JP2872816B2 - Ammoxidation method - Google Patents
Ammoxidation methodInfo
- Publication number
- JP2872816B2 JP2872816B2 JP3011779A JP1177991A JP2872816B2 JP 2872816 B2 JP2872816 B2 JP 2872816B2 JP 3011779 A JP3011779 A JP 3011779A JP 1177991 A JP1177991 A JP 1177991A JP 2872816 B2 JP2872816 B2 JP 2872816B2
- Authority
- JP
- Japan
- Prior art keywords
- elements selected
- catalyst
- oxygen
- reaction
- paraffins
- 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
-
- 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)
- Catalysts (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明はパラフィン類のアンモ酸
化によるα、β−不飽和ニトリル類の製造方法の改良に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improved method for producing .alpha.,. Beta.-unsaturated nitriles by ammoxidation of paraffins.
【０００２】[0002]
【従来の技術】プロパンとプロピレンとの価格差からプ
ロパンを原料とするアクリロニトリルの製造の試みは従
来より行われている。しかし、提案されている方法は、
反応温度が５００℃前後と高く、また活性、選択性を向
上させるために、ハロゲン化合物あるいはイオウ化合物
を添加するもので、高級な装置材質を必要とするという
問題があり、プロピレンとの価格差にも拘らずプロパン
を原料とするアクリロニトリルの製造は、まだ工業化さ
れていない。2. Description of the Related Art Attempts have been made to produce acrylonitrile using propane as a raw material due to the price difference between propane and propylene. However, the proposed method is
The reaction temperature is as high as about 500 ° C, and a halogen compound or a sulfur compound is added in order to improve the activity and selectivity. Nevertheless, the production of acrylonitrile using propane as a raw material has not yet been industrialized.
【０００３】また、ブタン類のアンモ酸化についても状
況は同じである。The situation is the same for the ammoxidation of butanes.
【０００４】触媒活性が高く、ハロゲン化合物などの反
応促進剤を必要としない、パラフィン類のアンモ酸化触
媒の検討の結果、本発明者らは既に特願平０２−で、燐
の酸化物と、錫またはインジウムの酸化物と、バナジウ
ム、タングステンおよびモリブデンの群から選ばれる１
種以上の元素を含有する触媒を用いるパラフィン類のア
ンモ酸化でニトリル類を製造する方法を提案した。しか
し、この方法ではオレフィン類の副生が多いため、副生
するオレフィン類を分離回収し、中間原料として循環使
用してニトリル類に転化する必要があり、プロセスが複
雑になるという問題があった。そのため、副生オレフィ
ン量を抑制し、ニトリル類への選択性がさらに高い触媒
の開発が望まれていた。化学構造式（３）〔化２〕As a result of a study on an ammoxidation catalyst for paraffins which has a high catalytic activity and does not require a reaction accelerator such as a halogen compound, the present inventors have already found in Japanese Patent Application No. Hei 02-02, an oxide of phosphorus, An oxide of tin or indium and one selected from the group consisting of vanadium, tungsten and molybdenum
A method for producing nitriles by ammoxidation of paraffins using catalysts containing more than one element was proposed. However, in this method, since there are many by-products of olefins, it is necessary to separate and recover olefins as by-products and to circulate them as intermediate materials to convert them to nitriles, which has a problem that the process becomes complicated. . Therefore, it has been desired to develop a catalyst that suppresses the amount of by-product olefin and has higher selectivity to nitriles. Chemical structural formula (3)
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、触媒
活性が高く、ハロゲン化合物などの反応促進剤を必要と
せず、ニトリル類への選択性が高く、かつ副生オレフィ
ンが少ないパラフィン類のアンモ酸化触媒を提供するこ
とである。SUMMARY OF THE INVENTION An object of the present invention is to provide paraffins which have high catalytic activity, do not require a reaction accelerator such as a halogen compound, have high selectivity to nitriles, and have low olefin by-products. It is to provide an ammoxidation catalyst.
【０００６】[0006]
【課題を解決するための手段】本発明者らは特願平０２
− で提案した触媒のニトリル類への選択性
をさらに高めるべく検討を行った結果、ある特定の元素
を添加するとニトリル類への選択性が高まることを見い
だして本発明の方法に至った。Means for Solving the Problems The present inventors have disclosed in Japanese Patent Application No.
As a result of investigations to further increase the selectivity of the catalyst proposed in-for nitrites, it was found that the addition of a specific element increased the selectivity for nitriles, leading to the method of the present invention.
【０００７】即ち、本発明の方法は、パラフィン類とア
ンモニアと酸素含有ガスとの気相接触反応でニトリル類
を製造する際、一般式 ＡａＢｂＣｃＰｄＥｅＯｇ（こ
こでＡはＩｎ、Ｓｎの中から選ばれる１種以上の元素、
ＢはＶ、Ｗ，Ｍｏから選ばれる１種以上の元素、ＣはＢ
ｉ、Ｐｂから選ばれる１種以上の元素、Ｐは燐、ＥはＦ
ｅ、Ｃｏ、Ｎｉから選ばれる１種以上の元素、Ｏは酸素
を表す。ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇは各元素の原子比
率を表し、ａを基準にとり、ａ＝１とした時、ｂ＝０．
１〜１０、ｃ＝０．１〜１０、ｄ＝０．１〜１０、ｅ＝
０〜１０であり、ｇは前記各成分の原子価を満足するに
必要な酸素の原子比率である。）で示される組成物を含
有する触媒を用いることを特徴とする方法であり、従来
法の問題であるハロゲン化合物などの反応促進剤を必要
としない方法である。That is, according to the method of the present invention, when nitriles are produced by a gas-phase catalytic reaction between paraffins, ammonia and an oxygen-containing gas, the general formula AaBbCcPdEeOg (where A is selected from In and Sn) More than one element,
B is one or more elements selected from V, W and Mo, and C is B
one or more elements selected from i and Pb, P is phosphorus, E is F
O represents one or more elements selected from e, Co, and Ni, and O represents oxygen. a, b, c, d, e, f, and g represent the atomic ratio of each element, and when a = 1 with respect to a, b = 0.
1-10, c = 0.1-10, d = 0.1-10, e =
0 to 10, and g is an atomic ratio of oxygen necessary to satisfy the valence of each component. This method is characterized by using a catalyst containing the composition represented by the formula (1), and does not require a reaction accelerator such as a halogen compound, which is a problem of the conventional method.
【０００８】本発明で用いられる触媒は、一般式 Ａａ
ＢｂＣｃＰｄＥｅＯｇ（ここでＡはＩｎ、Ｓｎの中から
選ばれる１種以上の元素、ＢはＶ、Ｗ，Ｍｏから選ばれ
る１種以上の元素、ＣはＢｉ、Ｐｂから選ばれる１種以
上の元素、Ｐは燐、ＥはＦｅ、Ｃｏ、Ｎｉから選ばれる
１種以上の元素、Ｏは酸素を表す。ａ、ｂ、ｃ、ｄ、
ｅ、ｆ、ｇは各元素の原子比率を表し、ａを基準にと
り、ａ＝１とした時、ｂ＝０．１〜１０、ｃ＝０．１〜
１０、ｄ＝０．１〜１０、ｅ＝０〜１０であり、ｇは前
記各成分の原子価を満足するに必要な酸素の原子比率で
ある。）で示される組成物を含有する触媒である。この
触媒はこの分野で通常用いられる方法で調製される。例
えば、錫酸化物またはインジウム酸化物と燐酸化物（通
常、欄さ燐酸が使用される）とを混合する方法、錫また
はインジウムおよび燐の易加水分解性化合物の逐次的な
加水分解、同時加水分解による方法、錫またはインジウ
ムの易加水分解性化合物あるいは加水分解生成物と燐酸
化物（通常、燐酸が使用される）とを混合する方法など
により、燐と、錫またはインジウムの複合酸化物を調製
し、これにバナジウム、タングステンおよびモリブデン
から選ばれた１種以上の元素の易加水分解性化合物、加
水分解生成物を混合し焼成する方法、あるいは、錫また
はインジウムの酸化物とバナジウム、タングステンおよ
びモリブデンの群から選ばれた１種以上の元素の酸化物
とビスマスまたは鉛から選ばれた１種以上の元素の酸化
物との複合酸化物を調製し、燐の易加水分解性化合物あ
るいは燐酸化物（通常、燐酸が使用される）とを混合し
焼成する方法などで調製される。The catalyst used in the present invention has the general formula Aa
BbCcPdEeOg (where A is one or more elements selected from In and Sn, B is one or more elements selected from V, W and Mo, C is one or more elements selected from Bi and Pb, P represents phosphorus, E represents one or more elements selected from Fe, Co, and Ni, and O represents oxygen.
e, f, and g represent the atomic ratio of each element, and when a = 1 with respect to a, b = 0.1 to 10 and c = 0.1 to
10, d = 0.1 to 10 and e = 0 to 10, and g is the atomic ratio of oxygen necessary to satisfy the valence of each component. ). The catalyst is prepared by a method commonly used in this field. For example, a method of mixing a tin oxide or an indium oxide with a phosphoric acid (usually phosphoric acid is used), a sequential hydrolysis, a simultaneous hydrolysis of a readily hydrolyzable compound of tin or indium and phosphorus. , A composite oxide of phosphorus and tin or indium is prepared by mixing a readily hydrolyzable compound or hydrolysis product of tin or indium with a phosphoric acid (usually, phosphoric acid is used). A method in which a readily hydrolyzable compound of at least one element selected from vanadium, tungsten and molybdenum and a hydrolysis product are mixed and calcined, or an oxide of tin or indium and vanadium, tungsten and molybdenum are mixed. Complex oxidation of an oxide of one or more elements selected from the group and an oxide of one or more elements selected from bismuth or lead Were prepared, easily hydrolyzable compounds or phosphorus oxide of phosphorus (usually phosphoric acid is used) is prepared by a method of calcining a mixture of a.
【０００９】触媒の活性及び選択性を改善するために、
鉄、コバルトおよびニッケルから選ばれた１種以上の元
素及びナトリウム、カリウム、セシウム、ルビジウムお
よびタリウムから選ばれた１種以上の元素を添加する場
合は、これら元素の易加水分解性化合物、加水分解生成
物または酸化物を前記した調製過程のいずれかの工程で
添加混合することができる。To improve the activity and selectivity of the catalyst,
When one or more elements selected from iron, cobalt and nickel and one or more elements selected from sodium, potassium, cesium, rubidium and thallium are added, a readily hydrolyzable compound of these elements, The product or oxide can be added and mixed in any step of the preparation process described above.
【００１０】また、この分野で通常行われる方法である
が、この触媒は担体に担持した状態で使用しても良い。[0010] Although this method is generally used in this field, this catalyst may be used while being supported on a carrier.
【００１１】本発明の方法で原料として用いるパラフィ
ン類には特に制限はないが、入手の容易さ、得られるニ
トリル類の有用性の点からプロパンおよびブタン類が通
常、本発明の反応の対象となる。The paraffins used as a raw material in the method of the present invention are not particularly limited, but propane and butanes are usually used in the reaction of the present invention in view of availability and availability of the obtained nitriles. Become.
【００１２】本発明の方法で用いる酸素含有ガスには、
特に制限はないが、通常、純酸素、空気などが用いられ
る。The oxygen-containing gas used in the method of the present invention includes:
Although there is no particular limitation, usually, pure oxygen, air or the like is used.
【００１３】本発明の方法では、アンモニアを反応系に
添加するが、アンモニアは乾燥ガスでもよいが、アンモ
ニア水を蒸発器で気化して添加しても良い。In the method of the present invention, ammonia is added to the reaction system. The ammonia may be dry gas, or may be added by evaporating ammonia water in an evaporator.
【００１４】パラフィン類、酸素とアンモニアのフィー
ドモル比には、特に制限はないが、通常、安全性を考慮
して、燃焼範囲外となるように調整される。The feed molar ratio of paraffins, oxygen and ammonia is not particularly limited, but is usually adjusted to be outside the combustion range in consideration of safety.
【００１５】反応温度は、原料の種類、原料濃度、フィ
ードモル比、接触時間により異なるが、通常、２００℃
〜６００℃の範囲である。The reaction temperature varies depending on the kind of the raw material, the raw material concentration, the feed molar ratio, and the contact time.
~ 600 ° C.
【００１６】反応圧は、通常、１〜５０ｂａｒ．の範囲
である。The reaction pressure is usually between 1 and 50 bar. Range.
【００１７】[0017]
【実施例】次に、本発明の方法を実施例でさらに具体的
に説明する。 実施例１ 塩化スズ（関東化学製）２２．６ｇｒを４０℃に加熱し
た２Ｎ−塩酸溶液３００ｍｌに加え溶解させた後、水１
００ｍｌに溶解させた燐酸三ナトリウム（関東化学製）
３８．１ｇｒを加え沈澱を生成させた。この沈澱をデカ
ンテーションした後、吸引ろ過し、原料Ａとした。硝酸
ビスマス（関東化学製）３８８ｇｒと濃硝酸１６０ｇｒ
を水１２００ｍｌに溶解させた後、水２６００ｍｌに溶
解させたバナジン酸アンモン６６．４ｇｒ、水４００ｍ
ｌに溶解させたモリブデン酸アンモン４２．６ｇｒとコ
ロイダルシリカ（日産化学製）１７６０ｇｒを加え、８
０℃で４時間熟成し、噴霧乾燥し、２５０℃で２時間乾
燥して、原料Ｂとした。原料Ａ、原料Ｂに燐酸バナジル
３４．４ｇｒを加え混練りした。これを１２０℃で５時
間乾燥させ、さらに７００℃で４時間焼成した。これを
破砕し、１０−３２ｍｅｓｈにしたものを触媒とした。
この触媒を内径１７ｍｍのＳＵＳ３１６製反応器に８ｃ
ｃ．充填し、温度を３８０℃に保ち、プロパン／酸素／
アンモニアのモル比１０／６／３の混合ガスをＳＶ１０
００／Ｈｒで供給した。１５時間後に反応ガスを分析し
た。反応結果を表１に示した。 実施例２−４ 実施例１と同様にして表１に示した組成の触媒を調製
し、実施例１と同様にして触媒性能を評価した。反応結
果を表１に示した。 比較例１、２ Ｐｂ、Ｂｉの効果を明らかにするために、それら元素を
含まない触媒を実施例１と同様にして調製し、実施例１
と同様にして触媒性能を評価した。反応結果を表１に示
した。Next, the method of the present invention will be described more specifically with reference to examples. Example 1 After adding and dissolving 22.6 gr of tin chloride (manufactured by Kanto Chemical Co.) to 300 ml of a 2N hydrochloric acid solution heated to 40 ° C, water 1
Trisodium phosphate dissolved in 00ml (Kanto Chemical)
38.1 gr was added to form a precipitate. After the precipitate was decanted, it was subjected to suction filtration to obtain a raw material A. 388 gr of bismuth nitrate (Kanto Chemical) and 160 gr of concentrated nitric acid
Was dissolved in 1200 ml of water, and then 66.4 gr of ammonium vanadate dissolved in 2600 ml of water and 400 m of water.
Then, 42.6 gr of ammonium molybdate and 1760 gr of colloidal silica (manufactured by Nissan Chemical Industries, Ltd.) dissolved in
Aged at 0 ° C. for 4 hours, spray-dried, and dried at 250 ° C. for 2 hours to obtain raw material B. To raw material A and raw material B, 34.4 gr of vanadyl phosphate was added and kneaded. This was dried at 120 ° C. for 5 hours and fired at 700 ° C. for 4 hours. This was crushed and made into a 10-32 mesh catalyst.
This catalyst was placed in a SUS316 reactor having an inner diameter of 17 mm in 8 c.
c. Fill, keep temperature at 380 ° C, and add propane / oxygen /
A mixed gas of ammonia having a molar ratio of 10/6/3 was converted to SV10.
Supplied at 00 / Hr. After 15 hours, the reaction gas was analyzed. The reaction results are shown in Table 1. Example 2-4 A catalyst having the composition shown in Table 1 was prepared in the same manner as in Example 1, and the catalyst performance was evaluated in the same manner as in Example 1. The reaction results are shown in Table 1. Comparative Examples 1, 2 In order to clarify the effects of Pb and Bi, a catalyst containing no Pb or Bi was prepared in the same manner as in Example 1.
The catalyst performance was evaluated in the same manner as described above. The reaction results are shown in Table 1.
【００１８】[0018]
【表１】 [Table 1]
【００１９】[0019]
【発明の効果】本発明により、触媒活性が高く、ハロゲ
ン化合物などの反応促進剤を必要とせず、ニトリル類へ
の選択性が高く、かつ副生オレフィンが少ない触媒が得
られ、効率よくパラフィン類のアンモ酸化反応が実施で
きる。Industrial Applicability According to the present invention, a catalyst having high catalytic activity, not requiring a reaction accelerator such as a halogen compound, having high selectivity to nitriles, and having a small amount of by-product olefins can be obtained, and a paraffin can be efficiently obtained. Can be carried out.
フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ Continued on the front page (51) Int.Cl. 6 Identification code FI C07B 61/00 300 C07B 61/00 300
Claims (2)
スとの気相接触反応でニトリル類を製造する際、一般式
ＡａＢｂＣｃＰｄＥｅＯｇ（ここでＡはＩｎ、Ｓｎの
中から選ばれる１種以上の元素、ＢはＶ、Ｗ，Ｍｏから
選ばれる１種以上の元素、ＣはＢｉ、Ｐｂから選ばれる
１種以上の元素、Ｐは燐、ＥはＦｅ、Ｃｏ、Ｎｉから選
ばれる１種以上の元素、Ｏは酸素を表す。ａ、ｂ、ｃ、
ｄ、ｅ、ｆ、ｇは各元素の原子比率を表し、ａを基準に
とり、ａ＝１とした時、ｂ＝０．１〜１０、ｃ＝０．１
〜１０、ｄ＝０．１〜１０、ｅ＝０〜１０であり、ｇは
前記各成分の原子価を満足するに必要な酸素の原子比率
である。）で示される組成物を含有する触媒を用いるこ
とを特徴とするアンモ酸化方法。When a nitrile is produced by a gas phase reaction between paraffins, ammonia and an oxygen-containing gas, a general formula AaBbCcPdEeOg (where A is at least one element selected from In and Sn, Is one or more elements selected from V, W, and Mo; C is one or more elements selected from Bi and Pb; P is phosphorus; E is one or more elements selected from Fe, Co, and Ni; Represents oxygen, a, b, c,
d, e, f, and g represent the atomic ratio of each element. Based on a, when a = 1, b = 0.1 to 10 and c = 0.1
-10, d = 0.1-10, e = 0-10, and g is an atomic ratio of oxygen necessary to satisfy the valence of each component. Ammoxidation method characterized by using a catalyst containing the composition represented by the formula (1).
類である請求項１の方法2. The method according to claim 1, wherein the paraffin is propane or butane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3011779A JP2872816B2 (en) | 1991-02-01 | 1991-02-01 | Ammoxidation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3011779A JP2872816B2 (en) | 1991-02-01 | 1991-02-01 | Ammoxidation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04247060A JPH04247060A (en) | 1992-09-03 |
| JP2872816B2 true JP2872816B2 (en) | 1999-03-24 |
Family
ID=11787441
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3011779A Expired - Lifetime JP2872816B2 (en) | 1991-02-01 | 1991-02-01 | Ammoxidation method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2872816B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5906734B2 (en) * | 2011-12-28 | 2016-04-20 | 三菱レイヨン株式会社 | Method for producing nitrogen-containing compound |
-
1991
- 1991-02-01 JP JP3011779A patent/JP2872816B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04247060A (en) | 1992-09-03 |
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