JP2819078B2 - Method for filling molybdenum-containing oxide catalyst - Google Patents
Method for filling molybdenum-containing oxide catalystInfo
- Publication number
- JP2819078B2 JP2819078B2 JP3306528A JP30652891A JP2819078B2 JP 2819078 B2 JP2819078 B2 JP 2819078B2 JP 3306528 A JP3306528 A JP 3306528A JP 30652891 A JP30652891 A JP 30652891A JP 2819078 B2 JP2819078 B2 JP 2819078B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- filling
- molybdenum
- auxiliary material
- containing oxide
- 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.)
- Expired - Lifetime
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、モリブデン含有酸化物
触媒の反応器への充填方法に関する。The present invention relates to a method for charging a molybdenum-containing oxide catalyst into a reactor.
【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上部より投入落下させる方
法が採られている。この方法は触媒の投入落下時の物理
的衝撃により触媒が粉化・崩壊することがある。これを
防ぐためには触媒自体にある程度以上の機械的強度を持
たせるか、又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 In general, a fixed-bed reactor is charged with a molded catalyst or a supported catalyst by dropping it from the upper part of the reactor. In this method, the catalyst may be powdered or disintegrated due to physical impact when the catalyst is dropped. In order to prevent this, it is necessary to provide the catalyst itself with a certain level of mechanical strength or to apply some means to the filling method.
【０００３】[0003]
【発明が解決しようとする課題】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はな
い。The mechanical strength of the catalyst is as follows:
Adjusting the molding pressure and devising the molding or carrying operation can improve the results to some extent. However, a catalyst whose mechanical strength is increased by such a method generally has a smaller specific surface area of the catalyst, a smaller number of active sites effective for the reaction, and a smaller pore distribution effective for the reaction. The yield of the target product is low due to reasons such as uncontrollability, which is not practical.
【０００４】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いた。本発明
は、モリブデン含有酸化物触媒の新規な充填方法の提供
を目的としている。[0004] From such a viewpoint, there has been a demand for an effective means for charging a molded catalyst or a supported catalyst having a low mechanical strength into a reactor while minimizing powdering and disintegration of the catalyst. An object of the present invention is to provide a novel method for charging a molybdenum-containing oxide catalyst.
【０００５】[0005]
【課題を解決するための手段】本発明は、モリブデン含
有酸化物触媒を反応管に落下充填する際に、充填密度が
０．１〜１．０ｇ／mlであって、かつ、０．１kg／cm2
の力を加えた場合の充填体積減少率が１．０〜４０．０
％である充填補助材を、モリブデン含有酸化物触媒に対
して１〜７０重量％混合して反応管に充填する方法にあ
る。According to the present invention, when dropping and filling a molybdenum-containing oxide catalyst into a reaction tube, the packing density is 0.1 to 1.0 g / ml and 0.1 kg / ml. cm 2
The filling volume reduction rate when applying a force of 1.0 to 40.0
% Of a filling auxiliary material is mixed with the molybdenum-containing oxide catalyst in an amount of 1 to 70% by weight and filled in a reaction tube.
【０００６】本発明は、反応器に触媒を落下充填するに
当りクッション材を触媒の充填補助材として混合し、落
下時の物理的衝撃による触媒の粉化・崩壊を防止するも
のである。According to the present invention, when a catalyst is dropped and filled in a reactor, a cushion material is mixed as a catalyst filling auxiliary material to prevent powdering and collapse of the catalyst due to physical impact at the time of falling.
【０００７】クッション材として使用する充填補助材の
材質は、落下時の物理的衝撃により破損せず、反応温度
において安定であり、目的生成物の収率に影響を及ぼさ
ないものであればよく、例えば炭素鋼、ステンレス鋼、
チタン、セラミック等が挙げられる。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大きさであれば
とくに限定はなく、例えば球状、円柱状、円筒状、糸
状、帯状、板状、らせん状等が挙げられるが、空隙率の
高いものが好ましい。[0007] The material of the filling auxiliary material used as the cushioning material may be any material as long as it is not damaged by physical impact when dropped, is stable at the reaction temperature, and does not affect the yield of the target product. For example, carbon steel, stainless steel,
Titanium, ceramics and the like are mentioned. Further, the shape is not particularly limited constant if dropped substantially interfere not shape and size of catalysts, for example, spherical, columnar, cylindrical, thread, strip, plate, but a spiral, and the like And those having a high porosity are preferred.
【０００８】本発明において使用する充填補助材は、特
定の範囲の充填密度と充填体積減少率を持つものを使用
する。充填密度としては０．１〜１．０ｇ／mlの範囲の
ものが好ましく用いられる。充填密度が０．１ｇ／mlよ
り小さいと、触媒との混合がうまく行なえず、１．０ｇ
／mlより大きいと、落下時の衝突により、触媒の粉化・
崩壊を招き好ましくない。The filling auxiliary material used in the present invention has a specific range of packing density and packing volume reduction rate. A packing density of 0.1 to 1.0 g / ml is preferably used. If the packing density is less than 0.1 g / ml, mixing with the catalyst cannot be performed properly,
/ Ml, the catalyst at the time of falling will cause
Disintegration is not preferred.
【０００９】また、充填補助材は充填体積減少率が０．
１kg／cm2 の力を加えた場合１．０〜４０．０％の範囲
のものを用いる。充填体積減少率が１．０％より小さい
と、落下時の物理的衝撃を有効的に和らげることができ
ず、４０．０％より大きいと、変形により、充填補助材
が反応ガスの流路を塞ぐことがあり、好ましくない。Further, the filling auxiliary material has a filling volume reduction rate of 0.1.
When a force of 1 kg / cm 2 is applied, one having a range of 1.0 to 40.0% is used. If the filling volume reduction rate is less than 1.0%, the physical impact at the time of falling cannot be effectively attenuated. If the filling volume reduction rate is more than 40.0%, the filling auxiliary material blocks the reaction gas flow path due to deformation. It may block and is not preferred.
【００１０】充填補助材の使用量は、成型触媒又は担持
触媒に対し１〜７０重量％好ましくは１〜５０重量％の
範囲である。The use amount of the filling auxiliary material is in the range of 1 to 70% by weight, preferably 1 to 50% by weight based on the shaped catalyst or the supported catalyst.
【００１１】ここで、充填補助材の充填密度及び０．１
kg／cm2 の力を加えた場合の充填体積減少率は、断面積
１５．３５cm2 のガラス製シリンダに、充填補助材を１
００ml充填して測定したものである。１００ml充填した
充填補助材の重量がｓ（ｇ）、０．１kg／cm2 の力を加
えたときの充填体積がｔ（ml）であったとすると、充填
密度、充填体積減少率は次式の如く定義される。Here, the filling density of the filling auxiliary material and 0.1
fill volume reduction rate when a force is applied in kg / cm 2 is the glass cylinder of the cross-sectional area 15.35Cm 2, the filling auxiliary material 1
It was measured after filling with 00 ml. Assuming that the weight of the filling auxiliary material filled in 100 ml is s (g) and the filling volume when a force of 0.1 kg / cm 2 is applied is t (ml), the filling density and the filling volume reduction rate are as follows. Is defined as:
【００１２】[0012]
【数１】 (Equation 1)
【００１３】本発明において対象とするモリブデン含有
酸化物触媒としては、例えば不飽和アルデヒド製造用触
媒、不飽和カルボン酸製造用触媒、水素化分解用触媒、
脱硫用触媒等がある。The molybdenum-containing oxide catalysts to be used in the present invention include, for example, a catalyst for producing an unsaturated aldehyde, a catalyst for producing an unsaturated carboxylic acid, a catalyst for hydrocracking,
There are desulfurization catalysts and the like.
【００１４】不飽和アルデヒド製造用触媒及び不飽和カ
ルボン酸製造用触媒の例としては、プロピレンの酸化に
よるアクロレイン及びアクリル酸製造用触媒、アクロレ
インの酸化によるアクリル酸製造用触媒、イソブチレン
又は第三級ブタノールの酸化によるメタクロレイン及び
メタクリル酸製造用触媒及びメタクロレインの酸化によ
るメタクリル酸製造用触媒等がある。Examples of the catalyst for producing an unsaturated aldehyde and the catalyst for producing an unsaturated carboxylic acid include a catalyst for producing acrolein and acrylic acid by oxidizing propylene, a catalyst for producing acrylic acid by oxidizing acrolein, isobutylene and tertiary butanol. And a catalyst for producing methacrylic acid by oxidizing methacrolein.
【００１５】プロピレンの酸化によるアクロレイン及び
アクリル酸製造用触媒としては、一般式 Ｍｏa Ｂｉb Ｆｅc Ａd Ｘe Ｙf Ｚg Ｓｉh Ｏi （ここで式中Ｍｏ、Ｂｉ、Ｆｅ、Ｓｉ及びＯはそれぞれ
モリブデン、ビスマス、鉄、ケイ素及び酸素を示し、Ａ
はニッケル及び／又はコバルトを示し、Ｘはマグネシウ
ム、亜鉛、マンガン、カルシウム、クロム、ニオブ、
銀、バリウム、スズ、タンタル及び鉛からなる群より選
ばれた少なくとも一種の元素を示し、Ｙはリン、ホウ
素、硫黄、セレン、テルル、セリウム、タングステン、
アンチモン及びチタンからなる群より選ばれた少なくと
も一種の元素を示し、Ｚはリチウム、ナトリウム、カリ
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一種の元素を示す。ａ、ｂ、ｃ、
ｄ、ｅ、ｆ、ｇ、ｈ及びｉは各元素の原子比率を表し、
ａ＝１２のときｂ＝０．０１〜３、ｃ＝０．０１〜５、
ｄ＝１〜１２、ｅ＝０〜６、ｆ＝０〜５、ｇ＝０．００
１〜１、ｈ＝０〜２０であり、ｉ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。）で表される
組成を有するものが挙げられる。[0015] As the acrolein and catalyst for acrylic acid production by oxidation of propylene, the formula Mo a Bi b Fe c A d X e Y f Z g Si h O i ( where in the formula Mo, Bi, Fe, Si and O represents molybdenum, bismuth, iron, silicon, and oxygen, respectively;
Represents nickel and / or cobalt, and X represents magnesium, zinc, manganese, calcium, chromium, niobium,
Represents at least one element selected from the group consisting of silver, barium, tin, tantalum and lead, and Y is phosphorus, boron, sulfur, selenium, tellurium, cerium, tungsten,
Z represents at least one element selected from the group consisting of antimony and titanium, and Z represents at least one element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, and thallium. a, b, c,
d, e, f, g, h and i represent the atomic ratio of each element,
When a = 12, b = 0.01-3, c = 0.01-5,
d = 1 to 12, e = 0 to 6, f = 0 to 5, g = 0.00
1 to 1, h = 0 to 20, and i is the number of oxygen atoms necessary to satisfy the valence of each component. )).
【００１６】アクロレインの酸化によるアクリル酸製造
用触媒としては、一般式 Ｍｏa Ｖb Ｓｉc Ａd Ｘe Ｙf Ｏg （ここで式中Ｍｏ、Ｖ、Ｓｉ及びＯはそれぞれモリブデ
ン、バナジウム、ケイ素及び酸素を示し、Ａは鉄、コバ
ルト、クロム及びストロンチウムからなる群より選ばれ
た少なくとも一種の元素を示し、Ｘはゲルマニウム、ホ
ウ素、ヒ素、セレン、銀、ナトリウム、スズ、テルル、
セリウム及びサマリウムからなる群より選ばれた少なく
とも一種の元素を示し、Ｙはマグネシウム、アルミニウ
ム、チタン、マンガン、銅、亜鉛、ジルコニウム、ニオ
ブ、タングステン、タンタル、アンチモン及びビスマス
からなる群より選ばれた少なくとも一種の元素の元素を
示す。ａ、ｂ、ｃ、ｄ、ｅ、ｆ及びｇは各元素の原子比
率を表し、ａ＝１２のときｂ＝０．１〜６、ｃ＝０．１
〜１５、ｄ＝０．１〜３、ｅ＝０〜３、ｆ＝０〜２０で
あり、ｇ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。）で表される組成を有するものが挙げ
られる。[0016] As the catalyst for production of acrylic acid by oxidation of acrolein, the general formula Mo a V b Si c A d X e Y f O g ( wherein wherein Mo, V, Si and O represent molybdenum, vanadium, silicon A represents at least one element selected from the group consisting of iron, cobalt, chromium and strontium, and X represents germanium, boron, arsenic, selenium, silver, sodium, tin, tellurium,
Y represents at least one element selected from the group consisting of cerium and samarium, and Y is at least one selected from the group consisting of magnesium, aluminum, titanium, manganese, copper, zinc, zirconium, niobium, tungsten, tantalum, antimony, and bismuth. Indicates one kind of element. a, b, c, d, e, f and g represent the atomic ratio of each element, and when a = 12, b = 0.1 to 6 and c = 0.1
-15, d = 0.1-3, e = 0-3, f = 0-20, and g is the number of oxygen atoms necessary to satisfy the valence of each component. )).
【００１７】イソブチレン又は第三級ブタノールの酸化
によるメタクロレイン及びメタクリル酸製造用触媒とし
ては、一般式 Ｍｏa Ｂｉb Ｆｅc Ａd Ｘe Ｙf Ｚg Ｏh （ここで式中Ｍｏ、Ｂｉ、Ｆｅ及びＯはそれぞれモリブ
デン、ビスマス、鉄及び酸素を示し、Ａはニッケル及び
／又はコバルトを示し、Ｘはカリウム、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種の元素を示し、Ｙはマグネシウム、亜鉛、マンガ
ン、鉛、錫及びクロムからなる群より選ばれた少なくと
も１種の元素を示し、Ｚはリン、ホウ素、アンチモン、
ケイ素、硫黄、テルル、タングステン及びセリウムから
なる群より選ばれた少なくとも１種の元素を示す。ａ、
ｂ、ｃ、ｄ、ｅ、ｆ、ｇ及びｈは各元素の原子比率を表
し、ａ＝１２のときｂ＝０．０１〜３、ｃ＝０．５〜
４、ｄ＝１〜１２、ｅ＝０．０１〜２、ｆ＝０〜５、ｇ
＝０〜２０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。）で表される組成を有す
るものが挙げられる。The isobutylene or a tertiary butanol methacrolein and methacrylic acid production catalyst for the oxidation of the general formula Mo a Bi b Fe c A d X e Y f Z g O h ( wherein wherein Mo, Bi, Fe and O each represent molybdenum, bismuth, iron and oxygen; A represents nickel and / or cobalt; X represents at least one element selected from the group consisting of potassium, rubidium, cesium and thallium; Represents at least one element selected from the group consisting of magnesium, zinc, manganese, lead, tin and chromium, and Z represents phosphorus, boron, antimony,
It represents at least one element selected from the group consisting of silicon, sulfur, tellurium, tungsten and cerium. a,
b, c, d, e, f, g and h represent the atomic ratio of each element, and when a = 12, b = 0.01 to 3 and c = 0.5 to
4, d = 1 to 12, e = 0.01 to 2, f = 0 to 5, g
= 0 to 20, and h is the number of oxygen atoms necessary to satisfy the valence of each component. )).
【００１８】また、メタクロレインの酸化によるメタク
リル酸製造用触媒としては、一般式 Ｐa Ｍｏb Ｖc Ｘd Ｙe Ｚf Ｏg （ここで式中Ｐ、Ｍｏ、Ｖ及びＯはそれぞれリン、モリ
ブデン、バナジウム及び酸素を示し、Ｘはヒ素、アンチ
モン、ビスマス、ゲルマニウム、ジルコニウム、テル
ル、銀、セレン及びホウ素からなる群より選ばれた少な
くとも１種の元素を示し、Ｙは鉄、銅、亜鉛、クロム、
マグネシウム、タンタル、マンガン、バリウム、ガリウ
ム、セリウム及びランタンからなる群より選ばれた少な
くとも１種の元素を示し、Ｚはカリウム、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。ａ、ｂ、ｃ、ｄ、ｅ、ｆ及びｇは
各元素の原子比率を表し、ｂ＝１２のときａ＝０．５〜
３、ｃ＝０．０１〜３、ｄ＝０〜３、ｅ＝０〜３、ｆ＝
０．０１〜３であり、ｇ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。）で表される組成を有
するものが挙げられる。Further, as the catalyst for producing methacrylic acid by oxidation of methacrolein, the general formula P a Mo b V c X d Y e Z f O g ( wherein wherein P, Mo, V and O represent phosphorus, X represents molybdenum, vanadium and oxygen, X represents at least one element selected from the group consisting of arsenic, antimony, bismuth, germanium, zirconium, tellurium, silver, selenium and boron, and Y represents iron, copper, zinc, chromium,
Magnesium, tantalum, manganese, barium, gallium, cerium, and at least one element selected from the group consisting of lanthanum, wherein Z is potassium, rubidium,
It shows at least one element selected from the group consisting of cesium and thallium. a, b, c, d, e, f and g represent the atomic ratio of each element, and when b = 12, a = 0.5 to
3, c = 0.01-3, d = 0-3, e = 0-3, f =
G is the number of oxygen atoms necessary to satisfy the valence of each component. )).
【００１９】これらモリブデン含有酸化物触媒は、成型
触媒でも担持触媒でもよい。成型触媒の形状については
どくに限定はなく、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る。ま
た、その形状についてもとく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。These molybdenum-containing oxide catalysts may be shaped catalysts or supported catalysts. The shape of the molded catalyst is not particularly limited, and may be spherical, cylindrical, cylindrical, star-shaped, etc.
What is molded by a usual tableting machine, an extrusion molding machine, a rolling granulator, or the like is used. When using a supported catalyst, the type of carrier is silica, alumina, silica-alumina,
Conventional carriers such as magnesia and titania are used. Further, the shape is not particularly limited, and examples thereof include a sphere, a column, a cylinder, and a plate.
【００２０】[0020]
【実施例】以下、実施例を挙げて本発明を更に説明す
る。なお文中「部」は重量部を意味する。また、成型触
媒又は担持触媒の充填粉化率（％）は次のように定義さ
れる。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。The present invention will be further described below with reference to examples. In the description, "parts" means parts by weight. The filling powder ratio (%) of the molded catalyst or the supported catalyst is defined as follows. It is assumed that the catalyst a part is filled from the upper part of the reactor installed vertically to the horizontal direction, and that the catalyst recovered from the reactor bottom part after the filling does not pass through the 14-mesh sieve is part b.
【００２１】[0021]
【数２】 (Equation 2)
【００２２】実施例１ プロピレンの酸化によるアクロレイン及びアクリル酸製
造用触媒である下記の組成の触媒粉末を調製した。 Ｍｏ12Ｗ0.3 Ｂｉ1 Ｆｅ1 Ｃｏ5 Ｋ0.06Ｔｅ0.1 Ｏx （式中元素記号右下の数字は各元素の原子比を表わし、
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３mmの円筒形に打錠成型した。Example 1 A catalyst powder having the following composition, which is a catalyst for producing acrolein and acrylic acid by propylene oxidation, was prepared. Mo 12 W 0.3 Bi 1 Fe 1 Co 5 K 0.06 Te 0.1 O x (The numbers at the lower right of the element symbols represent the atomic ratio of each element,
x is the number of oxygen atoms necessary to satisfy the valence of each component. same as below. ) After 970 parts of the obtained catalyst powder were mixed well with 30 parts of graphite powder, the outer diameter was 5 mm,
It was tableted into a cylinder having an inner diameter of 2 mm and a height of 3 mm.
【００２３】上記で得られた成型触媒２kgに充填補助材
として、岩尾磁器工業社製のステンレス製マクマホン・
パッキング ３／８インチ（充填密度０．３４ｇ／ml、
充填体積減少率３．９％）を１００ｇ混合して、内径３
cm、長さ５ｍのステンレス製円筒型反応器上部から落下
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。As a filling auxiliary material for 2 kg of the molded catalyst obtained above, a stainless steel McMahon made by Iwao Porcelain Industrial Co., Ltd.
Packing 3/8 inch (packing density 0.34g / ml,
100 g of a filling volume reduction rate of 3.9%),
The liquid was dropped and filled from the top of a stainless steel cylindrical reactor having a length of 5 m and a length of 5 cm. When the powdering ratio at this time was measured,
0.6%.
【００２４】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、充填補助材を使用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、４．７％であった。Comparative Example 1 The molded catalyst obtained in the same manner as in Example 1 was dropped and packed in the same reactor as in Example 1 without using a filling auxiliary material. When the powdering ratio at this time was measured, it was 4.7%.
【００２５】実施例２ アクロレインの酸化によるアクリル酸製造用触媒である
下記の組成の触媒粉末を調製した。 Ｍｏ12Ｖ3 Ｓｉ4 Ｎａ0.7 Ｆｅ0.5 Ｃｏ0.5 Ｏx 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, which is a catalyst for producing acrylic acid by oxidation of acrolein, was prepared. Mo 12 V 3 Si 4 Na 0.7 Fe 0.5 Co 0.5 O x 970 parts of the obtained catalyst powder were mixed well with 30 parts of graphite powder, and then tableted into a cylinder having a diameter of 5 mm and a height of 4 mm.
【００２６】この成型触媒２kgに充填補助材として、直
径６mm、高さ４mmの円柱形のセラミックファイバーボー
ド（充填密度０．４８ｇ／ml、充填体積減少率７．２
％）を５００ｇ混合して、実施例１と同様の反応器に落
下充填した。このときの充填粉化率を測定したところ、
０．３％であった。A cylindrical ceramic fiber board having a diameter of 6 mm and a height of 4 mm (filling density 0.48 g / ml, filling volume reduction rate 7.2) was added to 2 kg of the molded catalyst as a filling auxiliary material.
%) Was dropped and charged into the same reactor as in Example 1. When the powdering ratio at this time was measured,
0.3%.
【００２７】比較例２ 実施例２と同様にして得られた成型触媒２kgに、充填補
助材として、直径７mmのセラミックボール（充填密度
１．２５ｇ／ml、充填体積減少率０％）を５００ｇ混合
して、実施例１と同様の反応器に落下充填した。このと
きの充填粉化率を測定したところ、５．２％であった。Comparative Example 2 To 2 kg of the molded catalyst obtained in the same manner as in Example 2, 500 g of ceramic balls having a diameter of 7 mm (filling density: 1.25 g / ml, filling volume reduction rate: 0%) were mixed as a filling aid. Then, the same reactor as in Example 1 was dropped and filled. When the powdering ratio at this time was measured, it was 5.2%.
【００２８】実施例３ イソブチレン又は第三級ブタノールの酸化によるメタク
ロレイン及びメタクリル酸製造用触媒である下記の組成
の触媒粉末を調製した。 Ｍｏ12Ｗ0.2 Ｂｉ0.5 Ｆｅ2.5 Ｎｉ7 Ｃｓ0.5 Ｏx 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, which is a catalyst for producing methacrolein and methacrylic acid by oxidizing isobutylene or tertiary butanol, was prepared. Mo 12 W 0.2 Bi 0.5 Fe 2.5 Ni 7 Cs 0.5 O x 200 parts of the obtained catalyst powder were supported on 800 parts of a spherical alumina support having a diameter of 4 mm.
【００２９】この担持触媒２kgに充填補助材として、直
径略５mmに丸めたステンレス製たわし（充填密度０．７
８ｇ／ml、充填体積減少率２．５％）を３００ｇ混合し
て、実施例１と同様の反応器に落下充填した。このとき
の充填粉化率を測定したところ、０．１％であった。As a filling auxiliary material for 2 kg of the supported catalyst, a stainless steel scissor rounded to a diameter of about 5 mm (a packing density of 0.7 mm) was used.
300 g of the same reactor as in Example 1 was dropped and charged into the same reactor as in Example 1. The powdering ratio at this time was measured and found to be 0.1%.
【００３０】比較例３ 実施例３と同様にして得られた担持触媒２kgに、充填補
助材として、直径５mmのシリカ・アルミナ多孔体（充填
密度０．９７ｇ／ml、充填体積減少率０％）を３００ｇ
混合して、実施例１と同様の反応器に落下充填した。こ
のときの充填粉化率を測定したところ、１．２％であっ
た。Comparative Example 3 Porous silica-alumina having a diameter of 5 mm (packing density 0.97 g / ml, packing volume reduction rate 0%) was added to 2 kg of the supported catalyst obtained in the same manner as in Example 3 as a filling auxiliary material. 300g
After mixing, the mixture was dropped and filled in the same reactor as in Example 1. The powdering ratio at this time was measured and was found to be 1.2%.
【００３１】実施例４ メタクロレインの酸化によるメタクリル酸製造用触媒で
ある下記の組成の触媒粉末を調製した。 Ｐ1.5 Ｍｏ12Ｖ0.8 Ｓｂ0.5 Ｃｕ0.1 Ｋ1 Ｏx 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, which is a catalyst for producing methacrylic acid by oxidizing methacrolein, was prepared. A small amount of water was added to P 1.5 Mo 12 V 0.8 Sb 0.5 Cu 0.1 K 1 O x catalyst powder obtained, after mixing well,
It was molded into a cylinder having a diameter of 4 mm and a height of 5 mm by an extruder.
【００３２】この成型触媒２kgに充填補助材として、直
径３mm、高さ５mmの円筒状ステンレス製スプリング（充
填密度０．６５ｇ／ml、充填体積減少率２．３％）を４
００ｇ混合して、実施例１と同様の反応器に落下充填し
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。A cylindrical stainless steel spring having a diameter of 3 mm and a height of 5 mm (filling density: 0.65 g / ml, filling volume reduction rate: 2.3%) was added to 2 kg of the molded catalyst as a filling auxiliary material.
Then, the same reactor as in Example 1 was dropped and charged. When the powdering ratio at this time was measured, 0.2%
Met.
【００３３】比較例４ 実施例４と同様にして得られた成型触媒２kgに、充填補
助材として、直径５mm、幅５mmの渦巻き状ステンレス製
テープ（充填密度１．３５ｇ／ml、充填体積減少率２．
５％）を４００ｇ混合して、実施例１と同様の反応器に
落下充填した。このときの充填粉化率を測定したとこ
ろ、１．５％であった。Comparative Example 4 A spiral stainless steel tape having a diameter of 5 mm and a width of 5 mm (filling density 1.35 g / ml, filling volume reduction rate) was added to 2 kg of the molded catalyst obtained in the same manner as in Example 4 as a filling auxiliary material. 2.
5%) was dropped and charged into the same reactor as in Example 1. When the powdering ratio at this time was measured, it was 1.5%.
【００３４】[0034]
【発明の効果】本発明による方法で、充填補助材を触媒
に混合して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・崩壊が著しく防止できる。このためモ
リブデン含有酸化物触媒を用いる各種反応生成物の収率
向上に寄与する。また、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。したがって、触媒設計上の制限が少なくな
り、幅広い条件での触媒製造が可能となる。According to the method of the present invention, when a filling auxiliary material is mixed with a catalyst and charged into a reactor, powdering and collapse of the catalyst due to physical impact at the time of falling can be significantly prevented. This contributes to improving the yield of various reaction products using the molybdenum-containing oxide catalyst. In addition, there is no need to increase the mechanical strength of the catalyst more than necessary due to concern about powdering of the catalyst at the time of filling. Therefore, restrictions on catalyst design are reduced, and catalyst production under a wide range of conditions becomes possible.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０７Ｃ 57/055 Ｃ０７Ｃ 57/055 Ａ // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ (72)発明者 内藤 啓幸 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 (56)参考文献 特開 昭50−41782（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) B01J 8/02 C07B 61/00──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification symbol FI C07C 57/055 C07C 57/055 A // C07B 61/00 300 C07B 61/00 300 (72) Inventor Hiroyuki Naito Otake City, Hiroshima Prefecture 20-1 Miyukicho Inside the Central Research Laboratory, Mitsubishi Rayon Co., Ltd. (56) References JP-A-50-41782 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) B01J 8/02 C07B 61/00
Claims (1)
て、かつ、０．１kg／cm2 の力を加えた場合の充填体積
減少率が１．０〜４０．０％である充填補助材を、モリ
ブデン含有酸化物触媒に対して１〜７０重量％混合して
反応管に落下充填することを特徴とするモリブデン含有
酸化物触媒の充填方法。1. A packing density of 0.1 to 1.0 g / ml and a reduction rate of a filling volume of 1.0 to 40.0% when a force of 0.1 kg / cm 2 is applied. A method for filling a molybdenum-containing oxide catalyst, comprising mixing a certain filling auxiliary material in an amount of 1 to 70% by weight with respect to the molybdenum-containing oxide catalyst and dropping the mixture into a reaction tube.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3306528A JP2819078B2 (en) | 1991-10-25 | 1991-10-25 | Method for filling molybdenum-containing oxide catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3306528A JP2819078B2 (en) | 1991-10-25 | 1991-10-25 | Method for filling molybdenum-containing oxide catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05293359A JPH05293359A (en) | 1993-11-09 |
| JP2819078B2 true JP2819078B2 (en) | 1998-10-30 |
Family
ID=17958111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3306528A Expired - Lifetime JP2819078B2 (en) | 1991-10-25 | 1991-10-25 | Method for filling molybdenum-containing oxide catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2819078B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007289810A (en) * | 2006-04-21 | 2007-11-08 | Mitsubishi Rayon Co Ltd | Method for isolating auxiliary metallic filler |
| JP5112849B2 (en) * | 2007-12-28 | 2013-01-09 | 三菱レイヨン株式会社 | Fixed bed reactor and method for producing unsaturated carboxylic acid |
| JP5163273B2 (en) | 2008-05-16 | 2013-03-13 | 住友化学株式会社 | Method for producing catalyst for producing unsaturated aldehyde and / or unsaturated carboxylic acid, and method for producing unsaturated aldehyde and / or unsaturated carboxylic acid |
-
1991
- 1991-10-25 JP JP3306528A patent/JP2819078B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JPH05293359A (en) | 1993-11-09 |
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