The most critical issues faced by the world nowadays is to provide the sustainability of consumption for energy and natural resources. Lignin is said to be one of the alternative new discoveries best-suited lignocellulosic biomass due to its low cost, sufficient availability and environmentally safe. The valuable properties exhibited by lignin can give broader applications usage such as in composite materials, wood industries, polymer composite industries, pharmaceutical and corrosion inhibitor industries. Many biomass wastes resources, isolation processes and treatments are undergoing development in order to enhance the producing new lignin-based materials on an industrial scale. Therefore, this review discussed on the current knowledge on the structure and chemistry of isolation of lignin from different sources using various common methods, its characterization, properties and its applications.
Durian peel, an abundant waste in Malaysia could be a potential substrate for fermentable sugar recovery for value-added biochemical production. Common pretreatment such as acid or alkaline pretreatment resulted in the need for extensive solid washing which generated wastewater. Herein, this study aims to introduce sonication on top of chemical pretreatment to destruct lignin and reduce the chemical usage during the durian peel pretreatment process. In this study, the morphology and the chemical composition of the pretreated durian peels were studied. The sugar yield produced from the chemical pretreatment and the combined ultrasound and chemical pretreatment were compared. The morphology and chemical structure of durian peels were investigated by Scanning Electron Microscope (SEM), Fourier Transform Infrared (FTIR) analysis and X-ray diffraction (XRD). The SEM images showed that the structural change became more significant when sonication was introduced. Second, XRD profile indicated a relatively higher crystallinity index and FTIR spectra displayed a lower intensity of lignin and hemicellulose for ultrasound plus alkaline (UB) pretreatment as compared to acid, alkaline and ultrasound plus acid (UA) pretreatment. UB and UA pretreatment portrayed higher yield (376.60 ± 12.14 and 237.38 ± 3.96 mg reducing sugar/g dry biomass, respectively) than their controls without the application of ultrasound. Therefore, it could be concluded that ultrasound was able to intensify the fermentable sugar recovery from durian peel by inducing physical and chemical effect of cavitation to alter the morphology of durian peel. Fermentation of UB treated durian peel resulted in 2.68 mol hydrogen/mol consumed sugar and 131.56 mL/Lmedium/h of hydrogen productivity. This study is important because it will shed light on a way to handle durian waste disposal problems and generate fermentable sugars for the production of high value-added products.
In this study, oil palm empty fruit bunch (OPEFBF) was pretreated with alkali, and lignin was extracted for further degradation into lower molecular weight phenolic compounds using enzymes and chemical means. Efficiency of monomeric aromatic compounds production from OPEFBF lignin via chemical (nitrobenzene versus oxygen) and enzymatic [cutinase versus manganese peroxidase (MnP)] approaches was investigated. The effects of sodium hydroxide concentration (2, 5, and 10% wt.) and reaction time (30, 90, and 180 minutes) on the yield of aromatic compounds were studied. The results obtained indicated that nitrobenzene oxidation produced the highest yield (333.17 ± 49.44 ppm hydroxybenzoic acid, 5.67 ± 0.25 ppm p-hydroxybenzaldehyde, 25.57 ± 1.64 ppm vanillic acid, 168.68 ± 23.23 ppm vanillin, 75.44 ± 6.71 ppm syringic acid, 815.26 ± 41.77 ppm syringaldehyde, 15.21 ± 2.19 ppm p-coumaric acid, and 44.75 ± 3.40 ppm ferulic acid), among the tested methods. High sodium hydroxide concentration (10% wt.) was needed to promote efficient nitrobenzene oxidation. However, less severe oxidation condition was preferred to preserve the hydroxycinnamic acids (p-coumaric acid and ferulic acid). Cutinase-catalyzed hydrolysis was found to be more efficient than MnP-catalyzed oxidation in the production of aromatic compounds. By hydrolyzed 8% wt. of lignin with 0.625 mL cutinase g(-1) lignin at pH 8 and 55°C for 24 hours, about 642.83 ± 14.45 ppm hydroxybenzoic acid, 70.19 ± 3.31 ppm syringaldehyde, 22.80 ± 1.04 ppm vanillin, 27.06 ± 1.20 ppm p-coumaric acid, and 50.19 ± 2.23 ppm ferulic acid were produced.
In this study, acidic deep eutectic solvents (DES) synthesized from various organic carboxylic acid hydrogen bond donors were applied to lignocellulosic oil palm empty fruit bunch (EFB) pretreatment. The influence of functional group types on acid and their molar ratios with hydrogen bond acceptor on lignin extraction were evaluated. The result showed presence of hydroxyl group and short alkyl chain enhanced biomass fractionation and lignin extraction. Choline chloride:lactic acid (CC-LA) with the ratio of 1:15 and choline chloride:formic acid (CC-FA) with 1:2 ratio extracted more than 60 wt% of lignin. CC-LA DES-extracted lignin (DEEL) exhibited comparable reactivity with technical and commercial lignin based on its phenolic hydroxyl content (3.33-3.72 mmol/glignin). Also, the DES-pretreated EFB comprised of enriched glucan content after biopolymer fractionation. Both DES-pretreated EFB and DEEL can be potential feedstock for subsequent conversion processes. This study presented DES as an effective and facile pretreatment method for reactive lignin extraction.
The recent study focused on lignin-phenol-glyoxal (LPG) as an alternative way to replace toxic formaldehyde used in commercially available wood adhesives. The concern of the uses of carcinogenic formaldehyde in wood adhesive industry has become major problem over human health, environmental and economy issues. In this study, lignin isolated from Kenaf (Hibiscus cannabinus) via soda and Kraft pulping were modified into SLPG (soda lignin-phenol-glyoxal) and KLPG (Kraft lignin-phenol-glyoxal) adhesives and were compared to phenol-formaldehyde (PF). Complementary analyses such as Fourier Transform Infrared (FTIR) spectroscopy, 1H and 13C Nuclear Magnetic Resonance (NMR) spectroscopy, thermal stability; Thermogravimetric analysis (TGA) and Differential Scanning Calorimetry (DSC) were utilized to characterize all isolated lignin samples. The physical properties of the resins were further characterized in term of viscosity, gel time and total solid content. It was found that soda lignin comprised higher phenolic OH content and greater molecular weight compared to Kraft lignin. Various molar ratio of adhesives were applied on plywood and were mechanically tested. The 30% (w/w) SLPG has shown to have higher tensile strength and internal bonding stress at 72.08 MPa and 53.83 N mm-2 respectively to that of PF.
Biocomposites are materials that are easy to manufacture and environmentally friendly. Sugar palm fibre (SPF) is considered to be an emerging reinforcement candidate that could provide improved mechanical stiffness and strength to the biocomposites. Numerous studies have been recently conducted on sugar palm biocomposites to evaluate their physical, mechanical and thermal properties in various conditions. Sugar palm biocomposites are currently limited to the applications of traditional household products despite their good thermal stability as a prospective substitute candidate for synthetic fibres. Thus, thermal analysis methods such as TGA and DTG are functioned to determine the thermal properties of single fibre sugar palm composites (SPCs) in thermoset and thermoplastic matrix as well as hybrid SPCs. The biocomposites showed a remarkable change considering thermal stability by varying the individual fibre compositions and surface treatments and adding fillers and coupling agents. However, literature that summarises the thermal properties of sugar palm biocomposites is unavailable. Particularly, this comprehensive review paper aims to guide all composite engineers, designers, manufacturers and users on the selection of suitable biopolymers for sugar palm biocomposites for thermal applications, such as heat shields and engine components.
The conversion of starchy sago (Metroxylon sagu) pith waste (SPW), a lignocellulosic biomass waste, to fermentable sugars under mild conditions had been successfully demonstrated. The optimum depolymerization of SPW was achieved at 2 wt% sample loading which was catalyzed by 100 mM of oxalic acid in the presence of 25 wt% NaCl solution at 110 °C for 3 h. Up to 97% SPW sample was being converted into fermentable sugars with limited formation of by-products after two sequential depolymerization cycles. Both reaction temperature and concentration of oxalic acid were crucial parameters for the depolymerization of SPW which exhibited a high selectivity for the production of glucose over other reducing sugars.
Coating fertilizer particles with thin films is a possibility to control fertilizer release rates. It is observed that novel urea cross-linked starch-lignin composite thin films, prepared by solution casting, swell on coming into contact with water due to the increase in volume by water uptake by diffusion. The effect of lignin content, varied from 0% to 20% in steps of 5% at three different temperatures (25°C, 35°C and 45°C), on swelling of the film was investigated. By gravimetric analysis, the equilibrium water uptake and diffusion coefficient decrease with lignin content, indicating that the addition of lignin increases the hydrophobicity of the films. When temperature increases, the diffusion coefficient and the amount of water absorbed tend to increase. Assuming that swelling of the thin film is by water uptake by diffusion, the diffusion coefficient is estimated. The estimated diffusion coefficient decreases from 4.3 to 2.1 × 10-7 cm2/s at 25°C, from 5.3 to 2.9 × 10-7 cm2/s at 35°C and from 6.2 to 3.8 × 10-7 cm2/s at 45°C depending on the lignin content. Activation energy for the increase in diffusion coefficient with temperature is observed to be 16.55 kJ/mol. An empirical model of water uptake as a function of percentage of lignin and temperature was also developed based on Fick's law.
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.
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.
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.
Renewable energy from lignocellulosic biomass has been deemed an alternative to depleting fossil fuels. In order to improve this technology, we aim to develop robust mathematical models for the enzymatic lignocellulose degradation process. By analyzing 96 groups of previously published and newly obtained lignocellulose saccharification results and fitting them to Weibull distribution, we discovered Weibull statistics can accurately predict lignocellulose saccharification data, regardless of the type of substrates, enzymes and saccharification conditions. A mathematical model for enzymatic lignocellulose degradation was subsequently constructed based on Weibull statistics. Further analysis of the mathematical structure of the model and experimental saccharification data showed the significance of the two parameters in this model. In particular, the λ value, defined the characteristic time, represents the overall performance of the saccharification system. This suggestion was further supported by statistical analysis of experimental saccharification data and analysis of the glucose production levels when λ and n values change. In conclusion, the constructed Weibull statistics-based model can accurately predict lignocellulose hydrolysis behavior and we can use the λ parameter to assess the overall performance of enzymatic lignocellulose degradation. Advantages and potential applications of the model and the λ value in saccharification performance assessment were discussed.
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.
A study was carried out to determine the effectiveness of lignin, extracted from oil palm (Elaeis guineensis) biomass as water-in-oil (W/O) emulsifying agent. To achieve this goal, soda lignin (SL) was extracted via soda pulping process and a series of nanosized soda lignin (NSL) were prepared using homogenizer at three different speed i.e. 10,400 rpm (NSL 10), 11,400 rpm (NSL 11) and 12,400 rpm (NSL 12) for one hour. All prepared samples were characterized by FT-IR, UV-Vis spectroscopy, thermogravimetric analysis (TGA), zeta potential analyser, Transmission Electron Microscope (TEM) and Extreme High Resolution Field Emission Scanning Electron Microscope (XHR-FESEM). The result of FTIR showed that there is no prominent change occurred in spectra of all samples while a good stability was reflected by TGA curves. The percentage of creaming index and visual observations of all samples demonstrated that NSL 12 and dosage 2 g (out of 1 g, 1.5 g and 2 g) were found to be the best among all samples. Furthermore, the results of IFT indicate that NSL 12 was proven to be more stable than the commercial product. Therefore, NSL 12 is selected for toxicological studies and was found safe in both, in vitro and in vivo studies.
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.
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.