Progress 03/15/18 to 03/14/23
Outputs
Target Audience:The goal of this research program is to support Sustainable Bioenergy and Bioproducts development from forest and agricultural feedstocks by creating innovative lignin-to-value added products conversion technologies. The project aims at developing and demonstrating novel lignin-to-fuel and chemicals conversion processes that will help facilitate the commercialization of lignocellulosic biorefinery. Results generated from this project has been in several high impact scientific journals in the field of sustainable chemistry & material, e.g., Nature communicate, Scientific data (Nature), Green chemistry, ChemSusChem, ChemCatChem, ACS Applied Polymer Materials, Journal of Agricultural and Food Chemistry etc. During this project, we have also been actively working with several major industrial companies and developed new intellectual property. Our work on applying deep eutectic solvent extracted lignin for flexible polyurethane foam application has been highlighted by CEP Magazine https://www.aiche.org/resources/publications/cep/2022/april/catalyzing-commercialization-nanolignin-enables-synthesis-semi-flexible-polyurethane-foams. Two new concept provisional patents were filed based on the work resulting from this project. This project has trained a number of graduates, undergraduate students and post-doctoral associates at both Washington State University and University of Wisconsin Madison. Both Drs. Xiao Zhang and Xuejun Pan have made several presentations at conferences and to industrial companies. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?This project has trained two PhD students (Kuan-Ting Lin and JouChin Chan, Washington State University) and a Master student (Yueqing Wang, University of Wisconsin at Madison). This project also provided support to a number of postdoctoral research associates and undergraduate research assistants. most of them are continuing their career in science and engineering. How have the results been disseminated to communities of interest?A number of papers have been publised in peer reveiwed journals. Both Drs. Xiao Zhang and Xuejun Pan have made several presentations at conferences. Dr. Zhang has also inteacted with a number of industrial companies who have shown strong interests in utilizing renewable polymers. What do you plan to do during the next reporting period to accomplish the goals?
Nothing Reported
Impacts
What was accomplished under these goals?
Lignin is the most abundant renewable aromatic carbon on earth. It has been a formidable challenge to separate lignin from plant biomass without causing significant structural changes to the macromolecule. Despite a decades-long effort, there is no method capable of generating lignin from any biomass with consistent structural properties. The goal of this research program is to support Sustainable Bioenergy and Bioproducts development from forest and agricultural feedstocks by creating innovative lignin-to-value added products conversion technologies. We have accomplished all the major tasks of this project (see previous progress reports). During the last year of this project, we have demonstrated a novel lignin extraction method using lactic acid and pyrazole-based deep eutectic solvents (La-Py DES). By adjusting the treatment conditions as well as La-Py DES composition, lignin with targeted levels of ether linkages, phenolic hydroxyl group content and average molecular weight can be obtained. La-Py DES extraction provides a breakthrough in generating lignin from plant biomass in large quantities with high purity and controlled structural properties. A manuscript describing the results has been accepted by Proceedings of the National Academy of Sciences (PNAS) in 2023. We have also developed lignin peroxidase biomimetics using peptoid heme complex which have shown a high efficacy on depolymerization of a biorefinery lignin (https://www.nature.com/articles/s41467-022-30285-9). Because Pep/hemin catalysts are highly robust and tunable, we expect that they offer new opportunities to overcome the limitation of chemical and biological catalysts for lignin valorization to fuel and high value products.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2022
Citation:
Highly stable and tunable peptoid/hemin enzymatic mimetics with natural peroxidase-like activities
T Jian, Y Zhou, P Wang, W Yang, P Mu, X Zhang, X Zhang, CL Chen
Nature Communications 13 (1), 3025
- Type:
Journal Articles
Status:
Published
Year Published:
2022
Citation:
Deep Eutectic Solvent-Extracted Lignin as an Efficient Additive for Entirely Biobased Polylactic Acid Composites
S Pawale, K Kalia, S Alshammari, D Cronin, X Zhang, A Ameli
ACS Applied Polymer Materials 4 (8), 5861-5871
- Type:
Journal Articles
Status:
Published
Year Published:
2022
Citation:
Molecular structural dataset of lignin macromolecule elucidating experimental structural compositions
S Eswaran, S Subramaniam, U Sanyal, R Rallo, X Zhang
Scientific Data 9 (1), 647
- Type:
Theses/Dissertations
Status:
Published
Year Published:
2020
Citation:
DESIGN AND EVALUATE DEEP EUTECTIC SOLVENTS LIGNIN EXTRACTION FOR
ADVANCED MATERIAL APPLICATIONS
Kuan-ting Lin
- Type:
Theses/Dissertations
Status:
Published
Year Published:
2020
Citation:
INTERACTIONS BETWEEN DEEP EUTECTIC SOLVENT AND LACCASE
JouChin Chan
- Type:
Theses/Dissertations
Status:
Published
Year Published:
2022
Citation:
UNDERSTANDING THE MOLECULAR STRUCTURE OF LIGNIN MACROMOLECULE USING DATA ANALYTICS AND COMPUTATIONAL SIMULATION
SUDHA CHERANMA DEVI ESWARAN
- Type:
Journal Articles
Status:
Published
Year Published:
2023
Citation:
RSC Advances, 2023, 13, 59255932.
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Progress 03/15/21 to 03/14/22
Outputs
Target Audience:
Nothing Reported
Changes/Problems:An additional one-year project extension has been requested and approved. What opportunities for training and professional development has the project provided?A graduate students (UW, 1 FTE) and two postdoctal reserach asscociates (WSU, 1 FTE) worked on this project. How have the results been disseminated to communities of interest?We have published one journal publication. Dr. Dylan Cronin has presented the project work at Pacifichem 2021 Symposium (Dec. 2021). Two additional manuscripts areunder preparation. We have identified new applications of DES lignin for polyurenthane applications. What do you plan to do during the next reporting period to accomplish the goals?In the next year, we will complete the following tasks: 1. Demonstrate the feasibility of producing acrylic acid and open chain alkenes from ethenolysis of lignin dervied dicarboxylic acids 2.TEA analysis of the lignin-to-jet fuel conversion process and its integration with a biochemical based biorefinery 3. Prepare final report to USDA
Impacts
What was accomplished under these goals?
1. Demethylation of kraft lignin: Kraft lignin was depolymerized and demethylated via cleaving aryl and alkyl ether bonds in acidic lithium bromide trihydrate. It was found that the cleavage of the ether bonds followed the order of β-O-4 ether > aryl alkyl ether in phenylcoumaran > dialkyl ether in resinol > methoxyl (MeO). The depolymerization via β-O-4 cleavage occurred under mild conditions. Both depolymerization and demethylation generated new aromatic hydroxyl (ArOH). With 2.4 M HCl, MeO content dropped from 4.85 to 0.95 mmol/g lignin, and ArOH content increased from 2.78 to 5.09 mmol/g lignin. The depolymerized and demethylated kraft lignin showed excellent antioxidant activity and Cr(VI)-scavenging capacity, compared with original kraft lignin and tannins. 2. Preparation of dicarboxylic acids derived from lignin and its monomers for olefin metathesis reactions: We have applied peracetic acid/Fe system conduct ring opening reactions on several lignin and its monomer samples for the production of dicarboxylic acids (DCA). The ring open reactions was optimized based on reaction with catechol with has shown to achieve ~ 80% DCA recovery. In additional Grubb's catalyst, we have also identify rhenium oxide catalysts for the metathesis reaction. 3. Techno-economic analysis (TEA) of DES extraction of lignin from biomass resideus: We have constructred an Aspen Plus based process model to determinetechno-economic feasiblity of extract lignin oligomers from biomass residues for fuel and polymer conversion.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2021
Citation:
Depolymerization and Demethylation of Kraft Lignin in Molten Salt Hydrate and Applications as an Antioxidant and Metal Ion Scavenger, J. Agric. Food Chem. 2021, 69, 45,
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2021
Citation:
A novel treatment for the production of high purity lignin from corn stover hydrolysate via deep eutectic solvent extraction, oral presentation at Pacifichem 2021 (Virtual), by Dr. Dylan Cronin
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Progress 03/15/20 to 03/14/21
Outputs
Target Audience:This research program aims at supporting Sustainable Bioenergy and Bioproducts development from forest and agricultural feedstock by creating new lignin-to-value added products conversion technologies. The outcome of this project will benefit a number of industrial sectors, including agricultural, papermaking, chemicals and biorefinery. Changes/Problems:Thepandemic has created challenges to conduct experimental research. We hope ot catch up the progress in 2021. What opportunities for training and professional development has the project provided?Two postdoctoral research fellow (PDF) Dr. Dylan Cronin (Prof Zhang's group) and Dr. Zheng Li (Prof. Pan's group) have worked on this project this year. A PhD student Kuan-Ting Lin has contributed to DES treatment of biomass and conducted the ring opening and metathesis reactions. A female PhD student JouChin Chan has assisted enzyme and biomimetic depolymerization of lignin. How have the results been disseminated to communities of interest?Conference preseatnations (presenters underlined) "Deep Eutectic Solvent Treatment of Corn Stover Hydrolysate for the Production of High Purity Lignin", Dylan Cronin and Xiao Zhang* AICHE annual meeting (Virtual) Nov. 20th 2020 "Novel Deep Eutectic Solvent for Native Lignin Extraction through Heterocycle Induced Interaction:, Kuan-ting Lin and Xiao Zhang* AICHE annual meeting (Virtual) Nov. 16th 2020 "Demethylation of Lignin in Inorganic Ionic Liquid", Zhang Li, Xiao Zhang, Xuejun Pan, AICHE annual meeting (Virtual) Nov. 18th 2020. "Role of peracetic acid on the disruption of lignin packing structure and its consequence on lignin depolymerisation", Ruoshui Ma, Udishnu Sanyal, Mariefel Olarte, Heather M. Job, Marie S. Swita, Susanne B. Jones, Pimphan A. Meyera, Sarah D. Burton, John R. Cort, Mark E. Bowden, Xiaowen Chen, Michael P. Wolcott, and Xiao Zhang*, 2020 Thermal & Catalytic Sciences Virtual Symposium Oct. 5th 2020 'Deep Eutectic Solvent Treatment of Corn Stover Hydrolysate for the Production of High Purity Lignin", Dylan Cronin and Xiao Zhang* 2020 Thermal & Catalytic Sciences Virtual Symposium, Oct, 5th 2020 What do you plan to do during the next reporting period to accomplish the goals?We plan to complete the metathesis optimization experiment and conduced TEA analysis of lignin to fuel and bioproducts conversion process.
Impacts
What was accomplished under these goals?
We have conducted a detail investigation of deep eutectic solvent (DES) treatment of hydrolysate residues, corn stover hydrolysate (CSH), generated from a biorefinery process at National Renewable Energy Laboratory. The results of this work demonstrated that hydrolysate residues have the potential to be utilized as a feedstock for the production of high?purity lignin with controlled structural properties which has a great potential for use as a feedstock for the production biofuel and biocomposites. We have also conducted large scale extraction of DES lignin with an aim to produce kg of lignin for fuel and products conversion. In addition to chemical oxidation of lignin, we have also reviewed the previous work conduced on enzymatic oxidation of lignin. A review article is published in ChemCatChem in 2020. Working with Dr. Chunlong Chen at Pacific Northwest National Laboratory, we have also started to look into produce biometric enzymes based on heme and peptoid complex for lignin conversion. Dr. Xuejun Pan's group has produced four demethylated lignin sample which we have tested for ring opening reactions. We have conducted olefin metathesis reactions on lignin dervied dicarboxylic acids under different conditions. The inital resutls shown that both acrylates and hydrocarbon compounds can be produced from metathesis. However, the yield of hdyrcarbon fuel precuosrs obtained was low due the self- and cross-methethsis which leads to produce longer chain carboxylic acids products. We have identified several approaches to optimize the reaction conditions.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2020
Citation:
Deep Eutectic Solvent Extraction of High?Purity Lignin from a Corn Stover Hydrolysate, DJ Cronin, X Chen, L Moghaddam, X Zhang, ChemSusChem 13 (17), 4678-4690
- Type:
Journal Articles
Status:
Published
Year Published:
2020
Citation:
Enzymatic oxidation of lignin: challenges and barriers toward practical applications, JC Chan, M Paice, X Zhang
ChemCatChem 12 (2), 401-425
- Type:
Journal Articles
Status:
Published
Year Published:
2020
Citation:
Cleavage of ethers and demethylation of lignin in acidic concentrated lithium bromide (ACLB) solution, Z Li, E Sutandar, T Goihl, X Zhang, X Pan
Green Chemistry 22 (22), 7989-8001
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Progress 03/15/19 to 03/14/20
Outputs
Target Audience:The goal of this project is to support Sustainable Bioenergy and Bioproducts development from forest and agricultural feedstocks by creating innovative lignin-to-value added products conversion technologies. This research program will offer potential values to a number industrial sectors including agricultural and forest products, chemical industry, automobile industrial and aviation industry. This project targets on developing unique lignin conversion technologies. In this year, we have made a significant effort to engage serval key stakeholders from these industries (Idaho forest group, Ford Motors Company, John Deere etc). Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?Two postdoctoral research fellow (PDF) Dr. Dylan Cronin (Prof Zhang's group) and Dr. Zheng Li (Prof. Pan's group) have contributed to DES extraction of biomass lignin (and reactor design) and demethylation of lignin samples. A PhD student Kuan-Ting Lin has contributed to DES treatment of biomass and conducted the ring opening and metathesis reactions. A female PhD student JouChin Chan has contributed to the evaluate of DES interaction with lignin degradation enzymes. Three undergraduates students Dylan Hartwig (female from WSU), Thomas Ekstrom (From Seattle University) and Alan Ramirez (from University of California Merced) assisted graduate and PDF's research. Alan Ramirez and Thomas Ekstrom has attended Automotive Composites Conference & Exhibition held in Novi MI in September and presented poster entitled " DES Treatment of Corn Stover Hydrolysate for the Production of High Purity Lignin" and "Flexible Polyurethane Foam Production With Deep Eutectic Solvent Lignin as a Partial Substitution of Polyol Component". USDA/NIFA is acknowledged on the posters. How have the results been disseminated to communities of interest?Besides the paper and poster presentation mentioned in other sections. Prof. Zhang has given an invited seminar at Chemical and Environmental Engineering Graduate Seminar, University of Cincinnati, Cincinnati OH, March 15th 2019 as well as presented the lignin research to International paper research center in Cincinnati. What do you plan to do during the next reporting period to accomplish the goals? We will complete the DES lignin preparation and scale up and submit manuscripts. We will focus our research on optimizing ring opening reaction of the DES lignin and subsequent metathesis reactions. We will use the result to conduct a detailed TEA analysis.
Impacts
What was accomplished under these goals?
This year we have devoted a significant amount effort on optimizing deep eutectic solvent (DES) extraction of lignin from wheat straw, Douglas fir, white fir residues (from Idaho Forest Group) and corn stove hydrolysis/fermentation residues (obtained from National Renewable Energy Laboratory pilot plant). Beside the lactic acid and choline chloride based on DES system, we have formulated and tested heterocycles containing DES systems for lignin extraction. Our ongoing work shows that some of these novel DES can extraction lignin in a range of chemical properties. The characteristics of these DESL samples were investigated by GPC, NMR and wet chemistries. A manuscript is currently under preparation. In addition, we have also design a continues DES lignin extraction process aims at process DES lignin at 1 kg per day scale. In a parallel research activity, Co-PI Prof. Xuejun Pan's group has further development lignin demethylation procedure which was proved to be effective for the demethylation of several lignin samples, including hardwood kraft lignin, corn stover lignin, ethanol lodgepole pine lignin and DES lignin from white fir. A manuscript is under preparation. We have developed oxidative method based on transition metal catalyst/peracid to instigate the ring opening reaction on DES lignin. Dr. Pan's group has also tested the both acidic and basic oxidation of ethanol poplar lignin in H2O2/ethanol system to produce diacids and yielded oxalic acid (OA), malonic acid (MA), succinic acid (SA) and 4-hydrobenzoic acid (4-HBA) as major reactions products. We have constructed a reactor allow us to optimize the reaction conditions and evaluate the ring opening reaction of the DESL samples. DES treatment of biomass substrates can remove more than 80% of lignin and produce a substrate rich in cellulose which facility the downstream cellulose conversion often involved enzymatic hydrolysis and fermentation. One issue that has been overlooked is the effect of DES on enzyme activity. A female ChE PhD student has started to evaluate the effects of DES on enzyme activity. We have constructed a preliminary Aspen plus based TEA based model which the analysis of DES lignin extraction, conversion and products development for both fuel and polymer precursors.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2020
Citation:
Enzymatic Oxidation of Lignin: Challenges and Barriers Toward Practical Applications ChemCatChem 2020,12, 40142 DOI: 10.1002/cctc.201901480
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Progress 03/15/18 to 03/14/19
Outputs
Target Audience:A manucript has been submitted toACS sustainable chemistry & engineering and is in the final revision stage. We have outreached industrial companies briefing our project and seek their guidance to potentail application of DES lignin and other lignin derived products. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?A PhD (0.5 FTE) and two postdoctal research associates (1.5 FTE) worked on this project. in 2019, an undergraduate engineering student will also participate inthis project. How have the results been disseminated to communities of interest?A manuscript entitled "Facile Extraction of Wheat Straw by Deep Eutectic Solvent (DES) to Produce Lignin Nanoparticles" has been submitted and is currently in the final revision stage. Dr. Xiao Zhang has presented the results to Ford motor company and Hyundai/Kia company. Both companies are interested in utilizing DESL for biocomposite application. What do you plan to do during the next reporting period to accomplish the goals?In the next year, we (Drs. Xiao Zhang and Xuejun Pan) will focus on the following main research tasks. Complete the preparation and characterization of biorefinery lignin from representative softwood and agricultural biomass feedstock. Optimize the demethylation of lignin in the acidic LiBr system to maximize the demethylation rate and limit the lignin condensation as well as elucidate the mechanisms of lignin demethylation in the LiBr system. Conduct ring opening reactions on lignin and demethylated lignin to produce dicarboxylic acids (DCA). Establish a techno-economical analysis (TEA) model to identify key barriers in lignin-to-DCA conversion
Impacts
What was accomplished under these goals?
There are four specific tasks in the proposed research program: Task 1: Preparation and characterization of biorefinery lignin from representative softwood and agricultural biomass feedstock. Task 2: Optimizing lignin depolymerization and conversion to dicarboxylic acids. Task 3: Olefin metathesis (ethenolysis) of lignin derived dicarboxylic acids to produce acrylic acid and open chain alkenes. Task 4: TEA analysis of the lignin conversion process and its integration with a biochemical based biorefinery. In the first year of this project, we have focused our experiments related to the first two tasks. The major research activities are summarized below: Preparation of DES lignin from wheat straw: Based on the previous work on deep eutectic solvent extraction of lignin from D. fir, we have conducted a detail study to investigate the extraction of DES lignin from wheat straw. The extraction was conducted at a range of treatment conditions (90°C-150ºC, 2-24hours) on both air dry and oven dried wheat straw, using a lactic acid-choline chloride (Lac-ChCL) based DES. The ensuing lignin samples were characterized to determine their H:G:S ratio, ether bond content, molecular weight as well as particle size. The main objective of this experiment is to identify an extraction condition that can produce lignin in a high yield and high purity. We found that after DES treatment of wheat straw at 120ºC for 12 hour, a high purity lignin (>90% wt) can be separated from wheat straw with yield above 75% based on initial lignin content in wheat straw. This lignin has a low ether linkage content (less than 10%). Changing the treatment condition will have a significant impact on lignin extraction yield and ether linkage content. A more severe treatment (e.g. 150°C, 24 hours) led to reduced ether content, whoever a lower extraction yield. We have collected lignin samples from these extraction conditions and will be subjected to subsequent oxidation reaction to determine the effects of lignin structural changes on the ring opening reaction to produce dicarboxylic acids. 2. Demethylation of lignin As we have mentioned that the presence of methoxy group on lignin has a significant influence on ring opening reaction rate. Demethylation of lignin can facilitate ring opening reaction and improve dicarboxylic acid yield. During this year, Dr. Xuejun Pan's group has developed a lignin demethylation method based on LiBr system as shown in the following scheme. Three lignin monomers (creosol, syringol and 1,2,3-trimethoxybenzene) were first tested. This method can convert creosol (one methoxy group) to 4-methylcatechol with a yield of 79% and selectivity of 81%. However, syringol (two methoxy groups) and 1,2,3-trimethoxybenzene (three methoxy group) could not be fully demethylated to pyrogallol, and the terminal product was primarily 3-methoxycatechol. The results confirmed that the acidic lithium bromide system was able to cleave the aryl methyl ether bond and convert methoxyl group into hydroxyl group. The formation of catechol structural will facilitate the ring opening reaction toward muconic acid derivative formation. In addition to these model compounds, four lignin samples, hardwood kraft lignin, corn stover lignin, LPP lignin and poplar lignin, were subsequently treated in the LiBr/HBr system at 100 oC for 4 h. The original lignin samples and treated lignin samples were acetylated in pyridine/acetic anhydride (1 vol:1 vol), and subjected to 1H-NMR analysis 4-nitrobenzaldehyde (4-NBA) as internal standard to determined their methoxy groups (-OMe), aromatic hydroxy groups (ArOH) and alkyl hydroxy groups (AlkOH) contents. The molecules weight were of these lignin samples were also analyzed by GPC. The preliminary results are summarized in Table 1. After the treatment in the LiBr system, the content of -OMe groups in all lignin samples decreased significantly. Meanwhile, the amounts of ArOH in hard wood Kraft lignin, corns over lignin and poplar lignin increased resulting from the demethylation. However, it is also observed that the Mn and Mw of all lignin samples increased after the treatment suggesting condensation may occurred during the treatment. We are currently testing mild reaction conditions to minimize condensation reaction. Table 1 The contents of -OMe, ArOh and AlkOH in lignin samples -OMe (mmol/g) ArOH (mmol/g) AlkOH (mmol/g) Mn Mw Mw/Mn Hardwood Kraft lignin Original 12.8 6.32 6.56 848 1146 1.35 Demethylateda 7.04 9.49 7.33 1332 2302 1.73 Corn stover lignin Original 6.74 3.23 3.44 634 1090 1.72 Demethylateda 3.36 3.90 3.13 1367 3080 2.25 LPP lignin Original 12.8 5.46 8.12 1171 3200 2.73 Demethylateda 5.01 5.36 5.17 1601 4807 3.00 Poplar lignin Original 13.0 5.15 6.16 973 1487 1.53 Demethylateda 6.12 8.52 5.76 1482 3107 2.10 a: 0.5 g of lignin, 6.1 g of LiBr, 3.9 ml of water, and 1 ml of 48% HBr. 100 oC, 4 h.
Publications
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