Conversion Of Cellulose Research Articles

Lignin-derived carbon-based solid acid catalyst for the conversion of Pueraria cellulose to lactic acid

Lignin-derived carbon-based solid acid catalyst for the conversion of Pueraria cellulose to lactic acid

Optimization of potassium hydroxide combined urea pretreatment and enzymatic hydrolysis of wheat straw using response surface methodology for improving sugar production

To improve sugar yields from wheat straw (WS), response surface methodology (RSM) was adopted to optimize potassium hydroxide combined urea pretreatment and enzymatic hydrolysis of WS. Glucose and xylose yields from the pretreated WS were used as responses during the whole optimization. Potassium hydroxide concentration, time and temperature during pretreatment were found to have significant effects on sugar yields. Sugar yields could be enhanced while WS was pretreated using 45 g/L potassium hydroxide solution containing 15 g/L urea with solid to liquid ratio of 1:5 (g/mL) at 74.0 °C for 50 min. Cellulose recovery, hemicellulose recovery, and lignin removal after optimization were 98.1%, 72.6%, and 75.8%, respectively. In addition, enzyme loading, biomass loading, and reaction time during enzymatic hydrolysis also had significant effects on sugar yields. Maximal yields of glucose (610.25 mg/gds, miligram per gram dry substrate) and xylose (221.26 mg/gds) could be achieved while hydrolysis was carried out at 50 °C for 32.8 h with 141 g/L of biomass loading, 8.1 FPU/gds (filter paper activity unit per gram dry substrate) of enzyme loading and 0.4% (w/v) of polysorbate 80. The corresponding cellulose conversion and hemicellulose conversion were 97.2% and 90.4%, respectively.

Theoretical and experimental study of 5-ethoxymethylfurfural and ethyl levulinate production from cellulose

Theoretical simulations and experiments were taken to explore the mechanism of cellulose conversion into 5-ethoxymethylfurfural (EMF) and ethyl levulinate (EL) catalyzed by a mixed acid of Lewis acid and Brønsted acid. Up to 64.8 % total yield of EMF and EL can be obtained when the ratios of Lewis/Brønsted acid and water/ethanol (v/v) were 1:2 and 3:7 respectively. The results showed that Lewis acid and water could reduce the activation energy of EMF formation from 75.6 to 47.9 kJ mol−1, and mixed acids and water/ethanol system were beneficial to the accumulation of EMF. Moreover, the results of molecular dynamics (MD) simulation indicated that Lewis acid could promote the distribution of Bronsted acid around the β-1,4 glycosidic bond of cellobiose. The combination of DFT and frontier molecular orbital (FMO) calculation demonstrated that the breakage of the β-1,4 glycosidic bond was the main rate-limiting step of cellulose hydrolysis. Meanwhile, the mixed acid and water/ethanol system could accelerate the hydrolysis due to the reducing energy barrier and HOMO-LUMO gap. This study gave a deep insight into the mechanism of Lewis acid with Brønsted acid on cellulose conversion into EMF and EL.

Enhanced 5-hydroxymethylfurfural production from cellulose in monophasic molten salt hydrate: Insights into the effect of catalyst acidity on conversion

Production of 5-HMF from cellulose is a promising approach for advanced bio-fuels preparation, but the degradation of active 5-hydroxymethylfurfural (5-HMF) is a critical challenge affecting 5-HMF selectivity. To address this issue, biphasic reaction system consisting of water and organic solvent is generally used to in-situ extract 5-HMF into organic phase to inhibit product degradation. Despite the high 5-HMF selectivity achieved in biphasic system, low product concentration and difficulty in separation restrict its industrial applications. Molten salt hydrate (MSH) is unique in cellulose conversion and 5-HMF preservation. In this work, MSH of LiBr was used as monophasic solvent for cellulose conversion and an acidity tunable solid acid AlSiO-x was used as the catalyst. It was found that a relatively high 5-HMF yield of 44.5% together with carbon balance of 75.0% were obtained at 170 °C for 20 min, which is higher than the results ever reported. Importantly, this work proved that the ratio of total Brønsted to Lewis acid sites on solid acid is the key issue affected 5-HMF yield. After reaction, solid acid can be recycled for more than 5 times without catalytic performance decline, and the dissolved 5-HMF can be sufficiently separated from MSH via hyper cross-linked polymer (HCP) adsorption.

Raspberry-like hydroxyl-rich carbon layer coated solid catalyst to promote the hydrolysis of cellulose to sugar through local strong absorption

Raspberry-like carbon layer coated silica nanoparticles (MSN-x-NH2 @C) with controllable hydroxyl-rich rough surface is designed and synthesized by use of alkaline etching strategy and hydrothermal carbonization (HTC) method, which is utilized as catalyst to provide particular interaction with cellulose between the solid-solid interfaces. Through the control of surface roughness of the raspberry-like catalyst, it induces the formation of local area with strong absorption on the surface and thus enhance the capability to disrupt the aggregated structure of cellulose. Accordingly, in low acidic aqueous system with MSN-x-NH2 @C, the cellulose conversion rate is up to 91.99% with the total reducing sugar yield at 81.46% and glucose yield of ∼70% after the second hydrolysis in aqueous system. Furthermore, the obtained MSN-x-NH2 @C exhibits good thermal stability and reusability. This research provides a new perspective for the design and preparation of nano-sized solid catalyst with controlled surface topological structure to enable the surface adsorption capability towards cellulose more efficiently in aqueous system.

Statistical Optimization of Tween-80-Assisted Potassium Hydroxide Pretreatment and Enzymatic Hydrolysis for Enhancing Sugar Yields from Corn Cob

With the addition of Tween 80, potassium hydroxide pretreatment and enzymatic hydrolysis were statistically optimized to maximize sugar yields from corn cob (CC). The results indicated that the sugar yields from CC could be influenced significantly by the potassium hydroxide concentration, temperature and time during pretreatment. The optimized pretreatment conditions were as follows: potassium hydroxide, 46 g·L−1; Tween 80, 3.0 g·L−1; solid dose, 200 g·L−1; temperature, 78 °C; and time, 50 min. After optimization, the lignin reduction and recoveries of cellulose and hemicellulose were 89.7%, 97.8% and 68.0%, respectively. In addition, sugar production could also be influenced by the biomass loading, enzyme loading and reaction time. A maximal glucose production (518.48 mg·gds−1, milligrams per gram of dry substrate) and xylose production (351.14 mg·gds−1), 97.2% cellulose conversion and 82.9% hemicellulose conversion from CC could be obtained when the biomass loading was 195 g·L−1 and the enzyme loading was 8.9 FPU·gds−1 (filter paper activity units per gram of dry substrate) and when the Tween 80 concentration was 3.0 g·L−1 at 50 °C for 30.4 h during hydrolysis. This is the first systematic study of combined Tween 80 pretreatment of CC by potassium hydroxide and hydrolysis of CC by cellulase preparation to increase sugar production.

Pore-scale study of phase transitions and humins coking in cellulose hydrolyzed to levulinic acid

Hydrothermal depolymerization of cellulose has generated tremendous excitement as a promising pathway to sustainable chemistry. Among these biomass products, levulinic acid (LA), as one of the most promising platform chemicals with rich chemistry, can be used as various fuel additives or further refined into sustainable biofuel and high-value chemicals. However, hydrothermal conversion of cellulose into chemicals involves complex physicochemical processes, suffering currently from insufficient understanding of processes coupling mechanisms and carbon deposition caused by coking side reaction. Here, we developed a pore-scale multiphase reactive transport model based on the lattice Boltzmann method (LBM), coupling the multicomponent multiphase flow, heterogeneous reaction, cellulose dissolution, and humins coking, to systematically explore the conversion of cellulose to LA over acid catalyst. A relationship with a monotonic increase between the coking appearance time and H+ concentration has been found when the coking amount shows a linear decrease over acid concentration. Our results underscore the importance of in-depth elucidation of process coupling mechanisms for the establishment of efficient hydrothermal preparation strategies from cellulose to platform chemicals.

Physicochemical Characterization of Potassium Hydroxide Pretreated Chestnut Shell and Its Bioconversion to Lactic Acid by Lacticaseibacillus rhamnosus

Lactic acid (LA) is an important platform chemical with a wide range of applications, including bioplastic materials, and demand for it is growing rapidly. However, the high cost of feedstock for LA production is a major barrier to industrial production. This study designed a process to produce LA from chestnut shell (CS), a low-cost biomass. The entire process includes KOH pretreatment, enzymatic saccharification, and fermentation. This study investigated the chemical compositions and physicochemical properties of raw CS and KOH pretreated CS (KpCS) to evaluate the impact of the pretreatment process that enhances the conversion of cellulose into glucose. The results showed that KOH affected the lignin removal and surface morphological changes of CS, and FT-IR and TGA patterns correlated to increased cellulose fractions were found. In the fermentation process, Lacticaseibacillus rhamnosus was selected as a prominent LA producer, and the fermentation using KpCS hydrolysate was carried out. As a result, cell growth (27%), glucose consumption (23%), and LA production (21%) were all achieved higher than the control group. The LA production yield from our suggested process was estimated to be 187 g/kg CS, and we concluded that CS has a high potential as a feedstock for LA production.

Robust fabrication of sulfonated graphene oxide/poly (ether sulfone) catalytic membrane reactor for efficient cellulose hydrolysis and product separation

The efficient conversion of cellulose to high value-added products is important for the utilization of cellulose biomass. Achieving efficient cellulose hydrolysis and timely products separation is the essential target. Herein, a modified sulfonated graphene oxide/polydopamine deposited polyethersulfone (mGO(SO3H)-PDA/PES) membrane reactor, combining in the same unit a conversion effect and a separation effect, was prepared by suction filtration and subsequent polymerization and adhesion. The structure of PES membrane and deposition of PDA was regulated to sure that small molecules can pass through the membrane, while cellulose could not. As a result, the mGO(SO3H)-PDA/PES membrane realized the efficient cellulose hydrolysis and timely products separation under cross-flow circulation mode at 0.1 MPa, avoiding the further degradation of reducing sugar products. The yields of total reducing sugar (TRS) and glucose in separated hydrolysate reached 93.2 % and 85.5 %, respectively. This strategy provides potential guidance for efficient conversion of cellulose.

Enhancement of Liquid Hot Water Pretreatment on Corn Stover with Ball Milling to Improve Total Sugar Yields

Conversion of the lignocellulosic biomass to bioethanol contributes to the reduction of greenhouse gas emissions, enhancement of energy security, utilization of waste materials, and the promotion of sustainable agricultural practices. In this study, we report the effect of combining ball milling followed by liquid hot water (LHW) pretreatment of corn stover to lower the amount of enzyme required while also greatly increasing the recovery of xylose in fermentable form compared to either pretreatment alone. Short-duration ball milling for 60 min reduces the particle size of corn stover to 37.3 μm; however, the glucose only increased to 47% compared to 32% for unpretreated corn stover. In contrast, liquid hot water pretreatment alone can achieve increasing enzyme hydrolysis yields of cellulose from 49% to 93% as the pretreatment severity factor is increased from 3.24 to 4.41. However, the xylose yield decreased to 36% due to the fact that a considerable part of the xylose was degraded into furfural and humins. Surprisingly, the combination of mild ball milling (30 min) followed by mild liquid hot water pretreatment (190 °C, 15 min) could achieve both high glucose (83%) and xylose (72%) yields for a total sugar yield of 79%, theoretically. Thus, combining ball milling with liquid hot water pretreatment allows for milder conditions for both processes that lead to enhanced cellulose conversion without sacrificing xylose to degradation, which hinders enzymatic hydrolysis.

A robust mesoporous sulfated zirconium‐doped KIT‐6 solid acid catalyst for the hydrolysis of microcrystalline cellulose

AbstractBACKGROUNDThe exploration of a robust solid acid catalyst for the efficient hydrolysis of cellulose is a research hotspot due to the need for clean production and sustainable development. KIT‐6 silica offers abundant three‐dimensionally interconnected mesopores, which are expected to be superior to mesoporous structures with one‐ or two‐dimensional channels due to faster diffusion of reactants and products during reaction. The catalytic conversion of microcrystalline cellulose is examined in detail over a functionalized KIT‐6 catalyst prepared by the method of Zr addition and subsequent sulfation.RESULTSIn terms of cellulose conversion and product yield, the activity of the catalysts followed the order of sulfated Zr‐KIT‐6 > Zr‐KIT‐6 > SO42−‐KIT‐6 > KIT‐6. Over the sulfated Zr‐KIT‐6 catalyst with a Si/Zr molar ratio of 7:1, a maximum cellulose conversion of 95.0% was achieved with glucose yield of 23.4%, 5‐hydroxymethylfufural yield of 4.9% and levulinic acid yield of 11.7% under the optimized reaction conditions: reaction temperature of 200 °C, reaction time of 2 h, catalyst amount of 0.3 g, cellulose‐to‐water mass ratio of 1:1.CONCLUSIONThe sulfated Zr‐KIT‐6 catalyst possessed the strongest and richest Brønsted acid sites, which readily provided protons for the cleavage of β‐1,4 glycosidic bonds in cellulose, thus conferring superior catalytic activity in cellulose hydrolysis. A plausible pathway at the initial stage of cellulose hydrolysis over the catalyst was proposed. © 2023 Society of Chemical Industry (SCI).

A novel solid acid bearing thiophene group: Preparation and catalytic performance in cellulose hydrolysis

Two different aromatic monomers, naphthalene and benzothiophene, were ingeniously selected to prepare a solid acid with thiophene groups, which can selectively convert cellulose into glucose. The content of thiophene groups in the solid acids was regulated by adjusting the proportion of aromatic monomers. The effect of thiophene groups on physico-chemical structures and catalytic activity of solid acids was discussed. The experiment results indicate that the sulfur content in solid acids was up to 19.57 wt%. The introduction of thiophene groups increased –SO3H group density and adsorption capacity by 30.99 % and 64.36 %, respectively. These positive changes result in excellent catalytic activity of solid acids. The cellulose conversion rate and glucose selectivity reached 78.9 % and 97.1 % respectively at 150 °C and 7 h.

Nickel-tungsten co-doped biochar catalyst boosting ethylene glycol production from cellulose hydrogenolysis

Promoted ethylene glycol (EG) yield from cellulose hydrogenolysis is achieved via using Nickel-tungsten doped carbon catalysts prepared from glucose (x%Ni-y%WOx-GCT). Synchronously metal loading and carbon formation endow the catalyst excellent catalytic performance and high stability. Mechanistic investigations of the effects of metal loading and BrØnsted acid on EG yield are conducted. Increasing W loading promotes the content of polymerized WOx and consequently increases the amount of polytungstate species, thus lead to an improved BrØnsted acid content. Results reveal that promotion of B/L acid facilitates cellulose hydrolysis and suppresses isomerization of glucose to fructose. Besides, high W loading is beneficial for reduction of WOx to form W5+, producing oxygen vacancies to promote retro aldol condensation (RAC) of glucose to form acetaldehyde alcohol (an important intermediate for EG). By adopting the optimized 9%Ni-12%WOx-GC700 catalyst, a 100% cellulose conversion with a high EG yield of 65% is obtained due to the synergistic interactions between BrØnsted acid, W5+ and Ni0+ active sites.

CARBOHYDRASES – 50 YEARS OF RESEARCH AT THE DEPARTMENT OF CHEMICAL ENZYMOLOGY OF LOMONOSOV MOSCOW STATE UNIVERSITY, HISTORY AND PROSPECTS

The review describes the history of the development of research on carbohydrasеs conducted at the Department of Chemical Enzymology from the mid-1970s to the present. The results concerning the study of the mechanism and kinetics of the processes of enzymatic conversion of cellulose and renewable plant raw materials under the action of a multi-enzyme cellulases complexes; the role of individual components of these complexes - basic (endoglucanases and cellobiohydrolases) and auxiliary enzymes (polysaccharide monooxygenase, β-glucosidase, xylanase) and their synergistic interaction. The features of using reactors of various designs for bioconversion of plant raw materials are described: periodic type, continuous column type, reactor for hydrolysis in a constant electric field, reactor with intensive mixing by ferromagnetic particles in magnetic field. The possibilities of increasing the reactivity of plant raw materials using various pretreatment methods, as well as the influence of the structural and physico-chemical properties of cellulose on the efficiency of its enzymatic conversion are discussed. Data on the creation of highly active strains of microscopic fungi-producers of cellulases and other carbohydrases using methods of induced mutagenesis - Trichoderma (Hypocrea), Penicillium (Talaromyces), Aspergillus, Chrysosporium (Myceliophtora) spp., as well as data on the composition of the enzyme complexes produced by them and the properties of the enzymes forming them are presented. It describes the creation of expression systems based on P. canescens and P. verruculosum and the production of recombinant producer strains with their help, which made it possible to obtain enzyme preparations (EP) that ensure high efficiency of bioconversion processes of plant raw materials, as well as to create producers of a wide range of carbohydrases for practical use in various fields of industry and agriculture. A number of industrially important EP obtained using the P. verruculosum expression system are currently being produced at the Agroferment LLC plant.

Photocatalytic conversion of cellulose into C5 oligosaccharides

Cellulose is made up of linear polymers of glucose monomers that could be a crucial source for valuable chemicals and sustainable liquid fuels. Cellulose is however, very stable and its conversion to a useful fuel or platform chemical products remains a significant challenge (Kimura et al 2015 Sci. Rep. 5 16266; Xia et al 2016 Nat. Commun. 7 11162). Photocatalysis is a versatile technology which has demonstrated potential for solar driven processes such as water splitting or solar fuels production and has also been applied to the degradation of pollutants in air and water and for the production of useful products from biomass. Here, we focus on the products that are produced from cellulose (a glucose (C6) based polymer) photocatalysis that compliment hydrogen production. Probing the initial steps via UV-TiO2 photocatalysis, we remarkably find that an array of oligosaccharides containing only five (C5) carbon units is initially produced. As the process continues, C6 oligo oligosaccharides grow to dominate. The photocatalytic process is generally not viewed as a controllable synthetic process; however, these findings show, on the contrary that photocatalysis at semiconductor surfaces can achieve novel reaction pathways yielding new products.

Sustainable Production of Lactic Acid from Cellulose Using Au/W-ZnO Catalysts.

The catalytic conversion of cellulose to lactic acid (LA) has garnered significant attention in recent years due to the potential of cellulose as a renewable and sustainable biomass feedstock. Here, a series of Au/W-ZnO catalysts were synthesized and employed to transform cellulose into LA. Through the optimization of reaction parameters and catalyst compositions, we achieved complete cellulose conversion with a selectivity of 54.6% toward LA over Au/W-ZnO at 245 °C for 4 h. This catalyst system also proved effective at converting cotton and kenaf fibers. Structural and chemical characterizations revealed that the synergistic effect of W, ZnO, and Au facilitated mesoporous architecture generation and the establishment of an adequate acidic environment. The catalytic process proceeded through the hydrolysis of cellulose to glucose, isomerization to fructose, and its subsequent conversion to LA, with glucose isomerization identified as the rate-limiting step. These findings provide valuable insights for developing high-performance catalytic systems to convert cellulose.

Extraction of super high-yield lignin-carbohydrate complexes from rice straw without compromising cellulose hydrolysis

Lignin-carbohydrate complexes (LCC) that exhibit both structural advantages of lignin and carbohydrates are promising amphiphilic biopolymers, but the extraction is challenged by its liable chemical bond cleavage between lignin and carbohydrates. This work proposed a facile chemical route to integrating the production of water-insoluble (WIS LCC) and water-soluble LCC (WS LCC) into the emerging deep eutectic solvent (DES) biorefinery at mild conditions. The tailored mechanochemical fractionation process of ball milling assisted aqueous alkaline DES could extract 24.2 % LCC in total, with the co-production of a highly hydrolysable cellulose fraction (98.7 % glucose conversion). The resulting LCC exhibited considerably high contents of β-O-4, phenyl glycoside, and ferulic acid linkage bonds. When 100 g starting straw was subjected to this technique route, 9.1 g WIS LCC, 15.1 g WS LCC and 45.5 g glucose were cascaded produced. It was proposed that the selective disruption of hydrogen bonding entangled network and the quasi-state dissolution of the whole biomass allowed the subsequent cascade fractionation of WIS LCC, WS LCC and highly hydrolysable cellulose through solution property adjustment. This work showed a promising approach for LCC production with high yield without compromising cellulose conversion potential, which has been challenging in the current lignocellulose biorefinery.

Effects of alkaline‐acid treatment on the physiochemical attributes of natural cellulosic fiber of Arundo donaxL

AbstractIn the present investigation, the cellulose fibers were extracted from Arundo donax through a three‐step treatment. The effects of the alkaline pre‐treatment, acid hydrolysis, and soxhlet‐based extraction on the qualitative and quantitative attributes of the resultant cellulose fibers were investigated. The results of the present study signify a positive correlation between chemical treatment and cellulose content. The overall yield conversion of cellulose was recorded as 156.67%, after Soxhlet‐based purification. It was also observed that the moisture content, percentage of water absorption, rate of water absorption, and ash mass fraction gradually declined after each treatment step. The correlation between the chemical treatment with quantitative and qualitative attributes revealed a gradual increment in cellulose content, crystallinity index, and purity of cellulose fiber extracted from A. donax. The FTIR spectra emphasized that the obtained cellulose was free from impurities after Soxhlet‐based extraction. Simultaneously the DTG curve of A. donax fiber revealed a low rate of derivatization in the fibers extracted after Soxhlet treatment. The SEM and EDX analysis illustrate that the cellulose fibers were devoid of impurities as well as contamination of heavy metal ions.

Rice straw-derived cellulose: a comparative study of various pre-treatment technologies and its conversion to nanofibres

Rice straw is a waste product generated after the harvesting of rice crops and is commonly disposed of by burning it off in open fields. This study explored the potential for the extraction and conversion of cellulose to cellulose nanofibres (CNFs) to be used as smart delivery systems for fertilizers applications. In this study, alkali, steam explosion, and organosolv treatments were investigated for cellulose extraction efficiency. The morphological characterization of cellulose showed smooth fibrillar structures. Fourier transform infrared spectroscopy represented significant removal of non-cellulosic components in treatments. The crystallinity increased from 52.2 to 65% in CNFs after fibrillation. Cellulose nanofibres (CNFs) had an average diameter of 37.4 nm and − 25.2 mV surface charges as determined by SEM and zeta potential, respectively, which have desired properties for holding fertilizers. Therefore, this study paves the way for value-added uses of rice straw as alternatives to current environmentally harmful practices.

Optimization of Alkaline Hydrogen Peroxide Pretreatment and Enzymatic Hydrolysis of Wheat Straw for Enhancing Sugar Yields

Optimization of alkaline hydrogen peroxide (AHP) pretreatment and enzymatic hydrolysis of wheat straw (WS) was carried out to enhance fermentable sugar yields with the use of glucose and xylose yields from the pretreated WS as responses. In the first step, variables including temperature, hydrogen peroxide concentration and time during pretreatment were detected to have significant effects on the sugar yields. The results indicate that maximal sugar yields could be obtained while the WS was pretreated using 71 g/L hydrogen peroxide solution with 200 g/L of solid loading at 50 °C for 7.6 h. The corresponding cellulose recovery, hemicellulose recovery and lignin removal were 97.5%, 84.3% and 75.0%, respectively. In the second step, enzymatic hydrolysis of the pretreated WS was optimized. The results show that the reaction time, enzyme loading and biomass loading during enzymatic hydrolysis also had significant effects on the sugar yields. The final maximum yields of glucose (552.7 mg/gds (mg/g dry substrate)) and xylose (223.6 mg/gds) could be obtained while enzymatic hydrolysis was carried out at 50 °C for 37.0 h using 10.8 FPU/gds (filter paper activity unit per gram dry substrate) of enzyme loading, 88 g/L of biomass loading and 0.3% (w/v) of Tween-80. The corresponding cellulose conversion and hemicellulose conversion were 94.0% and 83.5%, respectively.