メタノール合成触媒とゼオライト触媒との複合触媒による合成ガスからの低級オレフィンの直接合成

Direct Synthesis of Light Olefins from Synthesis Gas Utilizing Composite Catalyst of Methanol Synthesis Catalyst and Zeolite

Sano Tsuneji

Okabe Kiyomi

Syoji Hiroshi

Saito Kenji

Okado Hideo

Yasumoto Yoshio

Hagiwara Hiroyuki

Takaya Haruo

石油学会誌

メタノール合成触媒と各種ZSM-5型ゼオライト触媒とを機械的に混合した複合触媒による合成ガスからの低級オレフィン合成について検討した。その結果, アルカリ土類金属で修飾しオレフィン水素化能を抑制したH-ZSM-5型触媒を用いることにより, (C=2+C=3) 選択率が増加することがわかった。また, イソ合成触媒とこれらのアルカリ土類金属修飾H-ZSM-5型触媒との複合触媒においても, 比較的高い (C=2+C=3) 選択率が得られることがわかった。

The direct synthesis of light olefins from synthesis gas was studied on a composite catalyst composed of Zn-Cr oxide catalyst and ZSM-5 type zeolite modified with alkaline earth metals. The reaction was carried out at 300-450°C under 5-40kg/cm2, using a highpressure fixed bed flow system. The (C2=+C3=) selectivity increased in the following order: Zn-Cr/H-ZSM-5<Zn-Cr/Mg-H-ZSM-5<Zn-Cr/Ca-H-ZSM-5 <Zn-Cr/Sr-H-ZSM-5<Zn-Cr/Ba-H-ZSM-5 (Table 1). However, the activity decreased in this order. In order to clarify the effect of CO conversion on the (C2=+C3=) selectivity, the reaction was carried out under various pressures (Fig. 1). The (C2=+C3=) selectivity of the Zn-Cr/Ca-H-ZSM-5 catalyst was about 5% higher than that of the Zn-Cr/H-ZSM-5 catalyst with the same conversion of CO to hydrocarbons (E. Conv.). From these results, it can be concluded that the increase in the (C2=+C3=) selectivity is mainly attributed to the decrease in the catalytic activity of H-ZSM-5 zeolite for olefin hydrogenation when it is modified with alkaline earth metals. Table 2 shows the results of conversion of synthesis gas on the Zn-Cr/Ca-H-ZSM-5 catalyst under various reaction conditions. The (C2=+C3=) selectivity of about 30% was obtained with the CO conversion of about 8%. However, the high (C2=+C3=) selectivity could not be obtained with the high CO conversion.

The direct synthesis of light olefins from synthesis gas was also studied on the composite catalyst composed of an isosynthesis catalyst and the zeolite modified with alkaline earth metals (Table 3). In the case of the ZrO2/Ba•Ca-H-ZSM-5 catalyst, the (C2=+C3=) selectivity of about 23% was obtained with the high CO conversion of about 20%.

Alkaline earth metal

Composite catalyst

Light olefin

Methanol synthesis catalyst

Synthesis gas ZSM 5

Chemical technology [ 570 ]

jpn

石油学会

Copyright (c) 1986 (社)石油学会

本文データはJournal@rchiveから複製したものである

[ISSN] 0582-4664

[NCID] AN00130954

[URI] http://www.journalarchive.jst.go.jp/japanese/jnlabstract_ja.php?cdjournal=jpi1958&cdvol=29&noissue=2&startpage=178