Qualitative and Quantitative Analysis of Lignin Produced from Beech Wood by Different Conditions of the Organosolv Process

Lignins in general have been extensively studied, while beech wood lignin in particular is rarely researched. In the present work, Organosolv isolated lignin from beech wood (OBL) has been characterized. The isolation was done by two methods: (a) by using sulfuric acid at 170 °C and a reaction time of 120 min and (b) at a temperature of 180 °C for 240 min. A range of analytical methods were applied including elemental analysis, FT-IR, UV–Vis, ³¹P NMR, SEC, Pyrolysis-GC/MS and HPLC to gain information about establish the purity, structure, molecular weight, thermal behavior and to determine carbohydrate residues according to the NREL protocol. FT-IR and UV–Vis spectra of OBL revealed expected typical absorptions for lignins. NREL analysis presented a carbohydrate-free lignin fraction which has not been achieved to date. TGA and DSC are used to study the thermal behavior of the isolated lignins and showed a relatively low glass transition temperatures (T_g: 123 °C) and decomposition temperatures of 348 and 381 °C. The pyrograms generated from the pyrolysis–GC/MS at 550 °C consisted mainly of fragments of syringyl, guaiacyl and hydroxyphenyl units, thereby confirming the results of the NMR analysis. Our findings support Organolsolv as an efficient method to isolate pure lignin fractions from beech wood with practical value in industry.     

Behavior of bromine on the thermal decomposition of paper-based phenolic laminate wastes

We investigated the thermal properties and behavior of bromine on the thermal decomposition of paper-based phenolic laminate wastes containing polybrominated flame retardants. The thermal properties of the phenolic laminate wastes were measured with a thermogravimeter and a conduction-type scanning calorimeter (TG-CSC). The weight loss of the wastes on thermal decomposition was mainly in three phases between 40°C and 600°C. The enthalpy (ΔH) of the thermal decomposition was 104 cal/g. The material balance of the decomposition components was measured with batch-type thermal decomposition equipment. The ratios of carbon residue, liquid, and gas on decomposition at 800°C in a vacuum were 37 wt. %, 48 wt. %, and 15 wt. %, respectively. The bromine contents in the carbon residue and liquid were less than 0.02 wt. % and 10 wt. %, respectively. These results are useful both in the carbonization process of these wastes and in the application of carbon residue as carbon materials. Received: August 11, 2000 / Accepted: March 7, 2001     

Cellulose Fiber Isolation and Characterization from Sweet Blue Lupin Hull and Canola Straw

In this study, cellulose fibers were removed from crop by-products using a combination of sodium hydroxide treatment followed by acidified sodium chlorite treatment. The objective was to obtain high recovery of cellulose by optimizing treatment conditions with sodium hydroxide (5–20%, 25–75 °C and 2–10 h) followed by acidified sodium chlorite (1.7%, 75 °C for 2–6 h) to remove maximum lignin and hemicellulose, as well as to investigate the effect of lignin content of the starting materials on the treatment efficiency. Samples were characterized for their chemical composition, crystallinity, thermal behavior and morphology to evaluate the effects of treatments on the fibers’ structure. The optimum sodium hydroxide treatment conditions for maximum cellulose recovery was at 15% NaOH concentration, 99 °C and 6 h. Subsequent acidified sodium chlorite treatment at 75 °C was found to be effective in removing both hemicellulose and lignin, resulting in higher recovery of cellulose in lupin hull (~?95%) and canola straw (~?93%). The resultant cellulose fibers of both crop by-products had increased crystallinity without changing cellulose I structure (~?68–73%). Improved thermal stabilities were observed with increased onset of degradation temperatures up to 307–318 °C. Morphological investigations validated the effectiveness of treatments, revealing disrupted cell wall matrix and increased surface area due to the removal of non-cellulosics. The results suggest that the optimized combination of sodium hydroxide and acidified sodium chlorite treatments could be effectively used for the isolation of cellulose fibers from sweet blue lupin hull and canola straw, which find a great number of uses in a wide range of industrial applications.     

PET from Used Beverage Bottles: A Material for Preparation of Biologically Degradable Copolyesters

Poly(ethylene terephthalate) from used colorless beverage bottles was solvolyzed by ethane-1,2-diol. Hydroxyl end-groups present in the mixture of polyols formed were used to initiate the polymerization of ??-caprolactone (CLO) at 190?°C. Polycondensation (190?°C) of the reaction mixture containing an equilibrium amount of lactone corresponding to the reaction temperature yield an aliphatic?Caromatic copolyester. A variety of copolyesters containing 20?C60?mol. % CLO structural units was prepared. The microstructure of their macromolecules was analyzed using ¹H?NMR spectroscopy. Copolyesters were characterized by thermal analysis and tensile tests and their biodegradation potential was checked by the composting test.     

Blending of Epoxidised Palm Oil with Epoxy Resin: The Effect on Morphology, Thermal and Mechanical Properties

Epoxy resin prepared by the reaction of a diglycidyl ether of bisphenol A (DGEBA) and m-xylylenediamine (m-XDA) was modified with 10% wt of epoxidized palm oil (EPO). The EPO was first pre-polymerized with m-XDA at various temperatures and reaction times. The resulting product was then mixed with the epoxy resin at 40?°C and allowed to react at 120?°C for another 3?h. The fully reacted DGEBA/m-XDA/EPO blend was characterized by using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermal gravimetric analysis, tensile test, hardness indentation and dynamic mechanical analysis. The SEM study shows that different types of morphology, ranging from phase separated to miscible blends were obtained. A miscible blend was obtained when the m-XDA and EPO were reacted for more than 2?h. The results from DSC analysis show that the incorporation of EPO at 10% wt in the epoxy blend reduced the glass transition temperature (T _g). The lowered T _g and mechanical properties of the modified epoxy resins are caused by a reduction in crosslinking density and plasticizer effect.     

Styrene/Lignin-Based Polymeric Composites Obtained Through a Sequential Mass-Suspension Polymerization Process

A modified sequential mass-suspension polymerization was employed to ensure adequate dispersion of lignin into the monomeric phase. Due to its complex macromolecular structure and low compatibility with styrene, eucalyptus wood-extracted lignin, via a modified Kraft method, was esterified with methacrylic anhydride to ensure organic phase homogeneity into the reaction medium. Infrared spectroscopy showed a decrease in the hydroxyl band, a characteristic of natural lignin (3200–3400 cm^?1) and an increase in the characteristic ester band (1720–1740 cm^?1) whereas nuclear magnetic resonance measurements exhibited intense peaks in the range from 1.7 to 2.05 ppm (–CH₃) and 5.4 to 6.2 ppm (=CH₂), related to methacrylic anhydride. Comparatively, the esterified lignin also displayed an increase of its glass transition temperature for 98?°C, related to natural lignin, whose T _g was determined to be equal to 91?°C. Styrene/lignin-based polymers exhibited higher average molar masses in comparison to the values observed for polystyrene synthesized with similar amounts of benzoyl peroxide, due to the ability of lignin to act as a free-radical scavenger. Composites obtained with styrene and natural or esterified lignin were successfully synthesized, presenting regular morphology and proper lignin dispersion. Based on a very simple polymerization system, it is possible to enhance the final properties of polystyrene through the incorporation of lignin, which represents an important platform for developing attractive polymeric materials from renewable resources.     

Physical characteristics of sintered fly ash aggregate containing clay binders

A comprehensive research has been conducted to explore the influence of sintering on the properties of fly ash aggregate containing clay binders (bentonite and kaolinite). Fly ash aggregate containing clay binders, have been subjected to various sintering temperatures at different durations of 700?C1400?°C and 15?C120?min, respectively. The variation in aggregate properties, viz strength, water absorption, density and shrinkage during sintering, have been determined and discussed. In addition to these, the uniformity of sintering and rate of water absorption of sintered aggregate were also determined. No significant changes in aggregate properties were observed for aggregate sintered up to 900?°C, due to the insufficient sintering temperature range. However, the aggregate properties substantially enhanced for temperature above 1000?°C, which is attributed to the activation of liquid phase sintering. For temperatures between 1000 and 1300?°C, the aggregate with bentonite shows significant increase in shrinkage (30?%), density (density ratio 0.70), higher ten percent fines value (TPFV) (6.13?tonne), reduction in porosity (35?%), and water absorption of 4?%. However, at 1400?°C, the aggregate properties degraded due to the decomposition of mineral phases in bentonite. For aggregates with kaolinite, highest TPFV of 8.5?tonne with lowest water absorption of 2?% have been observed at 1400?°C. The presence of a higher amount of interconnected pores for aggregates sintered between 700 and 1000?°C leads to a higher rate of water absorption and then reduces to 30?% for temperatures between 1200 and 1300 and 1200 to 1400?°C for bentonite and kaolinite aggregates, respectively. This reduction is due to the reduced interconnected pores. Duration of sintering has no impact on the aggregate properties for temperatures up to 800 and 1000?°C for aggregates with bentonite and kaolinite, respectively. However, between 1000 and 1400?°C, there has been considerable improvement in the aggregate properties for increasing duration up to 60?min. In comparison, during sintering, aggregates with bentonite possessed better properties for temperature less than 1000?°C, whereas aggregates with kaolinite exhibited superior properties between 1100 and 1400?°C.     

Crosslinking of Polyvinyl Alcohol (PVA) and Effect of Crosslinker Shape (Aliphatic and Aromatic) Thereof

In the presented work, the effect of crosslinker geometry on the properties of PVA is reported. The aliphatic (suberic) and aromatic (terephthalic) dicarboxylic acids are used as crosslinker molecules. On the basis of tensile test and thermal properties, it is observed that crosslinking of PVA by suberic acid is more effective than terephthalic acid. The maximum strength measured in crosslinked samples is 32.5 MPa for suberic acid crosslinked PVA which is higher than that of neat PVA (22.6 MPa). Swelling study shows that 8 h crosslinked terephthalic acid (35% w/w) samples have a minimum of 5.4% of water uptake compared to neat PVA, which dissolves readily in water. DTGA shows that the decomposition temperature of crosslinked PVA is 345?°C while neat PVA has a decomposition temperature of 315?°C. FTIR spectroscopy confirms the formation of crosslink ester bond in crosslinked PVA. The crosslinked samples kept for bio-degradation show maximum degradation in terephthalic acid (15% w/w) crosslinked PVA.     

Effect of pressure and temperature on the hydropyrolysis of cotton residue

With growing concerns of fossil fuel resources availability and the volatility of crude oil price, it is becoming imperative day by day to utilize the renewable sources of energy in a sustainable, environment friendly and energy efficient manner. India is the world’s second largest producer of cotton after China. India also has several agricultural and forest residues, and cotton residue is one of the most abundant agricultural residues after rice and wheat residues. The hydropyrolysis of cotton residues has been carried out at various pressures (1, 20 and 40 bar) and temperatures (300, 350, 400 and 450 °C). The effects of temperature and pressure have been studied to understand their yield patterns, and it has been observed that 20 bar pressure and 400 °C are the optimum conditions. The thermogravimetric analysis shows that cotton residue has two significant decomposition temperatures. The SEM, XRD patterns and FT-IR spectra clearly indicate the decomposition of the macromolecular structure of the cotton residue and formation of low molecular weight hydrocarbons suitable for various applications.     

Thermal and FT-IR Characterization of Gigantochloa levis and Gigantochloa scortechinii Bamboo, a Naturally Occurring Polymeric Composite

This research presents, thermal (TGA, Kinetics, DSC) analysis and FT-IR characterization of two bamboo species viz. Gigantochloa levis and Gigantochloa scortechinii at different position and locations (Internode and node). The internodes and nodes of Gigantochloa levis and Gigantochloa scortechinii exhibited similar thermal stability, observed up to 200 °C. The decomposition of cellulose and hemicelluloses component of the bamboo species occurred between 220 and 390 °C, while the degradation of lignin was observed above 400 °C. The kinetic studies revealed that Gigantochloa levis is more sensitive to degradation as compared to Gigantochloa scortechinii. The FT-IR studies were carried to assign the functional groups available at different positions and locations.     

Debromination of flame-retarded TV housing plastic waste

The thermal stability and degradation kinetics of TV housing plastic and brominated flame retardants were studied by means of thermogravimetry. The effects of the treatment temperature on the removal rate of Br were investigated using a tube furnace reactor under isothermal and vacuum conditions. The results showed that the weight loss of TV housing plastic was divided into two stages: the thermal degradation of brominated flame retardants mainly occurred at 290°–350°C, and the degradation of the high-impact polystyrene resin mainly occurred at 350°–455°C. Nearly 90% of Br can be removed from TV housing plastic when the treatment temperature exceeds 280°C.     

Synthesis and Properties of Polyesters from Waste Grapeseed Oil: Comparison with Soybean and Rapeseed Oils

The aim of this study was to investigate the application of grapeseed oil, a waste product from the wine industry, as a renewable feedstock to make polyesters and to compare the properties of these materials with those derived from soybean and rapeseed oils. All three oils were epoxidized to give renewable epoxy monomers containing between 3.8 and 4.7 epoxides per molecule. Polymerisation was achieved with cyclic anhydrides catalysed by 4-methyl imidazole at 170 and 210 °C. Polymers produced from methyl tetrahydrophthalic anhydride (Aradur917^®) had greater tensile strength and Young’s Modulus (tensile strength = 12.8 MPa, Young’s Modulus = 1005 MPa for grapeseed) than methyl nadic anhydride (MNA) derived materials (5.6 and 468 MPa for grapeseed) due to increased volume of MNA decreasing crosslink density. Soybean and grapeseed oils produced materials with higher tensile strength (5.6–29.3 MPa) than rapeseed derived polyesters (2.5–3.9 MPa) due to a higher epoxide functionality increasing crosslinking. T _g’s of the polyesters ranged from ?36 to 62 °C and mirrored the trend in epoxide functionality with grapeseed producing higher T _g polymers (?17 to 17 °C) than soybean (?25 to 6 °C) and rapeseed (?36 to ?27 °C). Grapeseed oil showed similar properties to soybean oil in terms of T _g, thermal degradation and Young’s Modulus but produced polymers of lower tensile strength. Therefore grapeseed oil would only be a viable substitute for soybean for low stress applications or where thermal properties are more important.     

Characterization of human manure-derived biochar and energy-balance analysis of slow pyrolysis process

Biochars have received increasing attention in recent years because of their soil improvement potential, contaminant immobilization properties, and ability to function as carbon sinks. This study adopted a pyrolytic process to prepare a series of biochars from dried human manure at varying temperatures. The thermal analysis of human manure and physicochemical properties of the resulting biochars illustrated that human manure can be a favorable feedstock for biochar production. In particular, the porous texture and nutrient-rich properties of biochars produced from human manure and may significantly enhance soil fertility when used as used soil additives. A temperature range of 500–600 °C was optimal for human manure biochar production. Significantly, when the moisture content of the feedstock is lower than 57%, the system could not only harvest manure-derived biochar but also have a net energy output, which can be provide heat source for nearby users.     

Temperature-dependent pyrolytic product evolution profile for low-density polyethylene from gas chromatographic study

In this work, a product distribution study from thermal degradation of low-density polyethylene (LDPE) is presented. Thermal degradation of the polymer was investigated under dynamic condition in an inert environment using a thermo-gravimetric analyzer (TGA) coupled with evolved products’ analysis using a gas chromatograph (GC). Fractions evolved at nine different temperatures from 200 to 600 °C were injected into GC for a detailed product analysis. The main objective of the present investigation is to highlight the species-specific evolution profiles of LDPE pyrolyzates (C5–C44) at different stages of its degradation under an inert environment. Pyrograms have been analyzed in terms of amount of different products evolved at various pyrolysis temperatures. Volatile pyrolyzates essentially remain low at low decomposition temperature (200–300 °C) of the polymer, which gradually increase to attain a maximum at maximum decomposition temperature (470 °C) and finally level off at 600 °C. In the mechanistic approach adopted to understand the decomposition mechanism of LDPE, the following reaction types were considered: (a) main chain cleavage to form chain-terminus radicals; (b) intramolecular hydrogen transfer to generate internal radicals; (c) intermolecular hydrogen transfer to form both volatile products and radicals; and (d) β-scission to form both volatiles and terminally unsaturated polymer.     

Recovery of materials from waste printed circuit boards by vacuum pyrolysis and vacuum centrifugal separation

In this research, a two-step process consisting of vacuum pyrolysis and vacuum centrifugal separation was employed to treat waste printed circuit boards (WPCBs). Firstly, WPCBs were pyrolysed under vacuum condition at 600 °C for 30 min in a lab-scale reactor. Then, the obtained pyrolysis residue was heated under vacuum until the solder was melted, and then the molten solder was separated from the pyrolysis residue by the centrifugal force. The results of vacuum pyrolysis showed that the type-A of WPCBs (the base plates of which was made from cellulose paper reinforced phenolic resin) pyrolysed to form an average of 67.97 wt.% residue, 27.73 wt.% oil, and 4.30 wt.% gas; and pyrolysis of the type-B of WPCBs (the base plates of which was made from glass fiber reinforced epoxy resin) led to an average mass balance of 72.20 wt.% residue, 21.45 wt.% oil, and 6.35 wt.% gas. The results of vacuum centrifugal separation showed that the separation of solder was complete when the pyrolysis residue was heated at 400 °C, and the rotating drum was rotated at 1200 rpm for 10 min. The pyrolysis oil and gas can be used as fuel or chemical feedstock after treatment. The pyrolysis residue after solder separation contained various metals, glass fibers and other inorganic materials, which could be recycled for further processing. The recovered solder can be reused directly and it can also be a good resource of lead and tin for refining.     

Co-gasification of wood and polyethylene with the aim of CO and H2 production

This article describes the gasification of polyethylene–wood mixtures to form syngas (H₂ and CO) with the aim of feedstock recycling via direct fermentation of syngas to ethanol. The aim was to determine the effects of four process parameters on process properties that give insight into the efficiency of gasification in general, and particularly into the optimum gasification conditions for the production of ethanol by fermentation of producer gas. Gasification experiments (fluidized bed, 800°–950°C) were done under different conditions to optimize the composition of syngas suitable for fermentation purposes. The data obtained were used for statistical analysis and modeling. In this way, the effect of each parameter on the process properties was determined and the model was used to predict the optimum gasification conditions. The parameters varied during the experiment were gasification temperature, equivalence ratio, the ratio of plastic to wood in the feed, and the amount of steam added to the process. The response models obtained proved to be statistically significant in the experimental domain. The optimum gasification conditions for maximization of carbon monoxide and hydrogen production were identified. The conditions are: temperature 900°C, equivalence ratio 0.15, amount of plastic in the feed 0.11 g/g feed, and amount of steam added 0.42 g/g feed. These optimum conditions are at the edge of the present experimental domain. The maximum combined CO and H₂ efficiency was 42%, and for the maximum yield of CO and H₂ it is necessary to minimize the polyethylene content, minimize the added steam and the equivalence ratio, and maximize temperature.     

Laccase-Assisted Grafting of Acrylic Acid onto Lignin for its Recovery from Wastewater

The acrylic acid (AA) in the wastewater from paint manufacturing could be recovered by grafting to lignosulfonate in the presence of laccase and tert-butyl hydroperoxide (t-BHP). The low concentration of t-BHP did not inhibit the laccase activity, but improved the radical formation on lignin by laccase reaction, then initiated AA polymerization on lignin. The results showed laccase took a significant role for AA grafting to lignin. 94 % of AA could be polymerized on lignin by laccase/t-BHP, while only 32 % of AA was grafted on lignin with the same condition without laccase. The ratio of lignin to acrylic acid also affected AA recovery, and higher concentration of acrylic acid led to high recovery rate of AA. In this reaction system, the suitable range of temperature was 30–40 °C for the chemo-enzymatic reaction. The AA grafted on lignin could be precipitated by calcium ion and recovered.     

Investigation on thermal dechlorination and catalytic pyrolysis in a continuous process for liquid fuel recovery from mixed plastic wastes

A continuous system (feeding rate >1 kg/h) consisting of thermal dechlorination pre-treatment and catalytic pyrolysis with Fe-restructured clay (Fe-RC) catalyst was developed for feedstock recycling of PVC-containing mixed plastic waste. The vented screw conveyor which was specially designed for continuous dechlorination was able to achieve dechlorination efficiency of over 90 % with a feedstock retention time longer than 35.5 min. The chlorine content of the pyrolytic oil obtained after dechlorination was in the range of 6.08–39.50 ppm, which meet the specification for reclamation pyrolytic oil in Japan. Fe-RC was found to significantly improve the yield of pyrolytic oil (achieved to 83.73 wt%) at the optimized pyrolysis temperature of 450 °C and catalyst dosage of 60 g. With the optimized parameters, Fe-RC showed high selectivity for the C₉–C₁₂ and C₁₃–C₁₉ oil fraction, which are the major constituents of kerosene and diesel fuel, demonstrating that this catalyst can be applied in the pyrolysis of mixed plastic wastes for the production of kerosene and diesel fuel. Overall, the continuous process exhibited high stability and consistently high-oil yield upon reaching steady state, indicating its potential up-scaling application in the industry.     

Anaerobic co-digestion of dairy cow manure and high concentrated food processing waste

Anaerobic co-digestion of dairy manure (DM) and concentrated food processing wastes (FPW) under thermophilic (55 °C) and mesophilic (35 °C) temperatures, and fertilizer value of the effluent were investigated in this study. Two types of influent feedstock were utilized: 100 % DM and a 7:3 mixture (wet weight basis) of DM and FPW. The contents of the FPW, as feedstock were 3:3:3:1 mixture of cheese whey, animal blood, used cooking oil and residue of fried potato. Four continuous digestion experiments were carried out in 10 L digesters. Co-digestion under thermophilic temperature increased methane production per digester volume. However, co-digestion at 35 °C was inhibited. Total Kjeldahl nitrogen (N) recovered after digestion ranged from 73.1 to 91.9 %, while recoveries of ammonium nitrogen (NH₄-N) exceeded 100 %. The high recovery of NH₄-N was attributed to mineralization of influent organic N. The mixture of DM and FPW showed greater recoveries of NH₄-N after digestion compared to DM only, reflecting its greater organic N degradability. The ratios of extractable to total calcium, phosphorus and magnesium were slightly reduced after digestion. These results indicate that co-digestion of DM and FPW under thermophilic temperature enhances methane production and offers additional benefit of organic fertilizer creation.     

The mild hydrothermal synthesis of hydrogrossular from coal ash

In this study, an attempt was made to synthesize hydrogrossular, a group of garnet minerals, under hydrothermal conditions at temperatures below 180°C, using coal ash, which is the solid waste from thermal power plants, as a starting material. A single phase corresponding to hydrogrossular was found at around 120°C, and the hydrogrossular coexisted with 11-Å tobermorite above 140°C. The hydrogrossular phase decreased with increasing reaction temperature, while that of 11-Å tobermorite increased concurrently. The physicochemical properties of the hydrogrossular obtained from the hydrothermal synthesis was characterized by X-ray diffraction thermogravimetry/differential thermal, analysis, scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray fluorescence spectroscopy. Received: September 4, 2000 / Accepted: March 7, 2001