Oxygen-Containing Fuels from High Acid Water Phase Pyrolysis Bio-Oils by ZSM−5 Catalysis: Kinetic and Mechanism Studies

Abstract

This study developed an upgrading process focusing on acid transformations of water phase pyrolysis bio-oils to esters of oxygen-containing fuels via ZSM−5 catalyst. Temperature was set as a factor with five levels ranging from 60 to 135 °C with reaction time from 1 to 8 h. The results showed that 89% of high acid conversion and over 90% of ester selectivity was obtained from the feedstock via 2 wt % ZSM−5 catalysts in a fixed feedstock to methanol ratio analyzed by HPLC and GC-MS. The upgrading process followed Langmuir-Hinshelwood and reaction constants were calculated to build a practical upgrading model for bio-oil compounds. Thermodynamics of the process showed endothermic properties during the breaking bonds' reaction on carbonyl of acid while the reaction between the carbon in methanol and electrophile acid intermediate demonstrated exothermic performance. The optimum reaction conditions for the process was at a temperature of 100.1 °C with catalyst loading of 3.98 wt %.

Zeolit Alam Indonesia Sebagai Kandidat Katalis Asam Padat Yang Unggul Untuk Proses Upgrading Bio-Oil Melalui Teknik Esterifikasi

“…Studi lain juga melaporkan penggunaan katalis ZSM−5 sebagai katalis reaksi esterifikasi bio-oil yang mentransformasi asam-asam organik aldehida dan furfural dalam bio-oil menjadi senyawa-senyawa ester (Wei & Lei, 2014;Wei et al, 2015) pada temperatur 60-135 °C selama 1-8 jam. Sebanyak 89% asam organik dalam bio-oil mampu dikonversi menjadi ester dengan selektivitas lebih dari 90%.…”

“…Studi termodinamika menunjukkan bahwa proses ini bersifat endotermik yang melibatkan pemutusan ikatan pada gugus karbonil yang terikat pada asam organik. Selain itu, reaksi antara metanol dan intermediet asam yang bersifat elektrofilik menunjukkan sifat eksotermik (Wei et al, 2015).…”

Esterification of Bio-Oil Produced from Sengon (Paraserianthes falcataria) Wood Using Indonesian Natural Zeolites

“…However, the esterification of bio-oil catalysed by Indonesian natural zeolites is rarely found. In addition, studies on the esterification of bio-oil have focused on model compounds such acetic acid and phenol (Prasertpong & Tippayawong, 2019), acetic acid and ethanol (Liu et al, 2015), oleic acid and methanol (Fauzi et al, 2014) and certain fractions of bio-oil e.g., water-phase bio-oil (Wei et al, 2015). Therefore, this study focused on the esterification of real bio-oil catalysed by natural zeolite in Indonesia.…”

“…Esterification is a promising upgrading technique in order to improve the quality and stability of bio-oil produced from pyrolysis of biomass (Ciddor et al, 2015;Liu et al, 2015). In this study, the esterification of "real" bio-oil produced from the pyrolysis of Sengon wood at a temperature of 600 o C was carried out at 70 o C with a ratio of bio-oil to methanol of 1:3 and catalysed by the zeolite catalysts.…”

Kinetic Study on Microwave-Assisted Oligomerization of 1-Decene over a HY Catalyst

“…Formulation of the reaction rate equations followed the Eley-Rideal mechanism, which has been widely used for the oligomerization reaction [39,40]. The Eley-Rideal expression refers to a single site reaction where the reactant molecules adsorb on the active sites to directly interact with other reactant molecules in the bulk liquid phase or un-adsorbed reactant molecules [41].…”