Search results for: lignin conversion

Authors: Binod Shrestha, Sandrine Hoppe, Thierry Ghislain, Phillipe Marchal, Nicolas Brosse, Anthony Dufour

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The thermochemical conversion of lignin has received an increasing interest in the frame of different biorefinery concepts for the production of chemicals or energy. It is needed to better understand the physical and chemical conversion of lignin for feeder and reactor designs. In-situ rheology reveals the viscoelastic behaviour of lignin upon thermal conversion. The softening, re-solidification (char formation), swelling and shrinking behaviours are quantified during pyrolysis in real-time [1]. The in-situ rheology of an alkali lignin (Protobind 1000) was conducted in high torque controlled strain rheometer from 35°C to 400°C with a heating rate of 5°C.min-1. The swelling, through glass phase transition overlapped with depolymerization, and solidification (crosslinking and “char” formation) are two main phenomena observed during lignin pyrolysis. The onset of temperatures for softening and solidification for this lignin has been found to be 141°C and 248°C respectively. An ex-situ characterization of lignin/char residues obtained at different temperatures after quenching in the rheometer gives a clear understanding of the pathway of lignin degradation. The lignin residues were sampled from the mid-point temperatures of the softening range and solidification range to study the chemical transformations undergoing. Elemental analysis, FTIR and solid state NMR were conducted after quenching the solid residues (lignin/char). The quenched solid was also extracted by suitable solvent and followed by acetylation and GPC-UV analysis. The combination of 13C NMR and GPC-UV reveals the depolymerization followed by crosslinking of lignin/char. NMR and FTIR provide the evolution of functional moieties upon temperature. Physical and chemical mechanisms occurring during lignin pyrolysis are accounted in this study. Thanks to all these complementary methods.

Keywords: pyrolysis, bio-chemicals, valorization, mechanism, softening, solidification, cross linking, rheology, spectroscopic methods

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Authors: Shyh-Ming Chern, Wei-Ling Lin

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Lignin is a major constituent of woody biomass, and exists abundantly in nature. It is the major byproducts from the paper industry and bioethanol production processes. The byproducts are mainly used for low-valued applications. Instead, lignin can be converted into higher-valued gaseous fuel, thereby helping to curtail the ever-growing price of oil and to slow down the trend of global warming. Although biochemical treatment is capable of converting cellulose into liquid ethanol fuel, it cannot be applied to the conversion of lignin. Alternatively, it is possible to convert lignin into gaseous fuel thermochemically. In the present work, trans-4-hydroxycinnamic acid, a model compound for lignin, which closely resembles the basic building blocks of lignin, is gasified in an autoclave with ethanol at elevated temperatures and pressures, that are above the critical point of ethanol. Ethanol, instead of water, is chosen, because ethanol dissolves trans-4-hydroxycinnamic acid easily and helps to convert it into lighter gaseous species relatively well. The major operating parameters for the gasification reaction include temperature (673-873 K), reaction pressure (5-25 MPa) and feed concentration (0.05-0.3 M). Generally, more than 80% of the reactant, including trans-4-hydroxycinnamic acid and ethanol, were converted into gaseous products at an operating condition of 873 K and 5 MPa.

Keywords: ethanol, gasification, lignin, supercritical

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Authors: Somayyeh Kalami, Mojgan Nejad

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Based on the source (softwood, hardwood or annual crop) and isolation method (kraft, organosolv, sulfite or pre-enzymatic treatment), there are significant variations in lignin structure and properties. The first step in using lignin as biobased feedstock is to make sure that specific lignin is suitable for intended application. Complete characterization of lignin and measuring its chemical, physical and thermal properties can help to predict its suitability. To replace 100% phenol portion of phenolic adhesive, lignin should have high reactivity toward formaldehyde. Theoretically, lignins with closer backbone structure to phenol should be better candidate for this application. In this study, a number of different lignins were characterized and used to formulate phenolic adhesive. One of the main findings was that lignin sample with higher percentage of hydroxyl-phenyl units was better candidate than lignin with more syringyl units. This could be explained by the fact that hydroxyl-phenyl lignin units have two available ortho positions for reaction with formaldehyde while in syringyl units all ortho and para positions are occupied, and there is no available site in lignin structure to react with formaldehyde.

Keywords: lignin, phenolic adhesive, biobased, sustainable

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Authors: Iris Vural Gursel, Andrea Ramirez

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Effective utilization of lignin is an important mean for developing economically profitable biorefineries. Current literature suggests that large amounts of lignin will become available in second generation biorefineries. New conversion technologies will, therefore, be needed to carry lignin transformation well beyond combustion to produce energy, but towards high-value products such as chemicals and transportation fuels. In recent years, significant progress on catalysis has been made to improve transformation of lignin, and new catalytic processes are emerging. In this work, a techno-economic assessment of two of these novel conversion routes and comparison with more established lignin pyrolysis route were made. The aim is to provide insights into the potential performance and potential hotspots in order to guide the experimental research and ease the commercialization by early identifying cost drivers, strengths, and challenges. The lignin conversion routes selected for detailed assessment were: (non-catalytic) lignin pyrolysis as the benchmark, direct hydrodeoxygenation (HDO) of lignin and hydrothermal lignin depolymerisation. Products generated were mixed oxygenated aromatic monomers (MOAMON), light organics, heavy organics, and char. For the technical assessment, a basis design followed by process modelling in Aspen was done using experimental yields. A design capacity of 200 kt/year lignin feed was chosen that is equivalent to a 1 Mt/y scale lignocellulosic biorefinery. The downstream equipment was modelled to achieve the separation of the product streams defined. For determining external utility requirement, heat integration was considered and when possible gasses were combusted to cover heating demand. The models made were used in generating necessary data on material and energy flows. Next, an economic assessment was carried out by estimating operating and capital costs. Return on investment (ROI) and payback period (PBP) were used as indicators. The results of the process modelling indicate that series of separation steps are required. The downstream processing was found especially demanding in the hydrothermal upgrading process due to the presence of significant amount of unconverted lignin (34%) and water. Also, external utility requirements were found to be high. Due to the complex separations, hydrothermal upgrading process showed the highest capital cost (50 M€ more than benchmark). Whereas operating costs were found the highest for the direct HDO process (20 M€/year more than benchmark) due to the use of hydrogen. Because of high yields to valuable heavy organics (32%) and MOAMON (24%), direct HDO process showed the highest ROI (12%) and the shortest PBP (5 years). This process is found feasible with a positive net present value. However, it is very sensitive to the prices used in the calculation. The assessments at this stage are associated with large uncertainties. Nevertheless, they are useful for comparing alternatives and identifying whether a certain process should be given further consideration. Among the three processes investigated here, the direct HDO process was seen to be the most promising.

Keywords: biorefinery, economic assessment, lignin conversion, process design

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Authors: Fatemeh Saadat Ghareh Bagh, Srimanta Ray, Jerald Lalman

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Lignin, the largest inventory of organic carbon with a high caloric energy value is a major component in woody and non-woody biomass. In pulping mills, a large amount of the lignin is burned for energy. At the same time, the phenolic structure of lignin enables it to be converted to value-added compounds.This study has focused on extracting lignin from black liquor using deep eutectic solvents (DESs). Therefore, three choline chloride (ChCl)-DESs paired with lactic acid (LA) (1:11), oxalic acid.2H₂O (OX) (1:4), and malic acid (MA) (1:3) were synthesized at 90oC and atmospheric pressure. The kinetics of lignin recovery from black liquor using DES was investigated at three moderate temperatures (338, 353, and 368 K) at time intervals from 30 to 210 min. The extracted lignin (acid soluble lignin plus Klason lignin) was characterized by Fourier transform infrared spectroscopy (FTIR). The FTIR studies included comparing the extracted lignin with a model Kraft lignin. The extracted lignin was characterized spectrophotometrically to determine the acid soluble lignin (ASL) [TAPPI UM 250] fraction and Klason lignin was determined gravimetrically using TAPPI T 222 om02. The lignin extraction reaction using DESs was modeled by first-order reaction kinetics and the activation energy of the process was determined. The ChCl:LA-DES recovered lignin was 79.7±2.1% at 368K and a DES:BL ratio of 4:1 (v/v). The quantity of lignin extracted for the control solvent, [emim][OAc], was 77.5+2.2%. The activation energy measured for the LA-DES system was 22.7 KJ mol⁻¹, while the activation energy for the OX-DES and MA-DES systems were 7.16 KJ·mol⁻¹ and 8.66 KJ·mol⁻¹ when the total lignin recovery was 75.4 ±0.9% and 62.4 ±1.4, % respectively.

Keywords: black liquor, deep eutectic solvents, kinetics, lignin

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Authors: Ivana Brzonova, Asina Fnu, Alena Kubatova, Evguenii Kozliak, Yun Ji

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Bio-decomposition of lignin by Basidiomycetes in the presence of dimethyl sulfoxide (DMSO) was investigated. The addition of 3-5 vol% DMSO to lignin aqueous media significantly increased the lignin solubility based on UV absorbance. After being dissolved in DMSO, the thermal evolution profile also changed significantly, yielding more high-MW organic carbon at the expense of recalcitrant elemental carbon. Medical fungi C. versicolor, G. lucidum and P. pulmonarius, were observed to grow on the lignin in media containing up to 15 vol. % DMSO. Further detailed product characterization by chromatographic methods corroborated these observations, as more low-MW phenolic products were observed with DMSO as a co-solvent. These results may be explained by the high solubility of lignin in DMSO; thus, the addition of DMSO to the medium increases the lignin availability for microorganisms. Some of these low-MW phenolic products host a big potential to be used in medicine. No significant inhibition of enzymatic activity (laccase, MnP, LiP) was observed by the addition of up to 3 vol% DMSO.

Keywords: basidiomycetes, bio-degradation, dimethyl sulfoxide, lignin

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Authors: Juan C. Domínguez, Belén Del Saz-Orozco, María V. Alonso, Mercedes Oliet, Francisco Rodríguez

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In the present study, the kinetics of thermal degradation of a phenolic and lignin reinforced phenolic foams, and the lignin used as reinforcement were studied and the activation energies of their degradation processes were obtained by a DAEM model. The average values for five heating rates of the mean activation energies obtained were: 99.1, 128.2, and 144.0 kJ.mol-1 for the phenolic foam, 109.5, 113.3, and 153.0 kJ.mol-1 for the lignin reinforcement, and 82.1, 106.9, and 124.4 kJ. mol-1 for the lignin reinforced phenolic foam. The standard deviation ranges calculated for each sample were 1.27-8.85, 2.22-12.82, and 3.17-8.11 kJ.mol-1 for the phenolic foam, lignin and the reinforced foam, respectively. The DAEM model showed low mean square errors (< 1x10-5), proving that is a suitable model to study the kinetics of thermal degradation of the foams and the reinforcement.

Keywords: kinetics, lignin, phenolic foam, thermal degradation

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Authors: S. Totong, P. Daorattanachai, N. Laosiripojana

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Lignin depolymerization into phenolic-based chemicals is an interesting process for utilizing and upgrading a benefit and value of lignin. In this study, the depolymerization reaction was performed to convert alkaline lignin into smaller molecule compounds. Fumed SiO₂ was used as a catalyst to improve catalytic activity in lignin decomposition. The important parameters in depolymerization process (i.e., reaction temperature, reaction time, etc.) were also investigated. In addition, gas chromatography with mass spectrometry (GC-MS), flame-ironized detector (GC-FID), and Fourier transform infrared spectroscopy (FT-IR) were used to analyze and characterize the lignin products. It was found that fumed SiO₂ catalyst led the good catalytic activity in lignin depolymerization. The main products from catalytic depolymerization were guaiacol, syringol, vanillin, and phenols. Additionally, metal supported on fumed SiO₂ such as Cu/SiO₂ and Ni/SiO₂ increased the catalyst activity in terms of phenolic products yield.

Keywords: alkaline lignin, catalytic, depolymerization, fumed SiO₂, phenolic-based chemicals

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Authors: Abayneh Getachew Demesa

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Interest in renewable feedstock for the chemical industry has increased considerably over the last decades, mainly due to environmental concerns and foreseeable shortage of fossil raw materials. Lignocellulosic biomass is an abundant source of bio-based raw material that is readily available and can be utilized as an alternative source for chemical production. Lignin accrues in enormous amounts as a by-product of the pulping process in the pulp and paper industry. It is estimated that 70 million tons of lignin are annually processed worldwide from the pulp and paper industry alone. Despite its attractive chemical composition, lignin is still insufficiently exploited and mainly regarded as bio-waste. Therefore, an environmentally benign process that can completely and competitively convert lignin into different value-added chemicals is needed to launch its commercial success on industrial scale. Partial wet oxidation by molecular oxygen has received increased attention as a potential process for production of chemicals from biomass wastes. In this paper, the production of chemicals by oxidation of lignin is investigated. The factors influencing the different types of products formed during the oxidation of lignin and their yields and compositions are discussed.

Keywords: biomass, lignin, waste, chemicals

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Authors: Bahiru Tsegaye, Chandrajit Balomajumder, Partha Roy

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The limited supply and related negative environmental consequence of fossil fuels are driving researcher for finding sustainable sources of energy. Lignocellulose biomass like sorghum straw is considered as among cheap, renewable and abundantly available sources of energy. However, lignocellulose biomass conversion to bioenergy like bioethanol is hindered due to the reluctant nature of lignin in the biomass. Therefore, removal of lignin is a vital step for lignocellulose conversion to renewable energy. The aim of this study is to optimize microwave pretreatment conditions using design expert software to remove lignin and to release maximum possible polysaccharides from sorghum straw for efficient hydrolysis and fermentation process. Sodium hydroxide concentration between 0.5-1.5%, v/v, pretreatment time from 5-25 minutes and pretreatment temperature from 120-2000C were considered to depolymerize sorghum straw. The effect of pretreatment was studied by analyzing the compositional changes before and after pretreatments following renewable energy laboratory procedure. Analysis of variance (ANOVA) was used to test the significance of the model used for optimization. About 32.8%-48.27% of hemicellulose solubilization, 53% -82.62% of cellulose release, and 49.25% to 78.29% lignin solubilization were observed during microwave pretreatment. Pretreatment for 10 minutes with alkali concentration of 1.5% and temperature of 1400C released maximum cellulose and lignin. At this optimal condition, maximum of 82.62% of cellulose release and 78.29% of lignin removal was achieved. Sorghum straw at optimal pretreatment condition was subjected to enzymatic hydrolysis and fermentation. The efficiency of hydrolysis was measured by analyzing reducing sugars by 3, 5 dinitrisylicylic acid method. Reducing sugars of about 619 mg/g of sorghum straw were obtained after enzymatic hydrolysis. This study showed a significant amount of lignin removal and cellulose release at optimal condition. This enhances the yield of reducing sugars as well as ethanol yield. The study demonstrates the potential of microwave pretreatments for enhancing bioethanol yield from sorghum straw.

Keywords: cellulose, hydrolysis, lignocellulose, optimization

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Authors: Dipti Yadav, Latha Rangan, Pinakeswar Mahanta

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Recent fuel-development strategies to reduce oil dependency, mitigate greenhouse gas emissions, and utilize domestic resources have generated interest in the search for alternative sources of fuel supplies. Bioenergy production from lignocellulosic biomass has a great potential. Cellulose, hemicellulose and Lignin are main constituent of woods or agrowaste. In all the industries there are always left over or waste products mainly lignin, due to the heterogeneous nature of wood and pulp fibers and the heterogeneity that exists between individual fibers, no method is currently available for the quantitative isolation of native or residual lignin without the risk of structural changes during the isolation. The potential benefits from finding alternative uses of lignin are extensive, and with a double effect. Lignin can be used to replace fossil-based raw materials in a wide range of products, from plastics to individual chemical products, activated carbon, motor fuels and carbon fibers. Furthermore, if there is a market for lignin for such value-added products, the mills will also have an additional economic incentive to take measures for higher energy efficiency. In this study residual lignin were isolated from areca nut shells by acid hydrolysis and were analyzed and characterized by Fourier Transform Infrared (FTIR), LCMS and complexity of its structure investigated by NMR.

Keywords: Areca nut, Lignin, wood, bioenergy

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Authors: V. Girard, I. Ziegler-Devin, H. Chapuis, N. Canilho, L. Marchal-Heussler, N. Brosse

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Lignocellulosic biomass is made up of the three polymeric fractions that are cellulose, hemicellulose, and lignin, which are highly entangled. In this project, we are particularly interested in the under-valued lignin polymer, which is mainly used for thermal valorization. Lignin from Macro to Nanosize (LIMINA) project will first focus on the extraction of macro lignin from forestry waste (hardwood and softwood) by the mean of eco-friendly processes (organosolv and steam explosion) and then the valorization of nano lignins produced by using anti-solvent precipitation (UV-blocker, cosmetic, food products).

Keywords: nanolignin, nanoparticles, organosolv, steam explosion

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Authors: Agnė Kairyte, Saulius Vaitkus

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The gradual depletion of fossil feedstock and growing environmental concerns attracted extensive attention to natural resources due to their low cost, high abundance, renewability, sustainability, and biodegradability. Lignin is a significant by-product of the pulp and paper industry, having unique functional groups. Recently it became interesting for the manufacturing of high value-added products such as polyurethane and polyisocyanurate foams. This study focuses on the development of high-performance polyurethane foams with various amounts of lignin as a filler. It is determined that the incorporation of lignin as a filler material results in brittle and hard products due to the low molecular mobility of isocyanates and the inherent stiffness of lignin. Therefore, the current study analyses new techniques and possibilities of liquid glass infusion onto the surface of lignin particles to reduce the negative aspects and improve the performance characteristics of the modified foams. The foams modified with sole lignin and liquid glass-infused lignin had an apparent density ranging from 35 kg/m3 to 45 kg/m3 and closed-cell content (80–90%). The incorporation of sole lignin reduced the compressive and tensile strengths and increased dimensional stability and water absorption, while the contrary results were observed for polyurethane foams with liquid glass-infused lignin particles. The effect on rheological parameters of lignin and liquid glass infused lignin modified polyurethane premixes and morphology of polyurethane foam products were monitored to optimize the conditions and reveal the significant influence of the interaction between particles and polymer matrix.

Keywords: filler, lignin waste, liquid glass, polymer matrix, polyurethane foam, sustainability

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Authors: Samy Madbouly

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The relaxation behavior of biorenewable castor oil-based polyurethane-lignin thin films synthesized in homogenous waterborne dispersions was investigated as a function of concentration at different temperatures and frequencies using broadband dielectric relaxation spectroscopy (BDRS). The molecular dynamics of the glass relaxation process and the local relaxation process of the PU-LS thin films were studied over a wide range of temperatures (-70 to 30 ℃) and frequencies (5 × 10−2 to 0.5 × 107 Hz) for different lignin concentration. Four relaxation processes have been observed namely; ?-, β-, γ-relaxations and ionic conductivity for pure castor oil-based PU and castor oil-lignin-based PU thin films at different temperatures and frequencies ranges. The Vogel-Fulcher-Tammann equation was found to be well described the temperature dependence of the characteristic relaxation times of the ?-relaxation process. However, on the other hand, the molecular dynamics of both β- and γ-relaxation processes were given by the Arrhenius equation. The incorporation of lignin into the castor oil-based PU significantly increased the glass transition temperature and primitivity of the thin films. In addition, the broadness, intensity, and molecular dynamics of the only observed ?-relaxation process were found to be strongly dependent on lignin concentration.

Keywords: castor oil, lignin, polyurethane, dielectric, dispersions

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Authors: Muhammad Rizwan Tabassum, Ao Xia, Jerry D. Murphy

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The purpose of this work is to provide a comprehensive overview of seaweed as the alternative feedstock for biofuel production and key conversion technologies. Resource depletion and climate change are the driving forces to hunt for renewable sources of energy. Macroalgae can be preferred over land based crops for biofuel production because they are not in competition with food crops for arable land, high growth rates and low lignin contents which require less energy-intensive pre-treatments. However, some disadvantages, such as high moisture content, seasonal variation in chemical composition and process inhibition limit its economic feasibility. Seaweed can be converted into gaseous and liquid fuel by different conversion technologies, but biogas via anaerobic digestion from seaweed is attracting increased attention due to its dual benefit of an economic source of bio-fuel and environment-friendly technology. Biodiesel and bioethanol conversion technologies from seaweed are still under development. A selection of high yielding seaweed species, optimal harvesting season and process optimization make them economically feasible for the alternative source of renewable and sustainable feedstock for biofuel in future.

Keywords: anaerobic digestion, biofuel, bio-methane, conversion technologies, seaweed

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Authors: Joana Antunes, Thomas Levée, Barbara Radovani, Anu Suonpää, Paulina Saloranta, Liji Sobhana, Petri Ihalainen

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Lignin is an important component in the exploitation of lignocellulosic biomass. It has been shown that within the next years, the yield of added-value lignin-based chemicals and materials will generate renewable alternatives to oil-based products (e.g. polymeric composites, resins and adhesives) and enhance the economic feasibility of biorefineries. In this paper, a novel technology for lignin valorisation (METNIN™) is presented. METNIN™ is based on the oxidative action of an alkaliphilic enzyme in aqueous alkaline conditions (pH 10-11) at mild temperature (40-50 °C) combined with a cascading membrane operation, yielding a collection of lignin fractions (from oligomeric down to mixture of tri-, di- and monomeric units) with distinct molecular weight distribution, low polydispersity and favourable physicochemical properties. The alkaline process conditions ensure the high processibility of crude lignin in an aqueous environment and the efficiency of the enzyme, yielding better compatibility of lignin towards targeted applications. The application of a selected lignin fraction produced by METNIN™ as a suitable lignopolyol to completely replace a commercial polyol in polyurethane rigid foam formulations is presented as a prototype. Liquid lignopolyols with a high lignin content were prepared by oxypropylation and their full utilization in the polyurethane rigid foam formulation was successfully demonstrated. Moreover, selected technical specifications of different foam demonstrators were determined, including closed cell count, water uptake and compression characteristics. These specifications are within industrial standards for rigid foam applications. The lignin loading in the lignopolyol was a major factor determining the properties of the foam. In addition to polyurethane foam demonstrators, other examples of lignin-based products related to resins and sizing applications will be presented.

Keywords: enzyme, lignin valorisation, polyol, polyurethane foam

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Authors: Masoumeh Ghorbania, Falk Liebnerb, Hendrikus W.G. van Herwijnenc, Johannes Konnertha

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Phenol formaldehyde (PF) resins are widely used as wood adhesives for variety of industrial products such as plywood, laminated veneer lumber and others. Lignin as a main constituent of wood has become well-known as a potential substitute for phenol in PF adhesives because of their structural similarity. During the last decades numerous research approaches have been carried out to substitute phenol with pulping-derived lignin, whereby the lower reactivity of resins synthesized with shares of lignin seem to be one of the major challenges. This work reports about a systematic screening of different types of lignin (plant origin and pulping process) for their suitability to replace phenol in phenolic resins. Lignin from different plant sources (softwood, hardwood and grass) were used, as these should differ significantly in their reactivity towards formaldehyde of their reactive phenolic core units. Additionally a possible influence of the pulping process was addressed by using the different types of lignin from soda, kraft, and organosolv process and various lignosulfonates (sodium, ammonium, calcium, magnesium). To determine the influence of lignin on the adhesive performance beside others the rate of viscosity development, bond strength development of varying hot pressing time and other thermal properties were investigated. To evaluate the performance of the cured end product, a few selected properties were studied at the example of solid wood-adhesive bond joints, compact panels and plywood. As main results it was found that lignin significantly accelerates the viscosity development in adhesive synthesis. Bonding strength development during curing of adhesives decelerated for all lignin types, while this trend was least for pine kraft lignin and spruce sodium lignosulfonate. However, the overall performance of the products prepared with the latter adhesives was able to fulfill main standard requirements, even after exposing the products to harsh environmental conditions. Thus, a potential application can be considered for processes where reactivity is less critical but adhesive cost and product performance is essential.

Keywords: phenol formaldehyde resin, lignin phenol formaldehyde resin, ABES, DSC

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Authors: Prima Luna, Afroditi Chatzifragkou, Dimitris Charalampopoulos

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Sorghum byproducts, namely bran, stalk, and panicle are examples of lignocellulosic biomass. These raw materials contain large amounts of polysaccharides, in particular hemicelluloses, celluloses, and lignins, which if efficiently extracted, can be utilised for the development of a range of added value products with potential applications in agriculture and food packaging sectors. The aim of this study was to characterise fractions extracted from sorghum bran and stalk with regards to their physicochemical properties that could determine their applicability as food-packaging materials. A sequential alkaline extraction was applied for the isolation of cellulosic, hemicellulosic and lignin fractions from sorghum stalk and bran. Lignin content, phenolic content and antioxidant capacity were also investigated in the case of the lignin fraction. Thermal analysis using differential scanning calorimetry (DSC) and X-Ray Diffraction (XRD) revealed that the glass transition temperature (T_g) of cellulose fraction of the stalk was ~78.33 ^oC at amorphous state (~65%) and water content of ~5%. In terms of hemicellulose, the T_g value of stalk was slightly lower compared to bran at amorphous state (~54%) and had less water content (~2%). It is evident that hemicelluloses generally showed a lower thermal stability compared to cellulose, probably due to their lack of crystallinity. Additionally, bran had higher arabinose-to-xylose ratio (0.82) than the stalk, a fact that indicated its low crystallinity. Furthermore, lignin fraction had T_g value of ~93 ^oC at amorphous state (~11%). Stalk-derived lignin fraction contained more phenolic compounds (mainly consisting of p-coumaric and ferulic acid) and had higher lignin content and antioxidant capacity compared to bran-derived lignin fraction.

Keywords: alkaline extraction, bran, cellulose, hemicellulose, lignin, stalk

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Authors: Fnu Asina, Ivana Brzonova, Keith Voeller, Yun Ji, Alena Kubatova, Evguenii Kozliak

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Lignin, a heterogeneous three-dimensional biopolymer, is one of the building blocks of lignocellulosic biomass. Due to its limited chemical reactivity, lignin is currently processed as a low-value by-product in pulp and paper mills. Among various industrial lignins, Kraft lignin represents a major source of by-products generated during the widely employed pulping process across the pulp and paper industry. Therefore, valorization of Kraft lignin holds great potential as this would provide a readily available source of aromatic compounds for various industrial applications. Microbial degradation is well known for using both highly specific ligninolytic enzymes secreted by microorganisms and mild operating conditions compared with conventional chemical approaches. In this study, the degradation of Indulin AT lignin was assessed by comparing the effects of Basidiomycetous fungi (Coriolus versicolour and Trametes gallica) and Actinobacteria (Mycobacterium sp. and Streptomyces sp.) to two commercial laccases, T. versicolour ( ≥ 10 U/mg) and C. versicolour ( ≥ 0.3 U/mg). After 54 days of cultivation, the extent of microbial degradation was significantly higher than that of commercial laccases, reaching a maximum of 38 wt% degradation for C. versicolour treated samples. Lignin degradation was further confirmed by thermal carbon analysis with a five-step temperature protocol. Compared with commercial laccases, a significant decrease in char formation at 850ºC was observed among all microbial-degraded lignins with a corresponding carbon percentage increase from 200ºC to 500ºC. To complement the carbon analysis result, chemical characterization of the degraded products at different stages of the delignification by microorganisms and commercial laccases was performed by Pyrolysis-GC-MS.

Keywords: lignin, microbial degradation, pyrolysis-GC-MS, thermal carbon analysis

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Authors: Mohammed Saidu, Afiz Busari, Ali Yuzir, Mohd Razman Salim

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Degradation of agricultural residues from palm oil industry is increasing due to its expansion. Lignocelloulosic waste from these industry represent large amount of unutilized resources, this is due to their high lignin content. Since, white rot fungi are capable of degrading the lignin, its potential to degradation was accessed for upgrading it. The lignocellluloses content was measured before and after biodegradation and the rate of reduction was determined. From the results of biodegradation, it was observed that hemicellulose reduces by 22.62%, cellulose by 20.97% and lignin by 10.65% from the initials lignocelluloses contents. Thus, to improve the digestibility of palm oil mesocarp fibre, treatment by white rot-fungi is recommended.

Keywords: biological, fungi, lignocelluses, oil palm

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Authors: M. Goliszek, M. Sobiesiak, O. Sevastyanova, B. Podkoscielna

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Lignin is one of three main constituents of biomass together with cellulose and hemicellulose. It is a complex biopolymer, which contains a large number of functional groups, including aliphatic and aromatic hydroxyl groups, carbohylic groups and methoxy groups in its structure, that is why it shows potential capacities for process of sorption. Lignin is a highly cross-linked polymer with a three-dimentional structure which can provide large surface area and pore volumes. It can also posses better dispersion, diffusion and mass transfer behavior in a field of the removal of, e.g., heavy-metal-ions or aromatic pollutions. In this work emulsion-suspension copolymerization method, to synthesize the porous microspheres of divinylbenzene (DVB), styrene (St) and lignin was used. There are also microspheres without the addition of lignin for comparison. Before the copolymerization, modification lignin with methacryloyl chloride, to improve its reactivity with other monomers was done. The physico-chemical properties of the obtained microspheres, e.g., pore structures (adsorption-desorption measurements), thermal properties (DSC), tendencies to swell and the actual shapes were also studied. Due to well-developed porous structure and the presence of functional groups our materials may have great potential in sorption processes. To estimate the sorption capabilities of the microspheres towards phenol and its chlorinated derivatives the off-line SPE (solid-phase extraction) method is going to be applied. This method has various advantages, including low-cost, easy to use and enables the rapid measurements for a large number of chemicals. The efficiency of the materials in removing phenols from aqueous solution and in desorption processes will be evaluated.

Keywords: microspheres, lignin, sorption, solid-phase extraction

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Authors: Xiang Zheng, Zhaoping Zhong

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In this study, Aspen Plus was used to simulate the whole process of biomass conversion to liquid fuel in different ways, and the main results of material and energy flow were obtained. The process optimization and evaluation were carried out on the four routes of cellulosic biomass pyrolysis gasification low-carbon olefin synthesis olefin oligomerization, biomass water pyrolysis and polymerization to jet fuel, biomass fermentation to ethanol, and biomass pyrolysis to liquid fuel. The environmental impacts of three biomass species (poplar wood, corn stover, and rice husk) were compared by the gasification synthesis pathway. The global warming potential, acidification potential, and eutrophication potential of the three biomasses were the same as those of rice husk > poplar wood > corn stover. In terms of human health hazard potential and solid waste potential, the results were poplar > rice husk > corn stover. In the popular pathway, 100 kg of poplar biomass was input to obtain 11.9 kg of aviation coal fraction and 6.3 kg of gasoline fraction. The energy conversion rate of the system was 31.6% when the output product energy included only the aviation coal product. In the basic process of hydrothermal depolymerization process, 14.41 kg aviation kerosene was produced per 100 kg biomass. The energy conversion rate of the basic process was 33.09%, which can be increased to 38.47% after the optimal utilization of lignin gasification and steam reforming for hydrogen production. The total exergy efficiency of the system increased from 30.48% to 34.43% after optimization, and the exergy loss mainly came from the concentration of precursor dilute solution. Global warming potential in environmental impact is mostly affected by the production process. Poplar wood was used as raw material in the process of ethanol production from cellulosic biomass. The simulation results showed that 827.4 kg of pretreatment mixture, 450.6 kg of fermentation broth, and 24.8 kg of ethanol were produced per 100 kg of biomass. The power output of boiler combustion reached 94.1 MJ, the unit power consumption in the process was 174.9 MJ, and the energy conversion rate was 33.5%. The environmental impact was mainly concentrated in the production process and agricultural processes. On the basis of the original biomass pyrolysis to liquid fuel, the enzymatic hydrolysis lignin residue produced by cellulose fermentation to produce ethanol was used as the pyrolysis raw material, and the fermentation and pyrolysis processes were coupled. In the coupled process, 24.8 kg ethanol and 4.78 kg upgraded liquid fuel were produced per 100 kg biomass with an energy conversion rate of 35.13%.

Keywords: biomass conversion, biofuel, process optimization, life cycle assessment

Procedia PDF Downloads 43

Authors: Mohd Ishfaq Bhat, Navin Chandra Shahi, Umesh Chandra Lohani

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The present study aimed to evaluate the effect of microwave application in synergy with the conventional sodium chlorite delignification of rice straw biomass. For the study, Box-Behnken experimental design involving four independent parameters, each with three levels viz. microwave power (480-800 W), irradiation time (4-12 min), bleaching solution concentration (0.4-3.0%), and bleaching time (1-5h) was used. The response was taken in the form of delignification percentage. The optimization of process parameters was done through response surface methodology. The respective optimum parameters of microwave power, irradiation time, bleaching solution concentration, and bleaching time were obtained as 671 W, 8.66 min, 2.67%, and 1h. The delignification percentage achieved at optimum conditions was 93.51%. The spectral, morphological, and x-ray diffraction characteristics of the rice straw powder after delignification showed a complete absence of lignin peaks, deconstruction of lignocellulose complex, and an increase of crystallinity (from 39.8 to 61.6 %).

Keywords: lignocellulosic biomass, delignification, microwaves, rice straw, characterization

Procedia PDF Downloads 115

Authors: Nasim Rasuli, Akram Ahmadi, Hossein Riahi, Zeinab Shariatmadari, Majid Ghorbani Nohooji, Pooyan Mehraban Joubani

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Cyanobacteria are one of the most promising sources of new biostimulants and have received much attention due to their diverse applications in biotechnology. These microorganisms enhance the growth and productivity of plants by producing plant growth stimulants and fixing atmospheric nitrogen. Thymus vulgaris L., a valuable medicinal plant from the Lamiaceae family, is widely distributed across the globe. essential oil of T. vulgaris is best characterized by the prominence of phenols, making them the key compounds in its composition. Lignin biosynthesis as a natural plant polyphenol plays a crucial role in promoting plant growth, strengthening cell walls, and increasing resistance to pathogens. In this study, the bioelicitor activity of five cyanobacterial suspensions including Anabaena torulosa ISB213, Nostoc calcicola ISB215, Nostoc ellipsosporum ISB217, Trichormus doliolum ISB214, and Oscillatoria sp. ISB2116 on the lignin content of the T. vulgaris L. was investigated. Pot experiments were performed by inoculation of a %2 algal extract to the soil of treated plants one week before planting and then every 20 days. After four months, the lignin content in the leaves of both treated and control plants was evaluated. The results demonstrated that the application of cyanobacteria significantly increased the lignin content in the leaves of treated plants compared to the control. The treatment with Oscillatoria sp. ISB216 and N. ellipsosporum ISB217 resulted in the highest lignin content, with an increase of 93.33% and 86.67%, respectively. These findings highlight the potential of cyanobacteria as bioelicitors, offering a viable alternative for enhancing the production of secondary metabolites in T. vulgaris. Consequently, this could contribute to the economic value of this medicinal plant.

Keywords: cyanobacteria, bioelicitor, thymus vulgaris, lignin

Procedia PDF Downloads 36

Authors: L. Cesari, L. Canabady-Rochelle, F. Mutelet

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The thermal conversion of lignin produces bio-oils that contain many compounds with high added-value such as phenolic compounds. In order to efficiently extract these compounds, the possible use of choline bis(trifluoromethylsulfonyl)imide [Choline][NTf2] ionic liquid was explored. To this end, a multistep approach was implemented. First, binary (phenolic compound and solvent) and ternary (phenolic compound and solvent and ionic liquid) solutions were investigated. Eight binary systems of phenolic compound and water were investigated at atmospheric pressure. These systems were quantified using the turbidity method and UV-spectroscopy. Ternary systems (phenolic compound and water and [Choline][NTf2]) were investigated at room temperature and atmospheric pressure. After stirring, the solutions were let to settle down, and a sample of each phase was collected. The analysis of the phases was performed using gas chromatography with an internal standard. These results were used to quantify the values of the interaction parameters of thermodynamic models. Then, extractions were performed on synthetic solutions to determine the influence of several operating conditions (temperature, kinetics, amount of [Choline][NTf2]). With this knowledge, it has been possible to design and simulate an extraction process composed of one extraction column and one flash. Finally, the extraction efficiency of [Choline][NTf2] was quantified with real bio-oils from lignin pyrolysis. Qualitative and quantitative analysis were performed using gas chromatographic connected to mass spectroscopy and flame ionization detector. The experimental measurements show that the extraction of phenolic compounds is efficient at room temperature, quick and does not require a high amount of [Choline][NTf2]. Moreover, the simulations of the extraction process demonstrate that [Choline][NTf2] process requires less energy than an organic one. Finally, the efficiency of [Choline][NTf2] was confirmed in real situations with the experiments on lignin pyrolysis bio-oils.

Keywords: bio-oils, extraction, lignin, phenolic compounds

Procedia PDF Downloads 77

Authors: S. Hussain, N. Ahmad, S. Alam, M. Bezabhi, W. H. Hendriks, P. Yu, J. W. Cone

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The high content of lignin in cell walls is the major limiting factor in the digestion and utilisation of cereal crop residues by ruminants. The aim of this study was to evaluate the effectiveness of the white rot fungus, Pleurotus ostreatus (P. ostreatus), to degrade lignin and to enhance the rumen degradability of maize stover, rice straw, wheat straw and their mixture in equal proportion on a dry-matter (DM) basis. Four samples of each substrate were incubated aerobically in triplicate with P. ostreatus for 0 (Control), 21, 28 and 35 days under solid-state conditions (temperature, 24 ͦ C; humidity, 70± 5%). The changes in chemical composition, DM and nutrient losses, and rumen fermentation characteristics using in vitro DM digestibility (DMD) and the in vitro gas production (GP) technique were measured. The results showed that incubation with P. ostreatus decreased (P < 0.001) the contents of neutral detergent fibre and lignin with a concomitant increase (P < 0.001) in the contents of ash and crude protein. The losses of nutrients differed (P < 0.001) among the straw types, with rice straw and maize stover showing the largest (P < 0.05) lignin degradation compared to wheat and mixed straws. The DMD and 72-h cumulative GP increased (P < 0.001) consistently with increasing fungal incubation period and for all substrates the highest values of DMD and GP were measured after 35 days of incubation with P. ostreatus. The lignin degradation was strongly associated with hemicellulose degradation (r = 0.71) across the various straws. Results of the present study demonstrated that incubation of low-quality crop residues with P. ostreatus under solid-state conditions upgrades their feeding value by reducing the content of lignin and increasing the content of crude protein and ruminal degradation.

Keywords: crop residues, lignin degradation, maize stovers, wheat straws, white rot fungi

Procedia PDF Downloads 22

Authors: Ogemdi Chinwendu Anika, Anna Strzelecka, Yadira Bajón-Fernández, Raffaella Villa

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Anaerobic digestion (AD) has been used since time in memorial to take care of organic wastes in the environment, especially for sewage and wastewater treatments. Recently, the rising demand/need to increase renewable energy from organic matter has caused the AD substrates spectrum to expand and include a wider variety of organic materials such as agricultural residues and farm manure which is annually generated at around 140 billion metric tons globally. The problem, however, is that agricultural wastes are composed of materials that are heterogeneous and too difficult to degrade -particularly lignin, that make up about 0–40% of the total lignocellulose content. This study aimed to evaluate the impact of varying concentrations of lignin on biogas yields and their subsequent response to a commercial yeast-based bioadditive in batch anaerobic digesters. The experiments were carried out in batches for a retention time of 56 days with different lignin concentrations (200 mg, 300 mg, 400 mg, 500 mg, and 600 mg) treated to different conditions to first determine the concentration of the bioadditive that was most optimal for overall process improvement and yields increase. The batch experiments were set up using 130 mL bottles with a working volume of 60mL, maintained at 38°C in an incubator shaker (150rpm). Digestate obtained from a local plant operating at mesophilic conditions was used as the starting inoculum, and commercial kraft lignin was used as feedstock. Biogas measurements were carried out using the displacement method and were corrected to standard temperature and pressure using standard gas equations. Furthermore, the modified Gompertz equation model was used to non-linearly regress the resulting data to estimate gas production potential, production rates, and the duration of lag phases as indicatives of degrees of lignin inhibition. The results showed that lignin had a strong inhibitory effect on the AD process, and the higher the lignin concentration, the more the inhibition. Also, the modelling showed that the rates of gas production were influenced by the concentrations of the lignin substrate added to the system – the higher the lignin concentrations in mg (0, 200, 300, 400, 500, and 600) the lower the respective rate of gas production in ml/gVS.day (3.3, 2.2, 2.3, 1.6, 1.3, and 1.1), although the 300 mg increased by 0.1 ml/gVS.day over that of the 200 mg. The impact of the yeast-based bioaddition on the rate of production was most significant in the 400 mg and 500 mg as the rate was improved by 0.1 ml/gVS.day and 0.2 ml/gVS.day respectively. This indicates that agricultural residues with higher lignin content may be more responsive to inhibition alleviation by yeast-based bioadditive; therefore, further study on its application to the AD of agricultural residues of high lignin content will be the next step in this research.

Keywords: anaerobic digestion, renewable energy, lignin valorisation, biogas

Procedia PDF Downloads 55

Authors: Gabriela T. Nakashima, Ana Larissa S. Hansted, Gabriela B. Belini, Carlos R. Sette Jr, Hiroyuki Yamamoto, Fabio M. Yamaji

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The aim of this study was to determine the interference from contaminants in the characterization of sugarcane straw. The sugarcane straw was collected after the harvest and taken to the drying oven, and then it was crushed in the mill type Willey. Analyzes of ash contents and Klason lignin were done in triplicate and high heating value (HHV) in duplicate, according to ASTM standard. The results obtained for the sugarcane straw were 5.29% for ash content, 29.87% for Klason lignin and 17.67 MJ.kg-1 for HHV. Also, the material was analyzed by scanning electron microscope (SEM). The presence of contaminants was observed, such as silica. The high amount of contaminants in the samples may impact the results of analyzes, also raising its values, for example in the Klason lignin content. These contaminants can also adversely affect the quality of the biomass. Even using the standards is important to know what the purpose of the analysis and care mainly of sampling.

Keywords: biomass, bioenergy, residues, solid fuel

Procedia PDF Downloads 244

Authors: Deokyeong Choe, Keonwook Nam, Young Hoon Roh

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Wood waste is a potentially significant resource for economic and environment-friendly recycling. Wood waste represents a key sustainable source of biomass for transformation into bioethanol. Unfortunately, wood waste is highly recalcitrant for biotransformation, which limits its use and prevents economically viable conversion into bioethanol. As a result, an effective pretreatment is necessary to degrade cellulose of the wood waste, which improves the accessibility of cellulase. In this work, a H₃PO₄-acetone pretreatment was selected among the various pretreatment methods and used to dissolve cellulose and lignin. When the H₃PO₄ and acetone were used, 5–6% of the wood waste was found to be very appropriate for saccharification. Also, when the enzymatic saccharification was conducted in the mixture of the wood waste and 0.05 M citrate buffer solution, glucose and xylose were measured to be 80.2 g/L and 9.2 g/L respectively. Furthermore, ethanol obtained after 70 h of fermentation by S. cerevisiae was 30.4 g/L. As a result, the conversion yield from wood waste to bioethanol was calculated to be 57.4%. These results show that the pretreated wood waste can be used as good feedstocks for bioethanol production and that the H₃PO₄-acetone pretreatment can effectively increase the yield of ethanol production.

Keywords: wood waste, H₃PO₄-acetone, bioethanol, fermentation

Procedia PDF Downloads 540

Authors: I. Djefour, M. Saidi, I. Tlemsani, S. Toubal

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Lignin is a molecule derived from wood and also generated as waste from the paper industry. With a view to its valorization and protection of the environment, we are interested in its use as a superplasticizer-type adjuvant in mortars and concretes to improve their mechanical strengths. The additives of the concrete have a very strong influence on the properties of the fresh and / or hardened concrete. This study examines the development and use of industrial waste and lignin extracted from a renewable natural source (wood) in cementitious materials. The use of these resources is known at present as a definite resurgence of interest in the development of building materials. Physicomechanical characteristics of mortars are determined by optimization quantity of the natural superplasticizer. The results show that the mechanical strengths of mortars based on natural adjuvant have improved by 20% (64 MPa) for a W/C ratio = 0.4, and the amount of natural adjuvant of dry extract needed is 40 times smaller than commercial adjuvant. This study has a scientific impact (improving the performance of the mortar with an increase in compactness and reduction of the quantity of water), ecological use of the lignin waste generated by the paper industry) and economic reduction of the cost price necessary to elaboration of self-compacting mortars and concretes).

Keywords: biopolymer (lignin), industrial waste, mechanical resistances, self compacting mortars (SCM)

Procedia PDF Downloads 129