Chemicals and Materials from Lignocellulose: From Biomass to End Products

A special issue of Sustainable Chemistry (ISSN 2673-4079).

Deadline for manuscript submissions: closed (31 March 2021) | Viewed by 28276

Special Issue Editors

URD Agro-Biotechnologies (ABI), CEBB, AgroParisTech, 51110 Pomacle, France
Interests: biomass upgrading; bio-based building blocks, chemicals and materials; green chemistry; biotechnology; downstream process
Green Chemistry Centre of Excellence, Department of Chemistry, University of York, Heslington, York YO10 5DD, UK
Interests: bio-based products; clean synthesis; bio-based polymers; platform molecules
Special Issues, Collections and Topics in MDPI journals
Department of Chemical Engineering, Imperial College London, South Kensington Campus, London SW7 2AZ, UK
Interests: catalytic valorisation of lignin and cellulose by unconventional approaches; catalytic transfer hydrogenation; mechanocatalysis and solvent design

Special Issue Information

Dear Colleagues,

A sustainable chemical industry starts with renewable feedstock—with biomass by-products being ideal for this purpose. Although the chemical composition of waste biomass is incredibly diverse, it is the dominant lignocellulose that represents the only option to produce bio-based chemicals and materials on a significant scale. Indeed, the current petrochemical industry is primarily built around a small set of simple building blocks. These base chemicals are produced on the 10–100 MT scale annually. As such, the equivalent building blocks from biomass (so-called platform molecules) need to be produced in biorefineries on an equally large scale, though only the lignocellulose component of biomass is abundant enough to match these vast quantities. However, use of lignocellulose as a feedstock is not simple. It is highly recalcitrant, variable in composition and high in oxygen content, thus very different to the simpler carbon sources used for petrochemicals. Nevertheless, lignocellulose offers vast potential as each of its three components (cellulose, hemicellulose, and lignin) are the building blocks of numerous chemicals and materials. Global research efforts to fulfil this potential are ongoing and include characterisation of biomass, breakdown of lignocellulose (chemical, physical, thermal, and biological), synthesis and use of platform molecules, preparation of new bio-based products, engineering, life cycle assessment, and policy and regulations to support the aforementioned.

This Special Issue will bring together researchers from different disciplines with the aim of providing and demonstrating the use of lignocellulose to supply a sustainable chemical industry. Contributions from the areas of chemistry, biology, biochemistry, chemical engineering, material science, policy, and the environmental sciences are welcome. We invite the submission of original research as well as reviews that address some aspect of the Special Issue’s theme.

Prof. Dr. Florent Allais
Dr. Thomas J. Farmer
Dr. Roberto Rinaldi
Guest Editors

Manuscript Submission Information

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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. Sustainable Chemistry is an international peer-reviewed open access quarterly 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 1000 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

  • Lignocellulose
  • Platform molecules
  • Green chemistry
  • Sustainable processes
  • Bio-based products
  • Bio-based chemicals
  • Renewable resources
  • Biorefineries

Published Papers (8 papers)

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Research

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15 pages, 1568 KiB  
Article
Greenness Assessment and Synthesis for the Bio-Based Production of the Solvent 2,2,5,5-Tetramethyloxolane (TMO)
by Fergal P. Byrne, James H. Clark, Carlo Angelici, Ed de Jong and Thomas J. Farmer
Sustain. Chem. 2021, 2(3), 392-406; https://0-doi-org.brum.beds.ac.uk/10.3390/suschem2030023 - 28 Jul 2021
Cited by 5 | Viewed by 3799
Abstract
2,2,5,5-tetramethyloxolane (TMO) has recently been identified and demonstrated as a safer solvent to replace toluene, THF, and hydrocarbons in a handful of applications. Herein, several bio-based routes to TMO are presented and assessed for greenness, assisted by the CHEM21 Metrics Toolkit and BioLogicTool [...] Read more.
2,2,5,5-tetramethyloxolane (TMO) has recently been identified and demonstrated as a safer solvent to replace toluene, THF, and hydrocarbons in a handful of applications. Herein, several bio-based routes to TMO are presented and assessed for greenness, assisted by the CHEM21 Metrics Toolkit and BioLogicTool plots. Using glucose as a common starting point, two chemocatalytic routes and two biochemical routes to TMO were identified and the pathways compared using the aforementioned tools. In addition, bio-based TMO was synthesised via one of these routes; from methyl levulinate supplied by Avantium, a by-product of the sugar dehydration step during the production of 2,5-furandicarboxylic acid. First, methyl levulinate underwent triple methylation using methyl magnesium chloride (MeMgCl) to yield 2,5-dimethylhexane-2,5-diol (DHL) in high yields of 89.7%. Then DHL was converted to high purity TMO (>98.5%) by cyclodehydration using H-BEA zeolites based on the previously reported approach. Bio-based content of this TMO was confirmed by ASTM D6866-20 Method B and found to have 64% bio-based carbon, well above the threshold of 25% set by CEN/TC 411 standards and matching the anticipated content. This study represents the first demonstration of a bio-based synthesis of TMO and confirmation of bio-content by accepted standards. Full article
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16 pages, 3235 KiB  
Article
Markedly Different Decomposition Temperature and Products of Biomass Pyrolysis at Low Temperature—Differentiation of Acids in Their Effects on Pretreatment
by Peifang Yan, Xiumei Liu, Zhanwei Xu and Zongchao Conrad Zhang
Sustain. Chem. 2021, 2(1), 8-23; https://0-doi-org.brum.beds.ac.uk/10.3390/suschem2010002 - 12 Jan 2021
Cited by 3 | Viewed by 2317
Abstract
Pine as a softwood and poplar as a hardwood pretreated with hydrochloric acid (HCl), phosphoric acid (H3PO4), and hypophosphorous acid (H3PO2) are studied for the pyrolytic properties and products in thermogravimetry (TG) and fixed bed [...] Read more.
Pine as a softwood and poplar as a hardwood pretreated with hydrochloric acid (HCl), phosphoric acid (H3PO4), and hypophosphorous acid (H3PO2) are studied for the pyrolytic properties and products in thermogravimetry (TG) and fixed bed reactor. The pyrolysis performances are pronouncedly distinguished due to the compositional and structural changes induced by the acid pretreatments. Reduction in the mineral content in the biomass feedstocks by pretreatment with the acids results in significant changes in the pyrolytic products. The residual P in the H3PO2-pretreated biomass apparently catalyzed the biomass deeper dehydration in pyrolysis compared to the other two mineral acids. TG analysis shows a shift of the temperature of maximum mass loss (Tmax) by more than 40 °C to lower temperature in the decomposition of the H3PO2-pretreated biomass from that of the untreated and the HCl- and H3PO4-pretreated biomass. Inspired by the striking differences in TG profiles of biomass pretreated by the three acids, thermal pyrolysis of pretreated biomass was carried out in a fixed bed reactor aimed at producing biochemicals at low temperatures (330 °C and 400 °C). The liquid products obtained from the fixed bed reactor show remarkably different major anhydrosugars as a result of pretreatment by the three acids. While phenolics dominate in the collected pyrolysis liquid from untreated biomass samples, biomass pretreated with all three acids results in substantially reduced phenolics in the bio-oils. The reduction in phenolic compounds in the bio-oil may be attributed to the reduction in mineral content in the feedstock. Consequently, the yields of anhydrosugars, mainly levoglucosan (LG) and levoglucosenone (LGO) are increased. LG yields of 20.9–28.5% from the cellulose content are obtained from HCl- and H3PO4-pretreated pine/poplar, with very low LGO yield (less than 1.7%). However, H3PO2-pretreated biomass is selective to produce LGO, especially at 330 °C. LGO yields of 7.4% and 6.7% are obtained from H3PO2-pretreated pine and poplar, respectively. Full article
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11 pages, 5146 KiB  
Article
Enhancing the Oxygen Barrier Properties of Nanocellulose at High Humidity: Numerical and Experimental Assessment
by Ali H. Tayeb, Mehdi Tajvidi and Douglas Bousfield
Sustain. Chem. 2020, 1(3), 198-208; https://0-doi-org.brum.beds.ac.uk/10.3390/suschem1030014 - 24 Sep 2020
Cited by 15 | Viewed by 3597
Abstract
Films formed from cellulose nanofibrils (CNFs) are known to be good barrier materials against oxygen, but they lose this feature once placed in humid conditions. To tackle this issue, we applied an optimized pressing condition under elevated temperature to increase the films’ density [...] Read more.
Films formed from cellulose nanofibrils (CNFs) are known to be good barrier materials against oxygen, but they lose this feature once placed in humid conditions. To tackle this issue, we applied an optimized pressing condition under elevated temperature to increase the films’ density and improve their barrier performance. Furthermore, a water barrier coating was employed on the surfaces to control the moisture uptake at high relative humidity (RH). Neat self-standing films of CNF with the basis weight of 70 g/m2 were made through a filtration technique and pressed for 1 hour at 130 °C. The resulting nanostructures were covered on both sides using a water-borne barrier layer. Hot-pressing resulted in a significant reduction in oxygen transmission rate (OTR) values, from 516.7 to 3.6 (cm3/(m2·day)) and to some degree, helped preserve the reduced oxygen transmission at high relative humidity. Introducing 35 g/m2 of latex coating layer on both sides limited the films’ swelling at 90% RH for about 4 h and maintained the OTR at the same level. A finite element model was used to predict the dynamic uptake of water into the systems. The model was found to over-predict the rate of water uptake for uncoated samples but gave the correct order of magnitude results for samples that were coated. The obtained data confirmed the positive effect of hot-pressing combined with coating to produce a film with low oxygen transmission rate and potential to maintain its oxygen barrier feature at high relative humidity. Full article
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20 pages, 3995 KiB  
Article
Pt-Promoted Tungsten Carbide Nanostructures on Mesoporous Pinewood-Derived Activated Carbon for Catalytic Oxidation of Formaldehyde at Low Temperatures
by Qiangu Yan and Zhiyong Cai
Sustain. Chem. 2020, 1(2), 86-105; https://0-doi-org.brum.beds.ac.uk/10.3390/suschem1020008 - 07 Aug 2020
Cited by 2 | Viewed by 2700
Abstract
Tungsten carbide (WC) nanostructures were prepared by carbothermal reduction (CR) of tungsten-impregnated pinewood-derived activated carbon (AC) at 1000 °C under an inert atmosphere. Brunauer-Emmet-Teller (BET) surface area, pore structures of the AC, and catalyst samples were evaluated by N2 adsorption-desorption experiments. The [...] Read more.
Tungsten carbide (WC) nanostructures were prepared by carbothermal reduction (CR) of tungsten-impregnated pinewood-derived activated carbon (AC) at 1000 °C under an inert atmosphere. Brunauer-Emmet-Teller (BET) surface area, pore structures of the AC, and catalyst samples were evaluated by N2 adsorption-desorption experiments. The structures of the catalysts were characterized using X-ray powder diffraction (XRD). The morphologies and particle structures of the synthesized WC nanoparticles were investigated by field emission scanning electron microscopy (FESEM) and high-resolution transmission electron microscopy (HRTEM). The WC/AC material was used as support of the platinum catalysts for catalytic oxidation of formaldehyde (HCHO) from interior sources. Pt-WC/AC catalysts with different platinum loadings were assessed for the catalytic oxidation of HCHO at low temperature. The catalytic performance was found to be significantly influenced by reaction temperature, initial formaldehyde concentration, relative humidity, and space velocity. The testing results demonstrated that HCHO can be totally oxidized by the 1 wt% Pt-WC/AC catalyst in the gas hourly space velocity (GHSV) = 50,000 h−1 at 30 °C with a relative humidity (RH) of 40%. Full article
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Review

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15 pages, 706 KiB  
Review
Lignocellulosic-Based Sorbents: A Review
by Kaana Asemave, Ligom Thaddeus and Philip T. Tarhemba
Sustain. Chem. 2021, 2(2), 271-285; https://0-doi-org.brum.beds.ac.uk/10.3390/suschem2020016 - 10 Apr 2021
Cited by 15 | Viewed by 3330
Abstract
The combustion of fossil fuels is intensifying global warming and destructing the ecosystem with negative human health impacts as well. Even so, other anthropogenic activities have unfortunately constituted pollution also to our environment, say, in the form of waste waters. Beside these, the [...] Read more.
The combustion of fossil fuels is intensifying global warming and destructing the ecosystem with negative human health impacts as well. Even so, other anthropogenic activities have unfortunately constituted pollution also to our environment, say, in the form of waste waters. Beside these, the existing technologies for waste water treatment have problems such as high costs, sludge disposal challenges, etc. Thus, it is now important to find economically viable and safe alternatives to decontaminate waste waters. Hence, low cost, renewable, easily accessible, and readily prepared biosorbents have become favourable alternatives to traditional counterpart for the elimination of pollutants from aqueous systems. Fortunately, these biosorbents also have requisite and comparable properties necessary for adsorption of pollutants. Many studies have been reported on the application of biosorbents for pollutants removal. However, this paper provides an overview of biosorbents preparation, properties, their applications in pollutants removal and related use. Biosorbents are usually used in raw or processed forms such as activated carbon (AC), biobar (BC), and charcoal (CC) for removal of pharmaceuticals, pesticides, organics, inorganics, mycotoxins, etc. from aqueous systems. Besides classical sorption of the pollutants, biosorbents have prospect of applications as electrodes in the microbial fuel cells, green packaging materials, energy storage devices, catalysts, soil remediation agent, carbon sequestration, etc. Hence, further concerted investigations should be exercised to develop feasibly best conditions for the preparations and modifications of biosorbents. In addition, mean pore size, pore size distribution, porosity, surface functionality, and zeta potential studies are necessary to be had about biosorbents, especially novel types. There is need for development of biosorbents for specific tasks. Another essential thing is to determine desorption studies of these novel biosorbents. Focus should also be directed on more economically viable and sustainable biosorbents to enhance their use. Again, it is suggested that more suitable biomasses be identified to enable successful preparation of efficient biosorbents. More so, biosorbents can be recycled after use to avoid littering and possible pollution. Full article
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16 pages, 6924 KiB  
Review
Electrochemical Degradation of Lignin by ROS
by Haomin Jiang, Aiguo Xue, Zhaohui Wang, Ruyue Xia, Lei Wang, Yang Tang, Pingyu Wan and Yongmei Chen
Sustain. Chem. 2020, 1(3), 345-360; https://0-doi-org.brum.beds.ac.uk/10.3390/suschem1030023 - 12 Dec 2020
Cited by 9 | Viewed by 3927
Abstract
Lignin is a unique renewable aromatic resource in nature. In the past decades, researchers have attempted to breakdown the linkage bonds in lignin to provide aromatic platform chemicals that used to come from the petrochemical industry. In recent years, electrochemical lignin degradation under [...] Read more.
Lignin is a unique renewable aromatic resource in nature. In the past decades, researchers have attempted to breakdown the linkage bonds in lignin to provide aromatic platform chemicals that used to come from the petrochemical industry. In recent years, electrochemical lignin degradation under mild conditions has drawn much attention from the scientific community owing to its potential to scale up and its environmental friendliness. Sustainable electrochemical degradation of lignin consumes less energy and usually requires mild conditions, but low degradation efficiency and insufficient product selectivity are still significant challenges. The method for lignin degradation by reactive oxygen species (ROS) generated through the water oxidation reaction (WOR) at the anode and oxygen reduction reaction (ORR) at the cathode are more attractive for sustainable electrochemical degradation. The present contribution aims to review advancements in electrochemical degradation of lignin in aqueous or non-aqueous supporting electrolytes, focusing on the regulation of ROS in situ generated on the electrode. Full article
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19 pages, 1648 KiB  
Review
A Review of Cottonseed Protein Chemistry and Non-Food Applications
by H. N. Cheng, Zhongqi He, Catrina Ford, Wade Wyckoff and Qinglin Wu
Sustain. Chem. 2020, 1(3), 256-274; https://0-doi-org.brum.beds.ac.uk/10.3390/suschem1030017 - 05 Oct 2020
Cited by 25 | Viewed by 4739
Abstract
There has been increasing interest in recent years in the use of agro-based raw materials for the production of bio-friendly and sustainable products. Plant-based proteins are among the popular materials being studied. In particular, cottonseed protein (a byproduct of cotton fiber production) is [...] Read more.
There has been increasing interest in recent years in the use of agro-based raw materials for the production of bio-friendly and sustainable products. Plant-based proteins are among the popular materials being studied. In particular, cottonseed protein (a byproduct of cotton fiber production) is widely available and has useful properties. Although not as well-known as soy protein, cottonseed protein has been shown to be a potentially valuable raw material for numerous applications. In this review, the latest developments in isolation, composition and molecular weight, chemical and enzymatic modifications, and non-food applications are delineated. Among these applications, films and coatings, interfacial and emulsifying applications, adhesives, and bioplastics seem to attract the most attention. A particular effort has been made to cover the literature on these topics in the past 10 years. Full article
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Other

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10 pages, 4120 KiB  
Technical Note
Three-Dimensional Imaging of Plant Cell Wall Deconstruction Using Fluorescence Confocal Microscopy
by Aya Zoghlami, Yassin Refahi, Christine Terryn and Gabriel Paës
Sustain. Chem. 2020, 1(2), 75-85; https://0-doi-org.brum.beds.ac.uk/10.3390/suschem1020007 - 30 Jul 2020
Viewed by 2783
Abstract
Lignocellulosic biomass (LB) is recalcitrant to enzymatic hydrolysis due to its compact and complex cell wall structure. To identify the parameters behind LB recalcitrance, experimental data over hydrolysis time must be collected. Here, we describe a novel method to collect time-lapse images during [...] Read more.
Lignocellulosic biomass (LB) is recalcitrant to enzymatic hydrolysis due to its compact and complex cell wall structure. To identify the parameters behind LB recalcitrance, experimental data over hydrolysis time must be collected. Here, we describe a novel method to collect time-lapse images during cell wall deconstruction by enzymatic hydrolysis. The protocol includes instructions for sample preparation, layout of a custom designed incubation chamber and instructions for confocal time lapse acquisition. The protocol sets out a detailed plan where cross-sections of untreated and pretreated poplar samples are mounted in a sealed frame containing a buffer and an enzymatic cocktail. The sealed frame is then placed into an incubator to maintain the sample at a constant temperature of 50 °C, which is optimal for enzymatic reaction while avoiding enzymatic cocktail evaporation. Using lignin natural autofluorescence, confocal z-stacks of untreated and pretreated samples were acquired at regular time intervals during enzymatic hydrolysis for 24 h. Acquisition parameters were optimized to compromise between image resolution and reduced photo-bleaching. The acquired image might then be processed by further development of algorithms to extract precise quantitative information on cell wall deconstruction. This protocol is an important first step towards elucidating the underlying parameters of LB recalcitrance by allowing the acquisition of high-quality images of LB hydrolysis for extracting quantitative data on LB deconstruction. Full article
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