JP3032816B2 - Method for producing styrene monomer - Google Patents
Method for producing styrene monomerInfo
- Publication number
- JP3032816B2 JP3032816B2 JP9218411A JP21841197A JP3032816B2 JP 3032816 B2 JP3032816 B2 JP 3032816B2 JP 9218411 A JP9218411 A JP 9218411A JP 21841197 A JP21841197 A JP 21841197A JP 3032816 B2 JP3032816 B2 JP 3032816B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- styrene monomer
- reaction
- weight
- oxide
- 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)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、エチルベンゼンか
らスチレンモノマーを製造する方法に関するものであ
る。The present invention relates to a method for producing a styrene monomer from ethylbenzene.
【０００２】[0002]
【従来の技術】スチレンモノマーは、ポリスチレンをは
じめ各種の高分子化合物の原料となる重要な物質であ
る。現在、スチレンモノマーの工業的な製造法として
は、エチルベンゼンと水蒸気の混合気体(水蒸気/エチル
ベンゼン=７〜１２)を、酸化鉄及び酸化カリウムからな
る触媒に６００℃程度の温度で接触させる方法が採用さ
れている(触媒、Ｖｏｌ.３８ Ｎｏ．７ (１９９６)
５７２-５７９)。しかし、この方法は、水蒸気の製造に
多大なエネルギーが必要であり、また触媒成分のカリウ
ムが揮散しやすいなどの問題を有している。また、エチ
ルベンゼンを二酸化炭素の存在下、鉄酸化物、アルカリ
金属及び活性炭からなる触媒と接触させることによりス
チレンモノマーを製造する方法が知られている（Ａｐｐ
ｌｉｅｄ Ｃａｔａｌｙｓｉｓ Ａ Ｇｅｎｅｒａｌ，
１２１ （１９９５） １２５−１３７）。しかし、こ
の方法は触媒活性の長時間の安定性に問題があった。2. Description of the Related Art Styrene monomer is an important substance that is a raw material of various polymer compounds including polystyrene. At present, as an industrial production method of styrene monomer, a method is employed in which a mixed gas of ethylbenzene and steam (steam / ethylbenzene = 7 to 12) is brought into contact with a catalyst composed of iron oxide and potassium oxide at a temperature of about 600 ° C. (Catalyst, Vol. 38 No. 7 (1996)
572-579). However, this method has a problem that a large amount of energy is required for producing steam, and potassium as a catalyst component is easily volatilized. A method for producing a styrene monomer by contacting ethylbenzene with a catalyst comprising an iron oxide, an alkali metal and activated carbon in the presence of carbon dioxide is also known (App.
lied Catalyst A General,
121 (1995) 125-137). However, this method has a problem in long-term stability of catalyst activity.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、エチルベン
ゼンを二酸化炭素の存在下、触媒と接触させてスチレン
を製造する方法において、安価でかつ活性の低下が少な
い触媒を用いてスチレンモノマーを製造する方法を提供
することを課題とする。SUMMARY OF THE INVENTION The present invention relates to a method for producing styrene by contacting ethylbenzene with a catalyst in the presence of carbon dioxide, wherein a styrene monomer is produced using an inexpensive catalyst with a small decrease in activity. It is an object to provide a method.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意検討を重ねた結果、本発明を完成する
に至った。即ち、本発明によれば、エチルベンゼンを二
酸化炭素の存在下、酸化鉄、酸化カルシウム及び酸化ア
ルミニウムからなる触媒に、５００〜６５０℃の温度で
接触させることを特徴とするスチレンモノマーの製造方
法が提供される。Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, have completed the present invention. That is, according to the present invention, there is provided a method for producing a styrene monomer, comprising contacting ethylbenzene with a catalyst comprising iron oxide, calcium oxide and aluminum oxide in the presence of carbon dioxide at a temperature of 500 to 650 ° C. Is done.
【０００５】[0005]
【発明の実施の形態】以下本発明について詳細に説明す
る。本発明において使用する触媒は、酸化鉄、酸化カル
シウム及び酸化アルミニウムからなる触媒である。な
お、酸化鉄は２価及び３価の鉄の酸化物のいずれでもよ
い。この触媒中の各金属酸化物の組成は、酸化鉄：０．
５〜５０重量％、好ましくは３〜２０重量％、酸化カル
シウム：０．５〜３０重量％、好ましくは５〜１５重量
％、そして酸化アルミニウム：２０〜９９重量％、好ま
しくは６５〜９２重量％である。本発明において、触媒
成分となる酸化鉄、酸化カルシウム及び酸化アルミニウ
ムは、その原料としてそれぞれの金属の硝酸塩、塩酸
塩、硫酸塩、有機酸塩、水酸化物等を用い、共沈法、含
浸法、混合法、逐次沈殿法、アルコキシド法等の公知の
方法により、あるいはこれらの方法を組み合わせること
によって製造できる。なお触媒製造後、空気中で焼成す
ることにより触媒成分を安定な酸化物の状態にすること
が望ましい。この場合、焼成温度は特に限定しないが、
３００〜１０００℃の範囲が好ましく、６００〜８００
℃の範囲が特に好ましい。本発明に用いる触媒は、必ず
しも酸化鉄、酸化カルシウム及び酸化アルミニウムの３
成分のみに限定されず、適宜他の成分、例えばコロイダ
ルシリカ等を加えてもよい。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The catalyst used in the present invention is a catalyst comprising iron oxide, calcium oxide and aluminum oxide. The iron oxide may be any of divalent and trivalent iron oxides. The composition of each metal oxide in the catalyst was iron oxide: 0.1.
5 to 50% by weight, preferably 3 to 20% by weight, calcium oxide: 0.5 to 30% by weight, preferably 5 to 15% by weight, and aluminum oxide: 20 to 99% by weight, preferably 65 to 92% by weight It is. In the present invention, iron oxide, calcium oxide and aluminum oxide serving as catalyst components are prepared by coprecipitation method, impregnation method using nitrate, hydrochloride, sulfate, organic acid salt, hydroxide, etc. of each metal as a raw material. It can be produced by a known method such as a mixing method, a sequential precipitation method, an alkoxide method, or a combination of these methods. It is desirable that the catalyst component be converted into a stable oxide state by calcining in air after the production of the catalyst. In this case, the firing temperature is not particularly limited,
The range of 300 to 1000 ° C. is preferable, and the range of 600 to 800
The range of ° C. is particularly preferred. The catalyst used in the present invention is not limited to iron oxide, calcium oxide and aluminum oxide.
It is not limited only to the components, and other components such as colloidal silica may be added as appropriate.
【０００６】本発明において反応原料として用いるエチ
ルベンゼンは、特に高純度である必要はなく、触媒毒に
ならない成分であれば少量の不純物を含んでいてもよ
い。また、本発明の反応において使用される二酸化炭素
についても、特に高純度である必要はなく、不活性ガ
ス、例えば窒素等を含んでいてもよい。二酸化炭素の使
用割合は、エチルベンゼン１モル当り、０．１〜１００
モル、好ましくは１〜５０モルの割合である。本発明に
おいて、反応温度は５００〜６５０℃の範囲、好ましく
は５３０〜６３０℃である。５００℃を下回るとエチル
ベンゼンの十分な転化率が得られず、また６５０℃を上
回ると副生成物であるベンゼン、トルエン等の生成や、
触媒表面上における炭素析出あるいは生成物の重合が顕
著になり、触媒の活性や選択性が大きく低下する。[0006] Ethylbenzene used as a reaction raw material in the present invention does not need to be particularly high in purity, and may contain a small amount of impurities as long as it does not poison the catalyst. The carbon dioxide used in the reaction of the present invention does not need to be particularly high-purity, and may contain an inert gas such as nitrogen. The use ratio of carbon dioxide is 0.1 to 100 per mole of ethylbenzene.
Moles, preferably 1 to 50 moles. In the present invention, the reaction temperature is in the range of 500 to 650 ° C, preferably 530 to 630 ° C. If the temperature is lower than 500 ° C., a sufficient conversion of ethylbenzene cannot be obtained, and if the temperature is higher than 650 ° C., benzene and toluene as by-products are formed,
Precipitation of carbon or polymerization of the product on the catalyst surface becomes remarkable, and the activity and selectivity of the catalyst are greatly reduced.
【０００７】本発明の接触反応は、固定床、流動床等い
ずれの方式でも行なうことができる。触媒の粒子径、形
状は反応器の形式に応じて任意に選択できる。また、反
応圧力は、加圧、常圧、減圧いずれでも実施できるが、
０．２〜１．５気圧（絶対圧力）の範囲が特に好まし
い。反応圧が０．２気圧未満では減圧状態を維持するた
めにエネルギー消費量が大きくなり、１．５気圧を超え
ると熱力学的制約からスチレンモノマーの収率が低下す
る。なお、本発明の触媒は、一定時間使用後に活性が低
下した場合、空気中で再度焼成することにより活性を回
復させることができる。[0007] The contact reaction of the present invention can be carried out by any method such as a fixed bed and a fluidized bed. The particle size and shape of the catalyst can be arbitrarily selected according to the type of the reactor. In addition, the reaction pressure can be carried out under any of pressurized, normal pressure, and reduced pressure.
A range from 0.2 to 1.5 atmospheres (absolute pressure) is particularly preferred. If the reaction pressure is less than 0.2 atm, the energy consumption increases to maintain the reduced pressure state, and if it exceeds 1.5 atm, the yield of styrene monomer decreases due to thermodynamic restrictions. When the activity of the catalyst of the present invention decreases after a certain period of use, the activity can be recovered by calcining again in air.
【０００８】[0008]
【実施例】以下本発明を実施例により更に詳細に説明す
る。 実施例１ 硝酸鉄９水和物１１．５ｇ、硝酸カルシウム４水和物
６．９ｇ、硝酸アルミニウム６水和物９１．０ｇを溶解
した水溶液３００ｍｌと、炭酸ナトリウム５２．５ｇを
溶解した水溶液３００ｍｌを調製した。蒸留水７５０ｍ
ｌを激しく攪拌しながら前出の二種の水溶液を等量ずつ
ゆっくりと滴下した。得られた沈殿をイオン交換水で十
分洗浄、ろ過した後、１１０℃で乾燥後、空気中７５０
℃で焼成した。次に、焼成後の酸化物を２００ｋｇ/ｍ2
の圧力で圧縮後、粉砕し１８０〜３００μｍに粒度を調
節した。焼成後の触媒はＦｅ3Ｏ2１４重量％、ＣａＯ１
０重量％、Ａｌ2Ｏ3７６重量％であった。前記触媒１．
４ｇを、ステンレス製反応管に充填し、エチルベンゼン
蒸気：二酸化炭素＝１：１１の混合ガスを流速毎分１３
０ｍｌ、温度５５０℃で接触させた。反応後のガスを、
−５℃の冷却器および1℃の吸収液(ノルマルヘプタン)
に通じ、得られた液体成分をガスクロマトグラフで分析
した。その結果を、表１に示す。この結果は、この触媒
が長時間にわたって活性を保っていることを示してい
る。The present invention will be described in more detail with reference to the following examples. Example 1 300 ml of an aqueous solution in which 11.5 g of iron nitrate nonahydrate, 6.9 g of calcium nitrate tetrahydrate, and 91.0 g of aluminum nitrate hexahydrate were dissolved, and 300 ml of an aqueous solution in which 52.5 g of sodium carbonate was dissolved Prepared. 750m of distilled water
While stirring vigorously, the above two aqueous solutions were slowly dropped in equal amounts. The obtained precipitate is sufficiently washed with ion-exchanged water, filtered, dried at 110 ° C., and then dried in air at 750.
Fired at ℃. Next, the calcined oxide was reduced to 200 kg / m 2.
After compression at a pressure of, the powder was pulverized and the particle size was adjusted to 180 to 300 µm. The catalyst after calcination was Fe 3 O 2 14% by weight, CaO 1
0% by weight and 76% by weight of Al 2 O 3 . The catalyst 1.
4 g was charged into a stainless steel reaction tube, and a mixed gas of ethylbenzene vapor: carbon dioxide = 1: 11 was supplied at a flow rate of 13 / min.
0 ml was contacted at a temperature of 550 ° C. The gas after the reaction is
Cooler at -5 ° C and absorbing solution at 1 ° C (normal heptane)
, And the obtained liquid component was analyzed by gas chromatography. Table 1 shows the results. This result indicates that the catalyst has been active for a long time.
【０００９】[0009]
【表１】 [Table 1]
【００１０】比較例１ 実施例１で使用した触媒１．４ｇを、ステンレス製反応
管に充填し、エチルベンゼン蒸気：ヘリウム＝１：１１
の混合ガスを流速毎分１３０ｍｌ、温度５５０℃で接触
させ、実施例１と同様に分析を行なった。その結果を表
２に示す。Comparative Example 1 1.4 g of the catalyst used in Example 1 was charged into a stainless steel reaction tube, and ethylbenzene vapor: helium = 1: 11.
Was contacted at a flow rate of 130 ml / min at a temperature of 550 ° C., and analysis was carried out in the same manner as in Example 1. Table 2 shows the results.
【００１１】[0011]
【表２】 [Table 2]
【００１２】比較例２ 実施例１で使用した触媒１．４ｇを、ステンレス製反応
管に充填し、エチルベンゼン蒸気：ヘリウム：水蒸気＝
１：３．７：７．３の混合ガスを流速毎分１３０ｍｌ、
温度５５０℃で接触させ、実施例１と同様に分析を行な
った。その結果を表３に示す。Comparative Example 2 1.4 g of the catalyst used in Example 1 was charged into a stainless steel reaction tube, and ethylbenzene vapor: helium: water vapor =
1: 3.7: 7.3 mixed gas at a flow rate of 130 ml / min,
The contact was performed at a temperature of 550 ° C., and the analysis was performed in the same manner as in Example 1. Table 3 shows the results.
【００１３】[0013]
【表３】 [Table 3]
【００１４】比較例３ 硝酸鉄、硝酸アルミニウムを溶解した水溶液を原料に用
い、実施例１と同様の操作を行ない触媒を調製した。触
媒の組成は、Ｆｅ2Ｏ3１４重量％、Ａｌ2Ｏ3８６重量％
であった。この触媒を１．０ｇ用いたほかは、実施例１
と同様の条件で反応を行なった。この結果を、表４に示
す。Comparative Example 3 An aqueous solution in which iron nitrate and aluminum nitrate were dissolved was used as a raw material, and the same operation as in Example 1 was performed to prepare a catalyst. The composition of the catalyst, Fe 2 O 3 14 wt%, Al 2 O 3 86 wt%
Met. Example 1 was repeated except that 1.0 g of this catalyst was used.
The reaction was carried out under the same conditions as described above. Table 4 shows the results.
【００１５】[0015]
【表４】 [Table 4]
【００１６】比較例４ 硝酸カルシウム硝酸アルミニウムを溶解した水溶液を原
料に用い、実施例１と同様の操作を行ない触媒を調製し
た。触媒の組成は、ＣａＯ１０重量％、Ａｌ2Ｏ3９０重
量%であった。この触媒を用いて実施例１と同様に反応
を行なった。この結果を、表５に示す。Comparative Example 4 A catalyst was prepared in the same manner as in Example 1 except that an aqueous solution in which calcium aluminum nitrate was dissolved was used as a raw material. The composition of the catalyst was 10% by weight of CaO and 90% by weight of Al 2 O 3 . A reaction was carried out in the same manner as in Example 1 using this catalyst. Table 5 shows the results.
【００１７】[0017]
【表５】 [Table 5]
【００１８】比較例５ 硝酸鉄、硝酸カルシウムを溶解した水溶液を原料に用
い、実施例１と同様の操作を行ない触媒を調製した。触
媒の組成は、Ｆｅ2Ｏ3１４重量％、ＣａＯ８６重量％で
あった。この触媒を用いて実施例１と同様に反応を行な
った。この結果を、表６に示す。Comparative Example 5 A catalyst was prepared in the same manner as in Example 1 except that an aqueous solution in which iron nitrate and calcium nitrate were dissolved was used as a raw material. The composition of the catalyst was 14% by weight of Fe 2 O 3 and 86% by weight of CaO. A reaction was carried out in the same manner as in Example 1 using this catalyst. Table 6 shows the results.
【００１９】[0019]
【表６】 [Table 6]
【００２０】実施例２ 実施例１と同様に、触媒を調製した。触媒の組成はＦｅ
2Ｏ3５重量％、ＣａＯ１０重量％、Ａｌ2Ｏ3８５重量％
であった。調製した触媒を１．４ｇ用い、実施例１と同
様の条件で反応を行なった。結果を表７に示す。この結
果は、触媒組成を変更することにより、初期活性はあま
り高くないが、安定性の非常に高い触媒を得ることがで
きることを示す。Example 2 A catalyst was prepared in the same manner as in Example 1. The composition of the catalyst is Fe
2 O 3 5% by weight, CaO 10% by weight, Al 2 O 3 85% by weight
Met. A reaction was carried out under the same conditions as in Example 1 using 1.4 g of the prepared catalyst. Table 7 shows the results. This result indicates that by changing the catalyst composition, it is possible to obtain a catalyst whose initial activity is not so high but whose stability is very high.
【００２１】[0021]
【表７】 [Table 7]
【００２２】実施例３ 実施例２に用いた触媒を用い、反応温度５８０℃で反応
を行なった。その他の条件は、実施例２と同じになるよ
うにした。結果を表８に示す。Example 3 Using the catalyst used in Example 2, a reaction was carried out at a reaction temperature of 580 ° C. Other conditions were the same as in Example 2. Table 8 shows the results.
【００２３】[0023]
【表８】 [Table 8]
【００２４】実施例４ 実施例１と同様の触媒を調製する際、金属硝酸塩の水溶
液にコロイダルシリカ(日産化学スノーテックスＯ)１．
０ｇを分散させ、その他の触媒調製操作は実施例１と同
様に行なった。この触媒を１．４ｇ用い、実施例１と同
様の条件で反応を行った。結果を、表９に示す。Example 4 To prepare the same catalyst as in Example 1, colloidal silica (Nissan Chemical Snowtex O) was added to an aqueous solution of metal nitrate.
0 g was dispersed, and other catalyst preparation operations were performed in the same manner as in Example 1. Using 1.4 g of this catalyst, a reaction was carried out under the same conditions as in Example 1. Table 9 shows the results.
【００２５】[0025]
【表９】 [Table 9]
【００２６】実施例５ 実施例４で８．５時間反応に用いた触媒１．４ｇを、空
気中６００℃の温度で２時間再焼成した後、再度実施例
１と同様の条件で反応に用いた。結果を表１０に示す。
この結果は、触媒の再生後でも、長時間にわたって活性
が保たれていることを示している。Example 5 1.4 g of the catalyst used for the reaction for 8.5 hours in Example 4 was recalcined in air at a temperature of 600 ° C. for 2 hours, and then used again for the reaction under the same conditions as in Example 1. Was. Table 10 shows the results.
This result indicates that the activity is maintained for a long time even after regeneration of the catalyst.
【００２７】[0027]
【表１０】 [Table 10]
【００２８】[0028]
【発明の効果】本発明によれば、エチルベンゼンを二酸
化炭素の存在下触媒と接触させてスチレンモノマーを製
造するに当り、前記した安価でかつ長時間その活性の低
下が少ない触媒を用いたことにより、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。しかも、従来行
なわれているような水蒸気を使用する方法ではないの
で、水蒸気製造のための多大なエネルギー消費を必要と
しない。According to the present invention, when ethylbenzene is brought into contact with a catalyst in the presence of carbon dioxide to produce a styrene monomer, the catalyst is used which is inexpensive and has a small decrease in its activity for a long time. And styrene monomer can be produced industrially advantageously. Moreover, since the method does not use steam as conventionally performed, a large amount of energy is not required for producing steam.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 5/00 - 5/56 C07C 15/46 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 7 , DB name) C07C 5/00-5/56 C07C 15/46
Claims (1)
酸化鉄、酸化カルシウム及び酸化アルミニウムからなる
触媒に、５００〜６５０℃の温度で接触させることを特
徴とするスチレンモノマーの製造方法。1. The method according to claim 1, wherein ethylbenzene is dissolved in the presence of carbon dioxide.
A method for producing a styrene monomer, comprising contacting a catalyst comprising iron oxide, calcium oxide and aluminum oxide at a temperature of 500 to 650 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9218411A JP3032816B2 (en) | 1997-08-13 | 1997-08-13 | Method for producing styrene monomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9218411A JP3032816B2 (en) | 1997-08-13 | 1997-08-13 | Method for producing styrene monomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1160517A JPH1160517A (en) | 1999-03-02 |
| JP3032816B2 true JP3032816B2 (en) | 2000-04-17 |
Family
ID=16719500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9218411A Expired - Lifetime JP3032816B2 (en) | 1997-08-13 | 1997-08-13 | Method for producing styrene monomer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3032816B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7910784B2 (en) * | 2008-06-14 | 2011-03-22 | Lummus Technology Inc. | Process for the production of styrene monomer by improving energy efficiency and injecting a recycle gas into the EB vaporizer |
-
1997
- 1997-08-13 JP JP9218411A patent/JP3032816B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH1160517A (en) | 1999-03-02 |
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