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 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP3142549B2 (en) | Iron / antimony / molybdenum-containing oxide catalyst composition and method for producing the same | |
WO2005079980A1 (en) | Catalyst for partial oxidation and preparation method thereof | |
JP2841324B2 (en) | Method for producing methacrolein | |
JP2020527450A (en) | Fluidized bed catalyst suitable for the preparation of halogenated aromatic nitriles, its preparation and applications | |
US5166119A (en) | Preparation of catalysts for producing methacrolein and methacrylic acid | |
US4415482A (en) | Oxidation and ammoxidation catalyst | |
US7341974B2 (en) | Method for preparing a catalyst for partial oxidation of propylene | |
JPH02111444A (en) | Ammoxidation of paraffin and catalyst thereof | |
JP4081824B2 (en) | Acrylic acid production method | |
US4783545A (en) | Method for ammoxidation of paraffins and catalyst system therefor | |
JP2720215B2 (en) | Preparation of catalyst for methacrylic acid production | |
US7449426B2 (en) | Catalyst composition without antimony or molybdenum for ammoxidation of alkanes, a process of making and a process of using thereof | |
JP4182237B2 (en) | Catalyst for gas-phase catalytic oxidation reaction of isobutane and method for producing alkene and / or oxygen-containing compound using the same | |
JPH0316177B2 (en) | ||
JPH10128112A (en) | Catalyst for vapor phase contact oxidation reaction of isobutane and its preparation | |
JPH0791212B2 (en) | Method for producing methacrylic acid | |
JP2872816B2 (en) | Ammoxidation method | |
JP2558036B2 (en) | Method for producing methacrolein and / or methacrylic acid | |
JP4356303B2 (en) | Composite oxide catalyst and method for producing the same | |
JPH05177141A (en) | Preparation of methacrylic acid | |
JP3855298B2 (en) | Process for producing alkene and / or oxygen-containing compound | |
US4866024A (en) | Catalysts for ammoxidation of paraffins | |
JP2657693B2 (en) | Preparation of catalysts for the production of methacrolein and methacrylic acid | |
US4883895A (en) | Ammoxidation of paraffins and catalysts therefor | |
JP4629886B2 (en) | Catalyst for producing methacrolein and / or methacrylic acid, method for producing the same, and method for producing methacrolein and / or methacrylic acid |