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Biorefineries
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Biorefineries

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Green Chemistry".

Deadline for manuscript submissions: closed (1 June 2023) | Viewed by 33151

Special Issue Editors

Dr. Jalel Labidi

E-Mail Website
Guest Editor
Department of Chemical and Environmental Engineering, Faculty of Engineering Gipuzkoa, University of the Basque Country, Plaza Europa 1, 20018 Donostia-San Sebastián, Gipuzkoa, Spain
Interests: biomass biorefinery; wood based products; biobased composites; nanocellulose modification; lignin; lignin nanoparticles; coating formulation; LCA
Special Issues, Collections and Topics in MDPI journals
Dr. Xabier Erdocia

E-Mail Website
Guest Editor
Department of Chemical and Environmental Engineering, University of the Basque Country, UPV/EHU Plaza Europa 1, 20018 San Sebastián, Spain
Interests: biorefinery; lignocellulosic biomass; lignin; polyols
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Serveral countries have implemented strategies to shift from fossil fuel-based economies to biobased economies. This change requires the development of sustainable biorefining processes with low environmental impacts and new biobased building blocks as precursors for chemicals and polymers.

This Special Issue is focused on the production of new building blocks, chemicals, and polymers from biomasses using innovative and green processing technologies. The Special Issue will also include other topics, such as the structural characterization and applications of biobased products.

Topics:

Advances in pretreatment processes;
Sustainable chemistry;
Multiproduct biorefineries;
LCA;
New feedstocks;
Products and applications of biobased building blocks;
Advanced characterization.

Dr. Jalel Labidi
Dr. Xabier Erdocia
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Green extraction;
  • New building blocks;
  • LCA;
  • Biomass conversion;
  • Biobased products;
  • Simulation;
  • Thermochemical conversion;
  • Pretreatments.

Published Papers (10 papers)

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Research

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14 pages, 3036 KiB  
Article
Synthesis of Glycerol Carbonate from Ethylene Carbonate Using Zinc Stearate as a Catalyst: Operating Conditions and Kinetic Modeling
by Mariana Alvarez Serafini, David Gonzalez-Miranda, Gabriela Tonetto, Félix Garcia-Ochoa and Miguel Ladero
Molecules 2023, 28(3), 1311; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules28031311 - 30 Jan 2023
Cited by 3 | Viewed by 1608
Abstract
With the advent of biodiesel as a substitute/additive for diesel, the production of glycerol has experienced an increase, as it is an unavoidable byproduct of the biodiesel process; therefore, novel products and processes based on this triol are being very actively researched. Glycerol [...] Read more.
With the advent of biodiesel as a substitute/additive for diesel, the production of glycerol has experienced an increase, as it is an unavoidable byproduct of the biodiesel process; therefore, novel products and processes based on this triol are being very actively researched. Glycerol carbonate emerges as an advanced humectant from glycerol and a monomer for diverse polycarbonates. Its production in high yields and amounts can be achieved through the solventless transcarbonation of glycerol with other organic carbonates driven by alkaline catalysts, standing out amongst the cyclic carbonates due to its reactivity. Here, we have studied the main operational variables that affect the transcarbonation reaction of glycerol and ethylene carbonate catalyzed by zinc stearate: catalyst concentration, reagent molar ratio, and temperature. Subsequently, an appropriate kinetic model was fitted to all data obtained at 80 °C and several catalyst concentrations as well as reagent molar ratios. Finally, the selected kinetic model was extended and validated by fitting it to data obtained at several temperatures, finding that the activation energy of this reaction with this catalyst is around 69.2 kJ·mol−1. The kinetic model suggests that the reaction is bimolecular and elemental and that the process is interfacial in essence, with the catalyst dispersed in a narrow space between polar (glycerol) and nonpolar (ethylene carbonate) phases. Full article
(This article belongs to the Special Issue Biorefineries)
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16 pages, 3730 KiB  
Article
Cellulose Nanofibers from Schinus molle: Preparation and Characterization
by Abir Razzak, Ramzi Khiari, Younes Moussaoui and Mohamed Naceur Belgacem
Molecules 2022, 27(19), 6738; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules27196738 - 09 Oct 2022
Cited by 2 | Viewed by 1994
Abstract
Schinus molle (SM) was investigated as a primary source of cellulose with the aim of discovering resources to generate cellulose nanofibers (CNF). The SM was put through a soda pulping process to purify the cellulose, and then, the fiber was treated with an [...] Read more.
Schinus molle (SM) was investigated as a primary source of cellulose with the aim of discovering resources to generate cellulose nanofibers (CNF). The SM was put through a soda pulping process to purify the cellulose, and then, the fiber was treated with an enzymatic treatment. Then, a twin-screw extruder and/or masuko were utilized to help with fiber delamination during the nanofibrillation process. After the enzymatic treatment, the twin-screw extruder and masuko treatment give a yield of 49.6 and 50.2%, respectively. The optical and atomic force microscopy, morfi, and polymerization degrees of prepared cellulosic materials were established. The pulp fibers, collected following each treatment stage, demonstrated that fiber characteristics such as length and crystallinity varied according to the used treatment (mechanical or enzymatic treatment). Obviously, the enzymic treatment resulted in shorter fibers and an increased degree of polymerization. However, the CNF obtained after enzymatic and extrusion treatment was achieved, and it gave 19 nm as the arithmetic width and a Young’s modulus of 8.63 GPa. Full article
(This article belongs to the Special Issue Biorefineries)
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18 pages, 2423 KiB  
Article
Nutrient Recovery from Digestate of Agricultural Biogas Plants: A Comparative Study of Innovative Biocoal-Based Additives in Laboratory and Full-Scale Experiments
by Ievgeniia Morozova and Andreas Lemmer
Molecules 2022, 27(16), 5289; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules27165289 - 19 Aug 2022
Cited by 2 | Viewed by 1597
Abstract
Nutrients can be recovered from the digestate of an agricultural biogas plant in the form of solid fraction and serve as crop fertilizers. Removal of suspended solids with screw press separators is the most commonly used technique for treating digestate from biogas plants. [...] Read more.
Nutrients can be recovered from the digestate of an agricultural biogas plant in the form of solid fraction and serve as crop fertilizers. Removal of suspended solids with screw press separators is the most commonly used technique for treating digestate from biogas plants. To increase separation efficiency and nutrient transfer to the solid phase during separation, eight biocoal-based additives were investigated, which were based on beech wood and produced by pyrolysis at temperatures of 350 °C and 600 °C. Four of the biocoals were impregnated with CaCl2 or MgCl2 before pyrolysis. The reaction time between the additives and the digestate varied from 5 min to 2 weeks. The application of MgCl2-impregnated biocoal synthesized at 600 °C for 20 h increased the nutrient removal efficiency by 76.33% for ammonium and 47.15% for phosphorus, compared to the control (the untreated digestate). Full article
(This article belongs to the Special Issue Biorefineries)
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10 pages, 1705 KiB  
Article
Polysaccharides Release in a Laboratory-Scale Batch Hydrothermal Pretreatment of Wheat Straw under Rigorous Isothermal Operation
by Felicia Rodríguez, Efrén Aguilar-Garnica, Adrián Santiago-Toribio and Arturo Sánchez
Molecules 2022, 27(1), 26; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules27010026 - 22 Dec 2021
Cited by 9 | Viewed by 2171
Abstract
Hydrothermal pretreatment (HP) is an eco-friendly process for deconstructing lignocellulosic biomass (LCB) that plays a key role in ensuring the profitability of producing biofuels or bioproducts in a biorefinery. At the laboratory scale, HP is usually carried out under non-isothermal regimes with poor [...] Read more.
Hydrothermal pretreatment (HP) is an eco-friendly process for deconstructing lignocellulosic biomass (LCB) that plays a key role in ensuring the profitability of producing biofuels or bioproducts in a biorefinery. At the laboratory scale, HP is usually carried out under non-isothermal regimes with poor temperature control. In contrast, HP is usually carried out under isothermal conditions at the commercial scale. Consequently, significant discrepancies in the values of polysaccharide releases are found in the literature. Therefore, laboratory-scale HP data are not trustworthy if scale-up or retrofitting of HP at larger scales is required. This contribution presents the results of laboratory-scale batch HP for wheat straw in terms of xylan and glucan release that were obtained with rigorous temperature control under isothermal conditions during the reaction stage. The heating and cooling stages were carried out with fast rates (43 and −40 °C/min, respectively), minimizing non-isothermal reaction periods. Therefore, the polysaccharide release results can be associated exclusively with the isothermic reaction stage and can be considered as a reliable source of information for HP at commercial scales. The highest amount of xylan release was 4.8 g/L or 43% obtained at 180 °C and 20 min, while the glucan release exhibited a maximum of 1.2 g/L or 5.5%. at 160 °C/180 °C and 30 min. Full article
(This article belongs to the Special Issue Biorefineries)
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20 pages, 3717 KiB  
Article
Fractionation of Waste MDF by Steam Refining
by Sebastian Hagel and Bodo Saake
Molecules 2020, 25(9), 2165; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25092165 - 05 May 2020
Cited by 21 | Viewed by 4090
Abstract
In view of the expected increase in available waste medium-density fiberboard (MDF) and the current insufficient and unsatisfactory disposal capacities, efficient ways of recycling the waste material need to be developed. In this study, the potential of steam refining as a method to [...] Read more.
In view of the expected increase in available waste medium-density fiberboard (MDF) and the current insufficient and unsatisfactory disposal capacities, efficient ways of recycling the waste material need to be developed. In this study, the potential of steam refining as a method to hydrolyze the resins, isolate fibers, and obtain a hemicellulose-rich extract available for further utilization in the context of a biorefinery was assessed. Two different MDF waste samples, as well as poplar (Populus spp.) and spruce (Picea spp.) wood chips for benchmarking, were treated over a severity range from 2.47 to 3.95. The separated fiber and extract fractions were analyzed with regard to yield, content of carbohydrates, acids, degradation products, and nitrogen. A fiber fraction of more than 70% yield and an extract containing up to 30% of carbohydrates for further processing can be gained by steam-refining waste MDF. At low severities, most of the nitrogen-based compounds are solubilized. Increasing the severity leads to a decrease in nitrogen in the extract as the nitrogen compounds are converted into volatiles. A non-hydrolysable resin residue remains on the fibers, independent of the treatment severity. In comparison to the benchmark samples, the extract fraction of waste MDF shows a high pH of 8 and high amounts of acetic and formic acid. The generation of furfural and 5-hydroxymethylfurfural (5-HMF) on the other hand is suppressed. Distinct differences in carbohydrate hydrolysis behavior between waste MDF and conventional wood can be observed. Especially, the mannose-containing constituents seem to be resistant to hydrolysis reactions in the milieu created in MDF fractionation. Full article
(This article belongs to the Special Issue Biorefineries)
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12 pages, 1931 KiB  
Article
Ferrous and Ferric Ion-Facilitated Dilute Acid Pretreatment of Lignocellulosic Biomass under Anaerobic or Aerobic Conditions: Observations of Fe Valence Interchange and the Role of Fenton Reaction
by Hui Wei, Wei Wang, Peter N. Ciesielski, Bryon S. Donohoe, Min Zhang, Michael E. Himmel, Xiaowen Chen and Melvin P. Tucker
Molecules 2020, 25(6), 1427; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25061427 - 20 Mar 2020
Cited by 3 | Viewed by 2739
Abstract
Ferrous ion co-catalyst enhancement of dilute-acid (DA) pretreatment of biomass is a promising technology for increasing the release of sugars from recalcitrant lignocellulosic biomass. However, due to the reductive status of ferrous ion and its susceptibility to oxidation with exposure to atmosphere, its [...] Read more.
Ferrous ion co-catalyst enhancement of dilute-acid (DA) pretreatment of biomass is a promising technology for increasing the release of sugars from recalcitrant lignocellulosic biomass. However, due to the reductive status of ferrous ion and its susceptibility to oxidation with exposure to atmosphere, its effective application presumably requires anaerobic aqueous conditions created by nitrogen gas-purging, which adds extra costs. The objective of this study was to assess the effectiveness of oxidative iron ion, (i.e., ferric ion) as a co-catalyst in DA pretreatment of biomass, using an anaerobic chamber to strictly control exposure to oxygen during setup and post-pretreatment analyses. Remarkably, the ferric ions were found to be as efficient as ferrous ions in enhancing sugar release during DA pretreatment of biomass, which may be attributed to the observation that a major portion of the initial ferric ions were converted to ferrous during pretreatment. Furthermore, the detection of hydrogen peroxide in the liquors after DA/Fe ion pretreatment suggests that Fenton reaction chemistry was likely involved in DA/Fe ion pretreatments of biomass, contributing to the observed ferric and ferrous interchanges during pretreatment. These results help define the extent and specification requirements for applying iron ions as co-catalysts in DA pretreatments of biomass. Full article
(This article belongs to the Special Issue Biorefineries)
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Review

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21 pages, 1344 KiB  
Review
Application of Biomass Corrosion Inhibitors in Metal Corrosion Control: A Review
by Qihui Wang, Ruozhou Wang, Qi Zhang, Chongkang Zhao, Xing Zhou, Huahao Zheng, Rui Zhang, Yi Sun and Zhitao Yan
Molecules 2023, 28(6), 2832; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules28062832 - 21 Mar 2023
Cited by 13 | Viewed by 3582
Abstract
Corrosion is the process of damaging materials, and corrosion of metallic materials frequently results in serious consequences. The addition of corrosion inhibitors is the most effective means of preventing metal corrosion. Until now, researchers have made unremitting efforts in the research of high-efficiency [...] Read more.
Corrosion is the process of damaging materials, and corrosion of metallic materials frequently results in serious consequences. The addition of corrosion inhibitors is the most effective means of preventing metal corrosion. Until now, researchers have made unremitting efforts in the research of high-efficiency green corrosion inhibitors, and research on biomass corrosion inhibitors in a class of environmentally friendly corrosion inhibitors is currently quite promising. This work presents the classification of green biomass corrosion inhibitors in detail, including plant-based corrosion inhibitors, amino acid corrosion inhibitors, and biosurfactant corrosion inhibitors, based on the advantages of easy preparation, environmental friendliness, high corrosion inhibition efficiency, and a wide application range of biomass corrosion inhibitors. This work also introduces the preparation methods of biomass corrosion inhibitors, including hydrolysis, enzymatic digestion, the heating reflux method, and microwave extraction. In addition, the corrosion inhibition mechanisms of green biomass corrosion inhibitors, including physical adsorption, chemisorption, and film-forming adsorption, and evaluation methods of biomass corrosion inhibitors are also explicitly described. This study provides valuable insights into the development of green corrosion inhibitors. Full article
(This article belongs to the Special Issue Biorefineries)
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18 pages, 1003 KiB  
Review
Bread Surplus: A Cumulative Waste or a Staple Material for High-Value Products?
by Ines Ben Rejeb, Ichrak Charfi, Safa Baraketi, Hanine Hached and Mohamed Gargouri
Molecules 2022, 27(23), 8410; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules27238410 - 01 Dec 2022
Cited by 9 | Viewed by 2627
Abstract
Food waste has been widely valorized in the past years in order to develop eco-friendly materials. Among others, bread waste is currently of increasing interest, as it is considered a huge global issue with serious environmental impacts and significant economic losses that have [...] Read more.
Food waste has been widely valorized in the past years in order to develop eco-friendly materials. Among others, bread waste is currently of increasing interest, as it is considered a huge global issue with serious environmental impacts and significant economic losses that have become even greater in the post-pandemic years due to an increase in cereal prices, which has led to higher production costs and bread prices. Owing to its richness in polysaccharides, bread waste has been previously studied for its physico-chemical characteristics and its numerous biotechnological applications. The present review highlights the re-use of bread waste and its valorization as a valuable resource by making value-added products through numerous technological processes to increase efficiency at all stages. Many research studies reporting several transformation methods of surplus bread into ethanol, lactic acid, succinic acid, biohydrogen, hydroxymethylfurfural, proteins and pigments, glucose–fructose syrup, aroma compounds, and enzymes are widely discussed. The wide variety of suggested applications for recycling bread waste provides significant insights into the role of technology development in potentially maximizing resource recovery and consequently contributing to environmental performance by reducing the amount of bread waste in landfills. Full article
(This article belongs to the Special Issue Biorefineries)
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22 pages, 2618 KiB  
Review
Engineered Multilayer Microcapsules Based on Polysaccharides Nanomaterials
by Salvatore Lombardo and Ana Villares
Molecules 2020, 25(19), 4420; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25194420 - 25 Sep 2020
Cited by 17 | Viewed by 3695
Abstract
The preparation of microcapsules composed by natural materials have received great attention, as they represent promising systems for the fabrication of micro-containers for controlled loading and release of active compounds, and for other applications. Using polysaccharides as the main materials is receiving increasing [...] Read more.
The preparation of microcapsules composed by natural materials have received great attention, as they represent promising systems for the fabrication of micro-containers for controlled loading and release of active compounds, and for other applications. Using polysaccharides as the main materials is receiving increasing interest, as they constitute the main components of the plant cell wall, which represent an ideal platform to mimic for creating biocompatible systems with specific responsive properties. Several researchers have recently described methods for the preparation of microcapsules with various sizes and properties using cell wall polysaccharide nanomaterials. Researchers have focused mostly in using cellulose nanomaterials as structural components in a bio-mimetic approach, as cellulose constitutes the main structural component of the plant cell wall. In this review, we describe the microcapsules systems presented in the literature, focusing on the works where polysaccharide nanomaterials were used as the main structural components. We present the methods and the principles behind the preparation of these systems, and the interactions involved in stabilizing the structures. We show the specific and stimuli-responsive properties of the reported microcapsules, and we describe how these characteristics can be exploited for specific applications. Full article
(This article belongs to the Special Issue Biorefineries)
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30 pages, 3519 KiB  
Review
Liquefaction of Biomass and Upgrading of Bio-Oil: A Review
by Shiqiu Zhang, Xue Yang, Haiqing Zhang, Chunli Chu, Kui Zheng, Meiting Ju and Le Liu
Molecules 2019, 24(12), 2250; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules24122250 - 17 Jun 2019
Cited by 83 | Viewed by 7561
Abstract
The liquefaction of biomass is an important technology to converse the biomass into valuable biofuel. The common technologies for liquefaction of biomass are indirect liquefaction and direct liquefaction. The indirect liquefaction refers to the Fischer–Tropsch (F–T) process using the syngas of biomass as [...] Read more.
The liquefaction of biomass is an important technology to converse the biomass into valuable biofuel. The common technologies for liquefaction of biomass are indirect liquefaction and direct liquefaction. The indirect liquefaction refers to the Fischer–Tropsch (F–T) process using the syngas of biomass as the raw material to produce the liquid fuel, including methyl alcohol, ethyl alcohol, and dimethyl ether. The direct liquefaction of biomass refers to the conversion biomass into bio-oil, and the main technologies are hydrolysis fermentation and thermodynamic liquefaction. For thermodynamic liquefaction, it could be divided into fast pyrolysis and hydrothermal liquefaction. In addition, this review provides an overview of the physicochemical properties and common upgrading methods of bio-oil. Full article
(This article belongs to the Special Issue Biorefineries)
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