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Catalytic Transformation of Lignocellulosic Platform Chemicals

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A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Biomass Catalysis".

Deadline for manuscript submissions: closed (31 May 2018) | Viewed by 18728

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Special Issue Editor

Prof. Dr. Anna Maria Raspolli Galletti

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Guest Editor

Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via G. Moruzzi 13, 56124 Pisa, Italy
Interests: catalysis for sustainability; MW-assisted chemistry; nanomaterials; catalytic conversion; lignocellulosic biomass; biofuels synthesis; heterogeneous catalysts; synthesis of tailored catalytic systems
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Special Issue Information

Dear Colleagues,

Diminishing reserves of the easily-available petroleum resources and the environmental impact of fossil fuels are the driving forces in the search of alternative energy and new carbon sources. Undoubtedly, renewable lignocellulosic biomass represents a sustainable feedstock for the chemical industry, also offering the opportunity for potentially CO₂-neutral products. Up to now, significant efforts have been devoted to the development of feasible routes for the conversion of biomass into valuable “primary” platformchemicals. In particular, furan compounds, such as furfural and 5-hydroxymethylfurfural (HMF), and levulinic acid have great potential for the production of chemicals and fuels. Many “secondary” strategic products can be obtained by the catalytic conversion of these lignocellulosic platform chemicals using homogeneous, heterogeneous or enzymatic reactions of hydrogenation, oxidation, etherification, esterification, ketalization, hydrogen transfer, etc.

The aim of this Special Issue is

to cover the innovative results in the field of catalytic conversion applied to primary bio-based platform chemicals or directly starting from biomass in a multistep or in a one-pot approach to give secondary bio-based chemicals.
to deep the different catalytic reactions (homogeneous, heterogeneous and enzymatic as well as their combinations) using green reaction media (e.g., water, bioalcohols, ionic liquids, biphasic media, etc.);
to verify novel and combined process approaches, such as microwave irradiation, sonication, flow chemistry, microreactors, etc.

All suggestions and comments are really welcome!

Prof. Dr. Anna Maria Raspolli Galletti
Guest Editor

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Keywords

biomass conversion
green chemistry
homogeneous catalysis
heterogeneous catalysis
enzymatic catalysis
microwave irradiation
sonochemistry
levulinic acid
furfural
HMF

Published Papers (4 papers)

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Editorial

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2 pages, 150 KiB

Open AccessEditorial

Catalytic Transformation of Lignocellulosic Platform Chemicals

by Anna Maria Raspolli Galletti

Catalysts 2018, 8(9), 398; https://0-doi-org.brum.beds.ac.uk/10.3390/catal8090398 - 16 Sep 2018

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n/a Full article

(This article belongs to the Special Issue Catalytic Transformation of Lignocellulosic Platform Chemicals)

Research

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16 pages, 1940 KiB

Open AccessArticle

Cascade Strategy for the Tunable Catalytic Valorization of Levulinic Acid and γ-Valerolactone to 2-Methyltetrahydrofuran and Alcohols

by Domenico Licursi, Claudia Antonetti, Sara Fulignati, Michael Giannoni and Anna Maria Raspolli Galletti

Catalysts 2018, 8(7), 277; https://0-doi-org.brum.beds.ac.uk/10.3390/catal8070277 - 09 Jul 2018

Cited by 49 | Viewed by 5070

Abstract

A cascade strategy for the catalytic valorization of aqueous solutions of levulinic acid as well as of γ-valerolactone to 2-methyltetrahydrofuran or to monoalcohols, 2-butanol and 2-pentanol, has been studied and optimized. Only commercial catalytic systems have been employed, adopting sustainable reaction conditions. For the first time, the combined use of ruthenium and rhenium catalysts supported on carbon, with niobium phosphate as acid co-catalyst, has been claimed for the hydrogenation of γ-valerolactone and levulinic acid, addressing the selectivity to 2-methyltetrahydrofuran. On the other hand, the use of zeolite HY with commercial Ru/C catalyst favors the selective production of 2-butanol, starting again from γ-valerolactone and levulinic acid, with selectivities up to 80 and 70 mol %, respectively. Both levulinic acid and γ-valerolactone hydrogenation reactions have been optimized, investigating the effect of the main reaction parameters, to properly tune the catalytic performances towards the desired products. The proper choice of both the catalytic system and the reaction conditions can smartly switch the process towards the selective production of 2-methyltetrahydrofuran or monoalcohols. The catalytic system [Ru/C + zeolite HY] at 200 °C and 3 MPa H₂ is able to completely convert both γ-valerolactone and levulinic acid, with overall yields to monoalcohols of 100 mol % and 88.8 mol %, respectively. Full article

(This article belongs to the Special Issue Catalytic Transformation of Lignocellulosic Platform Chemicals)

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16 pages, 4962 KiB

Open AccessFeature PaperEditor’s ChoiceArticle

A Biorefinery Cascade Conversion of Hemicellulose-Free Eucalyptus Globulus Wood: Production of Concentrated Levulinic Acid Solutions for γ-Valerolactone Sustainable Preparation

by Sandra Rivas, Anna Maria Raspolli Galletti, Claudia Antonetti, Domenico Licursi, Valentín Santos and Juan Carlos Parajó

Catalysts 2018, 8(4), 169; https://0-doi-org.brum.beds.ac.uk/10.3390/catal8040169 - 21 Apr 2018

Cited by 29 | Viewed by 5175

Abstract

Eucalyptus globulus wood samples were subjected to preliminary aqueous processing to remove water-soluble extractives and hemicelluloses, and the resulting solid (mainly made up of cellulose and lignin) was employed as a substrate for converting the cellulosic fraction into mixtures of levulinic and formic acid through a sulfuric acid-catalyzed reaction. These runs were carried out in a microwave-heated reactor at different temperatures and reaction times, operating in single-batch or cross-flow modes, in order to identify the most favorable operational conditions. Selected liquid phases deriving from these experiments, which resulted in concentrated levulinic acid up to 408 mmol/L, were then employed for γ-valerolactone production by levulinc acid hydrogenation in the presence of the commercial 5% Ru/C catalyst. In order to assess the effects of the main reaction parameters, hydrogenation experiments were performed at different temperatures, reaction times, amounts of ruthenium catalyst and hydrogen pressure. Yields of γ-valerolactone in the range of 85–90 mol % were obtained from the hydrogenation of the wood-derived solutions containing levulinic acid, obtained by single-batch operation or by the cross-flow process. The negative effect of co-produced formic acid present in crude levulinic acid solutions was evidenced and counteracted efficiently by allowing the preliminary thermal decomposition of formic acid itself. Full article

(This article belongs to the Special Issue Catalytic Transformation of Lignocellulosic Platform Chemicals)

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12 pages, 1452 KiB

Open AccessArticle

Efficient Production of N-Butyl Levulinate Fuel Additive from Levulinic Acid Using Amorphous Carbon Enriched with Oxygenated Groups

by Jinfan Yang, Guangyi Li, Lulu Zhang and Sufeng Zhang

Catalysts 2018, 8(1), 14; https://0-doi-org.brum.beds.ac.uk/10.3390/catal8010014 - 09 Jan 2018

Cited by 43 | Viewed by 5469

Abstract

The aim of this study was to develop an effective carbonaceous solid acid for synthesizing green fuel additive through esterification of lignocellulose-derived levulinic acid (LA) and n-butanol. Two different sulfonated carbons were prepared from glucose-derived amorphous carbon (GC400) and commercial active carbon (AC400). They were contrastively studied by a series of characterizations (N₂ adsorption, X-ray diffraction, elemental analysis, transmission electron microscopy, Fourier transform infrared spectroscopy and NH₃ temperature programmed desorption). The results indicated that GC400 possessed stronger acidity and higher –SO₃H density than AC400, and the amorphous structure qualified GC400 for good swelling capacity in the reaction solution. Assessment experiments showed that GC400 displayed remarkably higher catalytic efficiency than AC400 and other typical solid acids (HZSM-5, Hβ, Amberlyst-15 and Nafion-212 resin). Up to 90.5% conversion of LA and 100% selectivity of n-butyl levulinate could be obtained on GC400 under the optimal reaction conditions. The sulfonated carbon retained 92% of its original catalytic activity even after five cycles. Full article

(This article belongs to the Special Issue Catalytic Transformation of Lignocellulosic Platform Chemicals)

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