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6682 Youness El Fouih and Chakib Bouallou / Energy Procedia 37 (2013) 6679 – 6686 conditions, selectivity for ethanol and C2 oxygenates [3]. The pathway which adopted in this paper is the direct synthesis of ethanol from syngas. Fig. 2: Possible pathways for syngas conversion to ethanol The direct conversion of syngas to ethanol is the most studied way in terms of used catalysts and operating conditions. Thus tens of catalysts have been developed in this perspective [3]. Considerable research has been conducted on this topic in order to understand more the reaction mechanism which remains currently poorly understood, and in order to characterize the kinetics of the reaction [8]. We can distinguish several types of catalysts, which can be used for the direct conversion of ethanol. We will limit ourselves in this study to two types (groups) catalysts most used and most effective, these two groups are: Rh based catalysts and Fischer-Tropsch modified catalysts [9]. The Rhodium based catalysts, which is a noble metal, are known to have the best selectivity to ethanol (to C2+ oxygenates in general) with a good carbon monoxide conversion [3, 9, 10]. Rhodium occupies an interesting position in the periodic table. It is located between the metals (eg, Fe and Co), which dissociate CO easily to form higher hydrocarbons, and atoms which do not dissociate CO and can produce methanol (for example, Pd, Pt and Ir). The catalysts with small amount of Rh can form methane, alcohol, or other oxygenated compounds, it also allow the hydrogenation of CO according to the media, promoter and reaction conditions [10]. These catalysts despite their performance are more expensive than the other catalysts. The Rhodium price, as a raw material, exceeds 200 $ per g. Velu Subramani et al (2008) suggested that the amount of Rh in the catalyst should be very small (less than 0.1 wt %) to develop a catalyst at a commercial level [3]. We should note that the latest researches (2010 and 2011) on this subject have led to a significant reduction of Rh weight percentage in the Rh-based catalysts, which decreased from 7% to 1% currently, keeping very good performance. This promises a further reduction of Rh amount in Rh-based catalysts. year, which means that the price of Rh-based catalysts must be re-evaluated according to this variation. The Fischer-Tropsch modified catalysts are based in general on Co, Ru and Fe. These catalysts have been reported to form higher alcohols when properly modified with additions [10]. Some researchers have reported the synthesis of higher alcohols using Ir/Ru-SiO2 or Ir/Co-SiO2 is due to the interaction between metals that easily dissociate CO (Ru and Co) and Ir which does not dissociate CO. The combination of these two metals would provide a catalyst which combines the separation and insertion of CO on the catalyst support [3]. The modified Fischer-Tropsch catalysts have a moderate selectivity to ethanol, a high selectivity to methanol and exhibit a high methane yield which is thermodynamically favorable [10]. The selectivity to ethanol is low for most of the catalysts which is due to the carbon chain growth mechanism for the formation of higher alcohols. While ethanol is formed from methanol by complicated and slow reaction, ethanol is rapidly converted to higher alcohols via a rapid carbon chain growth mechanism [3, 11]. We used the Rh-based catalysts, which allows you to have good selectivity to ethanol and minimize the selectivity to other products (methane, methanol, hydrocarbons...). This is veryPDF Image | Recycling of carbon dioxide to produce ethanol
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