Lignin for Bioeconomy: The Present and Future Role of Technical Lignin.

Lignin, the term commonly used in literature, represents a group of heterogeneous aromatic compounds of plant origin. Protolignin or lignin in the cell wall is entirely different from the commercially available technical lignin due to changes during the delignification process. In this paper, we assess the status of lignin valorization in terms of commercial products. We start with existing knowledge of the lignin/protolignin structure in its native form and move to the technical lignin from various sources. Special attention is given to the patents and lignin-based commercial products. We observed that the technical lignin-based commercial products utilize coarse properties of the technical lignin in marketed formulations. Additionally, the general principles of polymers chemistry and self-assembly are difficult to apply in lignin-based nanotechnology, and lignin-centric investigations must be carried out. The alternate upcoming approach is to develop lignin-centric or lignin first bio-refineries for high-value applications; however, that brings its own technological challenges. The assessment of the gap between lab-scale applications and lignin-based commercial products delineates the challenges lignin nanoparticles-based technologies must meet to be a commercially viable alternative.

Cellulose nanofibers from lignocellulosic biomass of lemongrass using enzymatic hydrolysis: characterization and cytotoxicity assessment.

BACKGROUND: The lemongrass (LG) leaves could be a useful source of cellulose after its oil extraction, which is still either dumped or burned, not considered as a cost-effective approach. The synthesis of cellulose nanofibers (CNF) from LG waste has emerged as a beneficial alternative in the value-added applications. The non-toxicity, biodegradability, and biocompatibility of CNF have raised the interest in its manufacturing. METHOD: In the present study, we have isolated and characterized CNFs using enzymatic hydrolysis. We also explored the cytotoxic properties of the final material. The obtained products were characterized using dynamic light scattering (DLS), fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), x-ray diffraction (XRD), and thermogravimetric/differential thermal gravimetric analysis (TG/DTG). The cytotoxicity of CNF was assessed by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) assay against three different cancer cell lines NCIH460, PA1, and L132 cells. RESULTS: The FT-IR results showed that the resulting sample was of cellulose species, and CNF was found free from the non-cellulosic components like lignin and hemicellulose. The SEM micrographs of the cellulose showed a bundle like structure. The TEM micrographs of CNF showed diverse long fibers structure with 105.7 nm particle size analysed using DLS. The TGA analysis revealed that the thermal stability was slightly lower, compared to cellulose. Additionally, CNF did not show the cytotoxic effect at the tested concentrations (~10-1000 µg/ml) in any of the cell lines. CONCLUSION: Overall, the results concluded that LG waste-derived CNF is a potential sustainable material and could be employed as a favourable reinforcing agent or nanocarriers in diverse areas, mainly in food and drug delivery sectors. Graphical abstract Systematic representation of the synthesis of the cellulose nanofibers: The lignocellulosic waste of lemongrass (after oil extraction) was pretreated for the isolation of raw cellulose, followed by enzyme hydrolysis for the synthesis of pure cellulose nanofibers.

Yeast derived from lignocellulosic biomass as a sustainable feed resource for use in aquaculture.

The global expansion in aquaculture production implies an emerging need of suitable and sustainable protein sources. Currently, the fish feed industry is dependent on high-quality protein sources of marine and plant origin. Yeast derived from processing of low-value and non-food lignocellulosic biomass is a potential sustainable source of protein in fish diets. Following enzymatic hydrolysis, the hexose and pentose sugars of lignocellulosic substrates and supplementary nutrients can be converted into protein-rich yeast biomass by fermentation. Studies have shown that yeasts such as Saccharomyces cerevisiae, Candida utilis and Kluyveromyces marxianus have favourable amino acid composition and excellent properties as protein sources in diets for fish, including carnivorous species such as Atlantic salmon and rainbow trout. Suitable downstream processing of the biomass to disrupt cell walls is required to secure high nutrient digestibility. A number of studies have shown various immunological and health benefits from feeding fish low levels of yeast and yeast-derived cell wall fractions. This review summarises current literature on the potential of yeast from lignocellulosic biomass as an alternative protein source for the aquaculture industry. It is concluded that further research and development within yeast production can be important to secure the future sustainability and economic viability of intensive aquaculture. © 2016 Society of Chemical Industry.

Comparison of lignin extraction processes: Economic and environmental assessment.

This paper presents the technical-economic and environmental assessment of four lignin extraction processes from two different raw materials (sugarcane bagasse and rice husks). The processes are divided into two categories, the first processes evaluates lignin extraction with prior acid hydrolysis step, while in the second case the extraction processes are evaluated standalone for a total analysis of 16 scenarios. Profitability indicators as the net present value (NPV) and environmental indicators as the potential environmental impact (PEI) are used through a process engineering approach to understand and select the best lignin extraction process. The results show that both economically and environmentally process with sulfites and soda from rice husk presents the best results; however the quality of lignin obtained with sulfites is not suitable for high value-added products. Then, the soda is an interesting option for the extraction of lignin if high quality lignin is required for high value-added products at low costs.

Mild alkali-pretreatment effectively extracts guaiacyl-rich lignin for high lignocellulose digestibility coupled with largely diminishing yeast fermentation inhibitors in Miscanthus.

In this study, various alkali-pretreated lignocellulose enzymatic hydrolyses were evaluated by using three standard pairs of Miscanthus accessions that showed three distinct monolignol (G, S, H) compositions. Mfl26 samples with elevated G-levels exhibited significantly increased hexose yields of up to 1.61-fold compared to paired samples derived from enzymatic hydrolysis, whereas Msa29 samples with high H-levels displayed increased hexose yields of only up to 1.32-fold. In contrast, Mfl30 samples with elevated S-levels showed reduced hexose yields compared to the paired sample of 0.89-0.98 folds at p<0.01. Notably, only the G-rich biomass samples exhibited complete enzymatic hydrolysis under 4% NaOH pretreatment. Furthermore, the G-rich samples showed more effective extraction of lignin-hemicellulose complexes than the S- and H-rich samples upon NaOH pretreatment, resulting in large removal of lignin inhibitors to yeast fermentation. Therefore, this study proposes an optimal approach for minor genetic lignin modification towards cost-effective biomass process in Miscanthus.

Structural elucidation of sorghum lignins from an integrated biorefinery process based on hydrothermal and alkaline treatments.

An integrated process based on hydrothermal pretreatment (HTP) (i.e., 110-230 °C, 0.5-2.0 h) and alkaline post-treatment (2% NaOH at 90 °C for 2.0 h) has been performed for the production of xylooligosaccharide, lignin, and digestible substrate from sweet sorghum stems. The yield, purity, dissociation mechanisms, structural features, and structural transformations of alkali lignins obtained from the integrated process were investigated. It was found that the HTP process facilitated the subsequent alkaline delignification, releasing lignin with the highest yield (79.3%) and purity from the HTP residue obtained at 190 °C for 0.5 h. All of the results indicated that the cleavage of the ß-O-4 linkages and degradation of ß-ß and ß-5 linkages occurred under the harsh HTP conditions. Depolymerization and condensation reactions simultaneously occurred at higher temperatures (≥ 170 °C). Moreover, the thermostability of lignin was positively related to its molecular weight, but was also affected by the inherent structures, such as ß-O-4 linkages and condensed units. These findings will enhance the understanding of structural transformations of the lignins during the integrated process and maximize the potential utilizations of the lignins in a current biorefinery process.

Broad bean and pea by-products as sources of fibre-rich ingredients: potential antioxidant activity measured in vitro.

BACKGROUND: By-products generated during the processing of plant food can be considered a promising source of dietary fibre as a functional compound. The dietary fibre composition, soluble sugars and antioxidant activity of the extractable polyphenols of pea and broad bean by-products have been analysed in this study. RESULTS: Total dietary fibre using AOAC methods plus hydrolysis (broad bean pod: 337.3 g kg⁻¹; pea pod: 472.6 g kg⁻¹) is higher (P < 0.05) in both by-products than with the Englyst method (broad bean pod: 309.7 g kg⁻¹; pea pod: 434.6 g kg⁻¹). The main monomers are uronic acids, glucose, arabinose and galactose in broad bean pods. However, pea pods are very rich in glucose and xylose. The soluble sugars analysed by high-performance liquid chromatography in both by-products have glucose as the most important component, followed by sucrose and fructose. The ferric reducing antioxidant power (broad bean pod: 406.4 µmol Trolox equivalents g⁻¹; pea pod: 25.9 µmol Trolox equivalents g⁻¹) and scavenging effect on 2,2-diphenyl-1-picrylhydrazyl radical (EC50 of broad bean pod: 0.4 mg mL⁻¹; EC50 of pea pod: 16.0 mg mL⁻¹) were also measured. CONCLUSIONS: Broad bean and pea by-products are very rich in dietary fibre, particularly insoluble dietary fibre and their extractable polyphenols demonstrate antioxidant activity. Therefore they might be regarded as functional ingredients.

Effect of additives on fiber yield improvement for kraft pulping of kadam (Anthocephalus chinensis).

Projected decline in future wood resources has prompted researchers to try various additives in existing pulping processes for fiber yield improvement. Many studies have been conducted in the past aimed at improving kraft pulp yield with the use of additives in the cooking liquor. In this study, the effects of anthraquinone (AQ) and 2-methylanthraquinone (MAQ) on the pulp yield of kadam (Anthocephalus chinensis) were investigated. Three different active alkali doses (14%, 16% and 19% as NaOH) along with 0.1% of AQ or MAQ on chips were used to obtain various levels of delignification of the hardwood. Addition of AQ or MAQ to kraft pulping, increased fiber yield (0.5-2.7% on chips) and improved delignification selectivity (lignin vs. carbohydrate removal). Increases in pulp yield due to AQ or MAQ were more significant at lower doses of active alkalis. The viscosities and the physical strength properties of the pulps with kappa numbers 16-19 were comparable to kraft although there was a minor decrease in tensile strength for the kraft/MAQ pulp.

Structural characterization and antioxidant activity evaluation of lignins from rice husk.

In recent years, lignin and extractives from herbaceous plants and crops are receiving increasing attention for their renewability and large annual biomass stock. It is worth noting that only a few studies deal with the chemical characterization of rice husk, a side product of one of the most important crops with regard to human nutrition. Thus, in this study lignin from rice husk was isolated and characterized. Two different extraction procedures were optimized and tested: acidolysis and alkaline enzymatic (AE). The different lignins isolated were fully characterized by means of gravimetric, chromatographic (GPC), and spectroscopic (31P NMR, 2D-HSQC-NMR) analyses with the aim to compare yields, sample purity, and chemical properties, recognized as key parameters for future development. Notwithstanding the extraction procedure, the results highlighted that rice husk lignin is mainly formed by guaiacyl and p-hydroxyphenyl units. The acidolytic approach showed an appreciable lignin recovery and high purity, whereas the AE lignin sample was found to be rich in residual polysaccharides and oxidized functionalities. Moreover, different rice husk extracts, along with acidolysis lignin and AE lignin specimens, were assayed for their antioxidant activity by means of a DPPH radical scavenging test.

Accelerated solvent extraction of lignin from Aleurites moluccana (Candlenut) nutshells.

Lignin from candlenut shells was isolated using an ethanol-water accelerated solvent extraction method. Yields (based on Klason lignin) increased from about 14 to 33% as temperature increased from 100 to 195 °C and were also influenced by the amount of aqueous acid used to precipitate lignin from the extraction liquor. These yields were higher than could be obtained using a conventional dioxane-water acidolysis method. The resulting lignin was characterized by IR, 31P NMR, and 1H-13C HMQC NMR spectroscopic techniques. The lignin contained predominantly guaiacyl units, and both the total hydroxyl group content and phenolic hydroxyl group content were high.

In-series columns adsorption performance of Kraft mill wastewater pollutants onto volcanic soil.

Two in-series columns systems with volcanic soil were tested for wastewater pollutants adsorption capacity. The first system was tested with acidified volcanic soil and the second with a reactivated volcanic soil. The reactivated soil was obtained by washing the previous spent acidified soil system with an acid solution. The systems parameters were obtained using the Bohardt and Adams model for fixed-beds. The acidified soil parameters indicated an adsorption capacity q of 28 and 139 mg/g of phenolic compounds and color, respectively (for each column), compared to 12 and 39 mg/g for the reactivated soil system. The adsorption rate constant k ranged between 1.5x10(-6) and 2.8x10(-6) l/min mg and no significant difference was observed for each analysed column system and pollutant. Furthermore, the molecular weight distribution analysis of input and output samples of one acidified soil column indicated that the fraction >30000 Da is the most adsorbed until the breakpoint. Moreover, the CODs and tannins and lignin removal efficiencies at the breakpoint reached values between 60% and 70% in each column and each system, indicating that lower biodegradable compounds were retained effectively. The results indicate that it is possible to compare the acidified volcanic soil adsorption capacity with natural zeolites, and a preliminary costs evaluation indicates that volcanic soil could be also competitive, even when comparing with activated carbon.

Cellulase recovery via membrane filtration.

A combined sedimentation and membrane filtration process was investigated for recycling cellulase enzymes in the biomass-to-ethanol process. In the first stage, lignocellulose particles longer than approx 50 microm were removed by means of sedimentation in an inclined settler. Microfiltration was then utilized to remove the remaining suspended solids. Finally, the soluble cellulase enzymes were recovered by ultrafiltration. The permeate fluxes obtained in microfiltration and ultrafiltration were approx 400 and 80 L/(m2 x h), respectively. A preliminary economic analysis shows that the cost benefit of enzyme recycling may be as much as 18 cents/gal of ethanol produced, provided that 75% of the enzyme is recycled in active form.