JPH0597730A - Packing of catalyst for methacrolein and methacrylic acid synthesis - Google Patents
Packing of catalyst for methacrolein and methacrylic acid synthesisInfo
- Publication number
- JPH0597730A JPH0597730A JP3287320A JP28732091A JPH0597730A JP H0597730 A JPH0597730 A JP H0597730A JP 3287320 A JP3287320 A JP 3287320A JP 28732091 A JP28732091 A JP 28732091A JP H0597730 A JPH0597730 A JP H0597730A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- reactor
- methacrylic acid
- methacrolein
- shape
- 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.)
- Pending
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
タクリル酸合成用成型触媒又は担持触媒の固定床反応器
えの充填方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for filling a fixed bed reactor of a molded catalyst or a supported catalyst for methacrolein and methacrylic acid synthesis.
【０００２】[0002]
【従来の技術】一般に、成型触媒又は担持触媒を固定床
反応器に充填するには反応器の上部より落下充填する方
法が採られている。この方法は触媒の落下時の物理的衝
撃による触媒が粉化・崩壊がみられる。これを防ぐた
め、触媒自体にある程度以上の機械的強度を持たせる
か、もしくは充填の手法に何らかの工夫を施す必要があ
る。2. Description of the Related Art Generally, in order to fill a fixed bed reactor with a molded catalyst or a supported catalyst, a method of dropping from the upper part of the reactor is adopted. In this method, the catalyst is pulverized and disintegrated due to physical impact when the catalyst falls. In order to prevent this, it is necessary to give the catalyst itself mechanical strength above a certain level, or to devise a filling method.
【０００３】触媒の機械的強度は成型圧力を調節した
り、成型又は担持の操作を工夫することで、ある程度は
改善される。しかし、このような手法で機械的強度を高
くした触媒は、概して触媒の持つ比表面積が小さくなっ
たり、反応に有効な活性点の数が減少したり、また反応
に有効な細孔分布が制御できない等の理由で目的生成物
の収率が低くなり実用的でない。The mechanical strength of the catalyst can be improved to some extent by adjusting the molding pressure or devising the molding or supporting operation. However, a catalyst whose mechanical strength is increased by such a method generally has a small specific surface area of the catalyst, the number of active sites effective for the reaction is decreased, and the pore distribution effective for the reaction is controlled. This is not practical because the yield of the target product is low due to reasons such as the inability to do so.
【０００４】[0004]
【発明が解決しようとする課題】このような見地から、
機械的強度の高くない成型触媒又は担持触媒の粉化・崩
壊を最小限に抑えて反応器に充填する有効な手段が望ま
れてた。本発明は、メタクロレイン及びメタクリル酸合
成用成型触媒又は担持触媒の反応器えの充填時に粉化・
崩壊の少ない充填方法の提供を目的としている。[Problems to be Solved by the Invention] From this point of view,
There has been a demand for an effective means for filling the reactor with a minimum of pulverization / disintegration of a molded catalyst or a supported catalyst having a low mechanical strength. The present invention is a method of pulverizing methacrolein and methacrylic acid when the molded catalyst or the supported catalyst for synthesizing methacrylic acid is charged into the reactor.
The purpose is to provide a filling method with less collapse.
【０００５】[0005]
【課題を解決するための手段】本発明は、イソブチレン
又は第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ための
成型触媒又は担持触媒を固定床反応器に上部より落下充
填するに際し、反応器内に、実質的に触媒の落下を妨げ
ない形状及び太さを有する少なくとも１本のひも状物質
を介在させ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充填方法にある。DISCLOSURE OF THE INVENTION The present invention relates to a fixed bed reactor in which a molded catalyst or a supported catalyst for the gas phase catalytic oxidation of isobutylene or tertiary butanol to synthesize methacrolein and methacrylic acid is synthesized. For methacrolein and methacrylic acid synthesis, at least one string-like substance having a shape and a thickness that does not substantially prevent the catalyst from dropping is interposed in the reactor when dropping and filling from above. There is a method of filling the catalyst.
【０００６】本発明において成型触媒を用いる場合、そ
の形状については特に限定はなく、球状、円柱状、円筒
状、星型状等通常の打錠機、押出成型機、転動造粒機等
で成型されるものが用いられる。また、担持触媒を用い
る場合、担体の種類としては、シリカ、アルミナ、シリ
カ・アルミナ、マグネシア、チタニア等の通常の担体が
用いられ、また、その形状についても特に限定されるも
のではなく、球状、円柱状、円筒状、板状等が挙げられ
る。When the molded catalyst is used in the present invention, its shape is not particularly limited, and it may be a usual tableting machine such as spherical, cylindrical, cylindrical or star-shaped, an extrusion molding machine, a rolling granulator and the like. What is molded is used. Further, when using a supported catalyst, as the type of carrier, silica, alumina, silica-alumina, magnesia, titania and the like usual carriers are used, and the shape thereof is not particularly limited, and spherical, Examples thereof include a cylindrical shape, a cylindrical shape, and a plate shape.
【０００７】本発明において、固定床反応器の形態につ
いては特に限定はなく、さまざまな形態の反応器に適用
することができる。なかでも多管垂直型反応器のよう
に、管径が狭く管長が長いものに適用する場合、非常に
有効な手段である。In the present invention, the form of the fixed bed reactor is not particularly limited, and it can be applied to reactors of various forms. In particular, it is a very effective means when applied to a narrow tube diameter and long tube length such as a multi-tube vertical reactor.
【０００８】反応器内に挿入介在させるひも状物質の材
質は特に限定はなく、落下する触媒との接触により破損
・破断しないものであればよい。また、その形状は触媒
の落下を実質的に妨げない形状及び太さであれば特に制
限を設ける必要はなく、例えば棒状、針金状、糸状、帯
状、チューブ状、鎖状、板状、らせん状等任意の形状が
挙げられ、更にその各々に枝状、ブラシ毛状、板状等の
ものを備えた形状のものが挙げられる。The material of the string-like substance inserted and interposed in the reactor is not particularly limited as long as it does not break or break due to contact with the falling catalyst. Further, the shape is not particularly limited as long as it is a shape and thickness that does not substantially prevent the catalyst from falling, and for example, a rod shape, a wire shape, a thread shape, a band shape, a tube shape, a chain shape, a plate shape, a spiral shape. Etc., and each of them may have a branch shape, a brush bristle shape, a plate shape, or the like.
【０００９】このひも状物質の長さは特に限定されるも
のではないが、あまり短すぎると触媒充填時の粉化・崩
壊を抑制する効果が低下するので反応器底部に届く程度
が好ましい。The length of the string-like substance is not particularly limited, but if it is too short, the effect of suppressing pulverization and disintegration at the time of filling the catalyst is lowered, so that it is preferable to reach the bottom of the reactor.
【００１０】また、ひも状物質の使用本数には制限はな
く、本数が多いほど触媒充填時の粉化・崩壊を抑制する
効果は大きい。しかし、本数が多すぎると触媒の落下の
妨げになることがあるため、挿入するひも状物質の形状
に応じて適当な本数を選ぶ。There is no limitation on the number of cord-like substances used, and the greater the number, the greater the effect of suppressing pulverization and disintegration during catalyst filling. However, if the number is too large, it may hinder the dropping of the catalyst. Therefore, select an appropriate number according to the shape of the string-like material to be inserted.
【００１１】反応器内に介在させたひも状物質は反応開
始前に除去してもよいし、しなくてもよい。用いたひも
状物質の形状及び材質が目的生成物であるメタクロレイ
ン及びメタクリル酸の収率に影響を及ぼさないものであ
れば、必ずしも触媒充填後に除去する必要はない。ま
た、用いたひも状物質が、充填した触媒の性能を変化さ
せない範囲の加熱処理により、容易に燃焼又は気化し除
去できるような材質のものであれば、触媒充填後に適当
な熱処理をすることにより除去することもできる。The string-like substance interposed in the reactor may or may not be removed before the start of the reaction. If the shape and material of the string-like substance used do not affect the yield of the target products methacrolein and methacrylic acid, it is not necessary to remove it after the catalyst is charged. If the string-like material used is a material that can be easily combusted or vaporized and removed by a heat treatment in a range that does not change the performance of the packed catalyst, then perform appropriate heat treatment after the catalyst is packed. It can also be removed.
【００１２】しかし、用いたひも状物質の形状及び材質
が前記のようなものでない場合は、反応開始前に除去す
る方が好ましい。その手段としては、反応器への触媒の
充填を終えた後に該ひも状物質を上部より引き抜くこと
は著しく困難であるため、触媒の充填と同時に上部より
徐々に引き上げる方法が好ましい。However, when the shape and material of the string-like substance used is not as described above, it is preferable to remove it before starting the reaction. As a means for this, since it is extremely difficult to pull out the string-like substance from the upper portion after the filling of the catalyst into the reactor is completed, a method of gradually raising the string material from the upper portion at the same time as filling the catalyst is preferable.
【００１３】ひも状物質を反応器内に介在させる手段と
しては、反応器内に挿入し吊下げる等の適宜の方法が採
用できる。また、ひも状物質の形状材質によっては固定
床反応器の底部に載置してもよい。As a means for interposing the string-like substance in the reactor, an appropriate method such as inserting into the reactor and suspending it can be adopted. Further, depending on the shape material of the string-like substance, it may be placed on the bottom of the fixed bed reactor.
【００１４】本発明では、イソブチレン又は第３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
ン及びメタクリル酸を合成するための成型触媒又は担持
触媒として、次の一般式で示される組成を有する触媒が
好ましく用いられる。In the present invention, a molded catalyst or supported catalyst for synthesizing methacrolein and methacrylic acid by vapor-phase catalytic oxidation of isobutylene or tertiary butanol with molecular oxygen has a composition represented by the following general formula. A catalyst is preferably used.
【００１５】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、セレ
ン、ゲルマニウム、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種の元素を示す。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＝１２のとき、０．１≦ｂ≦５、０．１
≦ｃ≦５、１≦ｄ≦１２、０≦ｅ≦５、０≦ｆ≦５、
０．０１≦ｇ≦３であり、ｈ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 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 and / or
Or cobalt, X is at least one element selected from the group consisting of magnesium, zinc, manganese, tin and lead, and Y is a group consisting of phosphorus, boron, sulfur, tellurium, silicon, selenium, germanium, tungsten and antimony. At least one element selected, 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 when a = 12, 0.1 ≦ b ≦ 5,0.1
≤c≤5, 1≤d≤12, 0≤e≤5, 0≤f≤5,
0.01 ≦ g ≦ 3, and h is the number of oxygen atoms required to satisfy the valence of each component. )
【００１６】上述の触媒において、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成り得る塩化
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。触媒はこれ等の原料より常法
により製造される。In the above-mentioned catalyst, 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 igniting. Salts, ammonium salts or mixtures thereof are used. The catalyst is produced from these raw materials by a conventional method.
【００１７】[0017]
【実施例】以下、実施例を挙げて、本発明を更に説明す
る。文中「部」は重量部を意味する。成型触媒又は担持
触媒の充填粉化率（％）は以下のように定義される。す
なわち、触媒ａ部を水平方向に対して垂直に設置した反
応器上部より充填し、充填後反応器底部より回収された
触媒のうち、１４メッシュのふるいを通過しないものが
ｂ部であったとする。EXAMPLES The present invention will be further described below with reference to examples. In the text, “part” means part by weight. The filling powder ratio (%) of the molded catalyst or the supported catalyst is defined as follows. That is, it is assumed that, of the catalysts which are filled from the upper part of the reactor vertically installed with respect to the horizontal direction of the catalyst a part and recovered from the bottom part of the reactor after filling, the part which does not pass through the 14-mesh sieve is the b part. ..
【００１８】[0018]
【数１】 [Equation 1]
【００１９】実施例１ 下記の組成の触媒粉末を調製した。 Ｍｏ12Ｂｉ0.6 Ｆｅ2 Ｎｉ4 Ｃｏ2 Ｍｇ2 Ｓｂ0.7 Ｃｓ
0.6 Ｏx （式中、Ｍｏ、Ｂｉ、Ｆｅ、Ｎｉ、Ｃｏ、Ｍｇ、Ｓｂ、
Ｃｓ及びＯはそれぞれモリブデン、ビスマン、鉄、ニッ
ケル、コバルト、マグネシウム、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（以下同じ）。）得られた
触媒粉末９７０部をグラファイト粉末３０部とよく混合
した後、外径５mm、内径２mm、高さ４mmの円筒形に打錠
成型した。Example 1 A catalyst powder having the following composition was prepared. Mo 12 Bi 0.6 Fe 2 Ni 4 Co 2 Mg 2 Sb 0.7 Cs
0.6 O x (in the formula, Mo, Bi, Fe, Ni, Co, Mg, Sb,
Cs and O represent molybdenum, bisman, iron, nickel, cobalt, magnesium, antimony, cesium and oxygen, respectively. The numbers in the lower right of the element symbols are the atomic ratios of each element, and x is the number of oxygen atoms required to satisfy the valence of each component (the same applies hereinafter). ) 970 parts of the obtained catalyst powder was thoroughly mixed with 30 parts of graphite powder, and then tablet-molded into a cylindrical shape having an outer diameter of 5 mm, an inner diameter of 2 mm and a height of 4 mm.
【００２０】内径３cm、長さ５ｍの鉄製円筒型反応器上
部より、外径１mm、長さ５ｍの針金を３本挿入した。前
記で得られた成型触媒２kgを反応器上部より落下充填し
た。このときの充填粉化率を測定したところ、１．０％
であった。From the upper portion of the iron cylindrical reactor having an inner diameter of 3 cm and a length of 5 m, three wires having an outer diameter of 1 mm and a length of 5 m were inserted. 2 kg of the molded catalyst obtained above was dropped and filled from the upper part of the reactor. The filling powder ratio at this time was measured to be 1.0%
Met.
【００２１】比較例１ 実施例１と同様にして得られた成型触媒を実施例１と同
様の反応器に針金を挿入することなくそのまま落下充填
した。このときの充填粉化率を測定したところ４．９％
であった。Comparative Example 1 The molded catalyst obtained in the same manner as in Example 1 was dropped and charged into the same reactor as in Example 1 without inserting a wire. The filling powder ratio at this time was measured to be 4.9%.
Met.
【００２２】実施例２ 下記の組成の触媒粉末を調製した。 Ｍｏ12Ｂｉ1 Ｆｅ3.2 Ｃｏ6 Ｒｂ0.4 Ｏx （式中、Ｍｏ、Ｂｉ、Ｆｅ、Ｃｏ、Ｒｂ及びＯはそれぞ
れモリブデン、ビスマス、鉄、コバルト、ルビジウム及
び酸素を表す。）得られた触媒粉末９７０部をグラファ
イト粉末３０部とよく混合した後、直径５mm、高さ４mm
の円柱形に打錠成型した。Example 2 A catalyst powder having the following composition was prepared. Mo 12 Bi 1 Fe 3.2 Co 6 Rb 0.4 O x (In the formula, Mo, Bi, Fe, Co, Rb and O represent molybdenum, bismuth, iron, cobalt, rubidium and oxygen.) Obtained catalyst powder 970 Well mixed with 30 parts of graphite powder, diameter 5mm, height 4mm
Tablet-molded into a cylindrical shape.
【００２３】内径２．７cm、長さ４ｍのステンレス製円
筒型反応器上部より、幅１cm、長さ３．６ｍのナイロン
製リボンを１本挿入した。前記で得られた成型触媒２kg
を、１００ｇ充填するごとにリボンを１５cm上部に引き
上げる要領で、反応器上部より落下充填した。このとき
の充填粉化率を測定したところ、０．５％であった。From the upper part of the stainless steel cylindrical reactor having an inner diameter of 2.7 cm and a length of 4 m, one nylon ribbon having a width of 1 cm and a length of 3.6 m was inserted. 2 kg of the molded catalyst obtained above
Was dropped and filled from the upper part of the reactor in such a manner that the ribbon was pulled up to 15 cm above every 100 g. The filling powder ratio at this time was measured and found to be 0.5%.
【００２４】比較例２ 実施例２と同様にして得られた成型触媒を実施例２と同
様の反応器にリボンを挿入することなくそのまま落下充
填した。このときの充填粉化率を測定したところ２．３
％であった。Comparative Example 2 The molded catalyst obtained in the same manner as in Example 2 was dropped and packed in the same reactor as in Example 2 without inserting a ribbon. The filling powder ratio at this time was measured to be 2.3.
%Met.
【００２５】実施例３ 下記の組成の触媒粉末を調製した。 Ｍｏ12Ｂｉ0.5 Ｆｅ3 Ｎｉ9 Ｍｇ1 Ｍｎ0.3 Ｂ0.2 Ｔｅ
0.1 Ｓｉ0.4 Ｋ0.1 Ｃｓ0.3 Ｏx （式中、Ｍｏ、Ｂｉ、Ｆｅ、Ｎｉ、Ｍｇ、Ｍｎ、Ｂ、Ｔ
ｅ、Ｓｉ、Ｋ、Ｃｓ及びＯはそれぞれモリブデン、ビス
マス、鉄、ニッケル、マグネシウム、マンガン、ホウ
素、テルル、ケイ素、カリウム、セシウム及び酸素を表
す。）得られた触媒粉末２００部を直径４mmの球状アル
ミナ担体８００部に担持した。Example 3 A catalyst powder having the following composition was prepared. Mo 12 Bi 0.5 Fe 3 Ni 9 Mg 1 Mn 0.3 B 0.2 Te
0.1 Si 0.4 K 0.1 Cs 0.3 O x (in the formula, Mo, Bi, Fe, Ni, Mg, Mn, B, T
e, Si, K, Cs and O represent molybdenum, bismuth, iron, nickel, magnesium, manganese, boron, tellurium, silicon, potassium, cesium and oxygen, respectively. ) 200 parts of the obtained catalyst powder was supported on 800 parts of a spherical alumina carrier having a diameter of 4 mm.
【００２６】内径３cm、長さ４．５ｍのステンレス製円
筒型反応器上部より、羊毛製で長さ１cmのブラシ毛を備
えた直径０．８mm、長さ４．２ｍの針金を１本挿入し
た。前記で得られた担持触媒２kgを、１００ｇ充填する
ごとにブラシ毛付き針金を１２cm上部に引き上げる要領
で、反応器上部より落下充填した。このときの充填粉化
率を測定したところ、０．２％であった。From the upper portion of the stainless steel cylindrical reactor having an inner diameter of 3 cm and a length of 4.5 m, one wire having a diameter of 0.8 mm and a length of 4.2 m equipped with a brush bristle of 1 cm in length was inserted. .. 2 kg of the supported catalyst obtained above was dropped from the upper part of the reactor so that the wire with brush bristles was pulled up to 12 cm every time 100 g was charged. The filling powder ratio at this time was measured and found to be 0.2%.
【００２７】比較例３ 実施例３と同様にして得られた担持触媒を実施例３と同
様の反応器にブラシ毛付き針金を挿入することなくその
まま落下充填した。このときの充填粉化率を測定したと
ころ１．６％であった。Comparative Example 3 The supported catalyst obtained in the same manner as in Example 3 was dropped and filled in the same reactor as in Example 3 as it was without inserting a wire with brush bristles. The filling powder ratio at this time was measured and found to be 1.6%.
【００２８】実施例４ 下記の組成の触媒粉末を調製した。 Ｍｏ12Ｂｉ1 Ｆｅ3.1 Ｃｏ3 Ｎｉ3 Ｍｇ1 Ｐｂ1 Ｗ0.1
Ｇｅ0.1 Ｓｂ0.8 Ｃｓ0.3 Ｔｌ0.3 Ｏx （式中、Ｍｏ、Ｂｉ、Ｆｅ、Ｃｏ、Ｎｉ、Ｍｇ、Ｐｂ、
Ｗ、Ｇｅ、Ｓｂ、Ｃｓ、Ｔｌ及びＯはそれぞれモリブデ
ン、ビスマス、鉄、コバルト、ニッケル、マグネシウ
ム、鉛、タングステン、ゲルマニウム、アンチモン、セ
シウム、タリウム及び酸素を表す。）得られた触媒粉末
に少量の水を加え、よく混合した後、押出成型機によ
り、直径４mm、高さ５mmの円柱形に成型した。Example 4 A catalyst powder having the following composition was prepared. Mo 12 Bi 1 Fe 3.1 Co 3 Ni 3 Mg 1 Pb 1 W 0.1
Ge 0.1 Sb 0.8 Cs 0.3 Tl 0.3 O x (in the formula, Mo, Bi, Fe, Co, Ni, Mg, Pb,
W, Ge, Sb, Cs, Tl and O represent molybdenum, bismuth, iron, cobalt, nickel, magnesium, lead, tungsten, germanium, antimony, cesium, thallium and oxygen, respectively. ) A small amount of water was added to the obtained catalyst powder, mixed well, and then molded into a cylindrical shape having a diameter of 4 mm and a height of 5 mm by an extruder.
【００２９】内径３cm、長さ５．５ｍのステンレス製円
筒型反応器上部より、外径６mm、内径３mm、長さ５．２
ｍのポリテトラフルオロエチレン製チューブを２本挿入
した。前記で得られた成型触媒２kgを、１００ｇ充填す
るごとにチューブを１２cm上部に引き上げる要領で、反
応器上部より落下充填した。このときの充填粉化率を測
定したところ、０．４％であった。From the upper part of a stainless steel cylindrical reactor having an inner diameter of 3 cm and a length of 5.5 m, an outer diameter of 6 mm, an inner diameter of 3 mm and a length of 5.2.
Two polytetrafluoroethylene tubes of m were inserted. 2 kg of the molded catalyst obtained above was dropped and filled from the upper part of the reactor in such a manner that the tube was pulled up to 12 cm every time 100 g was filled. The filling powder ratio at this time was measured and found to be 0.4%.
【００３０】比較例４ 実施例４と同様にして得られた成型触媒を実施例４と同
様の反応器にポリテトラフルオロエチレン製チューブを
挿入することなくそのまま落下充填した。このときの充
填粉化率を測定したところ１．８％であった。Comparative Example 4 The molded catalyst obtained in the same manner as in Example 4 was dropped and charged into the same reactor as in Example 4 as it was without inserting a polytetrafluoroethylene tube. The filling powder ratio at this time was measured and found to be 1.8%.
【００３１】実施例５ 下記の組成の触媒粉末を調製した。 Ｍｏ12Ｂｉ1.2 Ｆｅ2.5 Ｃｏ4 Ｎｉ3 Ｚｎ1 Ｓｎ0.2 Ｐ
0.05Ｓｅ0.1 Ｃｓ0.45Ｏx （式中、Ｍｏ、Ｂｉ、Ｆｅ、Ｃｏ、Ｎｉ、Ｚｎ、Ｓｎ、
Ｐ、Ｓｅ、Ｃｓ及びＯはそれぞれモリブデン、ビスマ
ス、鉄、コバルト、ニッケル、亜鉛、スズ、リン、セレ
ン、セシウム及び酸素を表す。）得られた触媒粉末に少
量の水を加え、よく混合した後、押出成型機により、外
径５mm、内径２mm、高さ７mmの円筒形に成型した。Example 5 A catalyst powder having the following composition was prepared. Mo 12 Bi 1.2 Fe 2.5 Co 4 Ni 3 Zn 1 Sn 0.2 P
0.05 Se 0.1 Cs 0.45 O x (in the formula, Mo, Bi, Fe, Co, Ni, Zn, Sn,
P, Se, Cs and O represent molybdenum, bismuth, iron, cobalt, nickel, zinc, tin, phosphorus, selenium, cesium and oxygen, respectively. ) A small amount of water was added to the obtained catalyst powder and mixed well, and then molded by an extruder into a cylindrical shape having an outer diameter of 5 mm, an inner diameter of 2 mm and a height of 7 mm.
【００３２】内径３cm、長さ５．５ｍのステンレス製円
筒型反応器上部より、横幅８mm、長さ５．２ｍの樹脂製
鎖を２本挿入した。前記で得られた成型触媒２kgを、１
００ｇ充填するごとに樹脂製鎖を１２cm上部に引き上げ
る要領で、反応器上部より落下充填した。このときの充
填粉化率を測定したところ、０．６％であった。Two resin chains having a width of 8 mm and a length of 5.2 m were inserted from the upper portion of a stainless steel cylindrical reactor having an inner diameter of 3 cm and a length of 5.5 m. 2 kg of the molded catalyst obtained above is
The resin chain was dropped from the upper part of the reactor in such a manner that the resin chain was lifted up to 12 cm every time it was charged with 00 g. The filling powder ratio at this time was measured and found to be 0.6%.
【００３３】比較例５ 比較例５と同様にして得られた成型触媒を実施例５と同
様の反応器に樹脂製鎖を挿入することなくそのまま落下
充填した。このときの充填粉化率を測定したところ２．
０％であった。Comparative Example 5 The molded catalyst obtained in the same manner as in Comparative Example 5 was dropped and packed into a reactor similar to that in Example 5 without inserting a resin chain. When the filling powder ratio at this time was measured, 2.
It was 0%.
【００３４】[0034]
【発明の効果】本発明による方法で、成型触媒又は担持
触媒を固定床反応器に充填すると、落下時の物理的衝撃
による触媒の粉化・崩壊が著しく少なくなる。このため
充填時における触媒の粉化等を懸念して触媒の機械的強
度を必要以上に高くする必要がなくなる。従って、触媒
設計上の制限が少なくなり、幅広い条件での触媒調製が
可能となる。When the molded catalyst or the supported catalyst is packed in the fixed bed reactor by the method according to the present invention, the powdering / disintegration of the catalyst due to the physical impact at the time of dropping is significantly reduced. Therefore, there is no need to raise the mechanical strength of the catalyst more than necessary because of concern about powdering of the catalyst during filling. Therefore, restrictions on catalyst design are reduced, and catalyst preparation under a wide range of conditions becomes possible.
───────────────────────────────────────────────────── 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 Ｃ０７Ｂ 41/06 Ａ 7419−4Ｈ Ｂ 7419−4Ｈ Ｃ０７Ｃ 47/22 Ａ 9049−4Ｈ Ｊ 9049−4Ｈ 57/05 6742−4Ｈ // Ｃ０７Ｂ 61/00 ３００ (72)発明者 大北 求 広島県大竹市御幸町20番１号 三菱レイヨ ン株式会社中央研究所内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical display location C07B 41/06 A 7419-4H B 7419-4H C07C 47/22 A 9049-4H J 9049-4H 57 / 05 6742-4H // C07B 61/00 300 (72) Inventor Okita Kita No. 20-1 Miyukicho, Otake City, Hiroshima Prefecture Mitsubishi Rayon Co., Ltd. Central Research Laboratory
Claims (2)
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ための成型触媒又は担持触媒を固
定床反応器に上部より落下充填するに際し、反応器内
に、実質的に触媒の落下を妨げない形状及び太さを有す
る少なくとも１個のひも状物質を介在させることを特徴
とするメタクロレイン及びメタクリル酸合成用触媒の充
填方法。1. When a molded catalyst or a supported catalyst for synthesizing methacrolein and methacrylic acid by vapor-phase catalytic oxidation of isobutylene or tertiary butanol with molecular oxygen is dropped and packed into a fixed bed reactor from above, A method for packing a catalyst for methacrolein and methacrylic acid synthesis, characterized in that at least one string-like substance having a shape and a thickness that does not substantially prevent the catalyst from falling is interposed in the reactor.
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、セレ
ン、ゲルマニウム、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種の元素を示す。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＝１２のとき、０．１≦ｂ≦５、０．１
≦ｃ≦５、１≦ｄ≦１２、０≦ｅ≦５、０≦ｆ≦５、
０．０１≦ｇ≦３であり、ｈは前記各成分の原子価を満
足するのに必要な酸素原子数である。）で示される組成
を有することを特徴とする請求項１の触媒の充填方法。2. The molded catalyst or supported catalyst has a general formula of 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, iron and oxygen, respectively). Where 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, and Y is a group consisting of phosphorus, boron, sulfur, tellurium, silicon, selenium, germanium, tungsten and antimony. At least one element selected, 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 when a = 12, 0.1 ≦ b ≦ 5,0.1
≤c≤5, 1≤d≤12, 0≤e≤5, 0≤f≤5,
0.01 ≦ g ≦ 3, and h is the number of oxygen atoms required to satisfy the valence of each component. ) The method of filling a catalyst according to claim 1, wherein the method has the composition shown in FIG.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3287320A JPH0597730A (en) | 1991-10-08 | 1991-10-08 | Packing of catalyst for methacrolein and methacrylic acid synthesis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3287320A JPH0597730A (en) | 1991-10-08 | 1991-10-08 | Packing of catalyst for methacrolein and methacrylic acid synthesis |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0597730A true JPH0597730A (en) | 1993-04-20 |
Family
ID=17715836
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3287320A Pending JPH0597730A (en) | 1991-10-08 | 1991-10-08 | Packing of catalyst for methacrolein and methacrylic acid synthesis |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0597730A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003057653A1 (en) * | 2001-12-28 | 2003-07-17 | Mitsubishi Chemical Corporation | Method for vapor phase catalytic oxidation |
| WO2005053833A1 (en) * | 2003-12-01 | 2005-06-16 | Mitsubishi Rayon Co., Ltd. | Method of solid catalyst filling |
| US8252714B2 (en) | 2008-05-16 | 2012-08-28 | Sumitomo Chemical Company, Limited | Method for producing catalyst for use in production of unsaturated aldehyde and/or unsaturated carboxylic acid, and method for producing unsaturated aldehyde and/or unsaturated carboxylic acid |
-
1991
- 1991-10-08 JP JP3287320A patent/JPH0597730A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003057653A1 (en) * | 2001-12-28 | 2003-07-17 | Mitsubishi Chemical Corporation | Method for vapor phase catalytic oxidation |
| US7528281B2 (en) | 2001-12-28 | 2009-05-05 | Mitsubishi Chemical Corporation | Method for vapor phase catalytic oxidation |
| US7667072B2 (en) | 2001-12-28 | 2010-02-23 | Mitsubishi Chemical Corporation | Method for vapor phase catalytic oxidation |
| WO2005053833A1 (en) * | 2003-12-01 | 2005-06-16 | Mitsubishi Rayon Co., Ltd. | Method of solid catalyst filling |
| US8252714B2 (en) | 2008-05-16 | 2012-08-28 | Sumitomo Chemical Company, Limited | Method for producing catalyst for use in production of unsaturated aldehyde and/or unsaturated carboxylic acid, and method for producing unsaturated aldehyde and/or unsaturated carboxylic acid |
| US8586786B2 (en) | 2008-05-16 | 2013-11-19 | Sumitomo Chemical Company, Limited | Method for producing catalyst for use in production of unsaturated aldehyde and/or unsaturated carboxylic acid, and method for producing unsaturated aldehyde and/or unsaturated carboxylic acid |
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