JP2006116438A - Dehydrogenation catalyst of ethylbenzene in coexistence of carbon dioxide and method for producing styrene by using the catalyst - Google Patents
Dehydrogenation catalyst of ethylbenzene in coexistence of carbon dioxide and method for producing styrene by using the catalyst Download PDFInfo
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Abstract
Description
本発明は、エチルベンゼンを二酸化炭素共存下で脱水素反応させることによりスチレンモノマーを製造するために使用する触媒およびこの触媒を用いたスチレンの製造方法に関するものである。 The present invention relates to a catalyst used for producing a styrene monomer by dehydrogenating ethylbenzene in the presence of carbon dioxide and a method for producing styrene using this catalyst.
従来、スチレンモノマーを工業的に製造するには、エチルベンゼンを、大量の水蒸気共存下に、酸化鉄とカリウムを主成分とする触媒上に６００℃程度の温度で接触させる方法が採用されている（非特許文献１）。 Conventionally, in order to industrially produce a styrene monomer, a method in which ethylbenzene is brought into contact with a catalyst mainly composed of iron oxide and potassium in the presence of a large amount of water vapor at a temperature of about 600 ° C. is employed ( Non-patent document 1).
しかしながら、この方法は、（ｉ）大量の水蒸気を共存させるために、エネルギー消費量が大きいこと、（ii）スチレンモノマーの単通収率を高くするために、反応を減圧下で行う必要があること、（iii）反応中に触媒中のカリウムの揮散がおこることなど、改善すべき点も指摘されている。 However, in this method, (i) a large amount of water vapor coexists, the energy consumption is large, and (ii) the reaction must be performed under reduced pressure in order to increase the single yield of styrene monomer. In addition, it is pointed out that (iii) volatilization of potassium in the catalyst occurs during the reaction.
これらの問題点を解決するために、本発明者らは、先に水蒸気の代わりに、二酸化炭素を共存ガスに用いることにより、（イ）従来のプロセスよりエネルギー消費量が低くなる、（ロ）スチレンモノマーの単通収率が高くなる可能性を報告している(非特許文献２)。 In order to solve these problems, the present inventors previously used carbon dioxide as a coexisting gas instead of water vapor, so that (b) energy consumption is lower than that of conventional processes. It has been reported that the single yield of styrene monomer may increase (Non-patent Document 2).
しかしながら、この二酸化炭素を用いる新しい方法においても、優れた触媒が必要とされており、本発明者らは、既に、酸化鉄、酸化カルシウムおよび酸化アルミニウムからなる触媒（特許文献１）、酸化鉄、酸化アルミニウムおよび酸化セリウムを必須成分とする触媒（特許文献２）および酸化鉄、酸化アルミニウムおよび酸化イットリウムを必須成分とする触媒（特許文献３）を開発した。 However, even in this new method using carbon dioxide, an excellent catalyst is required, and the present inventors have already proposed a catalyst comprising iron oxide, calcium oxide and aluminum oxide (Patent Document 1), iron oxide, A catalyst having aluminum oxide and cerium oxide as essential components (Patent Document 2) and a catalyst having iron oxide, aluminum oxide and yttrium oxide as essential components have been developed (Patent Document 3).
本発明は、かかる特許発明を更に発展・飛躍させたものであり、エチルベンゼンを二酸化炭素共存下で脱水素反応させることによりスチレンモノマーを製造する方法において、更に高性能な触媒を提供することを目的とする。 The present invention is a further development and leap of the patented invention, and an object of the present invention is to provide a catalyst having higher performance in a method for producing a styrene monomer by dehydrogenating ethylbenzene in the presence of carbon dioxide. And
本発明者は、酸化鉄および酸化アルミニウムを主成分とする触媒の性能に及ぼす種々の添加物の影響を検討した結果、意外にもカリウムを添加することにより、触媒の活性を向上できることを見い出した。 As a result of examining the influence of various additives on the performance of a catalyst mainly composed of iron oxide and aluminum oxide, the present inventor has unexpectedly found that the activity of the catalyst can be improved by adding potassium. .
即ち、本発明によれば、第一に、酸化鉄および酸化アルミニウムを主成分とし更にカリウムを含有することを特徴とする二酸化炭素共存下でのエチルベンゼン脱水素反応用触媒が提供される。
第二に、酸化鉄および酸化アルミニウムを主成分とする触媒全体を１００重量％とするとき、含有されるカリウムが１〜１５重量％であることを特徴とする上記第一に記載のエチルベンゼンベンゼン脱水素反応用触媒が提供される。
第三に、エチルベンゼンを二酸化炭素共存下で脱水素反応させることによりスチレンを製造する方法において、触媒として上記第一又は第二に記載の触媒を用いることを特徴とするスチレンの製造方法が提供される。
That is, according to the present invention, firstly, there is provided a catalyst for dehydrogenation of ethylbenzene in the coexistence of carbon dioxide, characterized by containing iron oxide and aluminum oxide as main components and further containing potassium.
Second, the ethylbenzenebenzene dehydration according to the first aspect, wherein the content of potassium is 1 to 15% by weight when the total amount of the catalyst mainly composed of iron oxide and aluminum oxide is 100% by weight. A catalyst for elementary reactions is provided.
Third, in a method for producing styrene by dehydrogenating ethylbenzene in the presence of carbon dioxide, a method for producing styrene is provided, wherein the catalyst described in the first or second is used as a catalyst. The
本発明の触媒は、酸化鉄および酸化アルミニウムを主成分とし、更にカリウムを含有することから、二酸化炭素共存下でのエチルベンゼン脱水素反応を著しく高めることができる。従って、エチルベンゼンからスチレンモノマーを工業的有利に製造することができる。 Since the catalyst of the present invention contains iron oxide and aluminum oxide as main components and further contains potassium, the ethylbenzene dehydrogenation reaction in the presence of carbon dioxide can be remarkably enhanced. Therefore, a styrene monomer can be produced industrially advantageously from ethylbenzene.
本発明の触媒は、酸化鉄および酸化アルミニウムを主成分とする触媒に、更にカリウムが含有されていることを特徴とする。 The catalyst of the present invention is characterized in that potassium is further contained in a catalyst mainly composed of iron oxide and aluminum oxide.
補助成分として含有させたカリウムの作用の内容は現時点では完全には明らかになっているわけではないが、カリウムが塩基性を示すことにより、反応中の触媒表面に二酸化炭素を吸着し、脱水素反応により生成する水素と二酸化炭素との反応を促進するものと推察している。 The details of the action of potassium contained as an auxiliary component are not completely clarified at the present time. However, when potassium is basic, carbon dioxide is adsorbed on the surface of the catalyst during the reaction, and dehydrogenation occurs. It is assumed that the reaction between hydrogen produced by the reaction and carbon dioxide is promoted.
カリウムの添加量は、特に限定されないが、酸化鉄および酸化アルミニウムを主成分とする触媒全体を１００重量％とするとき、１〜１５重量％とされる。このような量的範囲において、組成を反応条件に応じて適切に定めることにより、その反応条件に適した触媒性能を得ることができる。 The amount of potassium added is not particularly limited, but is 1 to 15% by weight when the total amount of the catalyst mainly composed of iron oxide and aluminum oxide is 100% by weight. In such a quantitative range, by appropriately determining the composition according to the reaction conditions, catalyst performance suitable for the reaction conditions can be obtained.
添加するカリウムの原料としては、水酸化物、炭酸塩、炭酸水素塩、硝酸塩、有機酸塩等を用いることができる。触媒へのカリウムの添加は、含浸法などの公知の方法により行なうことができる。カリウムを含有する触媒前駆体を調製し、次いで、触媒前駆体を空気中で焼成することによりカリウム添加触媒が製造できる。触媒前駆体の焼成温度は、特に限定しないが、３００〜１０００℃の範囲が好ましく、４００〜８００℃が特に好ましい。 As the raw material of potassium to be added, hydroxides, carbonates, hydrogen carbonates, nitrates, organic acid salts and the like can be used. The addition of potassium to the catalyst can be performed by a known method such as an impregnation method. A potassium-added catalyst can be produced by preparing a catalyst precursor containing potassium and then calcining the catalyst precursor in air. Although the calcination temperature of a catalyst precursor is not specifically limited, The range of 300-1000 degreeC is preferable and 400-800 degreeC is especially preferable.
このようにして製造されたカリウム添加触媒は、そのままで、あるいは適当な方法により造粒または打錠成型して用いる。触媒の粒子径や形状は、反応方式、反応器の形状によって任意に選択できる。すなわち、本発明による触媒は、固定床、流動床等いずれの反応方式においても用いることができる。 The potassium addition catalyst thus produced is used as it is or after being granulated or tableted by an appropriate method. The particle diameter and shape of the catalyst can be arbitrarily selected depending on the reaction system and the shape of the reactor. That is, the catalyst according to the present invention can be used in any reaction system such as a fixed bed and a fluidized bed.
また、本発明の触媒は、主成分として酸化鉄および酸化アルミニウムを補助成分としてカリウムが含有するものであるが、他の添加成分として発明者らが、既に開発した酸化カルシウム、酸化セリウム、酸化イットリウムを含むことができる。また、本発明の反応を損なわない範囲で、他の物質を含有させてもよい。このような物質としては、たとえば、酸化マグネシウム、酸化マンガン、酸化珪素、酸化ランタンなどが挙げられる。 Further, the catalyst of the present invention contains iron oxide and aluminum oxide as main components and potassium as auxiliary components. However, as other additive components, the inventors have already developed calcium oxide, cerium oxide, yttrium oxide. Can be included. Moreover, you may contain another substance in the range which does not impair the reaction of this invention. Examples of such substances include magnesium oxide, manganese oxide, silicon oxide, lanthanum oxide, and the like.
本発明によるカリウム添加触媒を用いて、エチルベンゼンの脱水素反応によりスチレンを製造する際の反応条件は、特許第３０３２８１６号公報あるいは特開２００３−１１７３９４号公報に記載された反応条件と同様であるが、二酸化炭素のエチルベンゼンに対する割合は、エチルベンゼン１モルあたり、０．１〜１００モル、好ましくは１〜５０モル、反応温度は５００〜６５０℃の範囲、好ましくは、５３０〜６３０℃、反応圧力は、加圧、常圧、減圧のいずれでも良く、好ましくは０．２〜１．５気圧（絶対圧力）である。また、本発明の触媒は、一定時間使用後に活性が低下した場合には、空気中で再度焼成することによりその性能を回復させることができる。 The reaction conditions for producing styrene by dehydrogenation of ethylbenzene using the potassium addition catalyst according to the present invention are the same as those described in Japanese Patent No. 3032816 or Japanese Patent Application Laid-Open No. 2003-117394. The ratio of carbon dioxide to ethylbenzene is 0.1 to 100 mol, preferably 1 to 50 mol, and the reaction temperature is in the range of 500 to 650 ° C, preferably 530 to 630 ° C, and the reaction pressure is 1 mol of ethylbenzene. Any of pressurization, normal pressure, and reduced pressure may be used, and preferably 0.2 to 1.5 atmospheres (absolute pressure). Further, when the activity of the catalyst of the present invention decreases after use for a certain period of time, its performance can be recovered by firing again in air.
以下、実施例をあげて本発明の特徴とするところをより一層明確にする。 Hereinafter, the features of the present invention will be further clarified by giving examples.
実施例１
硝酸鉄九水和物８．０ｇ、硝酸アルミニウム九水和物１０５．１ｇを蒸留水に溶解し、３００ｍｌの水溶液を調製し、Ａ液とした。一方、無水炭酸ナトリウム５２．５ｇを蒸留水に溶解し、３００ｍｌの水溶液を調製し、Ｂ液とした。Ａ液およびＢ液を、それぞれ、８ｍｌ／分の速度で良く攪拌した８００ｍｌの室温の蒸留水に、同時に滴下して沈殿物を得た。この沈殿物を室温にて１日間熟成させた後、ろ過、洗浄を行い、沈殿物中のナトリウムを除去した。その後、沈殿物を１１０℃で乾燥し、空気中、７５０℃で２時間焼成した。この焼成後の酸化物の組成は、酸化鉄１０重量％、酸化アルミニウム９０重量％であった。次に、焼成後の酸化物２．５ｇに、０．８４５重量％の水酸化カリウム水溶液１５．６ｇを添加し、１１０℃で乾燥し、２５０〜６００μｍに粒度調製して、触媒とした。この触媒の組成は、酸化鉄９．５重量％、酸化アルミニウム８５．５重量％、水酸化カリウム５重量％であった。
Example 1
Iron nitrate nonahydrate (8.0 g) and aluminum nitrate nonahydrate (105.1 g) were dissolved in distilled water to prepare a 300 ml aqueous solution. On the other hand, 52.5 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 300 ml aqueous solution, which was designated as solution B. Liquid A and liquid B were each added dropwise simultaneously to 800 ml of room temperature distilled water that was well stirred at a rate of 8 ml / min to obtain a precipitate. The precipitate was aged at room temperature for 1 day, and then filtered and washed to remove sodium in the precipitate. Thereafter, the precipitate was dried at 110 ° C. and calcined in air at 750 ° C. for 2 hours. The composition of the oxide after firing was 10% by weight of iron oxide and 90% by weight of aluminum oxide. Next, 15.6 g of 0.845% by weight potassium hydroxide aqueous solution was added to 2.5 g of the calcined oxide, dried at 110 ° C., and the particle size was adjusted to 250 to 600 μm to prepare a catalyst. The composition of this catalyst was 9.5% by weight of iron oxide, 85.5% by weight of aluminum oxide, and 5% by weight of potassium hydroxide.
得られた触媒２ｇを反応管に充填し、二酸化炭素中で反応温度に昇温した後、２０容量％のエチルベンゼン蒸気および８０容量％の二酸化炭素からなる混合ガスを触媒層に通して、圧力０．１ＭＰａ、混合ガス流量２８ｍｌ／分、温度５８０℃の条件下に上記混合ガスを反応させた。反応生成ガスを−１℃で冷却して得られた液体成分をガスクロマトグラフで分析した。その結果、反応経過時間５時間後において、スチレン収率６２％、スチレン選択率９４％であった（表１参照）。 2 g of the catalyst thus obtained was charged into a reaction tube and heated to the reaction temperature in carbon dioxide, and then a mixed gas composed of 20% by volume of ethylbenzene vapor and 80% by volume of carbon dioxide was passed through the catalyst layer so that the pressure was 0. The mixed gas was reacted under the conditions of 1 MPa, a mixed gas flow rate of 28 ml / min, and a temperature of 580 ° C. The liquid component obtained by cooling the reaction product gas at -1 ° C was analyzed by gas chromatography. As a result, after 5 hours of reaction elapsed time, the styrene yield was 62% and the styrene selectivity was 94% (see Table 1).
実施例２
硝酸鉄九水和物３．９ｇ、硝酸アルミニウム九水和物１０８．９ｇを蒸留水に溶解し、３００ｍｌの水溶液を調製し、Ａ液とした。一方、無水炭酸ナトリウム５２．５ｇを蒸留水に溶解し、３００ｍｌの水溶液を調製し、Ｂ液とした。Ａ液およびＢ液を、それぞれ、８ｍｌ／分の速度で良く攪拌した８００ｍｌの室温の蒸留水に、同時に滴下して沈殿物を得た。この沈殿物を室温にて１日間熟成させた後、ろ過、洗浄を行い、沈殿物中のナトリウムを除去した。その後、沈殿物を１１０℃で乾燥し、空気中、７５０℃で２時間焼成した。この焼成後の酸化物の組成は、酸化鉄５重量％、酸化アルミニウム９５重量％であった。次に、焼成後の酸化物２．５ｇに、０．８４５重量％の水酸化カリウム水溶液１５．６ｇを添加し、１１０℃で乾燥し、２５０〜６００μｍに粒度調製して、触媒とした。この触媒の組成は、酸化鉄４．８重量％、酸化アルミニウム９０．２重量％、水酸化カリウム５重量％であった。
Example 2
Iron nitrate nonahydrate (3.9 g) and aluminum nitrate nonahydrate (108.9 g) were dissolved in distilled water to prepare a 300 ml aqueous solution. On the other hand, 52.5 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 300 ml aqueous solution, which was designated as solution B. Liquid A and liquid B were each added dropwise simultaneously to 800 ml of room temperature distilled water that was well stirred at a rate of 8 ml / min to obtain a precipitate. The precipitate was aged at room temperature for 1 day, and then filtered and washed to remove sodium in the precipitate. Thereafter, the precipitate was dried at 110 ° C. and calcined in air at 750 ° C. for 2 hours. The composition of the oxide after firing was 5% by weight of iron oxide and 95% by weight of aluminum oxide. Next, 15.6 g of 0.845% by weight potassium hydroxide aqueous solution was added to 2.5 g of the calcined oxide, dried at 110 ° C., and the particle size was adjusted to 250 to 600 μm to prepare a catalyst. The composition of this catalyst was 4.8% by weight of iron oxide, 90.2% by weight of aluminum oxide, and 5% by weight of potassium hydroxide.
得られた触媒２ｇを反応管に充填し、実施例１と同様にエチルベンゼンの脱水素反応を行った。その結果、反応経過時間５時間後において、スチレン収率５１％、スチレン選択率９４％であった（表１参照）。 2 g of the obtained catalyst was filled in a reaction tube, and ethylbenzene was dehydrogenated in the same manner as in Example 1. As a result, after 5 hours of reaction elapsed time, the styrene yield was 51% and the styrene selectivity was 94% (see Table 1).
実施例３
実施例２で調製した焼成後の酸化物２．５ｇに、０．８４５重量％の水酸化カリウム水溶液３２．９ｇを添加し、１１０℃で乾燥し、２５０〜６００μｍに粒度調製して、触媒とした。この触媒の組成は、酸化鉄４．５重量％、酸化アルミニウム８５．５重量％、水酸化カリウム１０重量％であった。
Example 3
To 2.5 g of the calcined oxide prepared in Example 2, 32.9 g of 0.845 wt% potassium hydroxide aqueous solution was added, dried at 110 ° C., and the particle size was adjusted to 250 to 600 μm. did. The composition of this catalyst was 4.5% by weight of iron oxide, 85.5% by weight of aluminum oxide, and 10% by weight of potassium hydroxide.
得られた触媒２ｇを反応管に充填し、実施例１と同様にエチルベンゼンの脱水素反応を行った。その結果、反応経過時間５時間後において、スチレン収率６６％、スチレン選択率９４％であった（表１参照）。 2 g of the obtained catalyst was filled in a reaction tube, and ethylbenzene was dehydrogenated in the same manner as in Example 1. As a result, after 5 hours of reaction elapsed time, the styrene yield was 66% and the styrene selectivity was 94% (see Table 1).
実施例４
硝酸鉄九水和物２．３ｇ、硝酸アルミニウム九水和物１１０．４ｇを蒸留水に溶解し、３００ｍｌの水溶液を調製し、Ａ液とした。一方、無水炭酸ナトリウム５２．５ｇを蒸留水に溶解し、３００ｍｌの水溶液を調製し、Ｂ液とした。Ａ液およびＢ液を、それぞれ、８ｍｌ／分の速度で良く攪拌した８００ｍｌの室温の蒸留水に、同時に滴下して沈殿物を得た。この沈殿物を室温にて１日間熟成させた後、ろ過、洗浄を行い、沈殿物中のナトリウムを除去した。その後、沈殿物を１１０℃で乾燥し、空気中、７５０℃で２時間焼成した。この焼成後の酸化物の組成は、酸化鉄３重量％、酸化アルミニウム９７重量％であった。次に、焼成後の酸化物２．５ｇに、０．８４５重量％の水酸化カリウム水溶液１５．６ｇを添加し、１１０℃で乾燥し、２５０〜６００μｍに粒度調製して、触媒とした。この触媒の組成は、酸化鉄２．９重量％、酸化アルミニウム９２．１重量％、水酸化カリウム５重量％であった。
Example 4
Iron nitrate nonahydrate 2.3 g and aluminum nitrate nonahydrate 110.4 g were dissolved in distilled water to prepare a 300 ml aqueous solution, which was designated as solution A. On the other hand, 52.5 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 300 ml aqueous solution, which was designated as solution B. Liquid A and liquid B were each added dropwise simultaneously to 800 ml of room temperature distilled water that was well stirred at a rate of 8 ml / min to obtain a precipitate. The precipitate was aged at room temperature for 1 day, and then filtered and washed to remove sodium in the precipitate. Thereafter, the precipitate was dried at 110 ° C. and calcined in air at 750 ° C. for 2 hours. The composition of the oxide after firing was 3% by weight of iron oxide and 97% by weight of aluminum oxide. Next, 15.6 g of 0.845% by weight potassium hydroxide aqueous solution was added to 2.5 g of the calcined oxide, dried at 110 ° C., and the particle size was adjusted to 250 to 600 μm to prepare a catalyst. The composition of this catalyst was 2.9% by weight of iron oxide, 92.1% by weight of aluminum oxide, and 5% by weight of potassium hydroxide.
得られた触媒２ｇを反応管に充填し、実施例１と同様にエチルベンゼンの脱水素反応を行った。その結果、反応経過時間５時間後において、スチレン収率３５％、スチレン選択率９４％であった（表１参照）。 2 g of the obtained catalyst was filled in a reaction tube, and ethylbenzene was dehydrogenated in the same manner as in Example 1. As a result, after 5 hours of reaction elapsed time, the styrene yield was 35% and the styrene selectivity was 94% (see Table 1).
実施例５
硝酸鉄九水和物８．１ｇ、硝酸アルミニウム九水和物９４．３ｇ、硝酸カルシウム６．７ｇを蒸留水に溶解し、３００ｍｌの水溶液を調製し、Ａ液とした。一方、無水炭酸ナトリウム５０．８ｇを蒸留水に溶解し、３００ｍｌの水溶液を調製し、Ｂ液とした。Ａ液およびＢ液を、それぞれ、８ｍｌ／分の速度で良く攪拌した８００ｍｌの室温の蒸留水に、同時に滴下して沈殿物を得た。この沈殿物を室温にて１日間熟成させた後、ろ過、洗浄を行い、沈殿物中のナトリウムを除去した。その後、沈殿物を１１０℃で乾燥し、空気中、７５０℃で２時間焼成した。この焼成後の酸化物の組成は、酸化鉄１０重量％、酸化アルミニウム８０重量％、酸化カルシウム１０重量％であった。次に、焼成後の酸化物２．５ｇに、０．８４５重量％の水酸化カリウム水溶液１５．６ｇを添加し、１１０℃で乾燥し、２５０〜６００μｍに粒度調製して、触媒とした。この触媒の組成は、酸化鉄９．５重量％、酸化アルミニウム７６重量％、酸化カルシウム９．５重量％、水酸化カリウム５重量％であった。
Example 5
Iron nitrate nonahydrate 8.1 g, aluminum nitrate nonahydrate 94.3 g, and calcium nitrate 6.7 g were dissolved in distilled water to prepare a 300 ml aqueous solution. On the other hand, 50.8 g of anhydrous sodium carbonate was dissolved in distilled water to prepare 300 ml of an aqueous solution. Liquid A and liquid B were each added dropwise simultaneously to 800 ml of room temperature distilled water that was well stirred at a rate of 8 ml / min to obtain a precipitate. The precipitate was aged at room temperature for 1 day, and then filtered and washed to remove sodium in the precipitate. Thereafter, the precipitate was dried at 110 ° C. and calcined in air at 750 ° C. for 2 hours. The composition of the oxide after firing was 10% by weight of iron oxide, 80% by weight of aluminum oxide, and 10% by weight of calcium oxide. Next, 15.6 g of 0.845% by weight potassium hydroxide aqueous solution was added to 2.5 g of the calcined oxide, dried at 110 ° C., and the particle size was adjusted to 250 to 600 μm to prepare a catalyst. The composition of this catalyst was 9.5% by weight of iron oxide, 76% by weight of aluminum oxide, 9.5% by weight of calcium oxide, and 5% by weight of potassium hydroxide.
得られた触媒２ｇを反応管に充填し、実施例１と同様にエチルベンゼンの脱水素反応を行った。その結果、反応経過時間１０時間後において、スチレン収率５９％、スチレン選択率９４％であった（表１参照）。 2 g of the obtained catalyst was filled in a reaction tube, and ethylbenzene was dehydrogenated in the same manner as in Example 1. As a result, after 10 hours of reaction elapsed time, the styrene yield was 59% and the styrene selectivity was 94% (see Table 1).
比較例１
実施例４で調製した水酸化カリウムを添加する以前の焼成後の酸化物を触媒として（この触媒の組成は、実施例４に記載したように、酸化鉄３重量％、酸化アルミニウム９７重量％であった）、この触媒２ｇを反応管に充填し、実施例１と同様にエチルベンゼンの脱水素反応を行った。その結果、反応経過時間５時間後において、スチレン収率１２％、スチレン選択率９０％であった（表１参照）。
Comparative Example 1
The oxide after calcining before adding potassium hydroxide prepared in Example 4 was used as a catalyst (the composition of this catalyst was 3% by weight of iron oxide and 97% by weight of aluminum oxide as described in Example 4). The catalyst was charged into a reaction tube and ethylbenzene was dehydrogenated in the same manner as in Example 1. As a result, after 5 hours of reaction elapsed time, the styrene yield was 12% and the styrene selectivity was 90% (see Table 1).
Claims (3)
A method for producing styrene by dehydrogenating ethylbenzene in the presence of carbon dioxide, wherein the catalyst according to claim 1 or 2 is used as a catalyst.
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| JPS61146347A (en) * | 1984-12-14 | 1986-07-04 | モ−ビル オイル コ−ポレ−ション | Iron oxide catalyst containing compounds of copper and zinc and dehydrogenation of ethyltoluene using said catalyst |
| JPH07328439A (en) * | 1994-06-06 | 1995-12-19 | Nissan Gaadoraa Shokubai Kk | Ethylbenzene dehydrogenation catalyst and its production |
| JPH11165069A (en) * | 1997-09-30 | 1999-06-22 | Korea Res Inst Chem Technol | Dehydrogenation catalyst of aromatic hydrocarbon using carbon dioxide |
| JP2002265396A (en) * | 2001-03-08 | 2002-09-18 | National Institute Of Advanced Industrial & Technology | Method for manufacturing styrene monomer |
| JP2003277299A (en) * | 2002-03-04 | 2003-10-02 | Korea Inst Of Chemical Technology | Catalytic dehydrogenation method of alkyl aromatic hydrocarbon by using carbon dioxide oxidizing agent |
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| JPS61146347A (en) * | 1984-12-14 | 1986-07-04 | モ−ビル オイル コ−ポレ−ション | Iron oxide catalyst containing compounds of copper and zinc and dehydrogenation of ethyltoluene using said catalyst |
| JPH07328439A (en) * | 1994-06-06 | 1995-12-19 | Nissan Gaadoraa Shokubai Kk | Ethylbenzene dehydrogenation catalyst and its production |
| JPH11165069A (en) * | 1997-09-30 | 1999-06-22 | Korea Res Inst Chem Technol | Dehydrogenation catalyst of aromatic hydrocarbon using carbon dioxide |
| JP2002265396A (en) * | 2001-03-08 | 2002-09-18 | National Institute Of Advanced Industrial & Technology | Method for manufacturing styrene monomer |
| JP2003277299A (en) * | 2002-03-04 | 2003-10-02 | Korea Inst Of Chemical Technology | Catalytic dehydrogenation method of alkyl aromatic hydrocarbon by using carbon dioxide oxidizing agent |
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