JPH09301945A - Production of alfa, beta-unsaturated nitrile - Google Patents
Production of alfa, beta-unsaturated nitrileInfo
- Publication number
- JPH09301945A JPH09301945A JP8114770A JP11477096A JPH09301945A JP H09301945 A JPH09301945 A JP H09301945A JP 8114770 A JP8114770 A JP 8114770A JP 11477096 A JP11477096 A JP 11477096A JP H09301945 A JPH09301945 A JP H09301945A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- propane
- benzyl alcohol
- gas
- essential components
- 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.)
- Pending
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]
【発明の属する技術分野】本発明はプロパンをアンモニ
アと分子状酸素の気相接触アンモ酸化反応によって、ア
クリロニトリルを製造する方法に関する。TECHNICAL FIELD The present invention relates to a method for producing acrylonitrile by subjecting propane to gas phase catalytic ammoxidation of ammonia and molecular oxygen.
【０００２】[0002]
【従来の技術】Ｃ3〜Ｃ5パラフィンを気相接触アンモ酸
化して、α，β−不飽和ニトリル類を製造する触媒は従
来数多く提案されている。中でも、プロパンのアンモ酸
化によるアクリロニトリル合成触媒については１９７０
年代から多くの提案がなされている。例えば、ＵＳＰ４
８８３８９５では、Ｖ−Ｐ−Ｗ系触媒およびＢｉ−Ｆｅ
−Ｍｏ系触媒の組み合わせが提案されている。また、Ｕ
ＳＰ４９７８７６４ではＣｓ−Ｋ−Ｎｉ−Ｃｏ−Ｍｎ−
Ｂｉ−Ｃｒ−Ｍｏ−Ｏからなる触媒、特開平６−８０６
２０ではＶ−Ｓｂ−Ｂｉ−Ｏからなる触媒、特開平６−
２２８０７３ではＷ−Ｖ−Ｔｅ−Ｎｂ−Ｏからなる触
媒、特開平７−１４４１３２ではＭｏ−Ｖ−Ｔｅ−Ｎｂ
−Ｏ／ＳｉＯ2からなる触媒が提案されている。2. Description of the Related Art A number of catalysts for producing α, β-unsaturated nitriles by gas-phase catalytic ammoxidation of C 3 -C 5 paraffins have been proposed. Among them, the acrylonitrile synthesis catalyst by ammoxidation of propane is 1970.
Many proposals have been made since the generation. For example, USP4
883895, V-P-W based catalyst and Bi-Fe
A combination of -Mo-based catalysts has been proposed. Also, U
Cs-K-Ni-Co-Mn- in SP4978764
A catalyst composed of Bi-Cr-Mo-O, JP-A-6-806.
In No. 20, a catalyst comprising V-Sb-Bi-O, JP-A-6-
228073 is a catalyst composed of W-V-Te-Nb-O, and in JP-A-7-144132, Mo-V-Te-Nb.
A catalyst composed of —O / SiO 2 has been proposed.
【０００３】一般に、パラフィンはオレフィンに比べ反
応性が低いため、従来触媒では、オレフィンのアンモ酸
化条件でのパラフィンの転化率が低い。そのため、これ
らの触媒では、パラフィンの酸化に比較的高い反応温度
が必要であり、併発する気相ラジカル反応、目的物であ
る不飽和化合物の逐次酸化などにより、不飽和ニトリル
への選択性が低いという問題があった。In general, since paraffin has a lower reactivity than olefin, the conventional catalyst has a low paraffin conversion rate under olefin ammoxidation conditions. Therefore, these catalysts require a relatively high reaction temperature for the oxidation of paraffin, and the selectivity to unsaturated nitrile is low due to the concurrent gas-phase radical reaction and the sequential oxidation of the target unsaturated compound. There was a problem.
【０００４】また、副生オレフィンが多いと分離回収
し、中間原料として循環使用し不飽和ニトリル類に転化
する必要があり、煩雑なプロセスになる問題点があっ
た。そのため、副生オレフィン量が少なく不飽和ニトリ
ルへの選択性が高い触媒の開発が望まれていた。Further, if a large amount of by-produced olefin is present, it is necessary to separate and collect it, and circulate it as an intermediate raw material to convert it into unsaturated nitriles, resulting in a complicated process. Therefore, it has been desired to develop a catalyst having a small amount of by-produced olefin and high selectivity to unsaturated nitrile.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、触媒
活性およびアクリロニトリルへの選択性が高く、プロピ
レン副生が少ない、プロパンのアンモ酸化触媒を提供す
ることにある。SUMMARY OF THE INVENTION It is an object of the present invention to provide a propane ammoxidation catalyst which has high catalytic activity, high selectivity to acrylonitrile, and low propylene by-product.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、プロパン
のアンモ酸化反応およびそれに用いる触媒について、活
性、アクリロニトリル選択性に優れた触媒を開発すべ
く、触媒成分、組成、調製法について鋭意検討をすすめ
た結果、ＶおよびＬｉを必須成分とする燐酸塩の構造を
系内に含有する触媒が、高い活性、アクリロニトリル選
択性を有する触媒であることを見いだし、本発明の方法
に至った。[Means for Solving the Problems] The present inventors diligently studied catalyst components, compositions, and preparation methods for the ammoxidation reaction of propane and the catalyst used therefor in order to develop a catalyst excellent in activity and acrylonitrile selectivity. As a result, the inventors have found that the catalyst containing in its system a phosphate structure containing V and Li as essential components is a catalyst having high activity and acrylonitrile selectivity, leading to the method of the present invention.
【０００７】即ち、本発明は、プロパン、アンモニアお
よび酸素含有ガスの気相接触アンモ酸化反応でアクリロ
ニトリルを製造する方法において、ＶおよびＬｉを必須
成分として含有する燐酸塩触媒の存在下で反応を行うこ
とを特徴とするアクリロニトリルの製造方法である。That is, according to the present invention, in a method for producing acrylonitrile by a gas phase catalytic ammoxidation reaction of propane, ammonia and an oxygen-containing gas, the reaction is carried out in the presence of a phosphate catalyst containing V and Li as essential components. And a method for producing acrylonitrile.
【０００８】また、本発明では、燐酸塩触媒が、一般式
（１）Further, in the present invention, the phosphate catalyst is represented by the general formula (1)
【０００９】[0009]
【化２】ＶＡaＢbＣcＬｉdＰeＯf （１） ［式中、ＡはＬａ，Ｎｂ，Ｔａ，Ｍｏ，Ｗ，Ｓｎ，Ｓ
ｂ，Ｂｉ，Ｆｅ，Ａｌ，Ｃｒ，Ｃｏ，Ｎｉ，Ｃｕ，Ｍ
ｇ，Ｃａ，ＳｒおよびＢａよりなる群から選ばれる１種
以上の元素、ＢはＮａ，Ｋ，ＲｂおよびＣｓよりなる群
から選ばれる１種以上の元素、ＣはＣｅ，ＰｒおよびＴ
ｂよりなる群から選ばれる１種以上の元素を表す。ａ，
ｂ，ｃ，ｄおよびｅはＶを基準にしたときの、各元素の
原子比を表し、ａは０〜０．５、ｂは０〜０．５、ｃは
０〜０．３、ｄは０．００１〜１、ｅは０．５〜１０で
ありｆは各成分元素の原子価を満足するに必要な原子数
である。］で示されるものが多用される また、燐酸塩触媒は、二種以上の燐酸塩を含有するもの
を用いることが出来る。## STR2 ## VA a B b C c Li d P e O f (1) [ In the formula, A La, Nb, Ta, Mo, W, Sn, S
b, Bi, Fe, Al, Cr, Co, Ni, Cu, M
at least one element selected from the group consisting of g, Ca, Sr and Ba; B is at least one element selected from the group consisting of Na, K, Rb and Cs; C is Ce, Pr and T
Represents one or more elements selected from the group consisting of b. a,
b, c, d and e represent atomic ratios of the respective elements based on V, a is 0 to 0.5, b is 0 to 0.5, c is 0 to 0.3, and d is 0.001-1, e is 0.5-10, and f is the number of atoms required to satisfy the valence of each component element. ] The one represented by the above formula is frequently used, and as the phosphate catalyst, one containing two or more kinds of phosphates can be used.
【００１０】[0010]
【発明の実施の形態】本発明の方法で使用する触媒、即
ちＶおよびＬｉを必須成分として含有する燐酸塩触媒、
および燐酸塩混合触媒は、この分野で通常用いられる公
知の方法で調製することができ、ＶとＬｉとの原子比Ｌ
ｉ／Ｖが０．００１〜１の範囲、好ましくは０．０１〜
０．５の範囲にあることが重要である。前記原子比が
０．００１より少ないとプロパン転化率が低く、副生成
物であるＣＯ、ＣＯ2の選択率が高くなり、１よりも多
いとプロパン転化率が低くなるので好ましくない。また
ＶとＰとの原子比Ｐ／Ｖが０．５〜１０の範囲、好まし
くは０．６〜３の範囲にあることが重要である。ＶとＰ
との原子比が前記範囲をはずれると、プロパン転化率、
アクリロニトリル選択率が低くなるので好ましくない。
この際用いるＶ、Ｌｉ源としては、特に制限はないが、
好ましくは酸化物、水酸化物、塩化物、硝酸塩、酢酸
塩、蓚酸塩等である。Ｐ源としては、特に制限はない
が、好ましくは燐酸を用いる。具体的には、例えば、次
のような方法で調製することができる。BEST MODE FOR CARRYING OUT THE INVENTION The catalyst used in the method of the present invention, namely a phosphate catalyst containing V and Li as essential components,
And the phosphate mixed catalyst can be prepared by a known method usually used in this field, and the atomic ratio L of V and Li is L.
i / V is in the range of 0.001 to 1, preferably 0.01 to
It is important to be in the range of 0.5. When the atomic ratio is less than 0.001, the propane conversion is low, the selectivity of CO and CO 2 by- products is high, and when it is more than 1, the propane conversion is low, which is not preferable. Further, it is important that the atomic ratio P / V of V and P is in the range of 0.5 to 10, preferably in the range of 0.6 to 3. V and P
When the atomic ratio of and is out of the above range, the propane conversion rate,
Acrylonitrile selectivity is low, which is not preferable.
The V and Li sources used at this time are not particularly limited,
Preferred are oxides, hydroxides, chlorides, nitrates, acetates, oxalates and the like. The P source is not particularly limited, but phosphoric acid is preferably used. Specifically, for example, it can be prepared by the following method.
【００１１】ベンジルアルコール中へＶ2Ｏ5と酢酸リチ
ウムを加え、これを攪拌しながら還流下加熱した後に９
８％Ｈ3ＰＯ4を加え、さらに加熱還流しベンジルアルコ
ールを蒸発させて乾燥し焼成する方法で調製される。V 2 O 5 and lithium acetate were added to benzyl alcohol, and the mixture was heated under reflux with stirring.
It is prepared by a method of adding 8% H 3 PO 4 and further heating under reflux to evaporate benzyl alcohol to dry and calcinate.
【００１２】また、必要に応じて、Ｌａ，Ｎｂ，Ｔａ，
Ｍｏ，Ｗ，Ｓｎ，Ｓｂ，Ｂｉ，Ｆｅ，Ａｌ，Ｃｒ，Ｃ
ｏ，Ｎｉ，Ｃｕ，Ｍｇ，Ｃａ，ＳｒおよびＢａよりなる
群から選ばれる１種以上の元素の化合物、例えば塩化
物、酸化物等を添加することができ、またＮａ、Ｋ、Ｒ
ｂおよびＣｓよりなる群から選ばれる１種以上の元素の
化合物、例えば酸化物、水酸化物、塩化物等を添加する
ことができる。 また、この分野で通常行われる方法で
あるが、この触媒をＳｉＯ2，Ａｌ2Ｏ3，ＳｉＣなどの
担体に担持した状態で使用しても良い。If necessary, La, Nb, Ta,
Mo, W, Sn, Sb, Bi, Fe, Al, Cr, C
Compounds of one or more elements selected from the group consisting of o, Ni, Cu, Mg, Ca, Sr and Ba, such as chlorides and oxides, may be added, and Na, K, R may be added.
Compounds of one or more elements selected from the group consisting of b and Cs, such as oxides, hydroxides and chlorides, can be added. Further, although it is a method which is usually carried out in this field, the catalyst may be used in a state of being supported on a carrier such as SiO 2 , Al 2 O 3 or SiC.
【００１３】乾燥温度は通常６０〜２００℃、乾燥時間
は特に制限はないが、好ましくは２〜１０時間である。
また焼成温度は通常２００〜１０００℃、好ましくは４
００〜６５０℃、焼成時間は特に制限はないが、好まし
くは２〜１０時間である。触媒は、粒状または成形体と
して固定床で使用されるが、移動床または流動床として
も使用できる。The drying temperature is usually 60 to 200 ° C., and the drying time is not particularly limited, but it is preferably 2 to 10 hours.
The firing temperature is usually 200 to 1000 ° C., preferably 4
The firing time is not particularly limited, but is preferably 2 to 10 hours. The catalysts are used in fixed beds as granulates or shaped bodies, but can also be used as moving beds or fluidized beds.
【００１４】本発明による気相接触アンモ酸化反応の原
料ガスとして、プロパン、アンモニアおよび分子状酸素
が用いられる、これら原料ガスの他に希釈ガスを用いる
ことも出来る。As a raw material gas for the gas phase catalytic ammoxidation reaction according to the present invention, propane, ammonia and molecular oxygen are used. In addition to these raw material gases, a diluent gas may be used.
【００１５】供給ガス中のプロパンに対する酸素の割合
は、プロパン１モルに対して酸素０．５〜５、好ましく
は０．８〜３の範囲である。またプロパンに対するアン
モニアの割合は０．３〜３、好ましくは０．５〜２の範
囲である。The ratio of oxygen to propane in the feed gas is in the range of 0.5 to 5, preferably 0.8 to 3, with respect to 1 mol of propane. The ratio of ammonia to propane is in the range of 0.3 to 3, preferably 0.5 to 2.
【００１６】本発明の方法で用いる分子状酸素源とし
て、通常は空気が使用されるが、純酸素を使用しても良
い。アンモニア源としては、乾燥ガスでも良いが、アン
モニア水を蒸発器で気化して使用しても良い。希釈ガス
としては、窒素、炭酸ガスなどの不活性ガスが使用され
る。反応ガスに含まれる非凝縮性ガスの一部を循環して
希釈ガスとして使用しても良い。As the molecular oxygen source used in the method of the present invention, air is usually used, but pure oxygen may be used. As the ammonia source, dry gas may be used, but ammonia water may be used after being vaporized by an evaporator. An inert gas such as nitrogen or carbon dioxide is used as the diluting gas. A part of the non-condensable gas contained in the reaction gas may be circulated and used as a diluent gas.
【００１７】希釈ガスとして、水蒸気を併せて使用する
ことが活性および選択性を高める上で好ましい。また、
希釈ガスとして水蒸気を併せて使用する場合、原料ガス
中の水蒸気は、通常６０容量％まで添加される。It is preferable to use water vapor together as a diluting gas in order to enhance activity and selectivity. Also,
When steam is also used as the diluent gas, the steam in the raw material gas is usually added up to 60% by volume.
【００１８】本発明による気相接触アンモ酸化反応は、
原料ガスを、前記した触媒上に３５０〜６００℃の温度
範囲、常圧〜１０気圧の圧力下、空間速度３００〜５０
００／ｈｒで導入することで実施される。The gas phase catalytic ammoxidation reaction according to the present invention comprises
The raw material gas is placed on the above-mentioned catalyst in the temperature range of 350 to 600 ° C., the atmospheric pressure to the pressure of 10 atm, and the space velocity of 300 to 50.
It is implemented by introducing at 00 / hr.
【００１９】[0019]
【実施例】実施例によって本発明をさらに詳細に説明す
る。転化率、アクリロニトリルおよびプロピレン選択率
は次のとうり定義される。The present invention will be described in more detail with reference to examples. The conversion, acrylonitrile and propylene selectivity are defined as follows.
【００２０】[0020]
【数１】転化率＝100×（反応したプロパンのモル数）
／（供給したプロパンのモル数）[Equation 1] Conversion = 100 x (number of moles of reacted propane)
/ (Number of moles of propane supplied)
【００２１】[0021]
【数２】アクリロニトリルの選択率＝100×(生成したア
クリロニトリルのモル数)／(反応したプロパンのモル
数)[Formula 2] Acrylonitrile selectivity = 100 × (number of moles of acrylonitrile formed) / (number of moles of reacted propane)
【００２２】[0022]
【数３】プロピレンの選択率＝100×（生成したプロピ
レンのモル数）／（反応したプロパンのモル数）[Equation 3] Propylene selectivity = 100 × (number of moles of propylene produced) / (number of moles of reacted propane)
【００２３】実施例１ ベンジルアルコール１５０ｍｌ中にＶ2Ｏ5１０ｇと酢酸
リチウム二水和物１．１２ｇを加え１００℃で１０時間
加熱還流した後９８％Ｈ3ＰＯ4を１１．１ｇ加えてさら
に２０時間還流した。さらに加熱してベンジルアルコー
ルを蒸発させて固体を得た。得られた固体を２％ブタン
を含む空気中で空間速度２４００／ｈｒ、４８０℃で８
ｈｒ活性化処理してＶ1.0Ｌｉ0.1Ｐ1.1ＯXなる組成の触
媒を得た。得られた触媒を通常の流通式反応器に充填
し、プロパン／酸素／アンモニア／ヘリウムのモル比が
６／１２／９／１３なる組成の原料ガスを、空間速度１
２００／ｈｒで供給した。反応温度を５２０℃に保っ
て、触媒の性能を評価した。評価結果を表１に示した。Example 1 To 150 ml of benzyl alcohol, 10 g of V 2 O 5 and 1.12 g of lithium acetate dihydrate were added, and the mixture was heated under reflux at 100 ° C. for 10 hours and then 11.1 g of 98% H 3 PO 4 was added. Refluxed for 20 hours. Further heating to evaporate the benzyl alcohol gave a solid. The obtained solid was placed in air containing 2% butane at a space velocity of 2400 / hr at 480 ° C. for 8 hours.
After hr activation treatment, a catalyst having a composition of V 1.0 Li 0.1 P 1.1 O X was obtained. The obtained catalyst was charged into a normal flow reactor, and a raw material gas having a composition of a propane / oxygen / ammonia / helium molar ratio of 6/12/9/13 was added at a space velocity of 1
Supplied at 200 / hr. The reaction temperature was kept at 520 ° C. to evaluate the performance of the catalyst. Table 1 shows the evaluation results.
【００２４】実施例２ ベンジルアルコール１５０ｍｌ中にＶ2Ｏ5１０ｇ，酢酸
リチウム二水和物１．１２ｇおよび塩化マグネシウム
１．０５ｇを加え１００℃で１０時間加熱還流した後９
８％Ｈ3ＰＯ4を１１．１ｇ加えてさらに２０時間還流し
た。さらに加熱してベンジルアルコールを蒸発させて固
体を得た。得られた固体を実施例１と同様の方法で活性
化処理してＶ1.0Ｌｉ0.1Ｍｇ0.1Ｐ1.1ＯXなる組成の触
媒を得た。得られた触媒を実施例１と同様にして評価し
た結果を表１に示した。Example 2 To 150 ml of benzyl alcohol, 10 g of V 2 O 5 , 1.12 g of lithium acetate dihydrate and 1.05 g of magnesium chloride were added, and the mixture was heated under reflux at 100 ° C. for 10 hours and then cooled to 9%.
11.1 g of 8% H 3 PO 4 was added and the mixture was refluxed for another 20 hours. Further heating to evaporate the benzyl alcohol gave a solid. The obtained solid was activated in the same manner as in Example 1 to obtain a catalyst having a composition of V 1.0 Li 0.1 Mg 0.1 P 1.1 O X. The results of evaluation of the obtained catalyst in the same manner as in Example 1 are shown in Table 1.
【００２５】実施例３〜８ 実施例２の塩化マグネシウムのかわりに塩化コバルト
１．４３ｇ、塩化ニッケル１．４３ｇ、第二塩化鉄１．
７８ｇ、塩化ランタン２．７０ｇ、塩化ニオブ２．９７
ｇまたはモリブデン酸１．７８ｇを使用した他は、実施
例２と同様にして表１に記載の触媒を調製し、実施例２
と同じ反応条件で評価した。その結果を表１に示した。Examples 3 to 8 1.43 g of cobalt chloride, 1.43 g of nickel chloride, ferric chloride 1.
78 g, lanthanum chloride 2.70 g, niobium chloride 2.97
g or molybdic acid 1.78 g, except that the catalysts listed in Table 1 were prepared in the same manner as in Example 2.
The same reaction conditions as above were evaluated. The results are shown in Table 1.
【００２６】比較例１ ベンジルアルコール１５０ｍｌ中にＶ2Ｏ5１０ｇを加え
８０℃で１０時間加熱還流した後９８％Ｈ3ＰＯ4を１
１．０ｇ加えてさらに２０時間還流した。得られた化合
物をトルエン中で洗浄し室温で乾燥し固体を得た。得ら
れた固体を２％ブタンを含む空気中で空間速度２４００
／ｈｒ、４８０℃で８ｈｒ活性化処理してＶ1.0Ｐ1.0Ｏ
Xなる組成の触媒を得た。得られた触媒を実施例１と同
様にして評価した結果を表１に示した。Comparative Example 1 10 g of V 2 O 5 was added to 150 ml of benzyl alcohol, and the mixture was heated under reflux at 80 ° C. for 10 hours, and then 98% H 3 PO 4 was added.
1.0 g was added and the mixture was refluxed for 20 hours. The obtained compound was washed in toluene and dried at room temperature to obtain a solid. The solid obtained was subjected to a space velocity of 2400 in air containing 2% butane.
/ Hr, activation treatment at 480 ° C. for 8 hours, V 1.0 P 1.0 O
A catalyst of composition X was obtained. The results of evaluation of the obtained catalyst in the same manner as in Example 1 are shown in Table 1.
【００２７】比較例２ ベンジルアルコール１５０ｍｌ中にＶ2Ｏ5１０ｇを加え
８０℃で１０時間加熱還流した後９８％Ｈ3ＰＯ4を１
１．１ｇ加えてさらに２０時間還流した。さらに加熱し
てベンジルアルコールを蒸発させて固体を得た。得られ
た固体を２％ブタンを含む空気中で空間速度２４００／
ｈｒ、４８０℃で８ｈｒ活性化処理してＶ 1.0Ｐ1.1ＯX
なる組成の触媒を得た。得られた触媒を実施例１と同様
にして評価した結果を表１に示した。Comparative Example 2 V in 150 ml of benzyl alcoholTwoOFiveAdd 10g
After heating under reflux at 80 ° C for 10 hours, 98% HThreePOFour1
1.1 g was added and the mixture was refluxed for 20 hours. Heat it up
The benzyl alcohol was evaporated to give a solid. Obtained
Space velocity 2400 / in air containing 2% butane
hr after activation for 8 hours at 480 ℃ 1.0P1.1OX
A catalyst having the following composition was obtained. The catalyst obtained is the same as in Example 1.
Table 1 shows the results of evaluation.
【００２８】[0028]
【表１】 表１ ──────────────────────────────────── 例 触 媒 プロパン アクリロ プロピレン ニトリル 転化率（％）選択率（％）選択率（％） ──────────────────────────────────── 実施例１ Ｖ1.0Ｌｉ0.1Ｐ1.1ＯX ５４．８ ５８．８ ２０．３ ２ Ｖ1.0Ｌｉ0.1Ｍｇ0.1Ｐ1.1ＯX ５８．３ ６０．９ ２０．７ ３ Ｖ1.0Ｌｉ0.1Ｃｏ0.1Ｐ1.1ＯX ７６．８ ６６．３ １４．２ ４ Ｖ1.0Ｌｉ0.1Ｎｉ0.1Ｐ1.1ＯX ６８．３ ６６．９ １４．６ ５ Ｖ1.0Ｌｉ0.1Ｆｅ0.1Ｐ1.1ＯX ７１．８ ６８．７ １２．６ ６ Ｖ1.0Ｌｉ0.1Ｌａ0.1Ｐ1.1ＯX ５８．３ ５８．８ ２２．６ ７ Ｖ1.0Ｌｉ0.1Ｎｂ0.1Ｐ1.1ＯX ６４．６ ５０．６ ３１．３ ８ Ｖ1.0Ｌｉ0.1Ｍｏ0.1Ｐ1.1ＯX ６１．８ ５０．６ ３３．８ 比較例１ Ｖ1.0Ｐ1.0ＯX ３８．２ ４５．９ ２２．８ ２ Ｖ1.0Ｐ1.1ＯX ２９．５ ４６．３ ２４．０ ────────────────────────────────────[Table 1] Table 1 ──────────────────────────────────── Example catalyst propane acrylo propylene nitrile conversion Rate (%) Selectivity (%) Selectivity (%) ───────────────────────────────────── Example 1 V 1.0 Li 0.1 P 1.1 O X 54.8 58.8 20.3 2 V 1.0 Li 0.1 Mg 0.1 P 1.1 O X 58.3 60.9 20.7 3 V 1.0 Li 0.1 Co 0.1 P 1.1 O X 76.8 66.3 14.2 4 V 1.0 Li 0.1 Ni 0.1 P 1.1 O X 68.3 66.9 14.6 5 V 1.0 Li 0.1 Fe 0.1 P 1.1 O X 71.8 68.7 12.6 6 V 1.0 Li 0.1 La 0.1 P 1.1 O X 58.3 58.8 22.6 7 V 1.0 Li 0.1 Nb 0.1 P 1.1 O X 64.6 50.6 31.3 8 V 1.0 Li 0.1 Mo 0.1 P 1.1 O X 61.8 50.6 33.8 Comparative Example 1 V 1.0 P 1.0 O X 38.2 45.9 22.8 2 V 1.0 P 1.1 O X 29.5 46.3 24.0 ─── ──────────────────────────────────
【００２９】[0029]
【発明の効果】本発明で使用するアンモ酸化触媒は、触
媒活性が高く、アクリロニトリルへの選択性が高いの
で、本発明の方法により、プロパンから効率よくアクリ
ロニトリルを製造することが出来る。The ammoxidation catalyst used in the present invention has high catalytic activity and high selectivity to acrylonitrile. Therefore, the method of the present invention enables efficient production of acrylonitrile from propane.
Claims (2)
スの気相接触アンモ酸化反応でアクリロニトリルを製造
する方法において、ＶおよびＬｉを必須成分として含有
する燐酸塩触媒の存在下で反応を行うことを特徴とする
アクリロニトリルの製造方法。1. A method for producing acrylonitrile by a gas phase catalytic ammoxidation reaction of propane, ammonia and an oxygen-containing gas, wherein the reaction is carried out in the presence of a phosphate catalyst containing V and Li as essential components. A method for producing acrylonitrile.
ｂ，Ｂｉ，Ｆｅ，Ａｌ，Ｃｒ，Ｃｏ，Ｎｉ，Ｃｕ，Ｍ
ｇ，Ｃａ，ＳｒおよびＢａよりなる群から選ばれる１種
以上の元素、ＢはＮａ，Ｋ，ＲｂおよびＣｓよりなる群
から選ばれる１種以上の元素、ＣはＣｅ，ＰｒおよびＴ
ｂよりなる群から選ばれる１種以上の元素を表す。ａ，
ｂ，ｃ，ｄおよびｅはＶを基準にしたときの、各元素の
原子比を表し、ａは０〜０．５、ｂは０〜０．５、ｃは
０〜０．３、ｄは０．００１〜１、ｅは０．５〜１０で
ありｆは各成分元素の原子価を満足するに必要な原子数
である。］で示されるものである請求項１記載の方法。2. A phosphate catalyst is represented by the general formula (1) ## STR1 ## VA a B b C c Li d P e O f (1) [ In the formula, A La, Nb, Ta, Mo, W, Sn, S
b, Bi, Fe, Al, Cr, Co, Ni, Cu, M
at least one element selected from the group consisting of g, Ca, Sr and Ba; B is at least one element selected from the group consisting of Na, K, Rb and Cs; C is Ce, Pr and T
Represents one or more elements selected from the group consisting of b. a,
b, c, d and e represent atomic ratios of the respective elements based on V, a is 0 to 0.5, b is 0 to 0.5, c is 0 to 0.3, and d is 0.001-1, e is 0.5-10, and f is the number of atoms required to satisfy the valence of each component element. ] The method of Claim 1 which is shown by these.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8114770A JPH09301945A (en) | 1996-05-09 | 1996-05-09 | Production of alfa, beta-unsaturated nitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8114770A JPH09301945A (en) | 1996-05-09 | 1996-05-09 | Production of alfa, beta-unsaturated nitrile |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09301945A true JPH09301945A (en) | 1997-11-25 |
Family
ID=14646261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8114770A Pending JPH09301945A (en) | 1996-05-09 | 1996-05-09 | Production of alfa, beta-unsaturated nitrile |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09301945A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013136540A (en) * | 2011-12-28 | 2013-07-11 | Daiyanitorikkusu Kk | Method of producing nitrogen-containing compound |
| KR20180027790A (en) * | 2016-09-07 | 2018-03-15 | 에쓰대시오일 주식회사 | Catalysts for propane ammoxidation, preparation method thereof and method for producing acrylonitrile using the same |
-
1996
- 1996-05-09 JP JP8114770A patent/JPH09301945A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013136540A (en) * | 2011-12-28 | 2013-07-11 | Daiyanitorikkusu Kk | Method of producing nitrogen-containing compound |
| KR20180027790A (en) * | 2016-09-07 | 2018-03-15 | 에쓰대시오일 주식회사 | Catalysts for propane ammoxidation, preparation method thereof and method for producing acrylonitrile using the same |
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