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Lignin as a renewable aromatic resource for the chemical industry

  • Biobased Chemistry and Technology

Research output : Thesis › internal PhD, WU

Valorization of lignin plays a key role in the further development of lignocellulosic biorefinery processes for biofuels and biobased materials production. Today’s increased demand for alternatives to fossil carbon-based products expands the interest and the need to create added value to the unconverted lignin fraction. The aim of the research was to study the potential of lignin to become a renewable aromatic resource for the chemical industry. Lignin can be considered as an abundantly available and cheap raw material for the manufacturing of an array of products. Development of applications needs to go hand in hand with the anticipated increased production of technical lignins derived from the pulp and paper industry and the emerging lignocellulosic biorefinery industry. Two promising lignin applications are studied in this thesis:

1)         the use of lignin in wood adhesives

2)         the use of lignin for the production of aromatic chemicals

PCA modeling was performed aimed at the prediction of the application potential of different technical lignins for wood adhesive production. The lignins and their fractions could be classified in different clusters based on their structure dependent properties. Lignins exhibiting sufficient reactive sites, medium molar mass and low level of impurities are most promising candidates for the development of lignin based wood adhesives. Both lignin reactivity and formaldehyde-free crosslinking agents are needed to develop emission-free adhesives. Periodate oxidation was studied as method to improve the lignin reactivity. Alternatives to formaldehyde- based glues are under investigation and a combination of lignin and furans might be an interesting concept to develop renewable adhesives. 

In this research a reliable SEC methodology was developed for the analysis of the molar mass distribution of a wide range of different lignins. The major drawback of this method is that the molar masses are calculated on a relative basis to sulfonated polystyrenes. Using MALDI-TOF-MS and prior fractionation of lignin did not solve all problems associated with the determination of the absolute molar mass of lignin.   

Supercritical depolymerisation of lignin using a carbon dioxide/acetone/water fluid resulted in a depolymerised lignin oil. In this oil some monomeric compounds are present in relatively high amounts up to 3.6% (based on dry lignin). These products maybe further isolated by downstream processing to obtain purified fine chemicals. For continuous operation of this supercritical process, the formation of char should be further limited. 

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.  

Original languageEnglish
QualificationDoctor of Philosophy
Awarding Institution
Supervisors/Advisors , Promotor , Co-promotor, External person , Co-promotor
Award date7 Dec 2011
Place of Publication[S.l.]
Print ISBNs9789461731005
Publication statusPublished - 7 Dec 2011
  • renewable resources
  • lignocellulose
  • lignocellulosic wastes
  • pulp and paper industry
  • biobased chemicals
  • biobased chemistry

This output contributes to the following UN Sustainable Development Goals (SDGs)

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  • https://edepot.wur.nl/186285

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  • Aromatics Engineering 100%
  • Renewables Engineering 100%
  • Molar Mass Engineering 100%
  • Fractionation Chemical Engineering 100%
  • Carbon Dioxide Chemical Engineering 100%
  • Polystyrene Chemical Engineering 100%
  • Time-of-Flight Mass Spectrometry Agricultural and Biological Sciences 100%
  • Alpha Oxidation Agricultural and Biological Sciences 100%

Projects per year

Lignin as the renewable resource for the future.

Gosselink, R. & Sanders, J.

1/06/05 → 7/12/11

Project : PhD

  • Aromatics 100%
  • Renewables 100%
  • Molar Mass 100%
  • Fractionation 100%
  • Carbon Dioxide 100%

T1 - Lignin as a renewable aromatic resource for the chemical industry

AU - Gosselink, R.J.A.

N1 - WU thesis no. 5138

PY - 2011/12/7

Y1 - 2011/12/7

N2 - Valorization of lignin plays a key role in the further development of lignocellulosic biorefinery processes for biofuels and biobased materials production. Today’s increased demand for alternatives to fossil carbon-based products expands the interest and the need to create added value to the unconverted lignin fraction. The aim of the research was to study the potential of lignin to become a renewable aromatic resource for the chemical industry. Lignin can be considered as an abundantly available and cheap raw material for the manufacturing of an array of products. Development of applications needs to go hand in hand with the anticipated increased production of technical lignins derived from the pulp and paper industry and the emerging lignocellulosic biorefinery industry. Two promising lignin applications are studied in this thesis: 1)         the use of lignin in wood adhesives 2)         the use of lignin for the production of aromatic chemicals PCA modeling was performed aimed at the prediction of the application potential of different technical lignins for wood adhesive production. The lignins and their fractions could be classified in different clusters based on their structure dependent properties. Lignins exhibiting sufficient reactive sites, medium molar mass and low level of impurities are most promising candidates for the development of lignin based wood adhesives. Both lignin reactivity and formaldehyde-free crosslinking agents are needed to develop emission-free adhesives. Periodate oxidation was studied as method to improve the lignin reactivity. Alternatives to formaldehyde- based glues are under investigation and a combination of lignin and furans might be an interesting concept to develop renewable adhesives.  In this research a reliable SEC methodology was developed for the analysis of the molar mass distribution of a wide range of different lignins. The major drawback of this method is that the molar masses are calculated on a relative basis to sulfonated polystyrenes. Using MALDI-TOF-MS and prior fractionation of lignin did not solve all problems associated with the determination of the absolute molar mass of lignin.    Supercritical depolymerisation of lignin using a carbon dioxide/acetone/water fluid resulted in a depolymerised lignin oil. In this oil some monomeric compounds are present in relatively high amounts up to 3.6% (based on dry lignin). These products maybe further isolated by downstream processing to obtain purified fine chemicals. For continuous operation of this supercritical process, the formation of char should be further limited.  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.  

AB - Valorization of lignin plays a key role in the further development of lignocellulosic biorefinery processes for biofuels and biobased materials production. Today’s increased demand for alternatives to fossil carbon-based products expands the interest and the need to create added value to the unconverted lignin fraction. The aim of the research was to study the potential of lignin to become a renewable aromatic resource for the chemical industry. Lignin can be considered as an abundantly available and cheap raw material for the manufacturing of an array of products. Development of applications needs to go hand in hand with the anticipated increased production of technical lignins derived from the pulp and paper industry and the emerging lignocellulosic biorefinery industry. Two promising lignin applications are studied in this thesis: 1)         the use of lignin in wood adhesives 2)         the use of lignin for the production of aromatic chemicals PCA modeling was performed aimed at the prediction of the application potential of different technical lignins for wood adhesive production. The lignins and their fractions could be classified in different clusters based on their structure dependent properties. Lignins exhibiting sufficient reactive sites, medium molar mass and low level of impurities are most promising candidates for the development of lignin based wood adhesives. Both lignin reactivity and formaldehyde-free crosslinking agents are needed to develop emission-free adhesives. Periodate oxidation was studied as method to improve the lignin reactivity. Alternatives to formaldehyde- based glues are under investigation and a combination of lignin and furans might be an interesting concept to develop renewable adhesives.  In this research a reliable SEC methodology was developed for the analysis of the molar mass distribution of a wide range of different lignins. The major drawback of this method is that the molar masses are calculated on a relative basis to sulfonated polystyrenes. Using MALDI-TOF-MS and prior fractionation of lignin did not solve all problems associated with the determination of the absolute molar mass of lignin.    Supercritical depolymerisation of lignin using a carbon dioxide/acetone/water fluid resulted in a depolymerised lignin oil. In this oil some monomeric compounds are present in relatively high amounts up to 3.6% (based on dry lignin). These products maybe further isolated by downstream processing to obtain purified fine chemicals. For continuous operation of this supercritical process, the formation of char should be further limited.  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.  

KW - vervangbare hulpbronnen

KW - lignine

KW - lignocellulose

KW - lignocellulosehoudend afval

KW - pulp- en papierwarenindustrie

KW - chemicaliën uit biologische grondstoffen

KW - chemie op basis van biologische grondstoffen

KW - renewable resources

KW - lignin

KW - lignocellulosic wastes

KW - pulp and paper industry

KW - biobased chemicals

KW - biobased chemistry

M3 - internal PhD, WU

SN - 9789461731005

CY - [S.l.]

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Lignin conversion to fine chemicals

de Albuquerque Fragoso, Danielle Munick (2018) Lignin conversion to fine chemicals. PhD thesis, University of Glasgow.


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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Item Type: Thesis (PhD)
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.
Subjects: >
>
Colleges/Schools: >
Supervisor's Name: Jackson, Professor Samuel David
Date of Award: 2018
Depositing User:
Unique ID: glathesis:2018-30847
Copyright: Copyright of this thesis is held by the author.
Date Deposited: 08 Oct 2018 12:45
Last Modified: 13 Nov 2018 08:00
URI:
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phd thesis on lignin

(2022) Doctoral (PhD) thesis, Memorial University of Newfoundland.

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Available under License - The author retains copyright ownership and moral rights in this thesis. Neither the thesis nor substantial extracts from it may be printed or otherwise reproduced without the author's permission.

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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Item Type: Thesis (Doctoral (PhD))
URI:
Item ID: 15354
Additional Information: Includes bibliographical references.
Department(s):
Date: January 2022
Date Type: Submission
Digital Object Identifier (DOI):
Library of Congress Subject Heading: Lignin--Newfoundland and Labrador; Lignin--Biodegradation--Newfoundland and Labrador; Wood--Chemistry; Softwood--Newfoundland and Labrador; Hardwoods--Newfoundland and Labrador; Extraction (Chemistry).

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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.

Supervisors: Budarin, Vitaliy and Macquarrie, Duncan
Awarding institution: University of York
Academic Units:
Depositing User: Mr long zhou
Date Deposited: 03 Dec 2018 16:02
Last Modified: 13 Nov 2023 01:05

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phd thesis on lignin

Green Chemistry

A 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.

Graphical abstract: A sustainable approach for lignin valorization by heterogeneous photocatalysis

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phd thesis on lignin

S. Li, S. Liu, J. C. Colmenares and Y. Xu, Green Chem. , 2016,  18 , 594 DOI: 10.1039/C5GC02109J

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  • Published: 25 March 2021

A strong, biodegradable and recyclable lignocellulosic bioplastic

  • Qinqin Xia   ORCID: orcid.org/0000-0003-2712-1083 1   na1 ,
  • Chaoji Chen   ORCID: orcid.org/0000-0001-9553-554X 1   na1 ,
  • Yonggang Yao 1 ,
  • Jianguo Li 1 ,
  • Shuaiming He 1 ,
  • Yubing Zhou 1 ,
  • Teng Li   ORCID: orcid.org/0000-0001-6252-561X 2 ,
  • Xuejun Pan   ORCID: orcid.org/0000-0002-6859-9342 3 ,
  • Yuan Yao   ORCID: orcid.org/0000-0001-9359-2030 4 &
  • Liangbing Hu   ORCID: orcid.org/0000-0002-9456-9315 1 , 5  

Nature Sustainability volume  4 ,  pages 627–635 ( 2021 ) Cite this article

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  • Chemical engineering
  • Environmental sciences
  • Sustainability

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.

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Acknowledgements

We acknowledge the support of the Maryland Nanocenter, its Surface Analysis Center and AIMLab. We acknowledge J. Gao for his experimental suggestions.

Author information

These authors contributed equally: Qinqin Xia, Chaoji Chen.

Authors and Affiliations

Department 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

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Contributions

L.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 authors

Correspondence to Yuan Yao or Liangbing Hu .

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The authors declare no competing interests.

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Peer 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 data

Extended 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 information

Supplementary information.

Supplementary Notes 1–8, Figs. 1–19, Tables 1–3 and refs. 1–60.

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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

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DOI : https://doi.org/10.1038/s41893-021-00702-w

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A review on lignin structure, pretreatments, fermentation reactions and biorefinery potential

Affiliations.

  • 1 Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung City, Taiwan; Research Center for Environmental Medicine, Kaohsiung Medical University, Kaohsiung City, Taiwan.
  • 2 Department of Environmental Energy Engineering, Kyonggi University, Suwon, Republic of Korea.
  • 3 Division of Chemistry, Faculty of Science and Humanities, Sree Sowdambika College of Engineering, Aruppukottai, Tamil Nadu, India.
  • 4 Department of Chemistry and Research Centre, Aditanar College of Arts and Science, Virapandianpatnam, Tiruchendur, Tamil Nadu, India.
  • 5 Department of Civil Engineering, Regional Campus Anna University Tirunelveli, Tamilnadu, India.
  • 6 Research Institute of Biotechnology and Medical Converged Science, Dongguk University, Seoul, Ilsandong-gu, Goyang-si, Gyeonggi-do 10326, Republic of Korea.
  • 7 Green Processing, Bioremediation and Alternative Energies Research Group, Faculty of Environment and Labour Safety, Ton Duc Thang University, Ho Chi Minh City, Viet Nam. Electronic address: [email protected].
  • PMID: 30270050
  • DOI: 10.1016/j.biortech.2018.09.070

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.

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PhD offer: Study of the pyrolysis of lignins extracted from black liquors (M/F)

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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).

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