Upgrading of biomass pyrolysis oil model compound via esterification: Kinetic study using heteropoly acid

Prasertpong, Prapaporn; Tippayawong, Nakorn

doi:10.1016/j.egypro.2019.02.144

Cited by 10 publications

(6 citation statements)

References 27 publications

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“…However, the promise of producing hydrocarbon fuels from biomass has been fraught with poor quality oils from conventional pyrolysis that do not lend themselves readily to being upgraded in traditional unit operations. Properties such as poor thermal and chemical stability, high moisture content, high acidity, high oxygen content, and low energy density make conventional pyrolysis oils unsuitable for direct application and upgrading. − Traditional upgrading methods such as solvent addition, , esterification, − hydrodeoxygenation, − supercritical fluid treatment, , aldol condensation, , and coprocessing with petroleum products − have all been investigated, but none of these methods have been commercialized. Current research efforts in pyrolysis oil stabilization and upgrading are focused on catalytic pyrolysis ( in situ and ex situ ) − followed by hydrotreatment and processing in either standalone units or as blending stock.…”

Section: Introductionmentioning

confidence: 99%

Reformulated Red Mud: a Robust Catalyst for In Situ Catalytic Pyrolysis of Biomass

et al. 2020

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Biomass feedstocks contain inorganic compounds generally classified as ash. The ash consists of compounds of potassium, calcium, magnesium, silicon, phosphorus. and other elements. These elements have been reported to influence both the pyrolysis reactions as well as the destabilization of the pyrolysis oils during storage. The inorganic elements have also been reported to deposit on catalyst surfaces during in situ catalytic pyrolysis leading to the eventual deactivation of acidic catalysts such as zeolites. The deposition of inorganic elements and their effects on formulated red mud (FRM) catalyst during in situ catalytic pyrolysis of pinyon juniper wood was investigated. The inorganic elements were measured for the fresh, coked, and regenerated catalysts. The BET specific surface area of the FRM catalyst decreased from 76 m2/g for the fresh catalyst to 53 m2/g for the stable regenerated catalyst. After three regenerations, the BET specific surface area stabilized at 53 m2/g and remained constant after all other regenerations. Potassium, calcium, magnesium, and phosphorus were deposited on the catalyst. Potassium deposition was linear with the number of regenerations while magnesium and calcium depositions were initially rapid but leveled-off after three regenerations of the catalyst. Phosphorus deposition was almost linear, but the data were more scattered compared to that of potassium. The potassium deposition was attributed to physical phenomenon whereas calcium and magnesium depositions were more akin to chemical reactions related to the loss of BET surface area of the catalyst. The deposition of these elements on the surface of the catalyst did not deactivate it. After each catalyst regeneration, the oil yield was not significantly affected and the oil oxygen content and viscosity decreased slightly. This clearly showed that formulated red mud is a robust catalyst suitable for in situ catalytic fast pyrolysis of biomass.

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Section: Introductionmentioning

confidence: 99%

Reformulated Red Mud: a Robust Catalyst for In Situ Catalytic Pyrolysis of Biomass

et al. 2020

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“…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.…”

Section: Research Articlementioning

confidence: 99%

“…Solid acid catalysts are of promising catalysts for bio-oil esterification. Amberlyst catalysts such as Amberlyst-15 (Weerachanchai et al, 2012), Amberlyst-70 (Wu et al, 2016;Hu et al, 2012), rice husk ash-based catalyst (Sutrisno & Hidayat, 2016), ion exchange resin (Wang et al, 2010), heteropoly acids (Prasertpong & Tippayawong, 2019), modified zirconia (Kim et al, 2012;Thitsartarn & Kawi, 2011), and zeolite-based catalysts (Milina et al, 2014;Nandiwale et al, 2013). Zeolite-based catalysts including natural zeolites have a great potential as a catalyst for esterification (Fattahi et al, 2019;Osatiashtiani et al, 2017).…”

Section: Introductionmentioning

confidence: 99%

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

Kadarwati

Apriliani

Annisa

et al. 2021

Int. J. Renew. Energy Dev.

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The bio-oil produced from pyrolysis of woody biomass typically shows unfavourable characteristics such as high acidity, hence it becomes highly corrosive. An upgrading process, e.g., esterification, is necessary to improve the bio-oil quality prior to its use as a transportation fuel. In this work, the bio-oil was produced through a fast pyrolysis of Sengon wood in a fixed-bed pyrolyser at various temperatures. The characteristics (density, viscosity, total acid number, relative concentration of acetic acid, etc.) of the bio-oil were evaluated. The bio-oil with the highest acidity underwent an esterification catalysed by Indonesian natural zeolites at 70 oC for 0-180 min with a ratio of bio-oil to methanol of 1:3. The catalytic performance of the Indonesian natural zeolites during the esterification was investigated. A significant decrease in the total acid number in the bio-oil was observed, indicating the zeolite catalyst’s good performance. No significant coke formation (0.002-3.704 wt.%) was obtained during the esterification. An interesting phenomenon was observed; a significant decrease in the total acid number was found in the heating up of the bio-oil in the presence of the catalyst but in the absence of methanol. Possibly, other reactions catalysed by the Brønsted and Lewis acids at the zeolite catalyst surface also occurred during the esterification.

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“…Several studies on the kinetics of fatty acid esterification over various catalysts have been conducted. Many of the reported studies advocated for the use of a pseudo-first-order kinetic model to evaluate the kinetic parameters 20 – 24 . A kinetic study with a second-order model for esterification of oleic acid over zinc acetate catalyst had been reported, and it agreed reasonably well with the experimental data obtained 25 .…”

Section: Introductionmentioning

confidence: 99%

Kinetic and thermodynamic study on the esterification of oleic acid over SO3H-functionalized eucalyptus tree bark biochar catalyst

Yusuff

2022

Sci Rep

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Herein, esterification of oleic acid (OA) over tosylic acid functionalized eucalyptus bark biochar (TsOH-MBC) to synthesize fatty acid methyl ester (FAME) was investigated. The TsOH-MBC catalyst was prepared via pyrolysis-activation-sulfonation process at various impregnation ratios and was characterized by SEM, FTIR, EDX, XRD, BET, TGA and acid site density techniques. The catalytic performance of the sulfonated biochar catalyst was described in terms of acidity and FAME yield. 6 g of sulfonic acid loaded on 10 g of MBC (6TsOH-MBC) appeared to be most appropriate combination to achieve a highly active catalyst for the esterification of OA with 96.28% conversion to FAME at 80 °C for 5 h with catalyst loading of 4.0 wt% and 8:1 methanol/OA molar ratio. The catalytic reaction kinetic data were very well described by the second-order model, with a rate coefficient of 0.223 mL mol−1 h−1 at 80 °C and activation energy of 81.77 kJ mol−1. The thermodynamic parameters such as $$\Delta H$$ Δ H , $$\Delta S$$ Δ S and $$\Delta G$$ Δ G were determined to be 78.94 kJ mol−1, 135.3 J mol−1 K−1 and 33.03 kJ mol−1, respectively. This research provided an environmentally friendly procedure for FAME production that could be replicated on a commercial scale.

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Upgrading of biomass pyrolysis oil model compound via esterification: Kinetic study using heteropoly acid

Cited by 10 publications

References 27 publications

Reformulated Red Mud: a Robust Catalyst for In Situ Catalytic Pyrolysis of Biomass

Reformulated Red Mud: a Robust Catalyst for In Situ Catalytic Pyrolysis of Biomass

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

Kinetic and thermodynamic study on the esterification of oleic acid over SO3H-functionalized eucalyptus tree bark biochar catalyst

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