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Advances in the Catalytic Conversion of Biomass Components to Ester...
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Advances in the Catalytic Conversion of Biomass Components to Ester Derivatives: Challenges and Opportunities

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

Deadline for manuscript submissions: closed (28 February 2022) | Viewed by 33152

Printed Edition Available!
A printed edition of this Special Issue is available here.

Special Issue Editor

Dr. Domenico Licursi

E-Mail Website
Guest Editor
Department of Chemistry and Industrial Chemistry, University of Pisa, Via Giuseppe Moruzzi 13, 56124 Pisa, Italy
Interests: biomass conversion; solvothermal/hydrothermal biomass processing; homogeneous and heterogeneous catalysis; ester derivatives; biofuels and biochemicals
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Biomass has received significant attention as a sustainable feedstock that can replace diminishing fossil fuels for the production of value-added chemicals and energy. Many new catalytic technologies have been developed for the conversion of biomass feedstocks into valuable biofuels and bioproducts. However, many of these still suffer from several disadvantages, such as weak catalytic performances, harsh reaction conditions, a high processing cost, and questionable sustainability, which limit their further applicability/development in the immediate future. In this context, the esterification of carboxylic acids represents a very valuable solution to these problems, requiring mild reaction conditions, and being advantageously integrable with many existing processes of biomass conversion. An emblematic example is the acid-catalyzed hydrothermal route for levulinic acid production, already upgraded to that of higher value alkyl levulinates, obtained by esterification or directly by biomass alcoholysis. Many other chemical processes benefit from esterification, such as the synthesis of bio-diesel, which includes mono-alkyl esters of long-chain fatty acids prepared from renewable vegetable oils and animal fats, or that of cellulose esters, mainly acetates, for textile uses. Even pyrolysis bio-oil should be stabilized by esterification to neutralize the acidity of carboxylic acids and moderate the reactivity of other typical biomass-derived compounds, such as sugars, furans, aldehydes, and phenolics.  

This Special Issue reports the main recent advances in the homogeneous/heterogeneous catalytic conversion of model/real biomass components to ester derivatives, which are extremely attractive for both the academic and industrial fields.   

Dr. Domenico Licursi
Guest Editors

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Keywords

  • Biomass conversion
  • Biofuels and biochemical
  • Biomass ester derivatives
  • Solvothermal processing
  • Homogeneous and heterogeneous catalysis
  • Carboxylic acid esterification
  • Alkyl levulinates
  • Biodiesel
  • Cellulose esters
  • Bio-oil esterification

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Published Papers (9 papers)

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Editorial

Jump to: Research

3 pages, 180 KiB  
Editorial
Advances in the Catalytic Conversion of Biomass Components to Ester Derivatives: Challenges and Opportunities
by Domenico Licursi
Catalysts 2022, 12(5), 455; https://doi.org/10.3390/catal12050455 - 20 Apr 2022
Cited by 1 | Viewed by 1639
Abstract
Sustainable conversion of biomass feedstocks into valuable bio-fuels and bio-products plays a strategic role within modern industrial catalysis [...] Full article
(This article belongs to the Special Issue Advances in the Catalytic Conversion of Biomass Components to Ester Derivatives: Challenges and Opportunities)
16 pages, 556 KiB  
Editorial
New Intensification Strategies for the Direct Conversion of Real Biomass into Platform and Fine Chemicals: What Are the Main Improvable Key Aspects?
by Claudia Antonetti, Domenico Licursi and Anna Maria Raspolli Galletti
Catalysts 2020, 10(9), 961; https://doi.org/10.3390/catal10090961 - 22 Aug 2020
Cited by 16 | Viewed by 3425
Abstract
Nowadays, the solvothermal conversion of biomass has reached a good level of development, and now it is necessary to improve the process intensification, in order to boost its further growth on the industrial scale. Otherwise, most of these processes would be limited to [...] Read more.
Nowadays, the solvothermal conversion of biomass has reached a good level of development, and now it is necessary to improve the process intensification, in order to boost its further growth on the industrial scale. Otherwise, most of these processes would be limited to the pilot scale or, even worse, to exclusive academic investigations, intended as isolated applications for the development of new catalysts. For this purpose, it is necessary to improve the work-up technologies, combining, where possible, reaction/purification unit operations, and enhancing the feedstock/liquid ratio, thus improving the final concentration of the target product and reducing the work-up costs. Furthermore, it becomes decisive to reconsider more critically the choice of biomass, solvent(s), and catalysts, pursuing the biomass fractionation in its components and promoting one-pot cascade conversion routes. Screening and process optimization activities on a laboratory scale must be fast and functional to the flexibility of these processes, exploiting efficient reaction systems such as microwaves and/or ultrasounds, and using multivariate analysis for an integrated evaluation of the data. These upstream choices, which are mainly of the chemist’s responsibility, are fundamental and deeply interconnected with downstream engineering, economic, and legislative aspects, which are decisive for the real development of the process. In this Editorial, all these key issues will be discussed, in particular those aimed at the intensification of solvothermal processes, taking into account some real case studies, already developed on the industrial scale. Full article
(This article belongs to the Special Issue Advances in the Catalytic Conversion of Biomass Components to Ester Derivatives: Challenges and Opportunities)

Research

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11 pages, 2624 KiB  
Article
MgO Catalysts for FAME Synthesis Prepared Using PEG Surfactant during Precipitation and Calcination
by Valdis Kampars, Ruta Kampare and Aija Krumina
Catalysts 2022, 12(2), 226; https://doi.org/10.3390/catal12020226 - 16 Feb 2022
Cited by 7 | Viewed by 2784
Abstract
To develop a method for the preparation of MgO nanoparticles, precatalyst synthesis from magnesium nitrate with ammonia and calcination was performed in presence of PEG in air. Without PEG, the catalysts are inactive. The conversion to hydroxide was performed using a PEG/MgO molar [...] Read more.
To develop a method for the preparation of MgO nanoparticles, precatalyst synthesis from magnesium nitrate with ammonia and calcination was performed in presence of PEG in air. Without PEG, the catalysts are inactive. The conversion to hydroxide was performed using a PEG/MgO molar ratio of 1, but, before the calcination, excess of PEG was either saved (PEG1) or increased to 2, 3, or 4 (PEG 2–4). Catalysts were calcined at 400–660 °C and characterized using XRD, N2 adsorption-desorption, TGA, FTIR, and SEM. The FAME yield in the reactions with methanol depend on the PEG ratio used and the calcination temperature. The optimal calcination temperature and highest FAME yield in the 6 h reactions for catalysts PEG1, PEG2, PEG3 and PEG4 were 400 °C, 74%; 500 °C, 80%; 500 °C, 51% and 550 °C, 31%, respectively. The yield dependence on calcination temperature for catalysts with a constant PEG ratio is similar to that of a bell curve, which becomes wider and flatters with an increase in PEG ratio. For most catalysts, the FAME yield increases as the size of the crystallites decreases. The dependence of FAME and the intermediate yield on oil conversion confirms that all catalysts have strong base sites. Full article
(This article belongs to the Special Issue Advances in the Catalytic Conversion of Biomass Components to Ester Derivatives: Challenges and Opportunities)
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19 pages, 2005 KiB  
Article
Sustainable Exploitation of Residual Cynara cardunculus L. to Levulinic Acid and n-Butyl Levulinate
by Anna Maria Raspolli Galletti, Domenico Licursi, Serena Ciorba, Nicola Di Fidio, Valentina Coccia, Franco Cotana and Claudia Antonetti
Catalysts 2021, 11(9), 1082; https://doi.org/10.3390/catal11091082 - 8 Sep 2021
Cited by 19 | Viewed by 3176
Abstract
Hydrolysis and butanolysis of lignocellulosic biomass are efficient routes to produce two valuable bio-based platform chemicals, levulinic acid and n-butyl levulinate, which find increasing applications in the field of biofuels and for the synthesis of intermediates for chemical and pharmaceutical industries, food [...] Read more.
Hydrolysis and butanolysis of lignocellulosic biomass are efficient routes to produce two valuable bio-based platform chemicals, levulinic acid and n-butyl levulinate, which find increasing applications in the field of biofuels and for the synthesis of intermediates for chemical and pharmaceutical industries, food additives, surfactants, solvents and polymers. In this research, the acid-catalyzed hydrolysis of the waste residue of Cynara cardunculus L. (cardoon), remaining after seed removal for oil exploitation, was investigated. The cardoon residue was employed as-received and after a steam-explosion treatment which causes an enrichment in cellulose. The effects of the main reaction parameters, such as catalyst type and loading, reaction time, temperature and heating methodology, on the hydrolysis process were assessed. Levulinic acid molar yields up to about 50 mol % with levulinic acid concentrations of 62.1 g/L were reached. Moreover, the one-pot butanolysis of the steam-exploded cardoon with the bio-alcohol n-butanol was investigated, demonstrating the direct production of n-butyl levulinate with good yield, up to 42.5 mol %. These results demonstrate that such residual biomass represent a promising feedstock for the sustainable production of levulinic acid and n-butyl levulinate, opening the way to the complete exploitation of this crop. Full article
(This article belongs to the Special Issue Advances in the Catalytic Conversion of Biomass Components to Ester Derivatives: Challenges and Opportunities)
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16 pages, 2260 KiB  
Article
A Novel and Efficient Method for the Synthesis of Methyl (R)-10-Hydroxystearate and FAMEs from Sewage Scum
by Luigi di Bitonto, Valeria D’Ambrosio and Carlo Pastore
Catalysts 2021, 11(6), 663; https://doi.org/10.3390/catal11060663 - 23 May 2021
Cited by 7 | Viewed by 2213
Abstract
In this work, the transesterification of methyl estolides (ME) extracted from the lipid component present in the sewage scum was investigated. Methyl 10-(R)-hydroxystearate (Me-10-HSA) and Fatty Acid Methyl Esters (FAMEs) were obtained in a single step. A three-level and four factorial [...] Read more.
In this work, the transesterification of methyl estolides (ME) extracted from the lipid component present in the sewage scum was investigated. Methyl 10-(R)-hydroxystearate (Me-10-HSA) and Fatty Acid Methyl Esters (FAMEs) were obtained in a single step. A three-level and four factorial Box–Behnken experimental design were used to study the effects of methanol amounts, catalyst, temperature, and reaction time on the transesterification reaction using aluminum chloride hexahydrate (AlCl3·6H2O) or hydrochloric acid (HCl) as catalysts. AlCl3·6H2O was found quite active as well as conventional homogeneous acid catalysts as HCl. In both cases, a complete conversion of ME into Me-10-HSA and FAMEs was observed. The products were isolated, quantified, and fully characterized. At the end of the process, Me-10-HSA (32.3%wt) was purified through a chromatographic separation and analyzed by NMR. The high enantiomeric excess (ee > 92%) of the R-enantiomer isomer opens a new scenario for the valorization of sewage scum. Full article
(This article belongs to the Special Issue Advances in the Catalytic Conversion of Biomass Components to Ester Derivatives: Challenges and Opportunities)
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14 pages, 4172 KiB  
Article
Guerbet Reactions for Biofuel Production from ABE Fermentation Using Bifunctional Ni-MgO-Al2O3 Catalysts
by Zhiyi Wu, Pingzhou Wang, Jie Wang and Tianwei Tan
Catalysts 2021, 11(4), 414; https://doi.org/10.3390/catal11040414 - 24 Mar 2021
Cited by 10 | Viewed by 3378
Abstract
To upgrade biomass-derived alcohol mixtures to biofuels under solvent-free conditions, MgO–Al2O3 mixed metal oxides (MMO) decorated with Ni nanoparticles (Ni–MgO–Al2O3) are synthesized and characterized. Based on the result, Ni nanoparticles are highly dispersed on the surface [...] Read more.
To upgrade biomass-derived alcohol mixtures to biofuels under solvent-free conditions, MgO–Al2O3 mixed metal oxides (MMO) decorated with Ni nanoparticles (Ni–MgO–Al2O3) are synthesized and characterized. Based on the result, Ni nanoparticles are highly dispersed on the surface of MgAl MMO. As the Ni loading content varies from 2 to 10 wt.%, there is a slight increase in the mean Ni particle size from 6.7 to 8.5 nm. The effects of Ni loading amount, reducing temperature, and Mg/Al ratio on the conversion and product distribution are investigated. With the increase in both the Ni loading amount and reducing temperature, dehydrogenation (the first step of the entire reaction network) is accelerated. This results in an increase in the conversion process and a higher selectivity for the dialkylated compounds. Due to the higher strength and density of basic sites under high Mg/Al ratios, double alkylation is preferred and more long-chain hydrocarbons are obtained. A conversion of 89.2% coupled with a total yield of 79.9% for C5–C15 compounds is acquired by the as-prepared catalyst (prepared with Ni loading of 6 wt.%, reducing temperature of 700 °C, and Mg/Al molar ratio of 3. After four runs, the conversion drops by 17.1%, and this loss in the catalytic activity can be attributed to the decrease in the surface area of the catalyst and the increase in the Ni mean particle size. Full article
(This article belongs to the Special Issue Advances in the Catalytic Conversion of Biomass Components to Ester Derivatives: Challenges and Opportunities)
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14 pages, 3237 KiB  
Article
Hydrogenative Cyclization of Levulinic Acid to γ-Valerolactone with Methanol and Ni-Fe Bimetallic Catalysts
by Ligang Luo, Xiao Han and Qin Zeng
Catalysts 2020, 10(9), 1096; https://doi.org/10.3390/catal10091096 - 21 Sep 2020
Cited by 20 | Viewed by 4092
Abstract
A series of Ni-Fe/SBA-15 catalysts was prepared and tested for the catalytic hydrogenation of levulinic acid to γ-valerolactone, adopting methanol as the only hydrogen donor, and investigating the synergism between Fe and Ni, both supported on SBA-15, towards this reaction. The characterization of [...] Read more.
A series of Ni-Fe/SBA-15 catalysts was prepared and tested for the catalytic hydrogenation of levulinic acid to γ-valerolactone, adopting methanol as the only hydrogen donor, and investigating the synergism between Fe and Ni, both supported on SBA-15, towards this reaction. The characterization of the synthesized catalysts was carried out by XRD (X-ray powder diffraction), TEM (transmission electron microscopy), H2-TPD (hydrogen temperature-programmed desorption), XPS (X-ray photoelectron spectroscopy), and in situ FT-IR (Fourier transform–infrared spectroscopy) techniques. H2-TPD and XPS results have shown that electron transfer occurs from Fe to Ni, which is helpful both for the activation of the C=O bond and for the dissociative activation of H2 molecules, also in agreement with the results of the in situ FT-IR spectroscopy. The effect of temperature and reaction time on γ-valerolactone production was also investigated, identifying the best reaction conditions at 200 °C and 180 min, allowing for the complete conversion of levulinic acid and the complete selectivity to γ-valerolactone. Moreover, methanol was identified as an efficient hydrogen donor, if used in combination with the Ni-Fe/SBA-15 catalyst. The obtained results are promising, especially if compared with those obtained with the traditional and more expensive molecular hydrogen and noble-based catalysts. Full article
(This article belongs to the Special Issue Advances in the Catalytic Conversion of Biomass Components to Ester Derivatives: Challenges and Opportunities)
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22 pages, 2494 KiB  
Article
One-Pot Alcoholysis of the Lignocellulosic Eucalyptus nitens Biomass to n-Butyl Levulinate, a Valuable Additive for Diesel Motor Fuel
by Claudia Antonetti, Samuele Gori, Domenico Licursi, Gianluca Pasini, Stefano Frigo, Mar López, Juan Carlos Parajó and Anna Maria Raspolli Galletti
Catalysts 2020, 10(5), 509; https://doi.org/10.3390/catal10050509 - 6 May 2020
Cited by 44 | Viewed by 6303
Abstract
The present investigation represents a concrete example of complete valorization of Eucalyptus nitens biomass, in the framework of the circular economy. Autohydrolyzed-delignified Eucalyptus nitens was employed as a cheap cellulose-rich feedstock in the direct alcoholysis to n-butyl levulinate, adopting n-butanol as [...] Read more.
The present investigation represents a concrete example of complete valorization of Eucalyptus nitens biomass, in the framework of the circular economy. Autohydrolyzed-delignified Eucalyptus nitens was employed as a cheap cellulose-rich feedstock in the direct alcoholysis to n-butyl levulinate, adopting n-butanol as green reagent/reaction medium, very dilute sulfuric acid as a homogeneous catalyst, and different heating systems. The effect of the main reaction parameters to give n-butyl levulinate was investigated to check the feasibility of this reaction and identify the coarse ranges of the main operating variables of greater relevance. High n-butyl levulinate molar yields (35–40 mol%) were achieved under microwave and traditional heating, even using a very high biomass loading (20 wt%), an eligible aspect from the perspective of the high gravity approach. The possibility of reprocessing the reaction mixture deriving from the optimized experiment by the addition of fresh biomass was evaluated, achieving the maximum n-butyl levulinate concentration of about 85 g/L after only one microwave reprocessing of the mother liquor, the highest value hitherto reported starting from real biomass. The alcoholysis reaction was further optimized by Response Surface Methodology, setting a Face-Centered Central Composite Design, which was experimentally validated at the optimal operating conditions for the n-butyl levulinate production. Finally, a preliminary study of diesel engine performances and emissions for a model mixture with analogous composition to that produced from the butanolysis reaction was performed, confirming its potential application as an additive for diesel fuel, without separation of each component. Full article
(This article belongs to the Special Issue Advances in the Catalytic Conversion of Biomass Components to Ester Derivatives: Challenges and Opportunities)
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27 pages, 7123 KiB  
Article
Acetylation of Eugenol on Functionalized Mesoporous Aluminosilicates Synthesized from Amazonian Flint Kaolin
by Alex de Nazaré de Oliveira, Erika Tallyta Leite Lima, Eloisa Helena de Aguiar Andrade, José Roberto Zamian, Geraldo Narciso da Rocha Filho, Carlos Emmerson Ferreira da Costa, Luíza Helena de Oliveira Pires, Rafael Luque and Luís Adriano Santos do Nascimento
Catalysts 2020, 10(5), 478; https://doi.org/10.3390/catal10050478 - 27 Apr 2020
Cited by 11 | Viewed by 4106
Abstract
The present work was aimed to investigate the catalytic activity of a mesoporous catalyst synthesized from 3-mercaptopropyltrimethoxysilane (MPTS) functionalized Amazonian flint kaolin in the acetylation of eugenol with acetic anhydride. Materials were characterized by thermogravimetry (TGA), N2 adsorption (BET), X-ray dispersive energy [...] Read more.
The present work was aimed to investigate the catalytic activity of a mesoporous catalyst synthesized from 3-mercaptopropyltrimethoxysilane (MPTS) functionalized Amazonian flint kaolin in the acetylation of eugenol with acetic anhydride. Materials were characterized by thermogravimetry (TGA), N2 adsorption (BET), X-ray dispersive energy spectroscopy (EDX), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and acid-base titration. The results presented proved the efficiency of flint kaolin as an alternative source in the preparation of mesoporous materials, since the material exhibited textural properties (specific surface area of 1071 m2 g−1, pore volume of 1.05 cm3 g−1 and pore diameter of 3.85 nm) and structural properties (d100 = 4.35 nm, a0 = 5.06 nm and Wt = 1.21 nm) within the required and characteristic material standards. The catalyst with the total amount of acidic sites of 4.89 mmol H+ g−1 was efficient in converting 99.9% of eugenol (eugenol to acetic anhydride molar ratio of 1:5, 2% catalyst, temperature and reaction time 80 °C and 40 min reaction). In addition, the reused catalyst could be successfully recycled with 92% conversion activity under identical reaction conditions. Full article
(This article belongs to the Special Issue Advances in the Catalytic Conversion of Biomass Components to Ester Derivatives: Challenges and Opportunities)
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