Direct Conversion of Glycerol into 1,3-Propanediol over Cu-H 4 SiW 12 O 40 /SiO 2 in Vapor Phase
- PDF / 334,766 Bytes
- 9 Pages / 595.276 x 790.866 pts Page_size
- 57 Downloads / 192 Views
Direct Conversion of Glycerol into 1,3-Propanediol over Cu-H4SiW12O40/SiO2 in Vapor Phase Long Huang Æ Yulei Zhu Æ Hongyan Zheng Æ Guoqiang Ding Æ Yongwang Li
Received: 10 January 2009 / Accepted: 19 February 2009 / Published online: 25 March 2009 Ó Springer Science+Business Media, LLC 2009
Abstract Using a SiO2 supported copper and H4SiW12O40 catalyst, it is demonstrated that glycerol can be directly converted to 1,3-Propanediol (1,3-PD) through vapor-phase process under pressure below 0.54 MPa, without employing environmentally harmful organic solvent. The formation of 1,3-PD is proved to proceed through the designed reaction pathway: (step 1) dehydration of glycerol to 3-hydroxypropanal on acid site of supported H4SiW12O40 (step 2) hydrogenation of 3-hydroxypropanal on supported copper metal. The effect of temperature, weight hourly space velocity, pressure, and initial water content was investigated to obtain the optimum conditions. The glycerol conversion and products distribution greatly depended on these factors. Both the 1,3-PD and 1,2-Propanediol selectivity improved with increasing hydrogen pressure. At 210 °C, 0.54 MPa and 83.4% conversion, the selectivity of 1,3-PD was up to 32.1%, together with a 22.2% selectivity of 1,2-Propanediol. The cyclic acetal, an important kind of byproducts, was identified by Gas Chromatogram–Mass Spectrometer (GC–MS). Electronic supplementary material The online version of this article (doi:10.1007/s10562-009-9914-1) contains supplementary material, which is available to authorized users. L. Huang Y. Zhu (&) G. Ding Y. Li Institute of Coal Chemistry, Chinese Academy of Sciences, P.O. Box 165, 030001 Taiyuan, People’s Republic of China e-mail: [email protected] L. Huang Graduate University of the Chinese Academy of Sciences, Chinese Academy of Sciences, 100039 Beijing, People’s Republic of China H. Zheng Synfuels CHINA Co. Ltd, 030001 Taiyuan, People’s Republic of China
123
Keywords Glycerol 1,3-Propanediol Hydrogenolysis Bifunctional catalyst
1 Introduction 1,3-Propanediol (1,3-PD) is a large-scale material for polymer, and there are two existing technologies based on fossil: Degussa–DuPont process via hydration of acrolein and Shell process via hydroformylation of ethylene oxide [1–3]. Recently, owing to a large surplus of glycerol from the biodiesel production, it becomes critical to convert glycerol into value-added derivatives [1–3]. Conversion of glycerol to 1,3-PD is regarded as important research direction. The fermentation process was relatively well developed for this reaction using bacterial strains and glycerol was converted to 1,3-PD in high yields [4–6]. However, this reaction proceeded slowly in two steps and with very low product concentration [4–6]. Direct hydrogenolysis of glycerol to 1,3-PD, perfectly at mild conditions, represents a sustainable alternative with valuable potential applications. Several studies have been devoted to attempt this reaction in solvent phase, and the results are summarized in Table 1. Earlier, Celanese developed
Data Loading...
