Insights into the evolution of chemical structures in lignocellulose and non-lignocellulose biowastes during hydrothermal carbonization (HTC)

Zhuang, Xinshu; Song, Yanpei; He, Chao; Huang, Yanqin; Yin, Xiuli; Wu, Chao

doi:10.1016/j.fuel.2018.09.019

Cited by 196 publications

(82 citation statements)

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“…The summary of the results of cellulose and corresponding hydrochars in terms of mass material under HTC condition [36,37]. Recent works demonstrated that HTC of residual biomass occurring at higher temperatures can also improve the rate of back polymerization of organics from the liquid to the solid phase, thus resulting in a decrease of liquid yield and the production of secondary char [45,46].…”

Section: Mass Yields and Hydrochar Energy Propertiesmentioning

confidence: 99%

“…activated carbons). According to our current knowledge, very few works attempted at describing the evolution of biomass chemical structure during HTC [36], some studies reported the reactivity of biomass macro-components during HTC albeit starting from commercially available single components and none of them studied how biomass macro-constituents reacted and/or interacted when intermeshed in lignocellulosic matrix [37][38][39]. Systematically larger char yields were observed from the pyrolysis of chemically isolated lignin, compared to expected yields from the pyrolysis of lignin embedded in plant material thus demonstrating that an entirely different reaction pathway is involved when the constituents are embedded in plant material [40].…”

Section: Introductionmentioning

confidence: 99%

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Reactivity of cellulose during hydrothermal carbonization of lignocellulosic biomass

Volpe

Messineo

Mäkelä

et al. 2020

Fuel Processing Technology

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Hydrothermal carbonization of pure cellulose and birchwood samples was carried out at temperatures between 160 and 280 °C, 0.5 h residence time and biomass-to-water ratio of 20 wt% dry basis, to investigate HTC reactivity of cellulose naturally occurring lignocellulosic biomass. Pure cellulose samples remained unaltered at temperatures up to 220 °C, but significantly decomposed at 230 °C producing a thermal recalcitrant aromatic, high energy-dense material, showing lignin-like behavior. Fourier Transform Infrared spectroscopy (FTIR) showed dehydration and aromatization reactions occurring at temperatures equal or higher than 230 °C for pure cellulose samples while similar increase in aromatization for birchwood hydrochars was evident only at temperatures equal or higher than 260 °C. Acid hydrolysis, Thermogravimetric analysis (TGA) and FTIR suggest that a higher thermal resistance of natural occurring cellulose in birchwood (when compared to pure cellulose sample) could be related to a 'protecting shield' offered by interlinked lignin in the plant matrix.

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Section: Mass Yields and Hydrochar Energy Propertiesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Reactivity of cellulose during hydrothermal carbonization of lignocellulosic biomass

Volpe

Messineo

Mäkelä

et al. 2020

Fuel Processing Technology

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“…If, on the one hand, many research groups have focused their studies on HTC reaction of different biomasses primarily to determine the influence of process parameters on hydrochar's chemical and physical properties, on the other hand, the kinetics of HTC of biomasses and its modeling still lacks of a deep investigation [33,34]. The HTC reaction mechanism is very complex and involves several pathways such as hydrolysis, dehydration, decarboxylation, aromatization, and condensation [35,36]. The complexity of the HTC reaction mechanism has led some authors to develop lumped kinetics models to describe it.…”

Section: Introductionmentioning

confidence: 99%

Hydrothermal Carbonization Kinetics of Lignocellulosic Agro-Wastes: Experimental Data and Modeling

2019

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Olive trimmings (OT) were used as feedstock for an in-depth experimental study on the reaction kinetics controlling hydrothermal carbonization (HTC). OT were hydrothermally carbonized for a residence time τ of up to 8 h at temperatures between 180 and 250 °C to systematically investigate the chemical and energy properties changes of hydrochars during HTC. Additional experiments at 120 and 150 °C at τ = 0 h were carried out to analyze the heat-up transient phase required to reach the HTC set-point temperature. Furthermore, an original HTC reaction kinetics model was developed. The HTC reaction pathway was described through a lumped model, in which biomass is converted into solid (distinguished between primary and secondary char), liquid, and gaseous products. The kinetics model, written in MATLABTM, was used in best fitting routines with HTC experimental data obtained using OT and two other agro-wastes previously tested: grape marc and Opuntia Ficus Indica. The HTC kinetics model effectively predicts carbon distribution among HTC products versus time with the thermal transient phase included; it represents an effective tool for R&D in the HTC field. Importantly, both modeling and experimental data suggest that already during the heat-up phase, biomass greatly carbonizes, in particular at the highest temperature tested of 250 °C.

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“…2c-f), whereas that of Co/CoO@C-600-EtOH suggested a higher concentration of oxygen species which are well coexisted with Co atoms. X-ray diffraction (XRD) has been widely accepted for the determination of crystalline structure in carbonaceous materials, while Raman spectroscopy has also been established as a unique technique in probing the microstructure of carbon-based supporter since Tuinstra and Koeniget first correlated Raman bands to structure parameters calculated from XRD in 1970 29,30 . Both of XRD and Raman function cooperatively to provide structural information for Co@C-600-EtOH sample.…”

Section: Preparation and Characterization Of Co-based Catalystsmentioning

confidence: 99%

Facile Manner in Regulating the Graphene-Shelled Structure of Cobalt Nanoparticles for the Synthesis of Amines

Zhuang¹,

Liu²,

Ma³

2021

Preprint

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The synthesis of pharmaceutical relevant compounds keeps close ties with the development of metalbased catalysts, which remains a common goal in chemical research to solve challenges of application, such as the deactivation of catalyst caused by its tender structure or metal leaching. In this work, we reported a simple and manageable method for the preparation of heterogeneous catalyst with stable cobalt nanoparticles that encapsulated by the outer graphitic shell, whose catalytic activity and selectivity for the synthesis of primary amines via a wide range of aldehydes (more than 52 examples), ketones (more than 26 examples), and nitriles (more than 18 examples) were proved to be broadly effective (but not all of them are shown). And also, subsequent synthesis of N, N-dimethylamine compounds following a brand-new tandem pot process by the same Co-based catalyst were simultaneously explored. In most cases, the Co-based catalyst enables easy substitution of –NH2 moiety towards functionalized and structurally diverse molecules under very mild industrially viable and scalable conditions, providing cost-effective access to numerous amines and other precursors for more complex drug products. More surprisingly, the Co-based catalyst can also be easily recycled due to its intrinsic magnetism and still remains excellent catalytic activity and selectivity for the target products even after reusing up to twelve times. Results from analytic technologies, including but not limited to XRD, XPS, TEM/Mapping and in-suit FTIR, reveals that the structural features of catalyst are closely in relation to its catalytic mechanisms; in simple terms, the outer graphitic shell is activated by the electronic interactions between the inner metallic nanoparticles and the carbon layer as well as the induced charge redistribution. Except for the gram-scale batch test in laboratory, we have firstly evaluated the lifecycle of Co-based catalyst on an automatic hydrogenation reactor by employing continuous flows of reactant (5 ml/min, react within 1.6 min) under the similar conditions (90 °C, 3 MPa H2, 0.1 mol/L), whose results suggests the theoretically minimal lifecycle of Co-based catalyst can reach a continuous period of 72 h without any significant loss of catalytic efficiency. In conclusion, the advantages of this newly developed method involving operational simplicity, high stability, easily recyclable, cost-effective of the catalyst, and good functional group compatibility for the synthesis of functional amines, as well as the highly efficient and industrial applicable tandem synthesis process. <br>

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Insights into the evolution of chemical structures in lignocellulose and non-lignocellulose biowastes during hydrothermal carbonization (HTC)

Cited by 196 publications

References 50 publications

Reactivity of cellulose during hydrothermal carbonization of lignocellulosic biomass

Reactivity of cellulose during hydrothermal carbonization of lignocellulosic biomass

Hydrothermal Carbonization Kinetics of Lignocellulosic Agro-Wastes: Experimental Data and Modeling

Facile Manner in Regulating the Graphene-Shelled Structure of Cobalt Nanoparticles for the Synthesis of Amines

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