Selective hydrogenation of vinyl acetylene to 1,3-butadiene in concentrated vinyl acetylene mixed C4 by Pd/Al2O3 catalyst Paisan Insorna, Katawut Choochuena,

Boonyarach Kitiyanana,b*, and Johannes Schwankc a The Petroleum and Petrochemical College, Chulalongkorn University, Bangkok 10330, Thailand b Center for Petroleum, Petrochemicals and Advanced Materials, Chulalongkorn University, Bangkok 10330, Thailand. email:Boonyarach.K@chula.ac.th c Department of Chemical Engineering, University of Michigan, 2300 Hayward, Ann Arbor, MI 48109-2136, United States The stream of high concentrated vinyl acetylene mixed C4 containing vinyl acetylene up to 30 wt% is currently treated by completely burning away. However, this stream still contains valuable products and should be upgraded to higher valuable chemicals such as 1,3-butadiene by selective hydrogenation. The selective hydrogenation of vinyl acetylene in gas phase1, and 1,3-butadiene2,3 and 1-butyne4 has been reported, but hydrogenation of vinyl acetylene in liquid phase mixed C4 has not been reported. This work studies the hydrogenation reaction of vinyl acetylene in this stream by using Pd/Al2O3 catalyst. The catalysts were prepared by incipient wetness impregnation method. The Pd loading was varied from 0.1 to 1.0 wt%. The reactor for hydrogenation is a recirculating liquid phase reactor coupling with an external fixed-bed reactor system. The reaction temperature and hydrogen pressure were varied in range of 25-45 C and 3.5-5.5 bar respectively. The quantitative analysis for the products was done by a gas chromatography. The vinyl acetylene conversion and 1,3-butadiene selectivity were evaluated and compared with the results of commercial catalyst. The reaction of C4 olefins in high concentrated VA mixed C4 is agreement with the literatures.1-4 The results indicated that Pd catalyst can be successfully applied for this stream. At the higher temperature, the VA conversion is better but the 1,3-BD selectivity is lower. Both of VA conversion and 1,3-BD selectivity at higher hydrogen pressure are greater than at lower hydrogen pressure. The percent of Pd loading significantly affected to the catalytic performances. The rate of VA conversion increased with increasing of Pd percent in the whole range of 0.1 to 1.0 wt% while the 1,3-BD selectivity was maximized at 0.3 wt% of Pd loading. The catalysts also have been characterized by BET surface area, H2 chemisorption, and XRD.

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