The potential for the transformation of lignocellulosic biomass into valuable commodities is rapidly growing through an environmentally sustainable approach to harness its abundance, cost-effectiveness, biodegradability, and environmentally friendly nature. Ionic liquids (ILs) have received considerable and widespread attention as a promising solution for efficiently dissolving lignocellulosic biomass. The fact that ILs can act as solvents and reagents contributes to their widespread recognition. In particular, ILs are desirable because they are inert, non-toxic, non-flammable, miscible in water, recyclable, thermally and chemically stable, and have low melting points and outstanding ionic conductivity. With these characteristics, ILs can serve as a reliable replacement for traditional biomass conversion methods in various applications. Thus, this comprehensive analysis explores the conversion of lignocellulosic biomass using ILs, focusing on main components such as cellulose, hemicellulose, and lignin. In addition, the effect of multiple parameters on the separation of lignocellulosic biomass using ILs is discussed to emphasize their potential to produce high-value products from this abundant and renewable resource. This work contributes to the advancement of green technologies, offering a promising avenue for the future of biomass conversion and sustainable resource management.
The conversion of lignocellulosic biomass into bioethanol or biochemical products requires a crucial pretreatment process to breakdown the recalcitrant lignin structure. This research focuses on the isolation and characterization of a lignin-degrading bacterial strain from a decaying oil palm empty fruit bunch (OPEFB). The isolated strain, identified as Streptomyces sp. S6, grew in a minimal medium with Kraft lignin (KL) as the sole carbon source. Several known ligninolytic enzyme assays were performed, and lignin peroxidase (LiP), laccase (Lac), dye-decolorizing peroxidase (DyP) and aryl-alcohol oxidase (AAO) activities were detected. A 55.3% reduction in the molecular weight (Mw) of KL was observed after 7 days of incubation with Streptomyces sp. S6 based on gel-permeation chromatography (GPC). Gas chromatography-mass spectrometry (GC-MS) also successfully highlighted the production of lignin-derived aromatic compounds, such as 3-methyl-butanoic acid, guaiacol derivatives, and 4,6-dimethyl-dodecane, after treatment of KL with strain S6. Finally, draft genome analysis of Streptomyces sp. S6 also revealed the presence of strong lignin degradation machinery and identified various candidate genes responsible for lignin depolymerization, as well as for the mineralization of the lower molecular weight compounds, confirming the lignin degradation capability of the bacterial strain.
Oil palm empty fruit bunch (EFB) was pretreated by Formiline process to overcome biomass recalcitrance and obtain hemicellulosic syrup and lignin. Higher formic acid concentration led to more lignin removal but also higher degree of cellulose formylation. Cellulose digestibility could be well recovered after deformylation with a small amount of lime. After digested by enzyme loading of 15 FPU+10 CBU/g solid for 48 h, the polysaccharide conversion could be over 90%. Simultaneous saccharification and fermentation (SSF) results demonstrated that ethanol concentration reached 83.6 g/L with approximate 85% of theoretic yield when performed at an initial dry solid consistency of 20%. A mass balance showed that via Formiline pretreatment 0.166 kg of ethanol could be produced from 1 kg of dry EFB with co-production of 0.14 kg of high-purity lignin and 5.26 kg hemicellulosic syrup containing 2.8% xylose. Formiline pretreatment thus can be employed as an entry for biorefining of EFB.
To isolate a bacterial strain capable of biotransforming ferulic acid, a major component of lignin, into vanillin and vanillic acid by a rapid colorimetric screening method.
Internal erosion is known as the most important cause of dam failure after overtopping. It is important to improve the erosion resistance of the erodible soil by selecting an effective technique along with the reasonable costs. To prevent internal erosion of embankment dams the use of chemical stabilizers that reduce the soil erodibility potential is highly recommended. In the present study, a lignin-based chemical, known as lignosulfonate, is used to improve the erodibility of clayey sand specimen. The clayey sand was tested in various hydraulic heads in terms of internal erosion in its natural state as well as when it is mixed with the different percentages of lignosulfonate. The results show that erodibility of collected clayey sand is very high and is dramatically reduced by adding lignosulfonate. Adding 3% of lignosulfonate to clayey sand can reduce the coefficient of soil erosion from 0.01020 to 0.000017. It is also found that the qualitative erodibility of stabilized soil with 3% lignosulfonate is altered from the group of extremely rapid to the group of moderately slow.
The composting of lignocellulosic oil palm empty fruit bunch (OPEFB) with continuous addition of palm oil mill (POME) anaerobic sludge which contained nutrients and indigenous microbes was studied. In comparison to the conventional OPEFB composting which took 60-90 days, the rapid composting in this study can be completed in 40 days with final C/N ratio of 12.4 and nitrogen (2.5%), phosphorus (1.4%), and potassium (2.8%), respectively. Twenty-seven cellulolytic bacterial strains of which 23 strains were closely related to Bacillus subtilis, Bacillus firmus, Thermobifida fusca, Thermomonospora spp., Cellulomonas sp., Ureibacillus thermosphaericus, Paenibacillus barengoltzii, Paenibacillus campinasensis, Geobacillus thermodenitrificans, Pseudoxanthomonas byssovorax which were known as lignocellulose degrading bacteria and commonly involved in lignocellulose degradation. Four isolated strains related to Exiguobacterium acetylicum and Rhizobium sp., with cellulolytic and hemicellulolytic activities. The rapid composting period achieved in this study can thus be attributed to the naturally occurring cellulolytic and hemicellulolytic strains identified.
Oil palm fronds are the most abundant lignocellulosic biomass in Malaysia. In this study, fronds were tested as the potential renewable biomass for ethanol production. The soaking in aqueous ammonia pretreatment was applied, and the fermentability of pretreated fronds was evaluated using simultaneous saccharification and fermentation. The optimal pretreatment conditions were 7 % (w/w) ammonia, 80 °C, 20 h of pretreatment, and 1:12 S/L ratio, where the enzymatic digestibility was 41.4 % with cellulase of 60 FPU/g-glucan. When increasing the cellulase loading in the hydrolysis of pretreated fronds, the enzymatic digestibility increased until the enzyme loading reached 60 FPU/g-glucan. With 3 % glucan loading in the SSF of pretreated fronds, the ethanol concentration and yield based on the theoretical maximum after 12 and 48 h of the SSF were 7.5 and 9.7 g/L and 43.8 and 56.8 %, respectively. The ethanol productivities found at 12 and 24 h from pretreated fronds were 0.62 and 0.36 g/L/h, respectively.
Sago pith residue is one of the most abundant lignocellulosic biomass which can serve as an alternative cheap substrate for fermentable sugars production. This residue is the fibrous waste left behind after the starch extraction process and contains significant amounts of starch (58%), cellulose (23%), hemicellulose (9.2%) and lignin (3.9%). The conversion of sago pith residue into fermentable sugars is commonly performed using cellulolytic enzymes or known as cellulases. In this study, crude cellulases were produced by two local isolates, Trichoderma asperellum UPM1 and Aspergillus fumigatus, UPM2 using sago pith residue as substrate. A. fumigatus UPM2 gave the highest FPase, CMCase and β-glucosidase activities of 0.39, 23.99 and 0.78 U/ml, respectively, on day 5. The highest activity of FPase, CMCase and β-glucosidase by T. asperellum UPM1 was 0.27, 12.03 and 0.42 U/ml, respectively, on day 7. The crude enzyme obtained from A. fumigatus UPM2 using β-glucosidase as the rate-limiting enzyme (3.9, 11.7 and 23.4 IU) was used for the saccharification process to convert 5% (w/v) sago pith residue into reducing sugars. Hydrolysis of sago pith residue using crude enzyme containing β-glucosidase with 23.4 IU, produced by A. fumigatus UPM2 gave higher reducing sugars production of 20.77 g/l with overall hydrolysis percentage of 73%.
The effect of chemical pretreatments using NaOH, H(2)O(2), and Ca(OH)(2) on Empty Palm Fruit Bunches (EPFB) to degrade EPFB lignin before pyrolysis was investigated. Spectrophotometer analysis proved consecutive addition of NaOH and H(2)O(2) decomposed almost 100% of EPFB lignin compared to 44% for the Ca(OH)(2), H(2)O(2) system while NaOH and Ca(OH)(2) used exclusively could not alter lignin much. Next, the pretreated EPFB was catalytically pyrolyzed. Experimental results indicated the phenolic yields over Al-MCM-41 and HZSM-5 catalysts were 90 wt% and 80 wt%, respectively compared to 67 wt% yield for the untreated sample under the same set of conditions. Meanwhile, the experiments with HY zeolite yielded 70 wt% phenols.
Currently, the transformation of lignocellulosic biomass into value-added products such as reducing sugars is garnering attention worldwide. However, efficient hydrolysis is usually hindered by the recalcitrant structure of the biomass. Many pretreatment technologies have been developed to overcome the recalcitrance of lignocellulose such that the components can be reutilized more effectively to enhance sugar recovery. Among all of the utilized pretreatment methods, inorganic salt pretreatment represents a more novel method and offers comparable sugar recovery with the potential for reducing costs. The use of inorganic salt also shows improved performance when it is integrated with other pretreatment technologies. Hence, this paper is aimed to provide a detailed overview of the current situation for lignocellulosic biomass and its physicochemical characteristics. Furthermore, this review discusses some recent studies using inorganic salt for pretreating biomass and the mechanisms involved during the process. Finally, some prospects and challenges using inorganic salt are highlighted.
Abundant lignocellulosic biomass from various industries provides a great potential feedstock for the production of value-added products such as biofuel, animal feed, and paper pulping. However, low yield of sugar obtained from lignocellulosic hydrolysate is usually due to the presence of lignin that acts as a protective barrier for cellulose and thus restricts the accessibility of the enzyme to work on the cellulosic component. This review focuses on the significance of biological pretreatment specifically using ligninolytic enzymes as an alternative method apart from the conventional physical and chemical pretreatment. Different modes of biological pretreatment are discussed in this paper which is based on (i) fungal pretreatment where fungi mycelia colonise and directly attack the substrate by releasing ligninolytic enzymes and (ii) enzymatic pretreatment using ligninolytic enzymes to counter the drawbacks of fungal pretreatment. This review also discusses the important factors of biological pretreatment using ligninolytic enzymes such as nature of the lignocellulosic biomass, pH, temperature, presence of mediator, oxygen, and surfactant during the biodelignification process.
Lignin was extracted from coconut husk via alkaline pulping, either Kraft or soda. The isolated lignin samples were classified as hydroxy-benzaldehyde, vanillin, and syringaldehyde type according to Fourier-transform Infrared Spectroscopy, 1H and 13C Nuclear Magnetic Resonance (NMR) spectra. Soda lignin (SL) showed higher thermal stability and glass transition temperature (Tg) than Kraft lignin (KL) as proven by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), respectively. The soda-lignin-phenol-glyoxal (SLPG) resins with the optimum percentage of lignin substitution at 30% showed improved solid content and gel time in comparison to 30% of Kraft-lignin-phenol-glyoxal (KLPG) and phenol-glyoxal (PG) resin. The good mechanical properties in SLPG is due to the higher amount of molecular weight as well as higher phenolic and G-type unit in lignin that improve the properties of 30% SLPG adhesive. Moreover, the addition of layered double hydroxides (LDH) as reinforced filler up to 15%-30% SLPG adhesive blend shows a great performance (especially mechanical properties) as compared to 30% SLPG adhesive alone.
The fast pyrolysis of waste lignin derived from biobutanol production process was performed to determine the optimal pyrolysis conditions and pyrolysis product properties. Four types of pyrolysis reactors, e.g.: micro-scale pyrolyzer-gas chromatography/mass spectrometry, lab and bench scale fixed bed (FB) reactors, and bench scale rotary kiln (RK) reactor, were employed to compare the pyrolysis reaction conditions and product properties obtained from different reactors. The yields of char, oil, and gas obtained from lab scale and bench scale reactor were almost similar compared to FB reactor. RK reactor produced desirable bio-oil with much reduced yield of poly aromatic hydrocarbons (cancer precursor) due to its higher cracking reaction efficiency. In addition, char agglomeration and foaming of lignin pyrolysis were greatly restricted by using RK reactor compared to the FB reactor.
Bacteria-derived enzymes that can modify specific lignin substructures are potential targets to engineer plants for better biomass processability. The Gram-negative bacterium Sphingobium sp. SYK-6 possesses a Cα-dehydrogenase (LigD) enzyme that has been shown to oxidize the α-hydroxy functionalities in β-O-4-linked dimers into α-keto analogues that are more chemically labile. Here, we show that recombinant LigD can oxidize an even wider range of β-O-4-linked dimers and oligomers, including the genuine dilignols, guaiacylglycerol-β-coniferyl alcohol ether and syringylglycerol-β-sinapyl alcohol ether. We explored the possibility of using LigD for biosynthetically engineering lignin by expressing the codon-optimized ligD gene in Arabidopsis thaliana. The ligD cDNA, with or without a signal peptide for apoplast targeting, has been successfully expressed, and LigD activity could be detected in the extracts of the transgenic plants. UPLC-MS/MS-based metabolite profiling indicated that levels of oxidized guaiacyl (G) β-O-4-coupled dilignols and analogues were significantly elevated in the LigD transgenic plants regardless of the signal peptide attachment to LigD. In parallel, 2D NMR analysis revealed a 2.1- to 2.8-fold increased level of G-type α-keto-β-O-4 linkages in cellulolytic enzyme lignins isolated from the stem cell walls of the LigD transgenic plants, indicating that the transformation was capable of altering lignin structure in the desired manner.
New and emerging demand for polyurethane (PU) continues to rise over the years. The harmful isocyanate binding agents and their integrated PU products are at the height of environmental concerns, in particular PU (macro and micro) pollution and their degradation problems. Non-isocyanate poly(hydroxy urethane)s (NIPUs) are sustainable and green alternatives to conventional PUs. Since the introduction of NIPU in 1957, the market value of NIPU and its hybridized materials has increased exponentially in 2019 and is expected to continue to rise in the coming years. The secondary hydroxyl groups of these NIPU's urethane moiety have revolutionized them by allowing for adequate pre/post functionalization. This minireview highlights different strategies and advances in pre/post-functionalization used in biobased NIPU. We have performed a comprehensive evaluation of the development of new ideas in this field to achieve more efficient synthetic biobased hybridized NIPU processes through selective and kinetic understanding.
This work reports on a complete isolation and characterization of lignocellulosic compounds from oil palm empty fruit bunch (OPEFB) by ionic liquid (IL) treatment and alkaline treatment processes. The fractionated lignocellulosic compounds were confirmed by FTIR and CP/MAS 13CNMR analyses. The yield of the cellulose, hemicellulose and lignin fractions was 52.72±1.50% wt., 27.17±1.68% wt. and 16.82±1.15% wt. with molecular weight of 1869g/mol, 1736g/mol and 2695g/mol, and degradation temperature of 325.65°C, 236.25°C, and 201.40°C, respectively. The SEM image illustrates the bundle-like fiber of cellulose fraction and smaller particle size of hemicellulose and lignin fractions with inconsistent shape. The XRD patterns depict the crystalline cellulose, amorphous lignin and partially amorphous hemicellulose fractions property. The IL could be recovered and reused with an overall recovery of 48% wt. after the fourth cycle.
Lignin extracted from oil palm fronds (OPF) underwent chemical modification by incorporating m-cresol into the lignin matrix. This study reports on the physicochemical properties and antioxidant activity of unmodified autohydrolyzed ethanol organosolv lignin (AH EOL) and the modified autohydrolyzed ethanol organosolv lignin (AHC EOL). The lignin samples were analyzed by FTIR, 1H and 13C NMR spectroscopy, 2D NMR: HSQC spectroscopy, CHN analysis, molecular weight distribution analysis; GPC and thermal analysis; DSC and TGA. The lignin modification has reduced the hydrophobicity of its complex structure by providing better quality lignin with smaller fragments and higher solubility rate in water (DAHCEOL: 42%>DAHEOL: 25%). It was revealed that the modification of lignin has improved their structural and antioxidant properties, thus venture their possible applications.
Lignocellulosic materials can significantly contribute to the development of eco-friendly wood adhesives. In this work, glyoxal-phenolic resins for plywood were prepared using organosolv lignin, which was isolated from black liquor recovered from organosolv pulping of oil palm fronds (OPF) and considered to be an alternative to phenol. Glyoxal, which is a dialdehyde obtained from several natural resources, was used as substitute for formaldehyde. The structure of organosolv lignin and the resins were characterized by FTIR and NMR, and for thermal stability by TGA and DSC. The resins were further studied for their viscosity, pH, solids content and gel times. The resins performance as wood adhesive was further established from mechanical test in terms of tensile strength and modulus of elasticity (MOE) to obtain the optimum ratios of organosolv lignin, which replaces phenol in organosolv lignin phenol glyoxal (OLPG) resins. The adhesive composition having 50% (w/w) of phenol substituted by organosolv lignin, termed as 50% OLPG showed highest adhesive strength compared to phenol formaldehyde (PF) commercial adhesive.
Lignocellulosic biomass waste is a cheap, eco-friendly, and sustainable raw material for a wide array of applications. In the present study, an easy, fast, and economically feasible route has been proposed for the preparation of different zero-valent metal nanoparticles (ZV-MNPs) based on Cu, Co, Ag, and Ni NPs using empty fruit bunch (EFB) biomass residue as support material. The catalytic efficiency of ZV-MNPs/EFB catalyst was investigated against five model pollutants, such as methyl orange (MO), congo red (CR), methylene blue (MB), acridine orange (AO), and 4-nitrophenol (4-NP) using NaBH4 as a source of hydrogen and electron. Comparative study revealed that among as-prepared ZV-MNPs/EFB catalysts, Cu-NPs immobilized onto EFB (Cu/EFB) exhibited maximum catalytic efficiency towards pollutant abasement. Degradation reactions were highly efficient, and were completed within a short time (4 min) in case of MO, CR, and MB, whilst AO and 4-NP were reduced in less than 15 min. Kinetic investigation revealed that the degradation rate of model pollutants accorded with pseudo-first order model. Furthermore, supported catalysts were easily recovered after the completion of experiment by simply pulling the catalyst from reaction system. Recyclability tests performed on Cu/EFB revealed that more than 97% of the reduction was achieved in case of MO dye for four successive cycles of reuse. The as-prepared heterostructure showed multifunctional properties, such as enhanced uptake of contaminants, high catalytic efficiency, and easy recovery, hence, offers great prospects in wastewater purification.
This study assesses the environmental impact of pine chip-based biorefinery processes, focusing on bioethanol, xylonic acid, and lignin production. A cradle-to-gate Life Cycle Assessment (LCA) is employed, comparing a novel biphasic pretreatment method (p-toluenesulfonic acid (TsOH)/pentanol, Sc-1) with conventional sulfuric acid pretreatment (H2SO4, Sc-2). The analysis spans biomass handling, pretreatment, enzymatic hydrolysis, yeast fermentation, and distillation. Sc-1 yielded an environmental impact of 1.45E+01 kPt, predominantly affecting human health (96.55%), followed by ecosystems (3.07%) and resources (0.38%). Bioethanol, xylonic acid, and lignin contributed 32.61%, 29.28%, and 38.11% to the total environmental burdens, respectively. Sc-2 resulted in an environmental burden of 1.64E+01 kPt, with a primary impact on human health (96.56%) and smaller roles for ecosystems (3.07%) and resources (0.38%). Bioethanol, xylonic acid, and lignin contributed differently at 22.59%, 12.5%, and 64.91%, respectively. Electricity generation was predominant in both scenarios, accounting for 99.05% of the environmental impact, primarily driven by its extensive usage in biomass handling and pretreatment processes. Sc-1 demonstrated a 13.05% lower environmental impact than Sc-2 due to decreased electricity consumption and increased bioethanol and xylonic acid outputs. This study highlights the pivotal role of pretreatment methods in wood-based biorefineries and underscores the urgency of sustainable alternatives like TsOH/pentanol. Additionally, adopting greener electricity generation, advanced technologies, and process optimization are crucial for reducing the environmental footprint of waste-based biorefineries while preserving valuable bioproduct production.