A mechanistic model of fast pyrolysis of hemicellulose

Zhou, Xiaowei; Li, Wenjun; Mabon, Ross; Broadbelt, Linda J.

doi:10.1039/c7ee03208k

Cited by 166 publications

(97 citation statements)

References 92 publications

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“…The initiation reactions yield monomeric units such as xylose or arabino-xylose and arabino-xylan chains with reduced DP. Further, these monomeric units undergo concerted reactions such as dehydration, ring-opening, retro-aldol and keto-enol tautomerization reactions similar to the glucose decomposition proposed by the earlier works of Broadbelt group (Vinu & Broadbelt, 2012;Zhou et al, 2018;Zhou, Nolte, et al, 2014).…”

Section: Hemicellulosementioning

confidence: 71%

“…Concerted reaction mechanisms proposed for xylose thermal decomposition during hemicellulose pyrolysis. (RO/RC: Ring opening/ring closing; EKT: Enol‐Keto tautomerisation; RA: Retro‐aldol condensation) (Adapted with permission from Zhou et al, . Copyright 2018 Royal Society of Chemistry)…”

Section: Mechanistic and Intrinsic Kinetic Studies Of Biomass Pyrolysismentioning

confidence: 99%

“…Besides, these studies can also help in designing a suitable catalyst to improve the selectivity towards desired products (Butler et al, ; Li et al, ). Numerous studies have been performed over the years to decode the kinetic mechanisms of biomass fast pyrolysis (Agarwal, Dauenhauer, Huber, & Auerbach, ; Bai et al, ; Bai & Brown, ; Banyasz, Li, Lyons‐Hart, & Shafer, ; Bradbury, Sakai, & Shafizadeh, ; Branca, Di Blasi, Mango, & Hrablay, ; Broido & Nelson, ; Choi et al, ; Chu, Subrahmanyam, & Huber, ; Custodis, Hemberger, Ma, & van Bokhoven, ; Debiagi et al, ; Faravelli, Frassoldati, Migliavacca, & Ranzi, ; Gai et al, ; Huang, Liu, Tong, Li, & Wu, ; Huang, Liu, Wei, Huang, & Li, ; Kawamoto, Murayama, & Saka, ; Kawamoto & Saka, ; Khachatryan, Xu, Wu, Pechagin, & Asatryan, ; Kim, Bai, & Brown, ; Lou, Wu, & Lyu, ; Mayes & Broadbelt, ; Mayes, Nolte, Beckham, Shanks, & Broadbelt, ; Mettler, Mushrif, et al, 2012; Miller & Bellan, ; Norinaga, Shoji, Kudo, & Hayashi, ; Nowakowska, Herbinet, Dufour, & Glaude, ; Patwardhan, Dalluge, Shanks, & Brown, ; Patwardhan, Satrio, Brown, & Shanks, ; Piskorz, Majerski, Radlein, Vladars‐Usas, & Scott, ; Piskorz, Radlein, & Scott, ; Ranzi et al, , ; Ranzi, Debiagi, & Frassoldati, , ; Ronsse, Dalluge, Prins, & Brown, ; Scheer et al, ; Scheer, Mukarakate, Robichaud, Nimlos, & Ellison, ; Shafizadeh & Fu, ; Shen & Gu, ; Shen, Gu, & Bridgwater, ; Shen, Xiao, Gu, & Luo, ; Varhegyi, Jakab, & Antal, ; Vasiliou et al, ; Vinu & Broadbelt, ; Wang, Ru, Lin, & Luo, ; Werner, Pommer, & Broström, ; Zhang, Li, Yang, & Blasiak, ; Zhang, Nolte, & Shanks, ; Zhou, Li, Mabon, & Broadbelt, ; Zhou, Nolte, Mayes, Shanks, & Broadbelt,…”

Section: Introductionmentioning

confidence: 99%

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Measuring biomass fast pyrolysis kinetics: State of the art

SriBala

Carstensen

Marin

2018

WIREs Energy & Environment

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Fast pyrolysis of lignocellulosic biomass is considered to be a promising thermochemical route for the production of drop‐in fuels and valuable chemicals. During the past decades, a comprehensive understanding of feedstock structure, fast pyrolysis kinetics, product distribution, and transport effects that govern the process has allowed to design better pyrolysis reactors and/or catalysts. A variety of lignocellulosic biomass feedstocks, like corn stover, pinewood, poplar, and model compounds like glucose, xylan, monolignols have been utilized to study the thermal decomposition at or close to fast pyrolysis conditions. Significant progress has been made in understanding the kinetics by developing unique setups such as drop‐tube, PHASR, and micropyrolyzer reactors in combination with the use of advanced analytical techniques such as comprehensive gas and liquid chromatography (GC, LC) with time‐of‐flight mass spectrometer (TOF‐MS). This has led to initial intrinsic kinetic models for biomass and its main components, namely cellulose, hemicellulose, and lignin, validated using experimental setups where the effects of heat and mass transfer on the performance of the process, expressed using Biot and pyrolysis numbers, are adequately negligible. Yet, not all aspects of fast pyrolysis kinetics of biomass components are equally well understood. The use of time‐resolved or multiplexed experimental techniques can further improve our understanding of reaction intermediates and their corresponding kinetic mechanisms. The novel experimental data combined with first principles based multiscale models can reshape biomass pyrolysis models and transform biomass fast pyrolysis to a more selective and energy efficient process. This article is categorized under: Energy and Climate > Climate and Environment Energy Research & Innovation > Science and Materials Bioenergy > Science and Materials

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Section: Hemicellulosementioning

confidence: 71%

Section: Mechanistic and Intrinsic Kinetic Studies Of Biomass Pyrolysismentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Measuring biomass fast pyrolysis kinetics: State of the art

SriBala

Carstensen

Marin

2018

WIREs Energy & Environment

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“…Dussan et al proposed a new semi-detailed kinetic mechanism based on a recent Ranzi scheme [29] respectively for hemicellulose [30] and lignin pyrolysis [31]. More advanced approaches would involve microkinetic mechanistic models based on theoretical calculations as proposed by the Broadbelt team for cellulose [32][33][34] and hemicellulose [35] and by Horton et al [36] for biomass pyrolysis and gasification.…”

Section: Introductionmentioning

confidence: 99%

Development of a detailed kinetic model for the combustion of biomass

Dhahak

Bounaceur

Dreff-Lorimier

et al. 2019

Fuel

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In the context of the growing utilization of biomass to produce energy and of the related need to decrease pollutant emissions from domestic wood combustion devices, this paper presents a new kinetic model of wood combustion considering especially in details the gas-phase reactions related to the combustion of the tars produced by the biomass devolatization. The tar production is predicted using a semi-detailed mechanism of the literature. The tar gas-phase combustion model has been built as a compilation of literature mechanisms already proposed for these species, except for hydroxyacetaldehyde for which a new oxidation mechanism has been written. Experiments on the thermochemical behavior of three types of wood (beech, fir and oak) were also performed in parallel of this work using Thermogravimetric Analysis (TGA). The new detailed kinetic model of wood combustion, BioPOx (Biomass Pyrolysis and Oxidation), has been tested against a wide range of experimental results published in literature. This model fairly reproduces experimental results for pyrolysis and combustion of biomass and its constituents, key produced tars from biomass pyrolysis, and key compounds for Polycyclic Aromatic Hydrocarbons (PAH) formation, for a wide range of experimental devices and operating conditions.

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“…[1][2][3][4] Typical composition of lignocellulosic biomass includes three main components, namely cellulose, hemicellulose, and lignin, and xylose is a representative sugar unit that makes up the largest proportion in hemicellulose structure. 5,6 Although great progress has been made for the conversion of biomass to chemicals and fuels in recent years, how to produce targeted products with high yields in a green and economic manner still remains as a challenge. 7,8 Furfural is a bio-based platform chemical from the thermochemical conversion of biomass hemicellulose, and it is extensively applied in the production of solvent, pharmaceuticals, liquid fuels, etc.…”

Section: Introductionmentioning

confidence: 99%

Dehydration of xylose to furfural in butanone catalyzed by Brønsted‐Lewis acidic ionic liquids

Zhao

et al. 2019

Energy Science & Engineering

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In this study, the most abundant C5 carbohydrate unit in biomass, namely xylose, was chosen as the feedstock, and its hydrothermal conversion for furfural production was carried out in a green and renewable solvent system composed of water and butanone, in order to study the role of FeCl3 and [bmim]Cl of ionic liquid catalyst in the conversion process of xylose. A key intermediate named xylulose from Lewis acid‐catalyzed xylose isomerization was quantified. It was concluded that appropriate content of FeCl3 and [bmim]Cl favored the isomerization‐dehydration reaction path along which xylose was converted into furfural, while excessive amount of either component would result in side reactions leading to furfural consumption at long reaction times. By comparison between ionic liquid catalysts that had different active metal sites, xylose conversion and furfural yields were found to increase when the Lewis acidity of the metal ions became stronger. Moreover, chlorometallate anions with better catalytic performance than the original neutral salts were formed during catalyst preparation, and in this way, the xylose conversion and furfural formation were further promoted. Finally, the optimized ionic liquid catalyst produced a highest furfural yield of 75% and xylose conversion of 99% at 140°C.

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A mechanistic model of fast pyrolysis of hemicellulose

Abstract: This work reports the first mechanistic model of fast pyrolysis of hemicellulose that describes detailed pathways of the decomposition of hemicellulose polymeric chains, the reactions of intermediates, and the formation of various experimentally observed products.

Cited by 166 publications

References 92 publications

Measuring biomass fast pyrolysis kinetics: State of the art

Measuring biomass fast pyrolysis kinetics: State of the art

Development of a detailed kinetic model for the combustion of biomass

Dehydration of xylose to furfural in butanone catalyzed by Brønsted‐Lewis acidic ionic liquids

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