JPH0748334A - Ammoxidation - Google Patents
AmmoxidationInfo
- Publication number
- JPH0748334A JPH0748334A JP5213541A JP21354193A JPH0748334A JP H0748334 A JPH0748334 A JP H0748334A JP 5213541 A JP5213541 A JP 5213541A JP 21354193 A JP21354193 A JP 21354193A JP H0748334 A JPH0748334 A JP H0748334A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- reaction
- propylene
- isobutylene
- formula
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、モリブデン、ビスマ
ス、鉄を含む多重促進酸化物触媒の存在下に、プロピレ
ンまたはイソブチレンをアンモニアおよび酸素と気相接
触させてアクリロニトリルまたはメタクリロニトリルを
製造する方法に関する。The present invention relates to a method for producing acrylonitrile or methacrylonitrile by vapor-phase contacting propylene or isobutylene with ammonia and oxygen in the presence of a multipromoting oxide catalyst containing molybdenum, bismuth and iron. Regarding
【０００２】[0002]
【従来の技術】プロピレンまたはイソブチレンをアンモ
ニアの存在下に分子状酸素によって気相酸化してアクリ
ロニトリルまたはメタクリロニトリルを製造する方法
は、「アンモ酸化プロセス」として広く知られ、現在工
業的規模で実施されている。この反応に使用されるモリ
ブデン、ビスマス、鉄を含む多数の触媒が発表されてい
る。例えば、特開昭５０−２５５２８号公報、特開平２
−２５１２５０号公報、特公昭５１−３３８８８号公
報、特公昭６０−３６８１２号公報、特公昭６１−２６
４１９号公報、特公昭６２−４２６５４号公報、米国特
許第４，１６７，４９４号などに、いわゆるモリブデ
ン、ビスマス、鉄を含む多成分酸化物触媒が開示されて
いる。2. Description of the Related Art A method for producing acrylonitrile or methacrylonitrile by gas phase oxidation of propylene or isobutylene with molecular oxygen in the presence of ammonia is widely known as "ammoxidation process" and is currently carried out on an industrial scale. Has been done. Numerous catalysts have been announced, including molybdenum, bismuth and iron used in this reaction. For example, JP-A-50-25528 and JP-A-2
No. 251250, Japanese Patent Publication No. 51-33888, Japanese Patent Publication No. 60-36812, and Japanese Patent Publication No. 61-26.
No. 419, Japanese Patent Publication No. 62-42654, and US Pat. No. 4,167,494 disclose a multi-component oxide catalyst containing so-called molybdenum, bismuth and iron.
【０００３】これらは種々の利点を有する優れた触媒で
あるが、アンモ酸化の副反応の抑制が不十分であり、目
的生成物の収率は未だ満足すべきものではない。These are excellent catalysts having various advantages, but the side reaction of ammoxidation is not sufficiently suppressed, and the yield of the target product is not yet satisfactory.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、上記
の従来触媒を基に改良された触媒を用いて、より高い収
率でアクリロニトリルまたはメタクリロニトリルを製造
する方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing acrylonitrile or methacrylonitrile in a higher yield by using an improved catalyst based on the above conventional catalyst. .
【０００５】[0005]
【課題を解決するための手段】本発明方法の主たる要件
は触媒にある。本発明者は、プロピレンまたはイソブチ
レンのアンモ酸化反応に用いるモリブデン、ビスマス、
鉄を含有する触媒を鋭意検討した結果、これらの成分と
さらに特定の金属成分を複合した酸化物が、アクリロニ
トリルまたはメタクリロニトリルの収率を一層向上させ
ることを見出し、本発明を完成するに至った。The main requirement of the process according to the invention lies in the catalyst. The present inventor has proposed molybdenum, bismuth, which is used for the ammoxidation reaction of propylene or isobutylene,
As a result of diligent examination of iron-containing catalysts, it was found that an oxide in which these components and further a specific metal component were combined further improved the yield of acrylonitrile or methacrylonitrile, and the present invention was completed. It was
【０００６】本発明の触媒は、一般組成式The catalyst of the present invention has a general compositional formula.
【０００７】[0007]
【化２】 （式中、Ｒはプラセオジムおよびネオジムの混合物、Ａ
はカリウム、ルジビウムおよびセシウムの中から選ばれ
る少なくとも一種の元素、Ｄはクロム、インジウム、コ
バルト、マンガン、マグネシウム、亜鉛、ナトリウムお
よびリンの中から選ばれる少なくとも一種の元素であ
り、ｍ、ｂ、ｆ、ｎ、ｒ、ａ、ｄおよびｘはそれぞれモ
リブデン、ビスマス、鉄、ニッケル、成分Ｒ、成分Ａ、
成分Ｄおよび酸素の原子比を表わし、ｍ＝１０〜１４、
好ましくは１１〜１３、ｂ＝０．１〜３、好ましくは
０．３〜２、ｆ＝０．１〜３、好ましくは０．５〜２．
５、ｎ＝４〜１０、好ましくは５〜９、ｒ＝０．１〜
２、好ましくは０．２〜１、ａ＝０．０１〜０．５、好
ましくは０．１〜０．４、ｄ＝０〜３、ｘは組成式中の
金属成分の原子価を満足する酸素の原子比である。）で
示される組成物を４０〜６０重量％のシリカに担持させ
たものである。[Chemical 2] Where R is a mixture of praseodymium and neodymium, A
Is at least one element selected from potassium, rudibium and cesium, D is at least one element selected from chromium, indium, cobalt, manganese, magnesium, zinc, sodium and phosphorus, and m, b, f , N, r, a, d and x are molybdenum, bismuth, iron, nickel, component R, component A,
Represents the atomic ratio of component D and oxygen, m = 10-14,
Preferably 11-13, b = 0.1-3, preferably 0.3-2, f = 0.1-3, preferably 0.5-2.
5, n = 4-10, preferably 5-9, r = 0.1
2, preferably 0.2 to 1, a = 0.01 to 0.5, preferably 0.1 to 0.4, d = 0 to 3, and x satisfies the valence of the metal component in the composition formula. It is the atomic ratio of oxygen. ) The composition represented by (4) is supported on 40 to 60% by weight of silica.
【０００８】本発明の触媒は、効果的な作用および特性
を得るために不可欠の成分Ｒを含有することを特徴とす
る。成分Ｒの量はビスマスに対する相対含量、すなわ
ち、ｒ／（ｒ＋ｂ）が０．７以下、好ましくは０．５以
下になるように決定することが望ましい。The catalyst according to the invention is characterized in that it contains the component R which is essential for obtaining effective action and properties. It is desirable to determine the amount of the component R so that the relative content with respect to bismuth, that is, r / (r + b) is 0.7 or less, preferably 0.5 or less.
【０００９】本発明の触媒において微量ではあるが不可
欠の成分Ａは、プロピレンまたはイソブチレンからのア
クリロニトリルまたはメタクリロニトリルへの選択率を
向上させる。成分Ａの中ではルビジウムまたはセシウム
を単独で用いる場合は、カリウムよりも少ない量でアク
リロニトリルまたはメタクリロニトリルの選択率を向上
させる。成分Ａは本発明の量範囲を越えて用いる場合
は、プロピレンまたはイソブチレンの反応活性を減じ
る。Ingredient A, although present in trace amounts in the catalyst of the present invention, improves the selectivity of propylene or isobutylene to acrylonitrile or methacrylonitrile. In the component A, when rubidium or cesium is used alone, it improves the selectivity of acrylonitrile or methacrylonitrile in an amount smaller than that of potassium. Component A reduces the reaction activity of propylene or isobutylene when used in excess of the amount range of the invention.
【００１０】任意成分Ｃは反応活性、触媒物性などの調
整のために適宜選択して用いることができる。成分Ｃの
リンは、触媒の耐摩耗性を向上させる場合がある。The optional component C can be appropriately selected and used in order to adjust the reaction activity and the physical properties of the catalyst. The component C phosphorus may improve the wear resistance of the catalyst.
【００１１】シリカは触媒の担体である。本発明のシリ
カ担持された触媒は、流動層アンモ酸化反応において優
れた流動性を有する。シリカの使用量が４０重量％以上
で優れた耐摩耗性が得られる。しかし、６０重量％を越
えて用いる場合は、触媒成分が稀釈され、十分な活性が
得られないばかりでなく、大きく選択率も減少する。本
発明の触媒は、先ず原料混合スラリーを調製し、次いで
該スラリーを噴霧乾燥し、最後に該乾燥品を焼成すると
いう三つの工程を経て好適に製造することができる。Silica is a catalyst carrier. The silica-supported catalyst of the present invention has excellent fluidity in a fluidized bed ammoxidation reaction. When the amount of silica used is 40% by weight or more, excellent wear resistance can be obtained. However, when it is used in an amount of more than 60% by weight, not only is the catalyst component diluted, sufficient activity is not obtained, but the selectivity is also greatly reduced. The catalyst of the present invention can be suitably produced through three steps of first preparing a raw material mixed slurry, then spray drying the slurry, and finally calcining the dried product.
【００１２】本発明の触媒の各成分は、水または硝酸に
可溶な塩の形で用いることが望ましい。モリブデン源と
しては、七モリブデン酸アンモニウムを用いることがで
きる。ビスマス、鉄、ニッケル、プラセオジム、ネオジ
ム、クロム、インジウム、コバルト、マンガン、マグネ
シウム、亜鉛およびナトリウム源としては、それぞれの
硝酸塩を用いることができる。プラセオジムとネオジム
源としては、ジジム酸化物として知られるプラセオジム
とネオジムの混合酸化物を硝酸に溶解して用いることが
できる。リン源としてはリン酸、そして、シリカ源とし
てはシリカゾルが好適である。用いるシリカゾルは、で
きるだけアルミニウム含量の少ない高純度であることが
望ましい。Each component of the catalyst of the present invention is preferably used in the form of a salt soluble in water or nitric acid. As the molybdenum source, ammonium heptamolybdate can be used. As the bismuth, iron, nickel, praseodymium, neodymium, chromium, indium, cobalt, manganese, magnesium, zinc and sodium sources, respective nitrates can be used. As a source of praseodymium and neodymium, a mixed oxide of praseodymium and neodymium known as didymium oxide can be dissolved in nitric acid and used. Phosphoric acid is preferable as the phosphorus source, and silica sol is preferable as the silica source. It is desirable that the silica sol used is of high purity with as little aluminum content as possible.
【００１３】原料混合スラリーの調製は、先ずシリカゾ
ルに攪拌しながらリン酸を、次いで七モリブデン酸アン
モニウムの水溶液を加え、最後にその他の成分の硝酸塩
の混合液を加えることによって、好適に行なうことがで
きる。原料混合スラリーを噴霧乾燥することによって流
動層反応に適した球形微粒子を得ることができる。The raw material-mixed slurry is preferably prepared by first adding phosphoric acid to the silica sol while stirring, then adding an aqueous solution of ammonium heptamolybdate, and finally adding a mixed solution of nitrates of other components. it can. By spray-drying the raw material mixed slurry, spherical fine particles suitable for fluidized bed reaction can be obtained.
【００１４】噴霧乾燥粒子は焼成の前に脱硝処理するこ
とが望ましい。脱硝処理は３５０〜４５０℃で０．５〜
２．０時間熱処理することによって行なうことができ
る。脱硝処理品は最後に５００〜６５０℃、好ましくは
５５０〜６３０℃にて焼成して触媒を得る。触媒の焼成
温度が低過ぎるとプロピレンまたはイソブチレンの反応
活性は大きいが、アクリロニトリルへの選択率が小さく
なるだけではなく、耐摩耗性も減少する。一方、焼成温
度が高過ぎる場合はプロピレンまたはイソブチレンの反
応活性が減少し、かつ次式によるアンモニアの燃焼が増
大する。Desirably, the spray-dried particles are subjected to a denitration treatment before firing. Denitration treatment is from 350 to 450 ℃ and 0.5 to
It can be performed by heat treatment for 2.0 hours. Finally, the denitration treated product is calcined at 500 to 650 ° C, preferably 550 to 630 ° C to obtain a catalyst. If the calcination temperature of the catalyst is too low, the reaction activity of propylene or isobutylene is large, but not only the selectivity to acrylonitrile decreases, but also the wear resistance decreases. On the other hand, when the firing temperature is too high, the reaction activity of propylene or isobutylene decreases and the combustion of ammonia according to the following equation increases.
【００１５】[0015]
【数１】 本発明の触媒の好適な焼成温度は、上記の５００〜６５
０℃の範囲から、アンモ酸化反応テストの結果をみて決
定することができる。通常、焼成時間は１〜５時間であ
る。[Equation 1] The preferable calcination temperature of the catalyst of the present invention is 500 to 65 above.
From the range of 0 ° C, it can be determined by looking at the result of the ammoxidation reaction test. Usually, the firing time is 1 to 5 hours.
【００１６】アンモ酸化反応の原料であるプロピレン、
イソブチレンおよびアンモニアは必ずしも高純度である
必要はなく、工業グレードのものを使用することができ
る。ターシャリーブタノールはイソブチレンの代替原料
として好適に用いることができる。酸素源としては通常
空気を用いる。プロピレンまたはイソブチレンに対する
アンモニアと空気の容積比は１：０．９〜１．３：７〜
１１、特に１：１．０〜１．２：８〜１０の範囲が好ま
しい。Propylene, which is a raw material for the ammoxidation reaction,
Isobutylene and ammonia do not necessarily need to be highly pure, and industrial grade ones can be used. Tertiary butanol can be suitably used as a substitute raw material for isobutylene. Air is usually used as the oxygen source. The volume ratio of ammonia and air to propylene or isobutylene is 1: 0.9-1.3: 7-
A range of 11, especially 1: 1.0 to 1.2: 8 to 10 is preferable.
【００１７】反応温度は４００〜４６０℃、特に４１０
〜４４０℃の範囲が好ましい。反応圧力は常圧〜３気圧
の範囲で行なうことができる。原料混合ガスと触媒との
接触時間は１〜８秒、好ましくは２〜６秒である。The reaction temperature is 400 to 460 ° C., especially 410
The range of ˜440 ° C. is preferable. The reaction pressure can be in the range of atmospheric pressure to 3 atm. The contact time between the raw material mixed gas and the catalyst is 1 to 8 seconds, preferably 2 to 6 seconds.
【００１８】[0018]
【実施例】以下、実施例により本発明を更に具体的に説
明する。The present invention will be described in more detail with reference to the following examples.
【００１９】（触媒製造実施例）５０重量％のシリカに
担持された下記の組成式を有する触媒１を以下のように
製造した。(Catalyst Production Example) A catalyst 1 having the following composition formula and supported on 50% by weight of silica was produced as follows.
【００２０】[0020]
【化３】 １６６７ｇの３０％シリカゾルに、水１２００ｇに七モ
リブデン酸アンモニウム〔（ＮＨ4 ）6 Ｍｏ7 Ｏ24・４
Ｈ2 Ｏ〕３９７．８ｇを溶解した液を攪拌下に加え、最
後に予め６００ｇの１３％硝酸に、６３．６ｇの硝酸ビ
スマス〔Ｂｉ（ＮＯ3 ）3 ・５Ｈ2 Ｏ〕、１１４．２ｇ
の硝酸第二鉄〔Ｆｅ（ＮＯ3 ）3 ・９Ｈ2 Ｏ〕、４６
０．１ｇの硝酸ニッケル〔Ｎｉ（ＮＯ3 ）2 ・６Ｈ
2 Ｏ〕、８．１２ｇの硝酸プラセオジム〔Ｐｒ（Ｎ
Ｏ3 ）3 ・６Ｈ2 Ｏ〕、８．１８ｇの硝酸ネオジム〔Ｎ
ｄ（ＮＯ3 ）3 ・６Ｈ2 Ｏ〕および３．７９ｇの硝酸カ
リウム〔ＫＮＯ3 〕を溶解した混合液を加えた。ここに
得られた原料混合液はスラリー状であり、ｐＨは０．５
であった。スラリーの噴霧化は乾燥器上部の中央に設置
されたところの皿型回転子を備えた遠心式噴霧化装置を
用いて行なった。乾燥器の入口空気温度を２５０℃に、
そして、出口温度を１３０℃に保持してスラリーの噴霧
乾燥を行なった。得られた乾燥粉体をキルンに移し、先
ず４００℃で１時間脱硝し、次いで５８０℃で２時間焼
成して触媒を得た。[Chemical 3] 30% silica sol 1667 g, ammonium heptamolybdate in water 1200g [(NH 4) 6 Mo 7 O 24 · 4
H 2 O] 397.8 g of the solution was added under stirring, and finally, 63.6 g of bismuth nitrate [Bi (NO 3 ) 3 .5H 2 O], 114.2 g was added to 600 g of 13% nitric acid in advance.
Of ferric nitrate [Fe (NO 3) 3 · 9H 2 O ], 46
0.1g of nickel nitrate [Ni (NO 3) 2 · 6H
2 O], 8.12 g of praseodymium nitrate [Pr (N
O 3) 3 · 6H 2 O], neodymium nitrate of 8.18g [N
d (NO 3) was added 3 · 6H 2 O] and 3.79g mixture was dissolved potassium nitrate [KNO 3] of. The raw material mixed solution obtained here is in the form of a slurry and has a pH of 0.5.
Met. Atomization of the slurry was performed using a centrifugal atomizer equipped with a dish rotor installed in the center of the upper part of the dryer. Inlet air temperature of the dryer to 250 ℃,
Then, the outlet temperature was maintained at 130 ° C., and the slurry was spray-dried. The obtained dry powder was transferred to a kiln, first denitrated at 400 ° C. for 1 hour, and then calcined at 580 ° C. for 2 hours to obtain a catalyst.
【００２１】上記と同様の方法により表１記載の組成を
有する触媒２〜１４と比較触媒１〜３を製造した。これ
らの触媒の製造に当って、Ｍｏ、Ｂｉ、Ｆｅ、Ｎｉ、Ｐ
ｒ、Ｎｄ、ＫおよびＳｉＯ2 源として触媒１と同じ原料
を用いた。触媒成分にルビジウム、セシウム、クロム、
インジウム、コバルト、マンガン、マグネシウム、亜
鉛、ナトリウム、リンが含まれる場合は、それぞれ硝酸
ルビジウム〔ＲｂＮＯ3〕、硝酸セシウム〔ＣｓＮ
Ｏ3 〕、硝酸クロム〔Ｃｒ（ＮＯ3 ）3 ・９Ｈ2 Ｏ〕、
硝酸インジウム〔Ｉｎ（ＮＯ3 ）3 ・３Ｈ2 Ｏ〕、硝酸
コバルト〔Ｃｏ（ＮＯ3 ）2 ・６Ｈ2 Ｏ〕、硝酸マンガ
ン〔Ｍｎ（ＮＯ3 ）2 ・６Ｈ2 Ｏ〕、硝酸マグネシウム
〔Ｍｇ（ＮＯ3 ）2 ・６Ｈ2 Ｏ〕、硝酸亜鉛〔Ｚｎ（Ｎ
Ｏ3 ）2 ・６Ｈ2 Ｏ〕、硝酸ナトリウム〔ＮａＮ
Ｏ3 〕、リン酸〔Ｈ3 ＰＯ4 〕を用いた。触媒５の製造
に当っては、プラセオジムとネオジム源としてＰｒとＮ
ｄを原子比で１：３．４１の割合で含むジジム酸化物を
硝酸に溶解した液を用いた。これらの触媒の焼成は、そ
れぞれ表１記載の温度で行なった。Catalysts 2 to 14 and comparative catalysts 1 to 3 having the compositions shown in Table 1 were produced in the same manner as above. In the production of these catalysts, Mo, Bi, Fe, Ni, P
The same raw materials as in Catalyst 1 were used as the r, Nd, K and SiO 2 sources. Rubidium, cesium, chromium as catalyst components,
When indium, cobalt, manganese, magnesium, zinc, sodium and phosphorus are contained, rubidium nitrate [RbNO 3 ] and cesium nitrate [CsN are contained, respectively.
O 3], chromium nitrate [Cr (NO 3) 3 · 9H 2 O ],
Indium nitrate [In (NO 3) 3 · 3H 2 O ], cobalt nitrate [Co (NO 3) 2 · 6H 2 O ], manganese nitrate [Mn (NO 3) 2 · 6H 2 O ], magnesium nitrate [Mg ( NO 3) 2 · 6H 2 O], zinc nitrate [Zn (N
O 3) 2 · 6H 2 O], sodium nitrate [NaN
O 3], using phosphoric acid [H 3 PO 4]. In the manufacture of the catalyst 5, praseodymium and neodymium as sources of Pr and N
A liquid in which didymium oxide containing d in an atomic ratio of 1: 3.41 was dissolved in nitric acid was used. The calcination of these catalysts was performed at the temperatures shown in Table 1, respectively.
【００２２】[0022]
【表１】 （プロピレンのアンモ酸化反応実施例）１０メッシュの
金網を１ｃｍ間隔で１２枚内蔵した内径２５ｍｍのバイ
コールガラス流動層反応管に５０ｃｃの触媒１をとり、
反応温度４３０℃、反応圧力常圧下に、プロピレン９容
積％の混合ガス（プロピレン：アンモニア：酸素：ヘリ
ウムの容積比が１：１．２：１．８５：７．０６）を毎
秒３．８８ｃｃ（ＮＴＰ換算）の流速で通過させた。こ
の反応の結果を下記式で定義されるプロピレン転化率、
アクリロニトリル選択率およびアクリロニトリル収率の
３つの指標によって評価し、それらの値を表２に記載し
た。[Table 1] (Example of ammoxidation reaction of propylene) 50 cc of catalyst 1 was placed in a Vycor glass fluidized bed reaction tube having an inner diameter of 25 mm and containing 12 pieces of 10-mesh wire mesh at 1 cm intervals.
At a reaction temperature of 430 ° C. and a normal pressure of reaction pressure, a mixed gas of propylene 9% by volume (volume ratio of propylene: ammonia: oxygen: helium 1: 1.2: 1.85: 7.06) was 3.88 cc / s. It was passed at a flow rate of NTP conversion). The result of this reaction is the propylene conversion rate defined by the following formula,
Acrylonitrile selectivity and acrylonitrile yield were evaluated by three indexes, and those values are shown in Table 2.
【００２３】[0023]
【数２】 触媒２、４、５、６、７、８、９、１０、１２、１３お
よび１４、そして、比較触媒１、２および３について上
と同様の反応を行なった。これらの反応は、原料混合ガ
スのプロピレンを９容積％、プロピレンに対するアンモ
ニアの容積比を１：１．２に固定し、プロピレンに対す
る酸素の容積比を１．８〜１．９の範囲から適宜選択し
て行なった。また、各触媒のプロピレン反応活性に応じ
て、反応温度および次式で定義される接触時間を適宜変
更した。各触媒の反応条件および反応成績を表２に示
す。[Equation 2] Catalysts 2, 4, 5, 6, 7, 8, 9, 10, 12, 13 and 14 and comparative catalysts 1, 2 and 3 were run as described above. In these reactions, propylene in the raw material mixed gas was fixed at 9% by volume, the volume ratio of ammonia to propylene was fixed to 1: 1.2, and the volume ratio of oxygen to propylene was appropriately selected from the range of 1.8 to 1.9. I did it. Further, the reaction temperature and the contact time defined by the following formula were appropriately changed according to the propylene reaction activity of each catalyst. Table 2 shows the reaction conditions and reaction results of each catalyst.
【００２４】[0024]
【数３】 但し、Ｖ：触媒量（ｃｃ） Ｆ：原料混合ガス流量（ｃｃ−ＮＴＰ／ｓｅｃ） Ｔ：反応温度（℃）[Equation 3] However, V: catalyst amount (cc) F: raw material mixed gas flow rate (cc-NTP / sec) T: reaction temperature (° C)
【００２５】[0025]
【表２】 （イソブチレンのアンモ酸化反応実施例）５０ｃｃの触
媒３を上記のプロピレンのアンモ酸化反応に用いた反応
管にとり、反応温度４２０℃、反応圧力常圧下に、イソ
ブチレン７．５容積％の混合ガス（イソブチレン：アン
モニア：酸素：水：ヘリウム＝１：１．２：１．９０：
１．８：７．４３）を毎秒４．３８ｃｃ（ＮＴＰ換算）
の流速で通過させた。この反応の結果をプロピレンの場
合と同様に定義されるイソブチレン転化率、メタクリロ
ニトリル選択率およびメタクリロニトリル収率の３つの
指標によって評価し、それらの値を表３に示した。[Table 2] (Example of ammoxidation reaction of isobutylene) A 50 cc catalyst 3 was placed in a reaction tube used for the ammoxidation reaction of propylene, and a mixed gas of 7.5% by volume of isobutylene (isobutylene was added at a reaction temperature of 420 ° C. and a normal reaction pressure). : Ammonia: Oxygen: Water: Helium = 1: 1.2: 1.90:
1.8: 7.43) 4.38cc per second (NTP conversion)
At a flow rate of The results of this reaction were evaluated by the three indices of isobutylene conversion, methacrylonitrile selectivity and methacrylonitrile yield, which were defined as in the case of propylene, and those values are shown in Table 3.
【００２６】触媒１１および比較触媒１２について、上
と同様の反応を行なった。各触媒の反応条件および反応
成績を表３に示す。The catalyst 11 and the comparative catalyst 12 were subjected to the same reaction as above. Table 3 shows the reaction conditions and reaction results of each catalyst.
【００２７】[0027]
【表３】 [Table 3]
【００２８】[0028]
【発明の効果】本発明によれば、プロピレンまたはイソ
ブチレンのアンモ酸化反応に用いるモリブデン、ビスマ
ス、鉄を含有する触媒成分に、さらに特定の金属成分を
複合した酸化物を触媒として用いることにより、アクリ
ロニトリルまたはメタクリロニトリルの収率を一層向上
することができる。INDUSTRIAL APPLICABILITY According to the present invention, the catalyst component containing molybdenum, bismuth and iron used for the ammoxidation reaction of propylene or isobutylene is further mixed with a specific metal component to form an acrylonitrile. Alternatively, the yield of methacrylonitrile can be further improved.
【手続補正書】[Procedure amendment]
【提出日】平成６年９月５日[Submission date] September 5, 1994
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１４[Correction target item name] 0014
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１４】噴霧乾燥粒子は焼成の前に脱硝処理するこ
とが望ましい。脱硝処理は３５０〜４５０℃で０．５〜
２．０時間熱処理することによって行なうことができ
る。脱硝処理品は最後に５００〜６５０℃、好ましくは
５５０〜６３０℃にて焼成して触媒を得る。触媒の焼成
温度が低過ぎるとプロピレンまたはイソブチレンの反応
活性は大きいが、アクリロニトリルまたはメタクリロニ
トリルへの選択率が小さくなるだけではなく、耐摩耗性
も減少する。一方、焼成温度が高過ぎる場合はプロピレ
ンまたはイソブチレンの反応活性が減少し、かつ次式に
よるアンモニアの燃焼が増大する。Desirably, the spray-dried particles are subjected to a denitration treatment before firing. Denitration treatment is from 350 to 450 ℃ and 0.5 to
It can be performed by heat treatment for 2.0 hours. Finally, the denitration treated product is calcined at 500 to 650 ° C, preferably 550 to 630 ° C to obtain a catalyst. If the calcination temperature of the catalyst is too low, the reaction activity of propylene or isobutylene is high, but the reaction temperature of acrylonitrile or methacrylonitrile is high.
Not only is the selectivity to the trill reduced, but the wear resistance is also reduced. On the other hand, when the firing temperature is too high, the reaction activity of propylene or isobutylene decreases and the combustion of ammonia according to the following equation increases.
Claims (1)
存在下アンモニアおよび酸素と高温で気相接触させてア
クリロニトリルまたはメタクリロニトリルを製造するに
当り、次の一般組成式 【化１】 （式中、Ｍｏはモリブデン、Ｂｉはビスマス、Ｆｅは
鉄、Ｎｉはニッケル、Ｒはプラセオジムおよびネオジム
の混合物、Ａはカリウム、ルジビウムおよびセシウムの
中から選ばれる少なくとも一種の元素、Ｄはクロム、イ
ンジウム、コバルト、マンガン、マグネシウム、亜鉛、
ナトリウムおよびリンの中から選ばれる少なくとも一種
の元素、Ｏは酸素であり、ｍ、ｂ、ｆ、ｎ、ｒ、ａ、ｄ
およびｘは原子比を表わし、ｍ＝１０〜１４、ｂ＝０．
１〜３、ｆ＝０．１〜３、ｎ＝４〜１０、ｒ＝０．１〜
２、ａ＝０．０１〜０．５、ｄ＝０〜３、ｘは組成式中
の金属成分の酸化物に対応する酸素の原子比である。）
で示される組成物を４０〜６０重量％のシリカに担持さ
れた触媒を使用することを特徴とするアクリロニトリル
またはメタクリロニトリルの製造法。1. In producing acrylonitrile or methacrylonitrile by vapor-phase contacting propylene or isobutylene with ammonia and oxygen in the presence of a catalyst at a high temperature, the following general composition formula: (In the formula, Mo is molybdenum, Bi is bismuth, Fe is iron, Ni is nickel, R is a mixture of praseodymium and neodymium, A is at least one element selected from potassium, rudibium and cesium, and D is chromium and indium. , Cobalt, manganese, magnesium, zinc,
At least one element selected from sodium and phosphorus, O is oxygen, and m, b, f, n, r, a, d
And x represent atomic ratios, m = 10 to 14, b = 0.
1-3, f = 0.1-3, n = 4-10, r = 0.1
2, a = 0.01 to 0.5, d = 0 to 3, and x is the atomic ratio of oxygen corresponding to the oxide of the metal component in the composition formula. )
A method for producing acrylonitrile or methacrylonitrile, which comprises using the composition represented by the formula (4) and a catalyst supported on 40 to 60% by weight of silica.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21354193A JP3403464B2 (en) | 1993-08-06 | 1993-08-06 | Ammoxidation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21354193A JP3403464B2 (en) | 1993-08-06 | 1993-08-06 | Ammoxidation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0748334A true JPH0748334A (en) | 1995-02-21 |
| JP3403464B2 JP3403464B2 (en) | 2003-05-06 |
Family
ID=16640904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21354193A Expired - Lifetime JP3403464B2 (en) | 1993-08-06 | 1993-08-06 | Ammoxidation method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3403464B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063679C (en) * | 1997-01-10 | 2001-03-28 | 中国石油化工总公司 | Fluidized bed catalyst containing halogen for producing acrylonitrile |
| WO2001028984A1 (en) * | 1999-10-18 | 2001-04-26 | Mitsubishi Rayon Co., Ltd. | Method for producing acrylonitrile, catalyst for use therein and the method for preparing the same |
-
1993
- 1993-08-06 JP JP21354193A patent/JP3403464B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063679C (en) * | 1997-01-10 | 2001-03-28 | 中国石油化工总公司 | Fluidized bed catalyst containing halogen for producing acrylonitrile |
| WO2001028984A1 (en) * | 1999-10-18 | 2001-04-26 | Mitsubishi Rayon Co., Ltd. | Method for producing acrylonitrile, catalyst for use therein and the method for preparing the same |
| EP1223162A1 (en) * | 1999-10-18 | 2002-07-17 | Mitsubishi Rayon Co., Ltd. | Method for producing acrylonitrile, catalyst for use therein and the method for preparing the same |
| US6642405B1 (en) | 1999-10-18 | 2003-11-04 | Mitsubishi Rayon Co., Ltd. | Method for producing acrylonitrile, catalyst for use therein and method for preparing the same |
| EP1223162A4 (en) * | 1999-10-18 | 2005-02-23 | Mitsubishi Rayon Co | Method for producing acrylonitrile, catalyst for use therein and the method for preparing the same |
| KR100681222B1 (en) * | 1999-10-18 | 2007-02-09 | 미쯔비시 레이온 가부시끼가이샤 | Method for producing acrylonitrile, catalyst for use therein and the method for preparing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3403464B2 (en) | 2003-05-06 |
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