo
- Publication number
- JPH05253480A JPH05253480A JP4088167A JP8816792A JPH05253480A JP H05253480 A JPH05253480 A JP H05253480A JP 4088167 A JP4088167 A JP 4088167A JP 8816792 A JP8816792 A JP 8816792A JP H05253480 A JPH05253480 A JP H05253480A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- dried product
- parts
- unsaturated
- carboxylic acid
- 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、不飽和アルデヒド及び
不飽和カルボン酸合成用触媒、すなわちプロピレン、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、アクロレイン及びアクリル酸又はメタク
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
の製造法に関する。TECHNICAL FIELD The present invention relates to a catalyst for the synthesis of unsaturated aldehydes and unsaturated carboxylic acids, that is, propylene, isobutylene or tertiary butanol by gas phase catalytic oxidation with molecular oxygen to obtain acrolein and acrylic acid or methacrolein. And a method for producing a catalyst used in synthesizing methacrylic acid.
【０００２】[0002]
【従来の技術】従来、不飽和アルデヒド及び不飽和カル
ボン酸合成用触媒の製造のために多数の方法が提案され
ている。イソブチレン又は三級ブタノールを原料とした
場合を例にとると、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５７−１３０９４９号公報、特開昭５９−３１７２
７号公報、特開昭６０−２８８２４号公報、特開昭６３
−６６１４１号公報等数多くの提案がなされている。し
かし、一般に触媒活性及び目的生成物の選択性等の触媒
性能の点で工業的見地から更に改良が望まれている。2. Description of the Related Art Conventionally, a number of methods have been proposed for producing catalysts for synthesizing unsaturated aldehydes and unsaturated carboxylic acids. Taking as an example the case where isobutylene or tertiary butanol is used as a raw material, a catalyst used in the production of methacrolein and methacrylic acid by catalytically oxidizing isobutylene or tertiary butanol under a high temperature gas phase is disclosed in 57-130949, JP-A-59-3172.
7, JP-A-60-28824, JP-A-63
Many proposals have been made such as the publication of -66141. However, in general, further improvement is desired from the industrial viewpoint in terms of catalytic performance such as catalytic activity and selectivity of target product.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、プロピレ
ン、イソブチレン又は三級ブタノールからアクロレイン
及びアクリル酸、又はメタクロレイン及びメタクリル酸
を有利に合成するための活性及び目的生成物の選択性の
優れた触媒の新規な製造法の提供を目的としている。The present invention provides excellent activity and selectivity of the desired product for the advantageous synthesis of acrolein and acrylic acid, or methacrolein and methacrylic acid from propylene, isobutylene or tertiary butanol. It is intended to provide a new method for producing a catalyst.
【０００４】[0004]
【課題を解決するための手段】本発明は、少なくともモ
リブデン化合物及びビスマス化合物を成分として含有す
る混合溶液又は水性スラリーを乾燥し、得られた乾燥物
を焼成することによりモリブデン及びビスマスを含む多
成分系の不飽和アルデヒド及び不飽和カルボン酸合成用
触媒を製造する方法において、焼成段階で乾燥物の３０
重量％以上の部分の層高が２０ｍｍ以上になるように保
ち、２００〜６００℃の範囲の温度で熱処理することを
特徴とする不飽和アルデヒド及び不飽和カルボン酸合成
用触媒の製造法にある。The present invention provides a multi-component containing molybdenum and bismuth by drying a mixed solution or an aqueous slurry containing at least a molybdenum compound and a bismuth compound as components and calcining the dried product. A method for producing a catalyst for synthesizing unsaturated aldehydes and unsaturated carboxylic acids, comprising:
A method for producing a catalyst for synthesizing unsaturated aldehydes and unsaturated carboxylic acids, characterized in that heat treatment is carried out at a temperature in the range of 200 to 600 ° C. while maintaining a layer height of 20% or more by weight in a portion of at least wt%.
【０００５】本発明において、触媒成分である元素の原
料としては特に限定されるものではないが、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、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。触媒成分を含む混合溶液又は水性ス
ラリーを乾燥する際、その方法及び得られる乾燥物の状
態については特に限定はなく、例えば、通常のスプレー
ドライヤー、スラリードライヤー、ドラムドライヤー等
を用いて、粉体状の乾燥物を得ても良いし、また、通常
の箱型乾燥機、トンネル型乾燥機等を用いて、ブロック
状又はフレーク状の乾燥物を得ても良い。In the present invention, the raw material of the element which is the catalyst component is not particularly limited, but it is usually an oxide or a chloride, a sulfate, a nitrate or a carbonate which can be converted into an oxide by being heated. , Ammonium salts or mixtures thereof are used. When drying the mixed solution or the aqueous slurry containing the catalyst component, there is no particular limitation on the method and the state of the dried product obtained, and for example, using an ordinary spray dryer, slurry dryer, drum dryer, etc. The dried product may be obtained, or a block-shaped or flake-shaped dried product may be obtained using an ordinary box-type dryer, tunnel-type dryer or the like.
【０００６】乾燥物を焼成する際の焼成炉の形式及びそ
の方法については特に限定はなく、例えば、通常の箱型
焼成炉、トンネル型焼成炉等を用いて、乾燥物を固定し
た状態で焼成しても良いし、また、ロータリーキルン焼
成炉等を用いて、乾燥物を流動させながら焼成しても良
い。There is no particular limitation on the type of firing furnace and the method for firing the dried product. For example, a conventional box-type firing furnace, tunnel-type firing furnace or the like is used to fire the dried product in a fixed state. Alternatively, the dried product may be fired while flowing it using a rotary kiln firing furnace or the like.
【０００７】本発明は、焼成段階において、乾燥物の３
０重量％以上の部分の層高が２０ｍｍ以上になるように
保ち、２００〜６００℃の範囲の温度で熱処理すること
により、目的生成物収率の高い触媒を再現性良く得るこ
とができる。According to the present invention, the dried product is
By maintaining the layer height of 0% by weight or more at 20 mm or more and performing heat treatment at a temperature in the range of 200 to 600 ° C., a catalyst with a high yield of the desired product can be obtained with good reproducibility.
【０００８】この際、すべての乾燥物を２０ｍｍ以上の
層高に保つ必要はないが、少なくとも乾燥物の３０重量
％以上の部分を２０ｍｍ以上の層高に保つのが好まし
い。乾燥物の層高を所定層高以上に保つ方法としては特
に限定はないが、例えば、箱型焼成炉等を用いて、乾燥
物を固定した状態で焼成する場合、該乾燥物を適当な容
器内に乾燥物の３０重量％以上の部分の層高が２０ｍｍ
以上となるように仕込み、該容器を焼成炉内に設置する
方法が考えられる。また、ロータリーキルン焼成炉等を
用いて、乾燥物を流動させながら焼成する場合は焼成炉
内への乾燥物の供給量及び焼成炉内での乾燥物の滞留時
間等を調節することにより、乾燥物の層高を所定層高以
上に保つ方法が考えられる。At this time, it is not necessary to keep all the dried products at a bed height of 20 mm or more, but it is preferable to keep at least 30% by weight or more of the dried products at a bed height of 20 mm or more. There is no particular limitation on the method for maintaining the layer height of the dried product at a predetermined layer height or more, but for example, when the dried product is baked in a fixed state using a box-type firing furnace or the like, the dried product is placed in a suitable container. The layer height of 30% by weight or more of the dried product is 20 mm
A method in which the container is charged as described above and the container is placed in a firing furnace is considered. Further, when the dried product is fired while being fluidized using a rotary kiln or the like, the amount of the dried product supplied to the firing furnace and the residence time of the dried product in the firing furnace are adjusted to adjust the dried product. A possible method is to keep the bed height above a predetermined bed height.
【０００９】本発明において、焼成段階における焼成温
度は２００〜６００℃の範囲が好ましい。この範囲外の
温度での焼成を行うと高性能な触媒が得られないことが
ある。また、所定の温度に到達してから熱処理を持続す
る時間については特に限定はないが、熱処理時間が短過
ぎると高性能な触媒が得られないことがあるため、１０
分以上持続するのが好ましい。In the present invention, the firing temperature in the firing step is preferably in the range of 200 to 600 ° C. If calcination is carried out at a temperature outside this range, a high performance catalyst may not be obtained. Further, the time for which the heat treatment is continued after reaching the predetermined temperature is not particularly limited. However, if the heat treatment time is too short, a high performance catalyst may not be obtained, so 10
It is preferable that it lasts more than a minute.
【００１０】本発明により得られた触媒を用いて、プロ
ピレン、イソブチレン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、アクロレイン及びアクリル酸
又は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、プロピレン、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。原料のプロ
ピレン、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良いが、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２００℃〜４５０℃の範囲が好ましく、
反応は流動床でも固定床でも実施できる。In producing acrolein and acrylic acid or methacrolein and methacrylic acid by gas phase catalytic oxidation of propylene, isobutylene or tertiary butanol with molecular oxygen using the catalyst obtained by the present invention, propylene is used. The molar ratio of isobutylene or tertiary butanol to oxygen is preferably 1: 0.5 to 3. The raw material propylene, isobutylene or tertiary butanol is preferably diluted with an inert gas before use. The molecular oxygen used for the oxidation may be pure oxygen gas, but industrially air is advantageous. The reaction pressure is from normal pressure to several atmospheres. The reaction temperature is preferably in the range of 200 ° C to 450 ° C,
The reaction can be carried out in a fluidized bed or a fixed bed.
【００１１】[0011]
【実施例】本発明の効果を以下実施例により示す。実施
例及び比較例中の「部」は「重量部」を意味する。分析
は、ガスクロマトグラフィーにより行った。反応用原料
としてのプロピレン、イソブチレン又は三級ブタノール
の反応率、生成される不飽和アルデヒド及び不飽和カル
ボン酸の選択率は下記のように定義される。EXAMPLES The effects of the present invention will be shown by the following examples. "Parts" in Examples and Comparative Examples mean "parts by weight". The analysis was performed by gas chromatography. The reaction rate of propylene, isobutylene or tertiary butanol as a raw material for reaction, and the selectivity of the unsaturated aldehyde and unsaturated carboxylic acid produced are defined as follows.
【００１２】[0012]
【数１】 [Equation 1]
【００１３】[0013]
【数２】 [Equation 2]
【００１４】[0014]
【数３】 [Equation 3]
【００１５】実施例１ 水１０００部にパラモリブデン酸アンモニウム５００
部、パラタングステン酸アンモニウム３０．８部、硝酸
セシウム３２．２部及び三酸化アンチモン５１．６部を
加え加熱撹拌した（Ａ液）。別に、水８５０部に６０％
硝酸水溶液２５０部を加え、均一にした後、硝酸ビスマ
ス９１．６部を加え溶解した。これに硝酸第二鉄２８
６．０部、硝酸ニッケル３４３．１部、硝酸コバルト６
８．７部、硝酸マグネシウム６０．５部、硝酸亜鉛７
０．２部及びホウ酸７．３部を順次加え溶解した（Ｂ
液）。Ａ液にＢ液を加えスラリー状とした後、加熱撹拌
し水の大部分を蒸発させた。Example 1 Ammonium paramolybdate 500 was added to 1000 parts of water.
Parts, ammonium paratungstate 30.8 parts, cesium nitrate 32.2 parts and antimony trioxide 51.6 parts were added and heated and stirred (solution A). Separately, 60% in 850 parts of water
After 250 parts of nitric acid aqueous solution was added and homogenized, 91.6 parts of bismuth nitrate was added and dissolved. Ferric nitrate 28
6.0 parts, nickel nitrate 343.1 parts, cobalt nitrate 6
8.7 parts, magnesium nitrate 60.5 parts, zinc nitrate 7
0.2 parts and 7.3 parts of boric acid were sequentially added and dissolved (B
liquid). Solution B was added to solution A to form a slurry, which was then heated and stirred to evaporate most of the water.
【００１６】得られたケーキ状物質を箱型乾燥機を用い
て乾燥させ、ブロック状の乾燥物を得た。このブロック
状乾燥物をステンレス製容器に、層高がおよそ５５ｍｍ
となるようにほぼ均一の層高で仕込み、箱型焼成炉内に
設置した。このように設置した乾燥物を室温から毎時５
０℃の速度で５００℃まで昇温し、続いて同温度で６時
間熱処理する方法で焼成した。The cake-like substance obtained was dried using a box dryer to obtain a block-like dried product. This block-shaped dried product is placed in a stainless steel container and the layer height is about 55 mm.
It was charged with a substantially uniform bed height so that The dried product placed in this way is heated from room temperature to 5
The temperature was raised to 500 ° C. at a rate of 0 ° C., and subsequently, heat treatment was performed at the same temperature for 6 hours to perform firing.
【００１７】こうして得られた触媒の組成は次式で示さ
れる。 Ｍｏ12Ｗ0.5 Ｂｉ0.8 Ｆｅ3 Ｎｉ5 Ｃｏ1 Ｍｇ1 Ｚｎ1
Ｂ0.5 Ｓｂ1.5 Ｃｓ0.7 Ｏx （式中、Ｍｏ、Ｗ、Ｂｉ、Ｆｅ、Ｎｉ、Ｃｏ、Ｍｇ、Ｚ
ｎ、Ｂ、Ｓｂ、Ｃｓ及びＯはそれぞれモリブデン、タン
グステン、ビスマス、鉄、ニッケル、コバルト、マグネ
シウム、亜鉛、ホウ素、アンチモン、セシウム及び酸素
を表す。また、元素記号右下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 represented by the following equation. Mo 12 W 0.5 Bi 0.8 Fe 3 Ni 5 Co 1 Mg 1 Zn 1
B 0.5 Sb 1.5 Cs 0.7 O x (in the formula, Mo, W, Bi, Fe, Ni, Co, Mg, Z
n, B, Sb, Cs and O represent molybdenum, tungsten, bismuth, iron, nickel, cobalt, magnesium, zinc, boron, antimony, cesium and oxygen, respectively. Further, the numbers in the lower right 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. )
【００１８】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１０％及び
窒素７３％の原料混合ガスを接触時間３．６秒で触媒層
を通過させ、３６５℃で反応させた。その結果、イソブ
チレンの反応率９６．５％、メタクロレインの選択率８
８．１％、メタクリル酸の選択率３．５％であった。The obtained catalyst was filled in a stainless steel reaction tube, and a raw material mixed gas of isobutylene 5%, oxygen 12%, steam 10% and nitrogen 73% was passed through the catalyst layer at a contact time of 3.6 seconds to give 365. The reaction was carried out at ° C. As a result, the reaction rate of isobutylene was 96.5% and the selectivity of methacrolein was 8
The selectivity was 8.1% and the selectivity of methacrylic acid was 3.5%.
【００１９】実施例２ 実施例１の触媒を用い、反応原料を三級ブタノールに変
更し、その他は実施例１と同様にして反応を行った。そ
の結果、三級ブタノールの反応率１００％、メタクロレ
インの選択率８６．１％、メタクリル酸の選択率２．８
％であった。Example 2 Using the catalyst of Example 1, the reaction raw material was changed to tertiary butanol and the reaction was carried out in the same manner as in Example 1. As a result, the conversion of tertiary butanol 100%, the selectivity of methacrolein 86.1%, the selectivity of methacrylic acid 2.8.
%Met.
【００２０】実施例３ 実施例１と同組成の触媒を焼成段階以外は実施例１と同
様にして調製した。すなわち、焼成するブロック状乾燥
物をステンレス製容器に仕込むに際し、層高がおよそで
２５ｍｍとなるようにほぼ均一の層高で仕込んだ。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
行った結果、イソブチレンの反応率９６．５％、メタク
ロレインの選択率８８．１％、メタクリル酸の選択率
３．５％であり、実施例１で得た触媒と同等の触媒が得
られた。Example 3 A catalyst having the same composition as in Example 1 was prepared in the same manner as in Example 1 except for the calcination step. That is, when the block-shaped dried product to be fired was charged into a stainless steel container, it was charged with a substantially uniform layer height such that the layer height was about 25 mm. Using the catalyst thus obtained, the reaction was carried out in the same manner as in Example 1. As a result, the conversion of isobutylene was 96.5%, the selectivity of methacrolein was 88.1%, and the selectivity of methacrylic acid was 3.5%. Therefore, a catalyst equivalent to the catalyst obtained in Example 1 was obtained.
【００２１】比較例１ 実施例１と同組成の触媒を焼成段階以外は実施例１と同
様にして調製した。すなわち、焼成するブロック状乾燥
物をステンレス製容器に仕込むに際し、層高がおよそ１
２ｍｍとなるようにほぼ均一の層高で仕込んだ。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
った結果、イソブチレンの反応率９４．８％、メタクロ
レインの選択率８７．８％、メタクリル酸の選択率３．
４％であり、実施例１の場合に比べ低い性能の触媒とな
った。Comparative Example 1 A catalyst having the same composition as in Example 1 was prepared in the same manner as in Example 1 except for the calcination step. That is, when the block-shaped dried product to be baked is charged into a stainless steel container, the layer height is about 1
It was charged with a substantially uniform layer height so as to be 2 mm. Using the catalyst thus obtained, a reaction was carried out in the same manner as in Example 1. As a result, the conversion of isobutylene was 94.8%, the selectivity of methacrolein was 87.8%, and the selectivity of methacrylic acid was 3.
It was 4%, which was a catalyst with lower performance than the case of Example 1.
【００２２】実施例４ 水１０００部にパラモリブデン酸アンモニウム５００
部、パラタングステン酸アンモニウム１８．５部及び硝
酸カリウム１．４部を加え加熱撹拌した（Ａ液）。別
に、水２５０部に６０％硝酸水溶液４１．９部を加え、
均一にした後、硝酸ビスマス１１４．５部を加え溶解し
た。これに硝酸第二鉄９５．３部、硝酸コバルト３０
９．０部、硝酸亜鉛７．０部及びテルル酸５．４部を順
次加え、さらに水７００部を加え溶解した（Ｂ液）。Ａ
液にＢ液を加えスラリー状とした後、スラリードライヤ
ーを用いて乾燥し、粉体状の乾燥物を得た。Example 4 500 parts of ammonium paramolybdate in 500 parts of water
Part, 18.5 parts of ammonium paratungstate and 1.4 parts of potassium nitrate were added, and the mixture was heated and stirred (Liquid A). Separately, add 41.9 parts of a 60% nitric acid aqueous solution to 250 parts of water,
After homogenizing, 114.5 parts of bismuth nitrate was added and dissolved. 95.3 parts of ferric nitrate and 30 parts of cobalt nitrate
9.0 parts, zinc nitrate 7.0 parts and telluric acid 5.4 parts were sequentially added, and further 700 parts of water was added and dissolved (solution B). A
Liquid B was added to the liquid to form a slurry, which was then dried using a slurry dryer to obtain a powdery dried product.
【００２３】得られた粉体状乾燥物を内径２００ｍｍ、
長さ８００ｍｍのロータリーキルン焼成炉に毎時１０ｋ
ｇの速度で供給し、乾燥物が焼成炉内に滞留する時間が
３０分となるように粉体流速を調節しながら５１５℃で
焼成を行った。なお焼成中における乾燥物の層高は最も
高い箇所で約５０ｍｍであり、６０重量％以上の部分が
常時２０ｍｍ以上の層高に保たれていた。The obtained powdery dried product was fed with an inner diameter of 200 mm,
10 km / h in 800 mm long rotary kiln firing furnace
The mixture was supplied at a rate of g and calcined at 515 ° C. while controlling the powder flow rate so that the dried product stayed in the calcining furnace for 30 minutes. The layer height of the dried product during firing was about 50 mm at the highest point, and the portion of 60% by weight or more was always kept at the layer height of 20 mm or more.
【００２４】こうして得られた触媒の組成は次式で示さ
れる。 Ｍｏ12Ｗ0.3 Ｂｉ1 Ｆｅ1 Ｚｎ0.1 Ｃｏ4.5 Ｋ0.06Ｔｅ
0.1 Ｏx （式中、Ｍｏ、Ｗ、Ｂｉ、Ｆｅ、Ｚｎ、Ｃｏ、Ｋ、Ｔｅ
及びＯはそれぞれモリブデン、タングステン、ビスマ
ス、鉄、亜鉛、コバルト、カリウム、テルル及び酸素を
表す。また、元素記号右下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 W 0.3 Bi 1 Fe 1 Zn 0.1 Co 4.5 K 0.06 Te
0.1 O x (in the formula, Mo, W, Bi, Fe, Zn, Co, K, Te
And O represent molybdenum, tungsten, bismuth, iron, zinc, cobalt, potassium, tellurium and oxygen, respectively. Further, the numbers in the lower right 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. )
【００２５】得られた触媒をステンレス製反応管に充填
し、プロピレン５％、酸素１２％、水蒸気１０％及び窒
素７３％の原料混合ガスを接触時間３．６秒で触媒層を
通過させ、３１０℃で反応させた。その結果、プロピレ
ンの反応率９９．２％、アクロレインの選択率８８．８
％、アクリル酸の選択率６．６％であった。The obtained catalyst was filled in a stainless steel reaction tube, and a raw material mixed gas of propylene 5%, oxygen 12%, water vapor 10% and nitrogen 73% was passed through the catalyst layer at a contact time of 3.6 seconds, and 310 The reaction was carried out at ° C. As a result, the reaction rate of propylene was 99.2% and the selectivity of acrolein was 88.8.
%, And the selectivity of acrylic acid was 6.6%.
【００２６】比較例２ 実施例４と同組成の触媒を焼成段階以外は実施例４と同
様にして調製した。すなわち、乾燥物をロータリーキル
ン焼成炉に供給する速度を毎時２ｋｇに変更した。なお
焼成中における乾燥物の層高は最も高い箇所で２２ｍｍ
であったが、８０重量％以上の部分は常時２０ｍｍ未満
の層高しかなかった。こうして得られた触媒を用いて実
施例４と同様にして反応を行った結果、プロピレンの反
応率９８．８％、アクロレインの選択率８７．５％、ア
クリル酸の選択率６．０％であった。Comparative Example 2 A catalyst having the same composition as in Example 4 was prepared in the same manner as in Example 4 except for the calcination step. That is, the rate of supplying the dried product to the rotary kiln firing furnace was changed to 2 kg / hour. The height of the dried product during firing is 22 mm at the highest point.
However, the portion of 80% by weight or more always had a layer height of less than 20 mm. Using the catalyst thus obtained, a reaction was carried out in the same manner as in Example 4. As a result, the conversion of propylene was 98.8%, the selectivity of acrolein was 87.5%, and the selectivity of acrylic acid was 6.0%. It was
【００２７】[0027]
【発明の効果】本発明の不飽和アルデヒド及び不飽和カ
ルボン酸合成用触媒の製造法によると目的生成物収率の
高い触媒を再現性良く得ることができる。According to the method for producing a catalyst for synthesizing an unsaturated aldehyde and an unsaturated carboxylic acid of the present invention, a catalyst having a high yield of a target product can be obtained with good reproducibility.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 57/05 7306−4Ｈ // Ｃ０７Ｂ 61/00 ３００ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location C07C 57/05 7306-4H // C07B 61/00 300
Claims (1)
ス化合物を成分として含有する混合溶液又は水性スラリ
ーを乾燥し、得られた乾燥物を焼成することによりモリ
ブデン及びビスマスを含む多成分系の不飽和アルデヒド
及び不飽和カルボン酸合成用触媒を製造する方法におい
て、焼成段階で、乾燥物の３０重量％以上の部分の層高
が２０ｍｍ以上になるように保ち、２００〜６００℃の
範囲の温度で熱処理することを特徴とする不飽和アルデ
ヒド及び不飽和カルボン酸合成用触媒の製造法。1. A multi-component unsaturated aldehyde and unsaturated containing molybdenum and bismuth by drying a mixed solution or an aqueous slurry containing at least a molybdenum compound and a bismuth compound as components and calcining the dried product. In the method for producing a catalyst for carboxylic acid synthesis, the layer height of 30% by weight or more of the dried product is maintained at 20 mm or more in the firing step, and heat treatment is performed at a temperature in the range of 200 to 600 ° C. And a method for producing a catalyst for synthesizing unsaturated aldehyde and unsaturated carboxylic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08816792A JP3154798B2 (en) | 1992-03-12 | 1992-03-12 | Method for producing catalyst for synthesizing unsaturated aldehydes and unsaturated carboxylic acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08816792A JP3154798B2 (en) | 1992-03-12 | 1992-03-12 | Method for producing catalyst for synthesizing unsaturated aldehydes and unsaturated carboxylic acids |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05253480A true JPH05253480A (en) | 1993-10-05 |
| JP3154798B2 JP3154798B2 (en) | 2001-04-09 |
Family
ID=13935365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP08816792A Expired - Lifetime JP3154798B2 (en) | 1992-03-12 | 1992-03-12 | Method for producing catalyst for synthesizing unsaturated aldehydes and unsaturated carboxylic acids |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3154798B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004351295A (en) * | 2003-05-28 | 2004-12-16 | Nippon Shokubai Co Ltd | Catalyst for manufacture of unsaturated aldehyde and unsaturated carboxylic acid, preparation method therefor, and method for manufacturing unsaturated aldehyde and unsaturated carboxylic acid |
| US7005542B2 (en) | 2002-02-28 | 2006-02-28 | Nippon Shokubai Co., Ltd. | Catalyst for synthesis of unsaturated aldehyde, production process for said catalyst, and production process for unsaturated aldehyde using said catalyst |
| JP2008149263A (en) * | 2006-12-18 | 2008-07-03 | Mitsubishi Rayon Co Ltd | Method for manufacturing oxide catalyst containing molybdenum, bismuth and iron |
| JP2008221032A (en) * | 2007-03-08 | 2008-09-25 | Nippon Shokubai Co Ltd | Method of manufacturing multiple oxide catalyst, and method of manufacturing unsaturated aldehyde and/or unsaturated carboxylic acid by using the catalyst |
| WO2014051090A1 (en) * | 2012-09-28 | 2014-04-03 | 旭化成ケミカルズ株式会社 | Oxide catalyst, method for producing same, and method for producing unsaturated aldehyde, diolefin or unsaturated nitrile |
| JP2015188802A (en) * | 2014-03-27 | 2015-11-02 | 旭化成ケミカルズ株式会社 | Oxide catalyst and production method thereof, and method for producing acrylonitrile |
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1992
- 1992-03-12 JP JP08816792A patent/JP3154798B2/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7005542B2 (en) | 2002-02-28 | 2006-02-28 | Nippon Shokubai Co., Ltd. | Catalyst for synthesis of unsaturated aldehyde, production process for said catalyst, and production process for unsaturated aldehyde using said catalyst |
| US7414008B2 (en) | 2002-02-28 | 2008-08-19 | Nippon Sholonbai Co., Ltd. | Catalyst for synthesis of unsaturated aldehyde, production process for said catalyst, and production process for unsaturated aldehyde using said catalyst |
| JP2004351295A (en) * | 2003-05-28 | 2004-12-16 | Nippon Shokubai Co Ltd | Catalyst for manufacture of unsaturated aldehyde and unsaturated carboxylic acid, preparation method therefor, and method for manufacturing unsaturated aldehyde and unsaturated carboxylic acid |
| JP2008149263A (en) * | 2006-12-18 | 2008-07-03 | Mitsubishi Rayon Co Ltd | Method for manufacturing oxide catalyst containing molybdenum, bismuth and iron |
| JP2008221032A (en) * | 2007-03-08 | 2008-09-25 | Nippon Shokubai Co Ltd | Method of manufacturing multiple oxide catalyst, and method of manufacturing unsaturated aldehyde and/or unsaturated carboxylic acid by using the catalyst |
| WO2014051090A1 (en) * | 2012-09-28 | 2014-04-03 | 旭化成ケミカルズ株式会社 | Oxide catalyst, method for producing same, and method for producing unsaturated aldehyde, diolefin or unsaturated nitrile |
| JP5908595B2 (en) * | 2012-09-28 | 2016-04-26 | 旭化成ケミカルズ株式会社 | Oxide catalyst and method for producing the same, and method for producing unsaturated aldehyde, diolefin and unsaturated nitrile |
| US9364817B2 (en) | 2012-09-28 | 2016-06-14 | Asahi Kasei Chemicals Corporation | Oxide catalyst and method for producing the same, and methods for producing unsaturated aldehyde, diolefin, and unsaturated nitrile |
| RU2615762C2 (en) * | 2012-09-28 | 2017-04-11 | Асахи Касеи Кемикалз Корпорейшн | Oxide catalyst and method of producing thereof, as well as methods of producing unsaturated aldehyde, diolefin and unsaturated nitrile |
| JP2015188802A (en) * | 2014-03-27 | 2015-11-02 | 旭化成ケミカルズ株式会社 | Oxide catalyst and production method thereof, and method for producing acrylonitrile |
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|---|---|
| JP3154798B2 (en) | 2001-04-09 |
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