JP3314457B2 - Process for producing unsaturated aldehyde and unsaturated carboxylic acid - Google Patents
Process for producing unsaturated aldehyde and unsaturated carboxylic acidInfo
- Publication number
- JP3314457B2 JP3314457B2 JP15488593A JP15488593A JP3314457B2 JP 3314457 B2 JP3314457 B2 JP 3314457B2 JP 15488593 A JP15488593 A JP 15488593A JP 15488593 A JP15488593 A JP 15488593A JP 3314457 B2 JP3314457 B2 JP 3314457B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- catalyst
- unsaturated
- carboxylic acids
- unsaturated carboxylic
- 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 - Fee Related
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
- Y02P20/584—Recycling of catalysts
Landscapes
- Catalysts (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、プロピレン又はイソブ
チレンを気相接触酸化して不飽和アルデヒドおよび不飽
和酸を製造する方法に関する。詳しくは該方法に用いる
複合酸化物触媒の性能劣化を抑制する方法に関する。The present invention relates to a process for producing unsaturated aldehydes and unsaturated acids by subjecting propylene or isobutylene to gas-phase catalytic oxidation. More specifically, the present invention relates to a method for suppressing the performance deterioration of the composite oxide catalyst used in the method.
【０００２】[0002]
【従来の技術】いわゆるモリブデン−ビスマス系複合酸
化物触媒を用いた気相接触酸化反応によるプロピレンか
らのアクロレイン及びアクリル酸の製造、イソブチレン
からのメタクロレイン及びメタクリル酸の製造、また気
相接触アンモ酸化によるアクリロニトリル、メタクリロ
ニトリルの製造はよく知られている。しかし、この触媒
は長期間、反応を継続すると、時間経過と共に触媒の性
能劣化により反応活性、選択性が低下するという問題点
を有している。2. Description of the Related Art Production of acrolein and acrylic acid from propylene, production of methacrolein and methacrylic acid from isobutylene by gas phase catalytic oxidation reaction using a so-called molybdenum-bismuth composite oxide catalyst, and gas phase catalytic ammoxidation The production of acrylonitrile and methacrylonitrile by the company is well known. However, this catalyst has a problem that if the reaction is continued for a long period of time, the activity and selectivity of the catalyst are reduced due to deterioration of the performance of the catalyst with the passage of time.
【０００３】この複合酸化物触媒の性能劣化を抑制する
方法はいくつか知られている。例えば、特開昭５９−１
９３１３６号には、不活性な耐熱性無機物質に酸化モリ
ブデンを担持した担持物を充填する方法が、特公昭６３
−３８３３１号には、モリブデン−ビスマス系多元触媒
の成分中のアルカリ金属とタリウム群元素の種類及び／
又は量を変えることにより、活性を制御された複数種の
触媒を用意し、原料ガス入口側より出口側に向かって活
性のより高い触媒を配置する方法が提案されている。Several methods are known for suppressing the performance deterioration of the composite oxide catalyst. For example, Japanese Unexamined Patent Publication No.
No. 93136 discloses a method of filling a support in which molybdenum oxide is supported on an inert heat-resistant inorganic substance.
No. 38331 describes the types of alkali metals and thallium group elements in the components of the molybdenum-bismuth multi-component catalyst and / or
Alternatively, a method has been proposed in which a plurality of types of catalysts whose activities are controlled by changing the amount are prepared, and a catalyst having higher activity is arranged from the inlet side of the raw material gas toward the outlet side.
【０００４】また、特公昭５３−３０６８８号には、触
媒の活性を反応管の入口から出口まで反応ガスの流れ方
向に連続的に、または段階的に１００％まで増大するよ
う不活性物質で希釈して変化させる方法が提案されてい
る。Japanese Patent Publication No. 53-30688 discloses that a catalyst is diluted with an inert substance so as to continuously or stepwise increase the activity of a catalyst from the inlet to the outlet of a reaction tube to 100% in the flow direction of the reaction gas. There has been proposed a method of changing this.
【０００５】[0005]
【発明が解決しようとする課題】上記の従来方法はそれ
ぞれ有効な方法ではあるが、例えば、特開昭５９−１９
３１３６号では、不活性な耐熱性無機物質に担持しなけ
ればならないという制約があること、また実施例による
と、不活性な耐熱性無機物質に担持したモリブデン酸ア
ンモニウムを５００℃で２時間焼成して使用している
が、本発明者らが検討したところによると、この方法で
は担体は不活性でもモリブデンが必ずしも不活性ではな
いため、選択性が悪くなり、実用上問題のあることがわ
かった。The above-mentioned conventional methods are respectively effective methods.
According to No. 3136, there is a restriction that it must be supported on an inert heat-resistant inorganic substance. According to the embodiment, ammonium molybdate supported on the inert heat-resistant inorganic substance is calcined at 500 ° C. for 2 hours. However, according to the study by the present inventors, it has been found that in this method, since the carrier is inactive but molybdenum is not necessarily inactive, the selectivity is deteriorated and there is a practical problem. .
【０００６】また、特公昭６３−３８３３１号および特
公昭５３−３０６８８号にみられる触媒の組成変更また
は触媒の希釈により活性を制御して、局部的な高温を避
ける方法は、劣化原因の一つである触媒中のモリブデン
の逃散をある程度抑制し、有効な方法であるものの、触
媒性能を長期的に抑制できるものではない等、工業的に
必ずしも十分満足できる方法ではない。The method of controlling the activity by changing the composition of the catalyst or diluting the catalyst as disclosed in JP-B-63-38331 and JP-B-53-30688 is one of the causes of deterioration. Although it is an effective method of suppressing the escape of molybdenum in the catalyst to some extent, it is not a method that is industrially sufficiently satisfactory, such as not being able to suppress catalyst performance for a long period of time.
【０００７】本発明者らは、かかる課題を解決するた
め、触媒の性能劣化原因の究明および触媒の使用方法に
ついて鋭意検討を重ねた結果、プロピレン又はイソブチ
レンを気相接触酸化して不飽和アルデヒド及び不飽和カ
ルボン酸を製造する方法において、該反応に優れた触媒
活性を有する複合酸化物触媒と共に反応に実質的に不活
性な酸化モリブデンを存在させて反応することにより、
長期にわたって該触媒の性能劣化が抑制されることを見
出し、本発明に至った。The inventors of the present invention have intensively studied the causes of catalyst performance degradation and studied how to use the catalyst in order to solve such problems. As a result, propylene or isobutylene was oxidized in the gas phase to oxidize unsaturated aldehydes and In the method for producing an unsaturated carboxylic acid, by reacting with a composite oxide catalyst having excellent catalytic activity in the reaction in the presence of molybdenum oxide substantially inert to the reaction,
The present inventors have found that performance deterioration of the catalyst is suppressed for a long period of time, and have reached the present invention.
【０００８】[0008]
【課題を解決するための手段】すなわち本発明は、一般
式 ＭｏaＢｉbＦｅcＡd Ｂ e Ｃ f Ｏx （Ｍｏ、ＢｉおよびＦｅはそれぞれモリブデン、ビスマ
スおよび鉄を表し、Ａはニッケルおよび／またはコバル
トを表し、Ｂはリン、ホウ素、ヒ素、テルル、タングス
テン、アンチモ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、Ｃはカリウム、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、ａ＝１２としたとき、０＜
ｂ≦１０、０＜ｃ≦１０、１≦ｄ≦１０、０≦ｅ≦１
０、０＜ｆ≦２であり、ｘは各元素の酸化状態により定
まる値である。）で示される複合酸化物触媒を用いてプ
ロピレン又はイソブチレンを分子状酸素で気相接触酸化
して相当する不飽和アルデヒド及び不飽和カルボン酸を
製造する方法において、複合酸化物触媒と共に反応に実
質的に不活性な酸化モリブデンを存在させて反応を行う
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
酸の製造方法である。That is, the present invention SUMMARY OF] represents a general formula Mo a Bi b Fe c A d B e C f O x (Mo, Bi and Fe represent molybdenum, bismuth and iron, A is nickel and / Represents cobalt , B represents at least one element selected from the group consisting of phosphorus, boron, arsenic, tellurium, tungsten, antimony and silicon; and C represents a group selected from the group consisting of potassium, rubidium, cesium and thallium. Represents at least one element, and when a = 12, 0 <
b ≦ 10 , 0 <c ≦ 10, 1 ≦ d ≦ 10 , 0 ≦ e ≦ 1
0, 0 < f ≦ 2, and x is a value determined by the oxidation state of each element. ), Wherein propylene or isobutylene is vapor-phase catalytically oxidized with molecular oxygen to produce the corresponding unsaturated aldehydes and unsaturated carboxylic acids using the composite oxide catalyst. the unsaturated aldehyde and a manufacturing method of an unsaturated carboxylic acid, wherein the <br/> carrying out the reaction in the presence of a inert molybdenum oxide.
【０００９】本発明はプロピレンを分子状酸素で気相接
触酸化してアクロレイン及びアクリル酸を製造する方
法、イソブチレンを分子状酸素で気相接触酸化してメタ
クロレイン及びメタクリル酸を製造する方法に適用され
る。なお、プロピレンを分子状酸素とアンモニアでアン
モ酸化してアクリロニトリルを製造する方法、イソブチ
レンを分子状酸素とアンモニアでアンモ酸化してメタク
リロニトリルを製造する方法にも適用できる。The present invention is applied to a method for producing acrolein and acrylic acid by gas-phase catalytic oxidation of propylene with molecular oxygen, and a method for producing methacrolein and methacrylic acid by gas-phase catalytic oxidation of isobutylene with molecular oxygen. Is done. The present invention can be applied to a method for producing acrylonitrile by ammoxidizing propylene with molecular oxygen and ammonia, and a method for producing methacrylonitrile by ammoxidizing isobutylene with molecular oxygen and ammonia.
【００１０】本発明の方法において用いられる触媒は、
通常、プロピレン又はイソブチレンの酸化又はアンモ酸
化に使用されている複合酸化物触媒であり、その組成は
上記一般式で示されるものであり、この範囲内では特に
制限されるものではない。The catalyst used in the method of the present invention is
Usually, it is a composite oxide catalyst used for oxidation or ammoxidation of propylene or isobutylene, and its composition is represented by the above general formula, and is not particularly limited within this range.
【００１１】この複合酸化物触媒は優れた触媒活性を有
するが、これを長期に使用していると、反応時間の経過
と共に触媒が性能劣化して、反応率、目的生成物の選択
率などの反応成績が悪くなる。その原因の一つは、触媒
中のモリブデンの一部が高温により昇華、逃散するため
と考えられている。Although this composite oxide catalyst has excellent catalytic activity, if it is used for a long period of time, the performance of the catalyst deteriorates as the reaction time elapses, and the reaction rate and the selectivity of the target product are reduced. Poor reaction performance. One of the causes is considered that a part of molybdenum in the catalyst sublimates and escapes due to high temperature.
【００１２】工業的なオレフィンの気相接触反応におい
て、一般に使用されている固定床反応器には、反応にお
いて多量に発生する熱による触媒層の温度分布を少なく
するために管径約２０〜５０ｍｍ、長さ約１〜６ｍの反
応管を複数本束ねた多管式のものが採用されている。し
かし、反応器内では、熱媒体と触媒層との温度差が約３
０〜１００℃になる場合があり、触媒層の温度も高温、
例えば４００℃以上の高温となることもある。また原料
ガス導入部分では、オレフィン濃度も高く反応熱も多量
であるため、特に熱媒体との温度差が大きくなり、触媒
中のモリブデンの昇華、逃散が多くなると考えられる。In an industrial olefin gas-phase catalytic reaction, a generally used fixed-bed reactor has a tube diameter of about 20 to 50 mm in order to reduce the temperature distribution of the catalyst layer due to heat generated in the reaction in a large amount. And a multi-tube type in which a plurality of reaction tubes having a length of about 1 to 6 m are bundled. However, in the reactor, the temperature difference between the heating medium and the catalyst layer is about 3
0 to 100 ° C., the temperature of the catalyst layer is also high,
For example, the temperature may be as high as 400 ° C. or more. Also, since the olefin concentration is high and the reaction heat is large in the raw material gas introduction part, it is considered that the temperature difference from the heat medium is particularly large, and sublimation and escape of molybdenum in the catalyst are increased.
【００１３】このことは、実際に数年間使用した触媒の
入口付近と中央以降の部分について組成分析及び性能評
価した結果、入口付近の方が触媒表面のモリブデン成分
が、中央及び出口部分より少なくなっており、またその
入口付近の方が活性及び選択性の低下が他の部分より大
きくなっていることから裏付けられる。[0013] This means that, as a result of analyzing the composition and evaluating the performance near the inlet and the center of the catalyst actually used for several years, the molybdenum component on the catalyst surface near the inlet is smaller than that at the center and the outlet. And that the decrease in activity and selectivity near the entrance is greater than in other parts.
【００１４】本発明において、上記の複合酸化物触媒と
共に反応に実質的に不活性な酸化モリブデンを存在させ
て使用する。このことにより触媒の性能劣化を長期にに
わたって抑制できる。In the present invention, molybdenum oxide which is substantially inert to the reaction is used together with the above-mentioned composite oxide catalyst. As a result, catalyst performance deterioration can be suppressed for a long period of time.
【００１５】本発明において使用される酸化モリブデン
は、反応に実質的に不活性なものであれば特に限定され
ないが、例えば市販のモリブデン酸アンモニウム、三酸
化モリブデン等のモリブデン化合物を空気中で約５５０
〜７００℃で焼成することにより得られる。これより低
温で焼成した三酸化モリブデンはオレフィンの完全酸化
活性を有しており、これを触媒と共存させた場合、反応
の選択性を悪くする原因となる。なお、既に不活性なも
のを改めて焼成する必要はなく、市販の三酸化モリブデ
ンの中から反応に不活性なものを用いることもできる。The molybdenum oxide used in the present invention is not particularly limited as long as it is substantially inert to the reaction. For example, a commercially available molybdenum compound such as ammonium molybdate and molybdenum trioxide can be used in the presence of about 550 in air.
It is obtained by firing at ~ 700 ° C. Molybdenum trioxide calcined at a lower temperature than this has a complete olefin oxidation activity, and when coexisting with a catalyst, it causes poor reaction selectivity. Note that it is not necessary to calcine the already inactive material again, and a commercially available molybdenum trioxide that is inert to the reaction can be used.
【００１６】反応に実質的に不活性な酸化モリブデンを
複合酸化物触媒と共存させる方法は特に限定されるもの
ではなく、反応に実質的に不活性な酸化モリブデンを単
独またはシリカなどの不活性な担体と共に、打錠、押出
し、含浸等の方法で成形したものを、成形した複合酸化
触媒と反応器に混合充填する方法、または触媒の成形段
階で、予め不活性化した酸化モリブデンの粉末を複合酸
化物触媒成分の粉体と混合し、それを打錠成形、押出し
成形または担持成形して得られる触媒を用いる方法でも
良い。The method of coexisting molybdenum oxide substantially inert to the reaction with the composite oxide catalyst is not particularly limited, and molybdenum oxide substantially inert to the reaction may be used alone or in an inert gas such as silica. A method of mixing and molding a molded article by a method such as tableting, extrusion, and impregnation together with a carrier, and mixing and filling the molded composite oxidation catalyst and a reactor, or a step of molding the catalyst, in which a powder of molybdenum oxide previously inactivated is combined. A method using a catalyst obtained by mixing with the powder of the oxide catalyst component and tableting, extruding or carrying and molding the mixture may be used.
【００１７】反応に実質的に不活性な酸化モリブデンを
複合酸化物触媒と共存させる位置および充填方法は、少
なくとも反応ガス入口部に共存させることを除いては特
に制限されるものではなく、触媒層全体にわたって共存
させてもよく、入口部だけに共存させてもよい。また連
続的に或いは段階的に共存させる濃度を変えて充填して
もよいが、ガス入口側から出口側に向けて触媒の活性が
高くなるように配置させるよう、少なくとも触媒の劣化
しやすい入口部のホットスポット付近に共存させる方法
がより効果的である。反応に実質的に不活性な酸化モリ
ブデンを共存させない場合、触媒の劣化はこのホットス
ポットで最も大きく、この部分だけで劣化防止の効果が
得られるだけでなく、触媒の希釈効果により入口部の発
熱を抑えることで過度の酸化を抑え選択性の向上または
単位触媒当たりの生産性の向上の効果が得られる。There is no particular limitation on the location and the method of filling the molybdenum oxide which is substantially inert to the reaction with the composite oxide catalyst, except that it is present at least at the reaction gas inlet. It may be made to coexist all over, or may be made to coexist only at the entrance. The gas may be filled continuously or stepwise at different concentrations, but at least at the inlet portion where the catalyst is apt to deteriorate so that the catalyst is arranged so that the activity of the catalyst increases from the gas inlet side toward the outlet side. The method of coexisting near the hot spot is more effective. When molybdenum oxide, which is substantially inactive in the reaction, is not present, the deterioration of the catalyst is the largest at this hot spot, and not only the effect of preventing the deterioration is obtained at this portion alone, but also the heat generation at the inlet due to the dilution effect of the catalyst. By suppressing the excessive oxidation, an effect of improving the selectivity or the productivity per unit catalyst can be obtained.
【００１８】プロピレン又はイソブチレンの分子状酸素
による気相接触酸化反応の反応条件は、従来公知の方法
で行うことができる。例えば、反応温度２８０〜４００
℃、反応圧力は減圧でも可能であるが、通常、常圧〜５
ａｔｍ、酸素／オレフィン（モル比）は１〜３、空間速
度ＳＶ＝５００〜５０００／Ｈで適宜行われる。The reaction conditions for the gas phase catalytic oxidation reaction of propylene or isobutylene with molecular oxygen can be carried out by a conventionally known method. For example, a reaction temperature of 280 to 400
℃, the reaction pressure can be reduced pressure, but usually from normal pressure to 5
Atm, oxygen / olefin (molar ratio) is 1 to 3, space velocity SV = 500 to 5000 / H.
【００１９】[0019]
【発明の効果】本発明の方法により、プロピレン又はイ
ソブチレンの気相接触酸化反応における複合酸化物触媒
の性能劣化を従来方法よりも長期にわたって抑制でき、
その工業的意義は非常に大きいものがある。According to the method of the present invention, the performance deterioration of the composite oxide catalyst in the gas phase catalytic oxidation reaction of propylene or isobutylene can be suppressed for a longer period than in the conventional method.
Its industrial significance is very large.
【００２０】[0020]
【実施例】以下、実施例を挙げて本発明をさらに詳細に
説明するが、本発明はこれに限定されるものではない。
なお、反応率（％）、選択率（％）は、次の如く定義す
る。 反応率(%) ＝（反応したオレフィンのモル数／供給した
オレフィンのモル数）×１００ 選択率(%) ＝（生成物のモル数／反応したオレフィンの
モル数）×（生成物の炭素数／原料オレフィンの炭素
数）×１００The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples.
The reaction rate (%) and the selectivity (%) are defined as follows. Conversion (%) = (moles of reacted olefin / moles of supplied olefin) × 100 Selectivity (%) = (moles of product / moles of reacted olefin) × (carbon number of product) / Carbon number of raw olefin) x 100
【００２１】実施例１ 〔複合酸化物触媒の調製〕 モリブデン酸アンモニウム
〔（ＮＨ4 ）6 Ｍｏ7 Ｏ 24・４Ｈ2 Ｏ〕１４４ｇを温水
４７０ｍｌに溶解し、さらに２０％シリカゾル（ＳｉＯ
2 ）２０．４ｇを加え、これをＡ液とする。硝酸ニッケ
ル〔Ｎｉ（ＮＯ3）2 ・６Ｈ2 Ｏ〕２ｇおよび硝酸コバ
ルト〔Ｃｏ（ＮＯ3 ）2 ・６Ｈ2 Ｏ〕１３８．５ｇおよ
び硝酸第二鉄〔Ｆｅ（ＮＯ3 ）3 ・９Ｈ2 Ｏ〕５５ｇお
よび硝酸タリウム（ＴｌＮＯ3 ）３．３ｇを温水２５０
ｍｌに溶解し、これをＢ液とする。純水４０ｍｌに６０
％硝酸９．４ｇを加え、硝酸ビスマス〔Ｂｉ（ＮＯ3 ）
3 ・５Ｈ2 Ｏ〕３３ｇを溶解し、これをＣ液とする。次
にＢ液とＣ液を混合する。Example 1 Preparation of Composite Oxide Catalyst Ammonium molybdate
[(NHFour)6Mo7O twenty four・ 4HTwoO] 144 g of warm water
470 ml, and further dissolved in 20% silica sol (SiO 2
Two) 20.4 g was added, and this was designated as solution A. Nickel nitrate
Ru [Ni (NOThree)Two・ 6HTwoO] 2 g and nitric acid nitrate
Ruto [Co (NOThree)Two・ 6HTwoO] 138.5 g and
Ferric nitrate [Fe (NOThree)Three・ 9HTwoO] 55g
And thallium nitrate (TlNOThree) 3.3 g of hot water 250
Dissolve in B.L. 60 in 40 ml of pure water
% Nitric acid (9.4 g) was added, and bismuth nitrate [Bi (NOThree)
Three・ 5HTwoO] 33 g was dissolved, and this was used as solution C. Next
Mix liquid B and liquid C.
【００２２】Ａ液を撹拌しながら、ＢとＣの混合液を添
加し、ついで燐酸（Ｈ3 ＰＯ4 ）０．８ｇを加えてスラ
リーを得る。これを濃縮乾燥後、空気流通下２００〜２
５０℃で塩分解する。その後粉砕し、５ｍｍФ×２ｍｍ
Ф×５ｍｍＨの円筒状に打錠成形し、４８０℃で６時間
空気中で焼成して触媒とした。触媒組成はＭｏ12Ｂｉ1
Ｆｅ2 Ｎｉ0.1 Ｃｏ7 Ｔｌ0.18Ｐ0.1 Ｓｉ1 （酸素を除
く。以下同様に記載する。）である。While stirring the solution A, a mixed solution of B and C is added, and then 0.8 g of phosphoric acid (H 3 PO 4 ) is added to obtain a slurry. After concentrating and drying this, under air circulation 200 to 2
Decomposes salt at 50 ° C. Then pulverize, 5mmФ × 2mm
A tablet was formed into a cylindrical shape of Ф × 5 mmH, and calcined at 480 ° C. for 6 hours in the air to obtain a catalyst. The catalyst composition is Mo 12 Bi 1
Fe 2 Ni 0.1 Co 7 Tl 0.18 P 0.1 Si 1 (excluding oxygen; hereinafter similarly described).
【００２３】別に、モリブデン酸アンモニウム〔（ＮＨ
4 ）6 Ｍｏ7 Ｏ24・４Ｈ2 Ｏ〕１００ｇを６５０℃で６
時間空気中で焼成して、ＭｏＯ3 をつくった。Separately, ammonium molybdate [(NH
4) The 6 Mo 7 O 24 · 4H 2 O ] 100g at 650 ° C. 6
Calcination was performed in air for hours to produce MoO 3 .
【００２４】〔反応〕 上記触媒３ｍｌと６５０℃で焼
成したＭｏＯ3 １ｇ（６〜１０メッシュ）を内径１８ｍ
ｍФのガラス反応管に充填した。充填方法は１４メッシ
ュのシリコンカーバイトで希釈して温度分布がほとんど
出来ないように、また触媒とＭｏＯ3 は、ほぼ均一にな
るようにした。反応温度を４１０℃で、プロピレン：空
気：スチーム＝１：７．５：３のモル比で、空間速度Ｓ
Ｖ＝３４００／Ｈの反応条件で加速試験を行った。その
結果を表１に示す。[Reaction] 1 g (6 to 10 mesh) of MoO 3 calcined at 650 ° C. with 3 ml of the above catalyst was treated with an inner diameter of 18 m.
Filled into a glass reaction tube of mФ. The filling method was such that the temperature distribution was hardly made by diluting with 14 mesh silicon carbide, and the catalyst and MoO 3 were made almost uniform. At a reaction temperature of 410 ° C., a propylene: air: steam = 1: 7.5: 3 molar ratio and a space velocity S
An acceleration test was performed under the reaction condition of V = 3400 / H. Table 1 shows the results.
【００２５】比較例１ ＭｏＯ3 を充填しなかった以外は実施例１と同様に行っ
た。その結果を表１に示す。実施例１と比較例１を比較
すると、ＭｏＯ3 を共存させることによる活性劣化の抑
制効果が現れている。Comparative Example 1 The same operation as in Example 1 was carried out except that MoO 3 was not filled. Table 1 shows the results. When Example 1 and Comparative Example 1 are compared, the effect of suppressing the deterioration of activity due to the coexistence of MoO 3 appears.
【００２６】比較例２ ６５０℃で焼成したＭｏＯ3 の代わりに、モリブデン酸
アンモニウムを５００℃で６時間空気中で焼成したＭｏ
Ｏ3 を使用した以外は、実施例１と同様に行った。その
結果を表１に示す。５００℃で焼成して得たＭｏＯ3 を
共存させた場合、初期から選択率が低く満足できるもの
になっていない。Comparative Example 2 In place of MoO 3 fired at 650 ° C., ammonium molybdate was fired in air at 500 ° C. for 6 hours.
The procedure was performed in the same manner as in Example 1 except that O 3 was used. Table 1 shows the results. When MoO 3 obtained by baking at 500 ° C. is allowed to coexist, the selectivity is low from the beginning and is not satisfactory.
【００２７】[0027]
【表１】 [Table 1]
【００２８】参考例１ モリブデン酸アンモニウムを３５０℃で３時間焼成して
ＭｏＯ3 を得た。若干の水分とステアリン酸１．５％を
混合して、５ｍｍФ×２ｍｍФ×５ｍｍＨの円筒状に打
錠成形し、６３０℃で６時間空気中で焼成した。これを
内径１８ｍｍФの反応管に１０ｍｌ充填し、反応温度３
６０〜４２０℃でプロピレン：空気：スチーム＝１：
７．５：３のモル比で空間速度ＳＶ＝１１００／Ｈの条
件で反応を行った。その結果、いずれもプロピレン反応
率は、０．５％未満で実質上反応していないことが認め
られた。Reference Example 1 Ammonium molybdate was calcined at 350 ° C. for 3 hours to obtain MoO 3 . A slight amount of water and 1.5% of stearic acid were mixed, tablet-formed into a cylinder having a size of 5 mmФ2 mmФ5 mmH, and calcined at 630 ° C. for 6 hours in air. 10 ml of this was filled into a reaction tube having an inner diameter of 18 mm, and a reaction temperature of 3
Propylene: air: steam = 1: 60-420 ° C
The reaction was carried out at a molar ratio of 7.5: 3 and a space velocity SV = 1100 / H. As a result, it was confirmed that the propylene conversion was substantially less than 0.5% and did not substantially react.
【００２９】参考例２ 参考例１と同様にＭｏＯ3 を調製し、最終焼成のみを５
００℃で６時間行ったＭｏＯ3 を使用して参考例１と同
じ実験を行った。その結果を表２に示す。不活性なＭｏ
Ｏ3 をつくるためには、５００℃の焼成では不完全であ
る。Reference Example 2 MoO 3 was prepared in the same manner as in Reference Example 1, and only
The same experiment as in Reference Example 1 was performed using MoO 3 performed at 00 ° C. for 6 hours. Table 2 shows the results. Inactive Mo
Firing at 500 ° C. is incomplete for producing O 3 .
【００３０】[0030]
【表２】 [Table 2]
【００３１】実施例２ 〔複合酸化物触媒の調製〕 硝酸ニッケルおよび燐酸を
使用しなかったこと、硝酸タリウムの代わりに硝酸セシ
ウム（ＣｓＮＯ3 ）を使用したこと、および調製規模を
８０倍スケールで行った以外は実施例１と同様に塩分
解、粉砕まで行ない触媒前駆体を調製した。別に、市販
のＭｏＯ3 を６３０℃で６時間焼成した。Example 2 [Preparation of composite oxide catalyst] Nickel nitrate and phosphoric acid were not used, cesium nitrate (CsNO 3 ) was used instead of thallium nitrate, and the preparation was carried out on an 80-fold scale. A catalyst precursor was prepared by performing salt decomposition and pulverization in the same manner as in Example 1 except for the above. Separately, commercially available MoO 3 was calcined at 630 ° C. for 6 hours.
【００３２】上記触媒前駆体５５部とＭｏＯ3 ４５部を
混合し、通常行われる方法で押出し成形して、４８０℃
で６時間焼成して触媒Ａをつくった。ＭｏＯ3 を混合し
ないで触媒前駆体のみをつかって押出し成形し、４８０
℃、空気中で焼成して触媒Ｂをつくった。 触媒Ａの組成：55（Ｍｏ12Ｂｉ1 Ｆｅ2 Ｃｏ7 Ｃｓ0.05
Ｓｉ1)＋45ＭｏＯ3 触媒Ｂの組成：Ｍｏ12Ｂｉ1 Ｆｅ2 Ｃｏ7 Ｃｓ0.05Ｓｉ
1 55 parts of the above-mentioned catalyst precursor and 45 parts of MoO 3 were mixed, extruded by a usual method, and 480 ° C.
For 6 hours to prepare Catalyst A. Extrusion molding using only the catalyst precursor without mixing MoO 3
The catalyst was calcined in air at 0 ° C. to prepare a catalyst B. Composition of catalyst A: 55 (Mo 12 Bi 1 Fe 2 Co 7 Cs 0.05
Si 1 ) +45 MoO 3 Composition of catalyst B: Mo 12 Bi 1 Fe 2 Co 7 Cs 0.05 Si
1
【００３３】〔反応〕 内径３０ｍｍФの反応管に、原
料ガス入口側の触媒として、触媒Ａを１．１５リット
ル、その後に触媒Ｂを２．３リットル充填し、反応管周
囲の熱媒温度３２５℃で、プロピレン：空気：窒素：ス
チーム＝１：８：３：１．５のモル比で空間速度ＳＶ＝
１３００／Ｈ、入口圧力２．８ａｔｍの条件で反応を行
った。その結果を表３に示す。[Reaction] A reaction tube having an inner diameter of 30 mm was filled with 1.15 liters of catalyst A and then 2.3 liters of catalyst B as a catalyst on the raw material gas inlet side, and a heating medium temperature around the reaction tube of 325 ° C. And propylene: air: nitrogen: steam = 1: 8: 3: 1.5 molar ratio and space velocity SV =
The reaction was performed under the conditions of 1300 / H and an inlet pressure of 2.8 atm. Table 3 shows the results.
【００３４】約１年間使用したこの触媒を抜き出して、
入口部と出口部の触媒をそれぞれ１０ｍｌ用いて上記条
件で反応を行った。その結果を表４に示す。The catalyst used for about one year was extracted and
The reaction was carried out under the above conditions using 10 ml of the catalyst at the inlet and 10 ml of the catalyst at the outlet. Table 4 shows the results.
【００３５】比較例３ 実施例２の触媒Ｂを使用して、原料ガス入口側に磁製ラ
ッシヒリング４５％と触媒Ｂ５５％を希釈混合して１．
１５リットル、その後に触媒Ｂを２．３リットル充填し
た。反応温度３２７℃で、その他は実施例１と同じ条件
で、反応を行った。その結果を表３に示す。COMPARATIVE EXAMPLE 3 Using Catalyst B of Example 2, 45% of a porcelain Raschig ring and 55% of Catalyst B were diluted and mixed at the raw material gas inlet side.
15 liters and then 2.3 liters of catalyst B were charged. The reaction was carried out at a reaction temperature of 327 ° C. and under the same conditions as in Example 1 except for the above. Table 3 shows the results.
【００３６】実施例２と同様に、入口部と出口部の触媒
１０ｍｌを評価した。その結果を表４に示す。本発明の
方法では約１年使用した触媒の入口部、出口部とも選択
率の低下は認められないが、ＭｏＯ3 を使用していない
場合、入口部の選択率が低下している。In the same manner as in Example 2, 10 ml of the catalyst at the inlet and the outlet was evaluated. Table 4 shows the results. In the method of the present invention, the selectivity of the inlet and the outlet of the catalyst used for about one year does not decrease, but when MoO 3 is not used, the selectivity of the inlet decreases.
【００３７】[0037]
【表３】 [Table 3]
【００３８】[0038]
【表４】 [Table 4]
【００３９】実施例３ 〔複合酸化物触媒の調製〕 実施例１に準じた調製法
で、Ｍｏ12Ｂｉ1.4 Ｆｅ2Ｎｉ5 Ｃｏ4 Ｔｌ0.5 Ｐ0.4
Ｓｉ15の組成の触媒をつくり、成形法はα−Ａｌ2Ｏ3
（５ｍｍФボール）に担持（３０％）して、５５０℃で
６時間、空気中で焼成して触媒とした。別に、市販のＭ
ｏＯ3 を６３０℃で６時間、空気中で焼成した。Example 3 [Preparation of Composite Oxide Catalyst] A method similar to that of Example 1 was used to prepare Mo 12 Bi 1.4 Fe 2 Ni 5 Co 4 Tl 0.5 P 0.4
A catalyst having a composition of Si 15 was prepared, and the forming method was α-Al 2 O 3
(5% ball) (30%), and calcined in air at 550 ° C. for 6 hours to obtain a catalyst. Separately, commercially available M
The oO 3 was calcined at 630 ° C. for 6 hours in air.
【００４０】〔反応〕 上記触媒１２ｍｌと６３０℃で
焼成したＭｏＯ3 １ｇ（６〜１０ｍｅｓｈ）を内径１８
ｍｍФのガラス反応管に充填した。ＭｏＯ3 は触媒層全
域にほぼ等分になるように充填した。反応温度４２０℃
で、イソブチレン：空気：スチーム＝１：２０：８のモ
ル比で、空間速度ＳＶ＝１５００／Ｈの反応条件で寿命
試験を行った。その結果を表５に示す。[Reaction] 1 g (6 to 10 mesh) of MoO 3 calcined at 630 ° C. with 12 ml of the above catalyst was treated with an inner diameter of 18 ml.
It was filled into a glass reaction tube of mmФ. MoO 3 was filled so as to be almost equally distributed over the entire area of the catalyst layer. Reaction temperature 420 ° C
A life test was performed under the reaction conditions of isobutylene: air: steam = 1: 20: 8 and space velocity SV = 1500 / H. Table 5 shows the results.
【００４１】比較例４ ＭｏＯ3 を充填しなかった以外は実施例３と同様に行っ
た。その結果を表５に示す。Comparative Example 4 The same operation as in Example 3 was carried out except that MoO 3 was not filled. Table 5 shows the results.
【００４２】[0042]
【表５】 [Table 5]
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０７Ｃ 57/05 Ｃ０７Ｃ 57/05 // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ (56)参考文献 特開 平４−279542（ＪＰ，Ａ) 特開 昭55−113730（ＪＰ，Ａ) 特開 昭59−76543（ＪＰ，Ａ) 特開 昭50−49201（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 27/00 C07C 47/00 C07C 57/00 C07B 61/00 ＣＡ（ＳＴＮ)──────────────────────────────────────────────────続 き Continuation of front page (51) Int.Cl. 7 Identification symbol FI C07C 57/05 C07C 57/05 // C07B 61/00 300 C07B 61/00 300 (56) References JP-A-4-279542 ( JP, A) JP-A-55-113730 (JP, A) JP-A-59-76543 (JP, A) JP-A-50-49201 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C07C 27/00 C07C 47/00 C07C 57/00 C07B 61/00 CA (STN)
Claims (5)
スおよび鉄を表し、Ａはニッケルおよび／またはコバル
トを表し、Ｂはリン、ホウ素、ヒ素、テルル、タングス
テン、アンチモ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、Ｃはカリウム、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、ａ＝１２としたとき、０＜
ｂ≦１０、０＜ｃ≦１０、１≦ｄ≦１０、０≦ｅ≦１
０、０＜ｆ≦２であり、ｘは各元素の酸化状態により定
まる値である。）で示される複合酸化物触媒を用いてプ
ロピレン又はイソブチレンを分子状酸素で気相接触酸化
して相当する不飽和アルデヒド及び不飽和カルボン酸を
製造する方法において、複合酸化物触媒と共に反応に実
質的に不活性な酸化モリブデンを存在させて反応を行う
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
酸の製造方法。1. A represents a general formula Mo a Bi b Fe c A d B e C f O x (Mo, Bi and Fe represent molybdenum, bismuth and iron, A represents nickel and / or cobalt, B is phosphorus Represents at least one element selected from the group consisting of boron, arsenic, tellurium, tungsten, antimony and silicon; and C represents at least one element selected from the group consisting of potassium, rubidium, cesium and thallium. , A = 12, 0 <
b ≦ 10 , 0 <c ≦ 10, 1 ≦ d ≦ 10 , 0 ≦ e ≦ 1
0, 0 < f ≦ 2, and x is a value determined by the oxidation state of each element. ), Wherein propylene or isobutylene is vapor-phase catalytically oxidized with molecular oxygen to produce the corresponding unsaturated aldehydes and unsaturated carboxylic acids using the composite oxide catalyst. a method for producing unsaturated aldehyde and unsaturated carboxylic acids in the presence of an inert molybdenum oxide, characterized in <br/> carrying out the reaction.
がアクロレイン及びアクリル酸又はメタクロレイン及び
メタクリル酸である請求項１記載の不飽和アルデヒド及
び不飽和カルボン酸の製造方法。2. The process for producing unsaturated aldehydes and unsaturated carboxylic acids according to claim 1, wherein the unsaturated aldehydes and unsaturated carboxylic acids are acrolein and acrylic acid or methacrolein and methacrylic acid.
がモリブデン化合物を５５０〜７００℃で焼成して得ら
れる酸化モリブデンである請求項１記載の不飽和アルデ
ヒド及び不飽和カルボン酸の製造方法。3. The process for producing unsaturated aldehydes and unsaturated carboxylic acids according to claim 1, wherein the molybdenum oxide substantially inert to the reaction is molybdenum oxide obtained by calcining a molybdenum compound at 550 to 700 ° C.
を複合酸化物触媒と混合成形して存在させて反応を行う
請求項１記載の不飽和アルデヒド及び不飽和カルボン酸
の製造方法。4. The production of unsaturated aldehydes and unsaturated carboxylic acids according to claim 1, wherein the reaction is carried out by mixing and presenting molybdenum oxide which is substantially inert to the reaction with the composite oxide catalyst. Method.
性な酸化モリブデンを存在させて反応を行う請求項１記
載の不飽和アルデヒド及び不飽和カルボン酸の製造方
法。5. The method for producing unsaturated aldehydes and unsaturated carboxylic acids according to claim 1, wherein the reaction is carried out in the presence of molybdenum oxide which is substantially inert to the reaction at the inlet side of the raw material gas.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15488593A JP3314457B2 (en) | 1993-06-25 | 1993-06-25 | Process for producing unsaturated aldehyde and unsaturated carboxylic acid |
| CN94107759A CN1062550C (en) | 1993-06-25 | 1994-06-24 | Process for production of unsaturated aldehyde and unsaturated carboxylic acid |
| EP94109830A EP0630879B2 (en) | 1993-06-25 | 1994-06-24 | Process for production of unsaturated aldehyde and unsaturated carboxylic acid |
| KR1019940014514A KR100277241B1 (en) | 1993-06-25 | 1994-06-24 | Process for preparing unsaturated aldehyde and unsaturated carboxylic acid |
| DE69407669T DE69407669T3 (en) | 1993-06-25 | 1994-06-24 | Process for the preparation of an unsaturated aldehyde and an unsaturated carboxylic acid |
| SG1996003814A SG43882A1 (en) | 1993-06-25 | 1994-06-24 | Process for production of unsaturated aldehyde and unsaturated carboxylic acid |
| US08/266,190 US5602280A (en) | 1993-06-25 | 1994-06-27 | Process for production of unsaturated aldehyde and unsaturated carboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15488593A JP3314457B2 (en) | 1993-06-25 | 1993-06-25 | Process for producing unsaturated aldehyde and unsaturated carboxylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0710799A JPH0710799A (en) | 1995-01-13 |
| JP3314457B2 true JP3314457B2 (en) | 2002-08-12 |
Family
ID=15594088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15488593A Expired - Fee Related JP3314457B2 (en) | 1993-06-25 | 1993-06-25 | Process for producing unsaturated aldehyde and unsaturated carboxylic acid |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3314457B2 (en) |
| SG (1) | SG43882A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040192973A1 (en) * | 2003-03-31 | 2004-09-30 | Saudi Basic Industries Corporation | Mixed metal oxide catalysts for the production of unsaturated aldehydes from olefins |
| DE102007010422A1 (en) * | 2007-03-01 | 2008-09-04 | Basf Se | Preparation of a catalyst, useful in the heterogeneously catalyzed partial gas phase oxidation of acrolein to acrylic acid, comprises attaching one of the active mass to the surface of the carrier body with the help of a binding agent |
| JP7207295B2 (en) * | 2017-03-17 | 2023-01-18 | 三菱ケミカル株式会社 | Catalytic oxidation method, method for producing oxidative dehydrogenation reaction product, and method for producing oxidation reaction product |
-
1993
- 1993-06-25 JP JP15488593A patent/JP3314457B2/en not_active Expired - Fee Related
-
1994
- 1994-06-24 SG SG1996003814A patent/SG43882A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0710799A (en) | 1995-01-13 |
| SG43882A1 (en) | 1997-11-14 |
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