Lignin oxidation by PCD technology

The purpose of this study is to investigate whether commercial Kraft lignin can be treated with pulsed corona discharge apparatus so that it becomes active. Active lignin refers to the kind of lignin that can be precipitated on the surface of a fiber by lowering the pH. A secondary agenda here is to remove the pungent smell of kraft lignin, which is caused by organically bound sulfur. It is expected that the study will identify mild processing conditions and parameters for achievement of the desired outcome. In the literature review, the properties of lignin are explained, as is their impact on any further processing. In addition, a number of processes are described for the oxidation of lignin in a variety of applications. In the experimental part of the study, test runs were conducted to determine the effects of oxygen supply and pulse frequency on oxidation results, where the purpose is to produce reactive lignin and to find a process that is feasible at an industrial scale. Based on the reported experiments, lignin could not be made active or precipitated to the surface of the fiber. Actual changes in the structure of lignin were not observed, but the pungent smell of lignin was removed. The exact reason for this change could not be established because sulfur NMR analysis did not work for the lignin samples.

Separation of lignin in Pulp Mill process and its effect on sodium sulphur balance

The aim of this thesis is to define effects of lignin separation process on Pulp mill chemical balance especially on sodium/sulphur-balance. The objective is to develop a simulation model with WinGEMS Process Simulator and use that model to simulate the chemical balances and process changes. The literature part explains what lignin is and how kraft pulp is produced. It also introduces to the methods that can be used to extract lignin from black liquor stream and how those methods affect the pulping process. In experimental part seven different cases are simulated with the created simulation model. The simulations are based on selected reference mill that produces 500 000 tons of bleached air-dried (90 %) pulp per year. The simulations include the chemical balance calculation and the estimated production increase. Based on the simulations the heat load of the recovery boiler can be reduced and the pulp production increased when lignin is extracted. The simulations showed that decreasing the waste acid stream intake from the chlorine dioxide plant is an effective method to control the sulphidity level when about 10 % of lignin is extracted. With higher lignin removal rates the in-mill sulphuric acid production has been discovered to be a better alternative to the sulphidity control.

Evaluation of lignin content of soybean seed coat stored in a controlled environment

Breeding soybean for high seed quality is an important approach for developing cultivars for tropical regions, and the lignin content in the seed coat is one of the screening parameters for this trait. Considering that many breeding lines are evaluated in each growing season using the presently recommended method for lignin determination, a long period is required for the evaluation of the whole breeding program. This time limitation may influence lignin content assessment, if lignin is degraded during storage. This research reported was designed to determine whether lignin was degraded in the seed coat of soybean seed cultivars stored for one year in a controlled environment (10°C temperature and 50% air relative humidity). Seeds of 12 selected soybean cultivars that had a range in seed coat lignin content were evaluated. Seeds were hand harvested just after physiological maturity and evaluated for seed coat lignin content at harvest and after one year of storage in a cold room (10°C and 50% RH). The lignin content in seed coats differed significantly among cultivars in both analyses, but for both results the sequence of cultivar classification and the lignin content values of each cultivar did not change. A regression analysis of lignin content at harvest and after one year of storage indicated a direct relationship between both lignin determinations suggesting no differences between the lignin content of each cultivar due to prolonged storage (r² = 0.98***). This indicates that the lignin determination in the soybean seed coat can be performed over a long time period without any bias due to change in its content.

Influence of lignin content in soybean seed coat on the incidence of the storage fungus Aspergillus flavus

Seed quality may be affected by several factors, including permeability, color, and lignin content in the seed coat. This study aimed at evaluating influence of lignin content in the tegument of seed samples of six different soybean cultivars, in which half of each sample was inoculated with the fungus Aspergillus flavus, on the physical and physiological quality, and on the seed health, during 180 days storage period, under cold chamber with controlled conditions of temperature and RH. For that, at each interval of 60 days, samples were removed, and the physiological quality of these seeds was assessed by means of moisture and lignin contents; and by tests of seed health, germination, and electrical conductivity. The moisture content of seeds remained constant during all storage period. In the seed health test, it was found that inoculation was efficient, once the minimum incidence of the fungus in the inoculated seeds was 85%. In the germination test, there was a trend of reduction on percentage germination with the increase in storage period. However, there was an increase on electrical conductivity of seeds assessed. It was concluded that there is no interference of the lignin content in the seed coat on the resistance to infection by the fungus Aspergillus flavus, even after seed storage for a period of 180 days.

Production and Characterization of Lignin Peroxidases from Mangrove Ascomycetes

In this thesis, the production and characterization of ligninolytic enzymes using the fungi isolated from mangrove area are studied. The objective of the present work are isolation and screening of dye decolorizing micro-organisms from mangrove area, screening of the selected microorganisms for the production of lignin degrading enzymes, identification of the potent micro-organisms, characterization of the crude enzyme, lignin peroxidase, of the selected fungi—Aspergillus sp. SIP 11 and Penicillium sp. SIP 10 etc. This included the determination of the optimum pH, temperature, veratryl alcohol and H2O2 concentration. Besides the stability of crude LiP at different pHs and temperatures were studied. The immense applications, particularly in bioremediation, to which the lignin degrading micro-organisms could be used make this study important, the ascomycetes and deuteromycetes fungi, especially form the marine environment were studied with respect to their ligninolytic enzyme system making this study an initial step in unraveling the vast hidden potential of these microbes in bioremediation, the marine microbes are halophilic in nature which make them better suited to cope with the high salinity of industrial effluents thereby giving them added advantage in the filed of bioremediation. The thesis deals with the isolation and screening of lignin degrading enzyme-producing microbes from mangrove area. The identification of the most potent fungal isolates and characterization of LiP from these are also done.

Production and Characterization of Lignin Peroxidases from Mangrove Ascomycetes

The continually growing worldwide hazardous waste problem is receiving much attention lately. The development of cost effective, yet efficient methods of decontamination are vital to our success in solving this problem.Bioremediation using white rot fungi, a group of basidiomycetes characterized by their ability to degrade lignin by producing extracellular LiP, MnP and laccase have come to be recognized globally which is described in detail in Chapter 1.These features provide them with tremendous advantages over other micro-organisms.Chapter 2 deals with the isolation and screening of lignin degrading enzyme producing micoro-organisms from mangrove area. Marine microbes of mangrove area has great capacity to tolerate wide fluctuations of salinitie.Primary and secondary screening for lignin degrading enzyme producing halophilic microbes from mangrove area resulted in the selection of two fungal strains from among 75 bacteria and 26 fungi. The two fungi, SIP 10 and SIP ll, were identified as penicillium sp and Aspergillus sp respectively belonging to the class Ascomycetes .Specific activity of the purified LiP was 7923 U/mg protein. The purification fold was 24.07 while the yield was 18.7%. SDS PAGE of LiP showed that it was a low molecular weight protein of 29 kDa.Zymogram analysis using crystal violet dye as substrate confirmed the peroxidase nature of the purified LiP.The studies on the ability of purified LiP to decolorize different synthetic dyes was done. Among the dyes studied, crystal violet, a triphenyl methane dye was decolorized to the greatest extent.

Lignin recovery, Biochar Production and Decolourisation of Coir pith Black Liquor

Coir pith black liquor obtained as a dark brown filtrate from oxidative delignification needs to be decolourised before releasing to open environment. From this liquor industrially valuable lignin was recovered using acid precipitation method. ‘Biochar’ was produced by slow pyrolysis of coir pith at 500oC and 600oC. Water holding capacity and pH of the biochar were estimated. CHNS analysis was carried out to identify the nutrient profile. Structural characterization was done using FTIR and SEM Studies. Biochar produced at 600oC was found to be more suitable for decolourisation of the coir pith black liquor. FTIR analysis indicated peak changes while SEM analysis indicated surface area and porosity changes. Biochar decolourisation experiments were carried out on crude coir pith black liquor and also on lignin recovered coir pith black liquor.

Dissolved Folin Phenol Active Substances (Tannin and Lignin) in the Seawater along the West Coast of India

Information on the distribution of dissolved Folin phenol active substances (FPAS) such as tannin and lignin in the seawater along the west coast of India is provided. Notable amounts of FPAS (surface concentrations: 80 f.1gll to 147 f.1gll and bottom concentrations: 80 f.1gll to 116 f.1gll) were detected in the seawater along the coast. The distribution pattern brings about a general depth-wise decrease. A seaward decrease was observed in the southern stations whereas reverse was the case in northern stations. A significant negative correlation was observed between FPAS concentration and dissolved oxygen in sub-surface samples. The appreciable amounts of FPAS detected in the coastal waters indicate the presence of organic matter principally originating from terrestrial (upland and coastal marsh) ecosystems in the marine environment. In this context, they may be used as tracers to determine the fate of coastalborn dissolved organic matter in the ocean and to determine directly the relationship between allochthonous and autochthonous organic matter

Optimization of Lignin Peroxidase, Manganese Peroxidase, and Lac Production from Ganoderma lucidum Under Solid State Fermentation of Pineapple Leaf

This study was undertaken to isolate ligninase-producing white-rot fungi for use in the extraction of fibre from pineapple leaf agriwaste. Fifteen fungal strains were isolated from dead tree trunks and leaf litter. Ligninolytic enzymes (lignin peroxidase (LiP), manganese peroxidase (MnP), and laccase (Lac)), were produced by solid-state fermentation (SSF) using pineapple leaves as the substrate. Of the isolated strains, the one showing maximum production of ligninolytic enzymes was identified to be Ganoderma lucidum by 18S ribotyping. Single parameter optimization and response surface methodology of different process variables were carried out for enzyme production. Incubation period, agitation, and Tween-80 were identified to be the most significant variables through Plackett-Burman design. These variables were further optimized by Box-Behnken design. The overall maximum yield of ligninolytic enzymes was achieved by experimental analysis under these optimal conditions. Quantitative lignin analysis of pineapple leaves by Klason lignin method showed significant degradation of lignin by Ganoderma lucidum under SSF

Monodisperse lignin fractions as standards in size-exclusion analysis Comparison with polystyrene standards

The difficulty of preparing monodisperse lignin fractions on a large scale is a limiting factor in many applications. The present paper addresses this problem by examining the properties and size-exclusion behavior of lignin isolated by the acetosolv pulping process from post-extraction crushed sugarcane bagasse. The isolated lignin was subjected to a solvent pretreatment, followed by preparative gel permeation chromatography fractionation. The fractions were analyzed by high-performance size-exclusion chromatography (HPSEC) and these samples showed a great decrease in polydispersity, compared to the original acetosolv lignin. Several fractions of very low polydispersity, close to unity, were employed as calibration curve standards in HPSEC analysis. This original analytical approach allowed calibration with these lignin fractions to be compared with the polystyrene standards that are universally employed for lignin molecular mass determination. This led to a noteworthy result, namely that the lignin fractions and polystyrene standards showed very similar behavior over a large range of molecular masses in a typical HPSEC analysis of acetosolv lignin. (C) 2009 Elsevier B.V. All rights reserved.

Valorization of an Industrial Organosolv-Sugarcane Bagasse Lignin: Characterization and Use as a Matrix in Biobased Composites Reinforced With Sisal Fibers

In the present study, the main focus was the characterization and application of the by-product lignin isolated through an industrial organosolv acid hydrolysis process from sugarcane bagasse, aiming at the production of bioethanol. The sugarcane lignin was characterized and used to prepare phenolic-type resins. The analysis confirmed that the industrial sugarcane lignin is of HGS type, with a high proportion of the less substituted aromatic ring p-hydroxyphenyl units, which favors further reaction with formaldehyde. The lignin-formaldehyde resins were used to produce biobased composites reinforced with different proportions of randomly distributed sisal fibers. The presence of lignin moieties in both the fiber and matrix increases their mutual affinity, as confirmed by SEM images, which showed good adhesion at the biocomposite fiber/matrix interface. This in turn allowed good load transference from the matrix to the fiber, leading to biobased composites with good impact strength (near 500 J m(-1) for a 40 wt% sisal fiber-reinforced composite). The study demonstrates that sugarcane bagasse lignin obtained from a bioethanol plant can be used without excessive purification in the preparation of lignocellulosic fiber-reinforced biobased composites displaying high mechanical properties. Biotechnol. Bioeng. 2010;107: 612-621. (C) 2010 Wiley Periodicals, Inc.

Indigestible cellulose and lignin in determining feces production and apparent digestibility in horses

Foram utilizados quatro cavalos castrados sem raça definida, distribuídos em blocos casualizados. Objetivou-se estudar a viabilização dos indicadores internos, celulose (CELi) e lignina indigestíveis (LIGi), para predizer a digestibilidade em cavalos. Os tratamentos consistiram na determinação da digestibilidade por método direto com a coleta total de fezes (CT) e indireto pelo uso CELi e LIGi obtidos pelas técnicas in situ (IS) na cavidade ruminal de bovinos e in vivo (IV) nos equinos por meio do saco de náilon móvel (SNM). A produção fecal e taxa de recuperação (p > 0,05) médios encontrados foram de 2,80 kg na MS e 101%, respectivamente. As estimativas dos CD dos nutrientes (p > 0,05) foram adequadamente preditos pela CELi e LIGi, obtidos in situ e in vivo, no qual os valores médios observados foram de 52,63, 54,17, 64,90, 43,73 e 98,28% para MS, MO, PB, FDN e Amido, respectivamente. Concluiu-se que a CELi e LIGi podem ser obtidas in vivo por meio do SNM em equinos, para predizer os coeficientes de digestibilidade de nutrientes, consumindo dieta mista.

Lignin from sugar cane bagasse: Extraction, fabrication of nanostructured films, and application

Four lignin samples were extracted from sugar cane bagasse using four different alcohols (methanol, ethanol, n-propanol, and 1-butanol) via the organosolv-CO2 supercritical pulping process. Langmuir films were characterized by surface pressure vs mean molecular area (Pi-A) isotherms to exploit information at the molecular level carrying out stability tests, cycles of compression/expansion (hysteresis), subphase temperature variations, and metallic ions dissolved into the water subphase at different concentrations. Briefly, it was observed that these lignins are relatively stable on the water surface when compared to those obtained via different extraction processes. Besides, the Pi-A isotherms are shifted to smaller molecular areas at higher subphase temperatures and to larger molecular areas when the metallic ions are dissolved into the subphase. The results are related to the formation of stable aggregates (domains) onto the water subphase by these lignins, as shown in the Pi-A isotherms. It was found as well that the most stable lignin monolayer onto the water subphase is that extracted with 1-butanol. Homogeneous Langmuir-Blodgett (LB) films of this lignin could be produced as confirmed by UV-vis absorption spectroscopy and the cumulative transfer parameter. In addition, FTIR analysis showed that this lignin LB film is structured in a way that the phenyl groups are organized preferentially parallel to the substrate surface. Further, these LB films were deposited onto gold interdigitated electrodes and ITO and applied in studies involving the detection of Cd+2 ions in aqueous solutions at low concentration levels throughimpedance spectroscopy and electrochemical measurements. FTIR spectroscopy was carried out before and after soaking the thin films into Cd+2 aqueous solutions, revealing a possible physical interaction between the lignin phenyl groups and the heavy metal ions. The importance of using nanostructured systems is demonstrated as well by comparing both LB and cast films.

Electrical conductivity of soybean seed and correlation with seed coat lignin content

The effects of soybean genotype and seed coat lignin content on bulk electrical conductivity were investigated. Seeds of nine soybean cultivars were hand harvested at R8 maturation stage in Londrina, PR., Brazil in 1995/96. Seeds were electrical conductivity tested using four replicates of 50 seeds per cultivar soaked in 75 mi of deionized water at 25 degrees C for 24 hours. Seed coat lignin content was determined using the potassium permanganate method. There was a significant relationship (R-2 = 0.84**) between electrical conductivity and seed coat lignin content, the latter being a characteristic that varies among soybean genotypes; the higher the amount of lignin in the seed coat, the lower the levels of seed exudates to the soaking solution and consequently the lower the electrical conductivity. It was concluded that seed soaking electrical conductivity is influenced by the seed coat lignin content, which is a characteristic that varies among soybean genotypes. Additionally, the EC test can be used as a valuable tool in the screening process for this characteristic, which is desirable for genetically improving soybean seed quality.

Thermal and photochemical stability of poly(vinyl alcohol)/modified lignin blends

A kraft lignin derivative (KLD) obtained by reaction with p-aminobenzoic acid/phthalic anhydride was blended with poly(vinyl alcohol) (PVA) by solution casting from DMSO. PVA and PVA/KLD films were exposed to ultraviolet radiation (24, 48, and 96 h) and analyzed by thermogravimetry (TG), differential scanning calorimetry (DSC), infrared spectroscopy (FTIR), hydrogen nuclear magnetic resonance (H-1 NMR) spectroscopy, and scanning electron microscopy (SEM). PVA films show a loss of thermal stability due to irradiation. PVA/KLD reveals greater thermal stability than PVA and an increase in thermal stability after irradiation. These results suggest that the incorporation of KLD into PVA provides a gain in thermal and photochemical stability. FTIR, H-1 NMR, DSC, and TG results obtained for the blends suggest that intermolecular interactions between PVA and KLD chains are present. SEM micrographs revealed blend miscibility for a KLD blend content of up to 15 wt%, as observed at magnification of 1000 times. (c) 2005 Elsevier Ltd. All rights reserved.