The large availability of Kraft lignin as an industrial by-product and its polyaromatic characteristic, is ideal to consider the potential for recycling it into fine chemicals. To depolymerise lignin, solvolysis and hydrogenolysis experiments were performed. This research considered whether the low yields of products (fine chemicals) were related to the low content of β-O-4 bonds or if it was also associated to the dissolution of lignin in the solvent solution employed in the reactions. The type of solvents chosen to check the dissolution effect were those with low cost and were more sustainable than traditional solvents. Water, ethanol, isopropanol (IPA) and acetone were used. The water mixtures were applied in the tests in various proportions (25:75, 50:50, 75:25 solvent/water v:v). Due to their ability to break C-C and C-O bonds in lignin model compounds [1][2], the efficiency of platinum and rhodium in these reactions supported on alumina was also studied. It was found that the non-catalysed (solvolysis) and catalysed reactions showed different selectivities but similar overall yields ~ 10 % wt of monomeric phenols. The difficulty in increasing yields was mainly associated with the highly condensed character of Kraft lignin and re-polymerisation issues. To achieve an understanding of Kraft lignin depolymerisation, isotopic labelling reactions were completed in the presence of deuterated solvents as well as deuterium gas. This gave information on how Kraft lignin depolymerises, the influence of solvent to products formation and the involvement of hydrogen in the rate determining steps in the reactions. These results have led to an initial mechanistic understanding on how this complex molecule may yield alky-phenolic compounds. It was revealed that the solvent was directly involved in the products’ formation and that they were not generated by simple thermolysis. In addition, the presence of catalysts and hydrogen influenced product formation. The compounds showed different kinetic isotopic values, suggesting that each of these molecules came from individual mechanisms, highlighting the complexity of their formation. This was a relevant study as most of lignin depolymerisation mechanistic insights are based on model compounds and not on lignin itself. It was of interest to this project to explore not only different catalysts and their relationship to lignin depolymerisation, but also different lignin types. A simple pre-treatment for lignin extraction using sawdust (from oak and birch wood) in a Parr autoclave reactor in the presence of hydrogen, solvent and high temperature was developed. The lignins obtained after the pre-treatment were named parr-lignin and successfully resulted in polyaromatic molecules with less condensed character compared to lignins from Soda or Kraft pulping. Reactions were carried out with these lignins and a sugar-cane lignin.
Different catalytic systems with these lignins were investigated and how depolymerisation was affected by the metal and support used. The catalysts involved in the reactions included platinum, rhodium, nickel and iron. Various supports such as alumina, zirconia and carbon were tested along with the metals described. It was found that the supports were not inert in these experiments presenting catalytic activity. Materials with low surface area (zirconium catalysts) gave a poor performance compared to the others. In addition, nickel, a non-noble metal, showed as good a catalytic effect in the depolymerisation of these lignins as Pt and Rh. The components in the system influenced the reactions to different extents, especially product distribution. The catalysts had different selectivities and the solvents were not only dissolving lignin but also influencing the results. GPC analysis was performed to give an overview of the condensed level of these lignins and degrees of depolymerisation compared to the original material. GC-MS enabled the identification and quantification of 18 monomeric compounds. The post reaction characterisation of selected alumina catalysts (Pt/Al2O3, Ni/Al2O3 and Al2O3) was performed using XRD, BET, CHN, TPO and Raman Analysis to study the nature of the carbonaceous layer deposited on these materials. The work showed that after reaction the catalysts turned black in colour and the carbon laydown consisted of not only one simple type of carbon, and included graphitic species. The amount of carbon deposited depended on the type of lignin. Oak and birch parr-lignins had the highest and lowest amount of carbon over the catalysts respectively. No obvious trend relating to the type of catalyst, lignin and solvent used to the carbon nature was identified. This work showed that lignins with less condensed nature were less susceptible to solvolysis and more to hydrogenolysis. For example, sugar-cane lignin gave 3.9% of phenolic compounds in the solvolysis while reaction with Rh/Al2O3 gave 12.9% of products. This indicated that more selective cleavage of bonds were promoted by heterogenous catalysts. The results suggested that some compounds were mainly generated via dealkylation and hydrodeoxygenation, allowing a future possibility to generate target molecules. These results were mainly due to the presence of more labile bonds, vulnerable to hydrogenolysis. Highlighting that prior to depolymerisation, the pre-treatment used to extract lignin must be appropriate to avoid depletion of the alkyl-aryl ether bonds (β-O-4 bonds, especially) relevant for fine chemicals generation.
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Qualification Level: | Doctoral | ||||||||||||||||||||||||||||||||||||||||||||||||||||||
Additional Information: | Supported by: Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) (scholarship) and financed by CNPq, Ministério da Ciência, Tecnologia, Inovações e Comunicações, Brazil. | ||||||||||||||||||||||||||||||||||||||||||||||||||||||
Keywords: | Lignin, depolymerisation, hydrogenolysis. | ||||||||||||||||||||||||||||||||||||||||||||||||||||||
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Supervisor's Name: | Jackson, Professor Samuel David | ||||||||||||||||||||||||||||||||||||||||||||||||||||||
Date of Award: | 2018 | ||||||||||||||||||||||||||||||||||||||||||||||||||||||
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Copyright: | Copyright of this thesis is held by the author. | ||||||||||||||||||||||||||||||||||||||||||||||||||||||
Date Deposited: | 08 Oct 2018 12:45 | ||||||||||||||||||||||||||||||||||||||||||||||||||||||
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(2022) Doctoral (PhD) thesis, Memorial University of Newfoundland.
Lignin is a complex biopolymer abundantly found in all vascular plants. It plays a key role in building connective tissues and giving them strength, rigidity, and resistance to environmental factors such as pathogens. Extracted lignin finds diverse applications in the commercial sector with immense potential in novel value-added applications. Therefore, it is important to develop optimum and sustainable processes for lignin extraction. To this end, one of the aims of the present research was to examine different lignin extraction methods on common wood species present in Newfoundland, Canada – balsam fir, pine, spruce (softwood), birch, maple, and oak (hardwood). Two different lignin extraction methods were studied: (1) the Formacell method, which uses acetic acid/formic acid/water; and (2) the BioEB method, which uses only formic acid/water. Various parameters were tested, including solvent concentration, temperature, cooking time, to determine the most optimal lignin extraction conditions. The results of this study can be applied to inform and improve industrial lignin extraction processes to obtain better yields in the most optimal manner. This thesis also discusses the latest developments in value-added uses of extracted lignin for the preparation of novel bio-based materials. Lastly, it provides a review of the mechanisms of microbial biodegradation of lignin. These microbial ligninolytic mechanisms provide a host of possibilities to overcome the challenges of using harmful chemicals to degrade lignin biowaste in many industries.
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Microwave-Assisted Treatments of Biomass: Lignin Isolation from Lignocellulose and Natural Products Recovery from Bilberry Presscake--> zhou, long (2018) Microwave-Assisted Treatments of Biomass: Lignin Isolation from Lignocellulose and Natural Products Recovery from Bilberry Presscake. PhD thesis, University of York. Abstract Microwave thermal treatment has generated an increasing interest in biomass valorisation. In this research, softwood, hardwood and straw are processed by microwave-assisted acidolysis, producing high quality residual lignin without significant modification, especially softwood (purity 93%, yield 82%). Under equivalent conditions, microwave treatment produces lignin with higher yield and purity than conventional treatment. The aqueous hydrolysate is fermented by two oleaginous yeasts, Cryptococcus curvatus and Metschnikowia pulcherrima. Both yeasts could grow on the hydrolysate and produce an oil with similar properties to palm oil. This preliminary work demonstrates new protocols of microwave-assisted acidolysis and therefore offers an effective approach to produce high purity lignin and fermentable chemicals, which is a key step towards developing a zero-waste lignocellulosic biorefinery. In addition, microwave conversions (lab and pilot scale) of bilberry presscake, aiming to fulfill multiple chemicals recovery, were carried out using only water as the solvent, ensuring all products are suitable for food grade status applications. Microwave hydrolysis gives much higher yield of mono-/disaccharides than conventional extraction, with the yield of rhamnose particularly high (10.8%). Pilot scale microwave conversions are also carried out with high conversion. It is believed microwave hydrolysis offers an efficient and green approach to convert bilberry presscake into value-added products for food industry and biorefinery.
--> Examined Thesis (PDF) -->Filename: thesis Long Zhou edited.pdf Embargo Date: You do not need to contact us to get a copy of this thesis. Please use the 'Download' link(s) above to get a copy. You can contact us about this thesis . If you need to make a general enquiry, please see the Contact us page. Green ChemistryA sustainable approach for lignin valorization by heterogeneous photocatalysis. * Corresponding authors a State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, P. R. China E-mail: [email protected] b College of Chemistry, New Campus, Fuzhou University, Fuzhou, P. R. China c Institute of Physical Chemistry of the Polish Academy of Sciences, ul. Kasprzaka 44/52, 01-224, Warsaw, Poland E-mail: [email protected] The depletion of the Earth's fossil fuel reserves and the rapid increase in the emission of greenhouse gases and other environmental pollutants are driving the development of renewable energy technologies. Lignin is one of the three main subcomponents of lignocellulosic biomass in terrestrial ecosystems and makes up nearly 30% of the organic carbon sequestered in the biosphere. As a result of its rich content of aromatic carbon, lignin has the potential to be decomposed to yield valuable chemicals and alternatives to fossil fuels. However, the complex and stable chemical bonds of lignin make the depolymerization of lignin a difficult challenge with regard to its valorization. In this review, we highlight recent advances in the selective decomposition of lignin-based compounds via photocatalysis into other value-added chemicals and the treatment of waste water containing lignin. The photocatalytic transformation of lignin under mild conditions is particularly promising. Article informationDownload citation, permissions. S. Li, S. Liu, J. C. Colmenares and Y. Xu, Green Chem. , 2016, 18 , 594 DOI: 10.1039/C5GC02109J To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page . If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given. If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page . Read more about how to correctly acknowledge RSC content . Social activitySearch articles by author, advertisements. Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.
A strong, biodegradable and recyclable lignocellulosic bioplastic
Nature Sustainability volume 4 , pages 627–635 ( 2021 ) Cite this article 19k Accesses 208 Altmetric Metrics details
An Author Correction to this article was published on 20 August 2021 Renewable and biodegradable materials derived from biomass are attractive candidates to replace non-biodegradable petrochemical plastics. However, the mechanical performance and wet stability of biomass are generally insufficient for practical applications. Herein, we report a facile in situ lignin regeneration strategy to synthesize a high-performance bioplastic from lignocellulosic resources (for example, wood). In this process, the porous matrix of natural wood is deconstructed to form a homogeneous cellulose–lignin slurry that features nanoscale entanglement and hydrogen bonding between the regenerated lignin and cellulose micro/nanofibrils. The resulting lignocellulosic bioplastic shows high mechanical strength, excellent water stability, ultraviolet-light resistance and improved thermal stability. Furthermore, the lignocellulosic bioplastic has a lower environmental impact as it can be easily recycled or safely biodegraded in the natural environment. This in situ lignin regeneration strategy involving only green and recyclable chemicals provides a promising route to producing strong, biodegradable and sustainable lignocellulosic bioplastic as a promising alternative to petrochemical plastics. This is a preview of subscription content, access via your institution Access optionsAccess Nature and 54 other Nature Portfolio journals Get Nature+, our best-value online-access subscription 24,99 € / 30 days cancel any time Subscribe to this journal Receive 12 digital issues and online access to articles 111,21 € per year only 9,27 € per issue Buy this article
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Catal. 1 , 772–780 (2018). Fraile, JoséM., Zoel Hormigón, J. I. G., Mayoral, J. A., Saavedra, C. J., & Salvatella, L. Role of substituents in the solid acid-catalyzed cleavage of the β-O-4 linkage in lignin models. ACS Sustain. Chem. Eng. 6 , 1837–1847 (2018). Sanderson, K. Lignocellulose: a chewy problem. Nature 474 , S12–S14 (2011). Jung, Y. H. et al. High-performance green flexible electronics based on biodegradable cellulose nanofibril paper. Nat. Commun. 6 , 7170 (2015). Ashter, S. A. in Thermoforming of Single and Multilayer Laminates Ch. 10 (William Andrew, 2013). Download references AcknowledgementsWe acknowledge the support of the Maryland Nanocenter, its Surface Analysis Center and AIMLab. We acknowledge J. Gao for his experimental suggestions. Author informationThese authors contributed equally: Qinqin Xia, Chaoji Chen. Authors and AffiliationsDepartment of Materials Science and Engineering, University of Maryland, College Park, MD, USA Qinqin Xia, Chaoji Chen, Yonggang Yao, Jianguo Li, Shuaiming He, Yubing Zhou & Liangbing Hu Department of Mechanical Engineering, University of Maryland, College Park, MD, USA Department of Biological Systems Engineering, University of Wisconsin-Madison, Madison, WI, USA Yale School of the Environment, Yale University, New Haven, CT, USA Center for Materials Innovation, University of Maryland, College Park, MD, USA Liangbing Hu You can also search for this author in PubMed Google Scholar ContributionsL.H., Q.X. and C.C. designed the experiments. Q.X. carried out experiments. Y.G.Y. and S.H. analysed the mechanical data. Y.Z. helped with the preparation of the large-scale bioplastic film. Q.X. and J.L. fabricated the lignocellulosic bioplastic parts by compression moulding. T.L. and X.P. provided some useful suggestions. Y.Y. provided the LCAs. L.H., Q.X. and C.C. collaboratively analysed the data and wrote the paper. All authors commented on the final manuscript. Corresponding authorsCorrespondence to Yuan Yao or Liangbing Hu . Ethics declarationsCompeting interests. The authors declare no competing interests. Additional informationPeer review information Nature Sustainability thanks Robert Allen, Eun Yeol Lee and Tong-Qi Yuan for their contribution to the peer review of this work. Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. Extended dataExtended data fig. 1 the fabrication mechanism of the lignocellulosic bioplastic.. Loose and porous wood powder, composed of cellulose, lignin and hemicellulose, serves as the starting material. After DES (ChCl/oxalic acid) treatment, the cellulose fibres are fibrillated into micro/nanofibrils while DES dissolves the lignin. Water can interact with the hydrophobic DES through hydrogen bonding interactions. Thus, water can be added as a green antisolvent in the system, causing the hydrophobic lignin to regenerate. After filtering, we obtain a cellulose–lignin slurry, the solid content of which we can control by varying the water content. The lignocellulosic bioplastic film can then be obtained by casting the slurry at room temperature. Extended Data Fig. 2 The structure of the wood powder.a-d , Photograph ( a ), SEM image ( b ), magnified SEM image ( c ) and SAXS pattern ( d ) of the wood powder. Compared to the isotropic structure of lignocellulosic bioplastic, the wood powder shows more structural inhomogeneity. Extended Data Fig. 3 The tensile strength and fracture surfaces of the lignocellulosic bioplastic.a , The tensile stress-strain curves of the cellulose film and lignocellulosic bioplastic. b , The strength and toughness of the cellulose film and lignocellulosic bioplastic. The lignocellulosic bioplastic demonstrates excellent mechanical properties with a high tensile strength of 128 MPa and toughness of 2.8 MJ·m 3 , which are 7- and 8-times higher than cellulose film (18 MPa and 0.35 MJ·m 3 ), respectively. c-d , Digital and SEM images of the fracture surfaces of the ( c ) lignocellulosic bioplastic and ( d ) cellulose film after tensile testing. The samples have ~1 wt.% water content. The cellulose film fractured by macro-fibre slippage from the loose fibre network structure, in which most fibres were not broken, indicating the binding strength between the cellulose fibres in the film is weaker than the strength of the fibres themselves. In contrast, broken fibres appear in the fracture zone of the lignocellulosic bioplastic, suggesting its binding strength is greater than the strength of its constituent fibres due to the intertwining cellulose micro/nanofibrils and lignin network. Such entangled interaction between the micro/nanofibrils and high adhesion mediated by the in situ regenerated lignin matrix with abundant hydrogen bonding and van der Waals forces contribute to the outstanding mechanical properties of the lignocellulosic bioplastic. Extended Data Fig. 4 The excellent mechanical strength of the lignocellulosic bioplastic.a , Photographs of the lignocellulosic bioplastic (8 cm×3.5 cm×0.1 cm), b , including under a heavy load (200 g). c-d , The excellent foldability of the lignocellulosic bioplastic. e , The unfolded lignocellulosic bioplastic features a sharp crease. f , Photograph of the unfolded lignocellulosic bioplastic bearing a heavy load (200 g). Although the lignocellulosic bioplastic had undergone folding, the creased material can still easily bear the applied weight without failing. Extended Data Fig. 5 The water stability of the lignocellulosic bioplastic.a . Photographs of water droplets on the cellulose film and lignocellulosic bioplastic surfaces over time (0–10 min). The lignocellulosic bioplastic has a higher water contact angle (90.0 ± 8°) than that of pure cellulose film (78.7 ± 10°), demonstrating its slightly greater tendency to repel water. After 10 minutes, the water droplet gradually spreads out and adheres to the cellulose film (28.2 ± 6°), whereas the shape of the droplet on the lignocellulosic bioplastic surface remains relatively stable (71.8 ± 7°). b , Water absorption of the cellulose film and lignocellulosic bioplastic over 140 min. The inset shows photographs of water droplets on a sloping lignocellulosic bioplastic surface (right), demonstrating the material’s excellent water stability, while the water is quickly absorbed on the cellulose film (left). The lignocellulosic bioplastic has exceptionally lower water absorption (~30%) than that of the cellulose film (~100%). In contrast, water droplets easily permeate into the hydrophilic cellulose film even on inclined surfaces. c , Water stability test of cellulose film and lignocellulosic bioplastic in water for 30 days. The cellulose film disintegrates while the lignocellulosic bioplastic film maintains its shape. We immersed the cellulose film and lignocellulosic bioplastic in water for thirty days. After this time, we found the cellulose film completely disintegrated into microfibers, while the lignocellulosic bioplastic showed good stability in the wet environment, retaining its shape without any fractures. Extended Data Fig. 6 The degradability tests of the lignocellulosic bioplastic and PVC materials.Direct outdoor exposure was carried out to evaluate the degradability of the lignocellulosic bioplastic, which was placed on grass and exposed to the sun, wind and rain (College Park, Maryland, U.S., from October 20, 2019 to March 10, 2020). After three months, the dimensions of the lignocellulosic bioplastic increased as it became more swollen. After ~4 months, the lignocellulosic bioplastic became cracked and fragmented and its original structure completely degraded after five months. Meanwhile, the PVC remained almost the same as on the first day, demonstrating it cannot be degraded under natural conditions. Extended Data Fig. 7 Flow diagram for continuous in situ lignin regeneration treatment and the recycling of the DES.After mixing and heating of the wood powder and DES, followed by the addition of water to in situ regenerate the lignin, we can use an in-line filter to separate the cellulose–lignin slurry and solvent, in which the DES and water make up the filter liquor. DES can then be purified by heating the mixture to remove water. The recovered DES can be recycled in the system to treat new lignocellulosic starting materials. Water can also be collected using a condenser and recycled again to serve as the antisolvent for lignin regeneration. Extended Data Fig. 8 The universality of in situ lignin regeneration approach.The lignocellulosic bioplastic can be derived from various lignocellulosic biomass sources, including wood, wheat straw, grass and bagasse, demonstrating the strong universality of this approach. Extended Data Fig. 9 The life cycle impact assessment results of lignocellulosic and other biodegradable plastics per cm 3 /MPa.Across most environmental impact categories, the lignocellulosic bioplastic developed in this work is more environmentally favourable than PHA, PLA, PBS, PCL and PBAT. There are a few exceptions. Compared with PBAT, the lignocellulosic bioplastic has higher impacts in three categories, including eutrophication, human health - carcinogenics and respiratory effects. For all three categories, the impacts of lignocellulosic bioplastics are driven by electricity consumption, which accounted for 71–86% of the results based on the contribution analysis. The electricity was assumed to be the U.S. average grid in this study. The environmental impacts could be lower if renewable energy were used. To estimate the impacts of using renewable energy, a scenario using electricity generated from wind was evaluated and the results are shown in Extended Data Fig. 9 as triangles. The Life Cycle Inventory (LCI) of wind energy was obtained from Ecoinvent database for onshore generation in the U.S. The environmental impacts of the lignocellulosic bioplastic using wind energy are the lowest across all the impact categories except fossil fuel depletion (close to the upper bounds of the results of PLA and PBAT). Extended Data Fig. 10 Environmental impacts of the moulded lignocellulosic bioplastic compared to PP, PET and ABS.Compared to PP and ABS, the lignocellulosic bioplastic is at the lower end across all environmental impact categories. Compared to PET, the lignocellulosic bioplastic has lower environmental impacts in categories such as ecotoxicity, eutrophication and human health. For other categories, the lignocellulosic bioplastic has comparable results with PET and close to the higher bounds of PET’s impacts in ozone depletion, smog formation and fossil fuel depletion. Similar to the LCAs for plastic films, we included a renewable energy scenario to investigate the impacts of using wind and the results are shown as triangles (Extended Data Fig. 10 ). Compared with PP, PET and ABS, the environmental impacts of the lignocellulosic bioplastic using wind energy were the lowest across all the impact categories, except for fossil fuel depletion (which was close to the upper bound of PET’s results). Supplementary informationSupplementary information. Supplementary Notes 1–8, Figs. 1–19, Tables 1–3 and refs. 1–60. Rights and permissionsReprints and permissions About this articleCite this article. Xia, Q., Chen, C., Yao, Y. et al. A strong, biodegradable and recyclable lignocellulosic bioplastic. Nat Sustain 4 , 627–635 (2021). https://doi.org/10.1038/s41893-021-00702-w Download citation Received : 29 September 2020 Accepted : 19 February 2021 Published : 25 March 2021 Issue Date : July 2021 DOI : https://doi.org/10.1038/s41893-021-00702-w Share this articleAnyone you share the following link with will be able to read this content: Sorry, a shareable link is not currently available for this article. 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A review on lignin structure, pretreatments, fermentation reactions and biorefinery potentialAffiliations.
In recent years, lignin valorization is commercially an important and advanced sustainable process for lignocellulosic biomass-based industries, primarily through the depolymerization path. The conversion of the lignin moieties into biofuels and other high value-added products are still challenging to the researchers due to the heterogeneity and complex structure of lignin-containing biomass. Besides, the involvement of different microorganisms that carries varying metabolic and enzymatic complex systems towards degradation and conversion of the lignin moieties also discussed. These microorganisms are frequently short of the traits which are obligatory for the industrial application to achieve maximum yields and productivity. This review mainly focuses on the current progress and developments in the pretreatment routes for enhancing lignin degradation and also assesses the liquid and gaseous biofuel production by fermentation, gasification and hybrid technologies along with the biorefinery schemes which involves the synthesis of high value-added chemicals, biochar and other valuable products. Keywords: Biofuel; Biorefinery; Hybrid–conversion; Lignin; Lignocellulosic biomass; Sustainability. Copyright © 2018 Elsevier Ltd. All rights reserved. PubMed Disclaimer Similar articles
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PhD offer: Study of the pyrolysis of lignins extracted from black liquors (M/F)Job InformationOffer description. This thesis will take place at the University of Lorraine (UL) at the Reaction and Process Engineering Laboratory (LRGP – UMR CNRS 7274) in Nancy (54000, France). The subject of this thesis concerns the precipitation step of lignin present in black liquors assisted by CO2 coupled with a conversion by pyrolysis to produce molecules of interest (phenols). One of the technological issue associated with the lignin pyrolysis is the agglomeration and clogging of the reactors. Indeed, during pyrolysis, the lignins form a sticky reactive intermediate material converted into char and liquid products (bio-oils) generated in the form of aerosols or vapors condensed in pyrolysis units. The scientific challenge of lignin pyrolysis is to control the composition of the liquids (monomers, suitable oligomers) and the structure of the char (biochar) produced. The objectives of this doctorate are: - ) to optimize the lignin precipitation step from black liquors from the DREAM project in a semi-continuous reactor: study of the effect of temperature, pressure, pH. Characterize the products obtained (GC, LC, NMR, IR, thermal analyses, etc.) -) study the pyrolysis of lignins obtained in a fluidized bed reactor (and others): flow rates, temperatures, fluidization behavior of the bed depending on the lignins. Hydrodynamic study by in-situ visualization of the reactor. Characterization of the products obtained (GC, LC, NMR, IR, thermal analyses, etc.). The development of alternative biosourced processes is one of the major challenges of a sustainable economy concerned with preserving the environment. In pulp mills (from wood raw material to pulp), cellulose (fibers) are separated from lignin, hemicellulose and inorganic molecules. Around 100 million tonnes of wood are recovered for a production of 85 million tonnes of pulp in Europe (2022 data, including the use of recycled paper – 185 million tonnes worldwide, 7 million tonnes in France). The most used process is the Kraft process (90% of world production) which involves the treatment (digestion) of wood fibers in an aqueous solution called white liquor containing sodium hydroxide and sodium sulphide. Thus, black liquors (BL) are a waste stream from the Kraft process obtained after delignification of the biomass (wood) during the digestion operation. With more than 500 million tonnes/year of BL generated worldwide, the treatment and recovery of BL is an important industrial and environmental issue. Currently, BLs are concentrated by multiple evaporator systems and are then burned to regenerate inorganic materials and recover heat necessary for the Kraft process. Since evaporation systems have a fixed capacity, they currently constitute a bottleneck compared to a potential increase in production within factories using the Kraft process. In fact, these factories cannot produce more paper pulp without taking the risk of not being able to regenerate all of the by-products formed. Thus, the exploration of alternative processes for a portion of the BL produced could benefit pulp mills by reducing CO2 emissions and producing a wide variety of biosourced compounds: lignin, phenolic compounds, aromatics, acids. In the medium term, these pulp mills have the potential to transform into integrated forest biorefineries, producing a wide range of bio-sourced products. Numerous valorization strategies have been explored to extract/separate the compounds of interest (membrane filtration, liquid-liquid extraction, decantation, distillation) or to transform BL directly into energy (gasification, pyrolysis, hydrothermal treatment). It is in this context of need for development that the EIC Pathfinder DREAM project (processing complex matrices: Description, REAction-separation, Modelling) financed by the European Council takes place. The DREAM project aims to contribute to major scientific advances in the study of complex matrices (black liquor as a case study) with potentially future “on-site” industrial development. Several separation/extraction routes are studied in the DREAM project (membrane separation, precipitation, membrane filtration) followed by several transformation/purification routes (Reactive distillation, thermochemical processes). Where to applyRequirements, additional information. https://cordis.europa.eu/project/id/101130523 Work Location(s)Share this page. |
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Lignin as a renewable aromatic resource for the chemical industry 195 pages PhD Thesis, Wageningen University, Wageningen, NL (2011) With propositions, and summaries in English and Dutch ISBN: 978-94-6173-100-5
3 Catalytic Upgrading of Lignin from Biomass by Michael L. Stone Submitted to the Department of Chemical Engineering on June 17, 2021 in partial fulfillment of the requirements for the degree of
Moreover, there are technical limitations to studying lignin formation: for example, the ability to detect crucial intermediate metabolites in the pathway such as 5-hydroxylated derivatives and CoA thioesters (R. Jaini, PhD thesis, Purdue University, 2017).
A thesis submitted to the School of Graduate Studies in partial fulfillment of the requirements for the degree of ... Faculty of Science Memorial University of Newfoundland St. John's, Newfoundland and Labrador . ii Abstract Lignin is a complex biopolymer abundantly found in all vascular plants. It plays a key role in building connective ...
The results presented in this thesis are expected to contribute - together with the many on-going activities worldwide - to the increased commercial utilisation of lignin in the future. Moreover, the obtained results contribute to the increasing knowledge on lignin analysis, chemistry and reactivity.
The first part of the thesis includes the elucidation of reaction kinetics and networks of a promising lignin depolymerization methodology previously developed.
de Albuquerque Fragoso, Danielle Munick (2018) Lignin conversion to fine chemicals. PhD thesis, University of Glasgow.
As an abundant aromatic biopolymer, lignin has the potential to produce various chemicals, biofuels of interest through biorefinery activities and is expected to benefit the future circular economy. However, lignin valorization is hindered by a series of constraints such as heterogeneous polymeric nature, intrinsic recalcitrance, strong smell ...
The results of this study can be applied to inform and improve industrial lignin extraction processes to obtain better yields in the most optimal manner. This thesis also discusses the latest developments in value-added uses of extracted lignin for the preparation of novel bio-based materials.
Despite the recent interest in lignin valorization from industry and researchers, this natural polymer is far from being fully exploited due to several limitations. The overall scope of this PhD Thesis is to address some of the challenges in lignin employment and to find new applications for this underutilized material.
zhou, long (2018) Microwave-Assisted Treatments of Biomass: Lignin Isolation from Lignocellulose and Natural Products Recovery from Bilberry Presscake. PhD thesis, University of York.
A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY in The Faculty of Graduate and Postdoctoral Studies (Chemical and Biological Engineering) ... lignin derivatives, mainly for synthesis of organic chemicals. This environmentally benign process
Lignin-degrading bacterial isolates from these environments and their phylogenetic characterization and ligninolytic enzyme activity analysis revealed varying utilization of oxidative enzymes by different isolates.
PhD Thesis MODIFIED LIGNIN AS FLAME RETARDANT FOR POLYMERIC MATERIALS PhD defended at UNIVERSITE LILLE1 SCIENCES ET TECHNOLOGIES ... work with them and to pass my PhD thesis in the R2Fire lab. Working with them was a great pleasure throughout these three years, on both the PhD thesis and the PHOENIX project. Their
PhD Thesis. Biomass properties and enzyme-lignin interactions in the enzymatic cellulose degradation of hydrothermally pretreated lignocellulosic grass feedstocks
However, the complex and stable chemical bonds of lignin make the depolymerization of lignin a difficult challenge with regard to its valorization. In this review, we highlight recent advances in the selective decomposition of lignin-based compounds via photocatalysis into other value-added chemicals and the treatment of waste water containing ...
In Chapter 6 the potential of lignin to become a resource for biobased materials. (wood adhesives) and biobased aromatic chemicals for the future chemical industry is. described and this chapter ...
The currently trend have shown that technical lignin sources may also be used as feedstock for phenol derived products, technical carbons, fuels, and adhesives. On the other hand, there are some ...
This in situ lignin regeneration strategy involving only green and recyclable chemicals provides a promising route to producing strong, biodegradable and sustainable lignocellulosic bioplastic as ...
This review mainly focuses on the current progress and developments in the pretreatment routes for enhancing lignin degradation and also assesses the liquid and gaseous biofuel production by fermentation, gasification and hybrid technologies along with the biorefinery schemes which involves the synthesis of high value-added chemicals, biochar ...
PhD Thesis, Wageningen University, Wageningen, NL (2011) ... lignin occurring in plant cell walls is commonly closely associated with polysaccharide structures of cellulose and hemicellulose ...
Biopolymers are promising materials for the production of CRFs, as they are biodegradable, biocompatible, and they contribute to improving of the soil quality. Lignin is a biopolymer found in the plant cell wall, together with cellulose and hemicellulose, presenting a cross-linked aromatic structure.2 This plant-derived polymer is a byproduct of the paper and pulp industry, produced in huge ...
Offer Description. This thesis will take place at the University of Lorraine (UL) at the Reaction and Process Engineering Laboratory (LRGP - UMR CNRS 7274) in Nancy (54000, France). The subject of this thesis concerns the precipitation step of lignin present in black liquors assisted by CO2 coupled with a conversion by pyrolysis to produce ...