First pilot scale study of basic vs acidic catalysts in biomass pyrolysis: Deoxygenation mechanisms and catalyst deactivation

Kalogiannis, Konstantinos G.; Stefanidis, Stylianos D.; Karakoulia, Stamatia A.; Triantafyllidis, Konstantinos S.; Yiannoulakis, H.; Michailof, Chrysoula M.; Lappas, Angelos A.

doi:10.1016/j.apcatb.2018.07.016

Cited by 112 publications

(43 citation statements)

References 41 publications

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“…Basic catalysts such as MgO or calcium-based materials are emerging as attractive and relatively economical catalysts with which to carry out catalytic pyrolysis [13][14][15]. In this regard, Kalogiannis et al [16] evaluated the fast catalytic pyrolysis of commercial lignocellulosic biomass at a representative scale using a circulating fluidised-bed facility with MgO catalysts and commercial zeolites. These authors found that ketonisation and aldol condensation reactions were promoted by the basic sites of MgO, resulting in a hydrogen-rich bio-oil being produced.…”

Section: Of 17mentioning

confidence: 99%

Ca-based Catalysts for the Production of High-Quality Bio-Oils from the Catalytic Co-Pyrolysis of Grape Seeds and Waste Tyres

et al. 2019

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The catalytic co-pyrolysis of grape seeds and waste tyres for the production of high-quality bio-oils was studied in a pilot-scale Auger reactor using different low-cost Ca-based catalysts. All the products of the process (solid, liquid, and gas) were comprehensively analysed. The results demonstrate that this upgrading strategy is suitable for the production of better-quality bio-oils with major potential for use as drop-in fuels. Although very good results were obtained regardless of the nature of the Ca-based catalyst, the best results were achieved using a high-purity CaO obtained from the calcination of natural limestone at 900 °C. Specifically, by adding 20 wt% waste tyres and using a feedstock to CaO mass ratio of 2:1, a practically deoxygenated bio-oil (0.5 wt% of oxygen content) was obtained with a significant heating value of 41.7 MJ/kg, confirming its potential for use in energy applications. The total basicity of the catalyst and the presence of a pure CaO crystalline phase with marginal impurities seem to be key parameters facilitating the prevalence of aromatisation and hydrodeoxygenation routes over the de-acidification and deoxygenation of the vapours through ketonisation and esterification reactions, leading to a highly aromatic biofuel. In addition, owing to the CO2-capture effect inherent to these catalysts, a more environmentally friendly gas product was produced, comprising H2 and CH4 as the main components.

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Section: Of 17mentioning

confidence: 99%

Ca-based Catalysts for the Production of High-Quality Bio-Oils from the Catalytic Co-Pyrolysis of Grape Seeds and Waste Tyres

et al. 2019

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“…Specific surface area was 138 m 2 •g −1 , mean pore diameter was 10 −10 m, micro-and mesoporosities were 0.037 and 0.071 cm 3 •g −1 , respectively. More details about these materials and their characterization can be found in previous work [32]. Regarding the pyrolysis runs, the experimental setup and procedure followed has been described elsewhere in detail [19].…”

Section: Bed Materialsmentioning

confidence: 99%

Aromatics from Beechwood Organosolv Lignin through Thermal and Catalytic Pyrolysis

et al. 2019

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Biomass fractionation, as an alternative to biomass pretreatment, has gained increasing research attention over the past few years as it provides separate streams of cellulose, hemicellulose, and lignin. These streams can be used separately and can provide a solution for improving the economics of emerging biorefinery technologies. The sugar streams are commonly used in microbial conversions, whereas during recent years lignin has been recognized as a valuable compound as it is the only renewable and abundant source of aromatic chemicals. Successfully converting lignin into valuable chemicals and products is key in achieving both environmental and economic sustainability of future biorefineries. In this work, lignin retrieved from beechwood sawdust delignification pretreatment via an organosolv process was depolymerized with thermal and catalytic pyrolysis. ZSM-5 commercial catalyst was used in situ to upgrade the lignin bio-oil vapors. Lignins retrieved from different modes of organosolv pretreatment were tested in order to evaluate the effect that upstream pretreatment has on the lignin fraction. Both thermal and catalytic pyrolysis yielded oils rich in phenols and aromatic hydrocarbons. Use of ZSM-5 catalyst assisted in overall deoxygenation of the bio-oils and enhanced aromatic hydrocarbons production. The oxygen content of the bio-oils was reduced at the expense of their yield. Organosolv lignins were successfully depolymerized towards phenols and aromatic hydrocarbons via thermal and catalytic pyrolysis. Hence, lignin pyrolysis can be an effective manner for lignin upgrading towards high added value products.

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“…Contents of Ca, K, Mg, and P linearly increased with time-on stream and reached 1.1 wt % after the reaction, indicating that biomass alkalis overtook the proton functionalities of acid sites on the HZSM-5 catalyst. In a comparison of natural MgO catalysts with ZSM-5 in a circulating fluidized-bed pilot scale unit, no alkali metals were found to deposit on MgO, indicating different deactivation mechanisms between acidic and basic catalysts in biomass fast pyrolysis [232].…”

Section: Catalyst Deactivation In Biomass Pyrolysismentioning

confidence: 96%

“…Magnesium oxide (MgO) was tested in a circulating fluidized bed pilot scale unit and was compared to a commercially available ZSM-5 catalyst [232]. The 2DGC-TOFMS analyses of the produced bio-oils indicated MgO enhanced ketonization and aldol condensation reactions.…”

Section: Alkali and Alkaline Earth Metallic (Aaem) Speciesmentioning

confidence: 99%

Catalytic Pyrolysis of Biomass and Polymer Wastes

et al. 2018

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Oil produced by the pyrolysis of biomass and co-pyrolysis of biomass with waste synthetic polymers has significant potential as a substitute for fossil fuels. However, the relatively poor properties found in pyrolysis oil—such as high oxygen content, low caloric value, and physicochemical instability—hampers its practical utilization as a commercial petroleum fuel replacement or additive. This review focuses on pyrolysis catalyst design, impact of using real waste feedstocks, catalyst deactivation and regeneration, and optimization of product distributions to support the production of high value-added products. Co-pyrolysis of two or more feedstock materials is shown to increase oil yield, caloric value, and aromatic hydrocarbon content. In addition, the co-pyrolysis of biomass and polymer waste can contribute to a reduction in production costs, expand waste disposal options, and reduce environmental impacts. Several promising options for catalytic pyrolysis to become industrially viable are also discussed.

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First pilot scale study of basic vs acidic catalysts in biomass pyrolysis: Deoxygenation mechanisms and catalyst deactivation

Cited by 112 publications

References 41 publications

Ca-based Catalysts for the Production of High-Quality Bio-Oils from the Catalytic Co-Pyrolysis of Grape Seeds and Waste Tyres

Ca-based Catalysts for the Production of High-Quality Bio-Oils from the Catalytic Co-Pyrolysis of Grape Seeds and Waste Tyres

Aromatics from Beechwood Organosolv Lignin through Thermal and Catalytic Pyrolysis

Catalytic Pyrolysis of Biomass and Polymer Wastes

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