Browsing by Author "Singh, Sandip K."

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Effect of catalyst and reaction conditions on aromatic monomer yields, product distribution, and sugar yields during lignin hydrogenolysis of silver birch wood
(2020-11) Phongpreecha, Thanaphong; Christy, Kendall F.; Singh, Sandip K.; Hao, Pengchao; Hodge, David B.
The impact of catalyst choice and reaction conditions during catalytic hydrogenolysis of silver birch biomass are assessed for their effect on aromatic monomer yields and selectivities, lignin removal, and sugar yields from enzymatic hydrolysis. At a reaction temperature of 220 °C with no supplemental H2, it was demonstrated that both Co/C and Ni/C exhibited aromatic monomer yields of >50%, which were close to the theoretical maximum expected for the lignin based on total β-O-4 content and exhibited high selectivities for 4-propylguaiacol and 4-propylsyringol. Pd/C exhibited a significantly different set of products, and using a model lignin dimer, showed a product profile that shifted upon inclusion of supplemental H2, suggesting that the generation of surface hydrogen is critical for this catalyst system. Lignin removal during hydrogenolysis could be correlated to glucose yields and inclusion of lignin depolymerizing catalysts significantly improves lignin removal and subsequent enzymatic hydrolysis yields.
Effect of Dilute Acid Pretreatment and Lignin Extraction Conditions on Lignin Properties and Suitability as a Phenol Replacement in Phenol-Formaldehyde Wood Adhesives
(American Chemical Society, 2022-12) Saulnier, Brian K.; Siahkamari, Mohsen; Singh, Sandip K.; Nejad, Mojgan; Hodge, David B.
Corn stover was subjected to dilute sulfuric acid pretreatment to assess the impact of pretreatment conditions on lignin extractability, properties, and utility as a phenol replacement in wood phenol-formaldehyde (PF) adhesives. It was identified that both formic acid and NaOH could extract and recover 60–70% of the lignin remaining after pretreatment and enzymatic hydrolysis under the mildest pretreatment conditions while simultaneously achieving reasonable enzymatic hydrolysis yields (>60%). The availability of reaction sites for the incorporation of lignins into the PF polymer matrix (i.e., unsubstituted phenolic hydroxyl groups) was shown to be strongly impacted by the pretreatment time and the recovery. Finally, a lignin-based wood adhesive was formulated by replacing 100% of the phenol with formic-acid-extracted lignin, which exhibited a dry shear strength exceeding a conventional PF adhesive. These findings suggest that both pretreatment and lignin extraction conditions can be tailored to yield lignins with properties targeted for this co-product application.
Extraction, recovery, and characterization of lignin from industrial corn stover lignin cake
(Elsevier BV, 2024-05) Bécsy-Jakab, Villő Enikő; Savoy, Anthony; Saulnier, Brian K.; Singh, Sandip K.; Hodge, David B.
Lignin utilization in value-added co-products is an important component of enabling cellulosic biorefinery economics. However, aqueous dilute acid pretreatments yield lignins with limited applications due to significant modification during pretreatment, low solubility in many solvents, and high content of impurities (ash, insoluble polysaccharides). This work addresses these challenges and investigates the extraction and recovery of lignins from lignin-rich insoluble residue following dilute acid pretreatment and enzymatic hydrolysis of corn stover using three extraction approaches: ethanol organosolv, NaOH, and an ionic liquid. The recovered lignins exhibited recovery yields ranging from 30% for the ionic liquid, 44% for the most severe acid ethanol organosolv condition tested, and up to 86% for the most severe NaOH extraction condition. Finally, the fractional solubilities of different recovered lignins were assessed in a range of solvents and these solubilities were used to estimate distributions of Hildebrand and Hansen solubility parameters using a novel approach.
Impact of dilute acid pretreatment conditions on p-coumarate removal in diverse maize lines
(2020-10) Saulnier, Brian K.; Phongpreecha, Thanaphong; Singh, Sandip K.; Hodge, David B.
Prior work has identified that lignins recovered from dilute acid-pretreated corn stover exhibit superior performance in phenol–formaldehyde resins used in wood adhesive applications when compared to diverse process-modified lignins derived from other sources. This improved performance is hypothesized to be due to the higher content of unsubstituted phenolic groups specifically p-coumarate lignin esters. In this work, a diverse set of corn stover samples are employed that exhibit diversity in p-coumarate content and total lignin content to explore the relationship between dilute acid pretreatment conditions, p-coumarate ester hydrolysis, xylan solubilization, and the resulting glucose enzymatic hydrolysis yields. The goal of this study is to identify pretreatment conditions that preserve a significant fraction of the p-coumarate esters while simultaneously achieving high enzymatic hydrolysis yields. Kinetic parameters for p-coumarate ester hydrolysis were quantified and pretreatment-biomass combinations were identified that result in glucose hydrolysis yields of more than 90% while retaining nearly 50 mg p-coumarate/g lignin.
Lignin properties and cell wall response to deconstruction by alkaline pretreatment and enzymatic hydrolysis in brown midrib sorghums
(Elsevier BV, 2022-04) Singh, Sandip K.; Saulnier, Brian K.; Hodge, David B.
Lignin has an adverse impact on the deconstruction of plant cell wall biopolymers in biorefining processes and its reduction and/or alteration during biosynthesis is one target for decreasing plant cell wall recalcitrance. In this work, the impact of two brown midrib mutations (bmr6 and bmr12) in two sorghum background lines (the commercial hybrid Atlas and near-isogenic BTx623) on lignin properties and the plants’ response to cell wall deconstruction to monomeric sugars via alkaline pretreatment and enzymatic hydrolysis is investigated with the goal of assessing how differences in lignin content and properties impact the plant’s response to pretreatment. We identify that both bmr sorghum lines show significantly lower abundance of water-extractable sugars (glucose, sucrose, and fructose) and alkali-saponifiable p-coumarate. Furthermore, both these properties exhibited identical trends across both background lines. Next, both untreated and mild alkali-pretreated bmr sorghums were shown to exhibit higher glucose hydrolysis yields following enzymatic hydrolysis than the control lines. Following pretreatment, the Atlas bmr sorghums exhibited more lignin solubilization and the solubilized lignin was of lower molar mass than the background control line suggesting that differences in the lignin response to pretreatment resulted these differences. Finally, significant differences were observed in the lignin content, lignin monomer distribution, and inter-unit linkages in the Atlas bmr line relative to the control line with key differences including lower syringyl monomer content in both bmr lines, higher relative abundance of β-O-4 linkages in the bmr6 line, and the presence of 5-hydroxy guaiacyl monomers and benzodioxane (α-O-5/β-O-4) linkages in the bmr12 line.
Lignin-Based Polyurethanes: Opportunities for Bio-Based Foams, Elastomers, Coatings and Adhesives
(2019-07-19) Alinejad, Mona; Henry, Christian; Nikafshar, Saeid; Gondaliya, Akasha; Bagheri, Sajad; Chen, Nusheng; Singh, Sandip K.; Hodge, David B.; Nejad, Mojgan
Polyurethane chemistry can yield diverse sets of polymeric materials exhibiting a wide range of properties for various applications and market segments. Utilizing lignin as a polyol presents an opportunity to incorporate a currently underutilized renewable aromatic polymer into these products. In this work, we will review the current state of technology for utilizing lignin as a polyol replacement in different polyurethane products. This will include a discussion of lignin structure, diversity, and modification during chemical pulping and cellulosic biofuels processes, approaches for lignin extraction, recovery, fractionation, and modification/functionalization. We will discuss the potential of incorporation of lignins into polyurethane products that include rigid and flexible foams, adhesives, coatings, and elastomers. Finally, we will discuss challenges in incorporating lignin in polyurethane formulations, potential solutions and approaches that have been taken to resolve those issues.
Manganese-modified lignin biochar as adsorbent for removal of methylene blue
(Elsevier BV, 2021-05) Liu, Xu-Jing; Li, Ming-Fei; Singh, Sandip K.
Methylene blue, a prevalent cationic type dye, has been extensively utilized in textile industry. Lignin generates as a byproduct and its utilization is required to add a potential economic benefit of a biorefinery process. Lignin-derived porous biochar, as a promising adsorbent, was propitiously prepared by chemical modification with different oxidation number manganese compounds (KMnO4, MnSO4, and MnO2). The adsorption capacity of MnO2-loaded biochar to methylene blue dye was substantially higher relative to original biochar. The maximum adsorption capacity was 248.96 mg/g and removal rate was 99.73%, as compared to 234.65 mg/g and 94.0% for unmodified biochar. In comparison, the decolorization rate of the modified biochar exceeded 95%. Substantial results showed that methylene blue has a strong binding affinity with MnO2 modified biochar. Adsorption kinetics was described by a quasi-second order model and methylene blue adsorption isotherm was better fitted by Langmuir model. The research provides a promising way for the removal of methylene blue from wastewater through the manufacture of adsorbent from byproduct of biorefinery process.
Scale-Up of a Two-Stage Cu-Catalyzed Alkaline-Oxidative Pretreatment of Hybrid Poplar
(American Chemical Society, 2024-03) Dülger, Dilara N.; Yuan, Zhaoyang; Singh, Sandip K.; Omolabake, Surajudeen; Czarnecki, Celeste R.; Nikafshar, Saeid; Li, Mingfei; Bécsy-Jakab, Villő E.; Park, Seonghyun; Park, Sunkyu; Nejad, Mojgan; Stahl, Shannon S.; Hegg, Eric L.; Hodge, David B.
A two-stage alkaline-oxidative pretreatment of hybrid poplar was investigated at scale (20 L reactor volume) with the goal of understanding how reaction conditions as well as interstage mechanical refining impact downstream process responses. The pretreatment comprises a first stage of alkaline delignification (alkaline pre-extraction) followed by a second delignification stage employing Cu-catalyzed alkaline hydrogen peroxide with supplemental O2 (O2-enhanced Cu-AHP). Increasing pre-extraction severity (i.e., temperature and alkali loading) and pretreatment oxidation (increasing H2O2 loading) were found to increase mass and lignin solubilization in each stage. Lignin recovered from the first stage was subjected to oxidative depolymerization and led to aromatic monomer yields as high as 23.0% by mass. Lignins recovered from the second-stage Cu-AHP pretreatment liquors were shown to exhibit aliphatic hydroxyl contents more than 6-fold higher than a typical hardwood kraft lignin, indicating that these lignins could serve as a biobased polyol for a range of polyurethane applications.