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.     

High Toughness and Fast Crystallization Poly(Lactic Acid)/Polyamide 11/SiO<Subscript>2</Subscript> Composites

A poly(lactic acid) (PLA)/polyamide 11 (PA11)/SiO₂ composite was mixed from PLA, PA11, and nanosilica particles through twin-screw extrusion. The PLA/PA11/SiO₂ composite was evaluated with tensile and Izod impact tests, light transmission and haze measurement, and isothermal and nonisothermal crystallization behavior determinations. The PLA/PA11/SiO₂ (97.0/3.0) composite had approximately 10.8% less ultimate tensile strength than neat PLA, but it had greater ductility and approximately ninefold greater elongation at break. A dimple morphology was observed on the fractural surface of the PLA/PA11/SiO₂ composite, indicating that the incorporation of PA11 and nanosilica particles increased the ductility of the PLA matrix. PLA with less than 3 wt% of PA11 and 0.5 phr of nanosilica particles had an Izod impact strength of 8.72 kJ/m². PA11 and nanosilica particles effectively toughened this PLA polymer; they accelerated both isothermal and nonisothermal crystallization rates and increased the crystallinities of the resulting composites under isothermal and nonisothermal crystallization processes.     

Lignin/Poly(ε-Caprolactone) Blends with Tuneable Mechanical Properties Prepared by High Energy Ball-Milling

Polymer blends between lignin, a natural, widely available, no-cost material, and Poly(ε-caprolactone) (PCL), a biodegradable polymer, have been prepared using the ‘clean’, friendly to the environment, technique of the High Energy Ball Milling (HEBM). Two kinds of lignin have been used, Straw lignin, obtained through the Steam Explosion process (SE lignin), and/or Lignosulphonated one (LS lignin). The tensile mechanical tests have shown that, at certain specific compositions, the blends, in particular those with both SE and LS lignin, have good mechanical properties. In particular, by varying the blend composition it is possible to obtain materials with tuneable properties, therefore useful for different applications. Dynamic-Mechanical-Thermal Analysis (DMTA) reveals substantial immiscibility of the blends. Experiments of UV irradiation show that lignin acts as an UV stabilizer for PCL. The effect is higher with SE lignin, likely due to its low molecular weight, which allows the short lignin chains to diffuse more easily within the amorphous regions of PCL.     

Recovery of Kraft Lignin from OPEFB and Using for Lignin–Agarose Hydrogel

Lignins from the spent pulping liquor were normally acquired as waste product of pulp and paper mills. The possibilities of utilizing kraft lignin have yet been developed for commercial innovation. The objectives of this research are to recovery and utilization of lignin from black liquor of oil palm empty fruit bunches (OPEFBs). Kraft lignins from the OPEFBs black liquor were recovered by acidification procedure. They were precipitated at pH 4, 3, and 2 in order that determine the optimum pH for isolation. It can be clearly seen that the best condition of lignin precipitation was at pH 3. It offered the highest yield and purity. The kraft lignin and agarose were utilized as the crude material for the production of lignin–agarose hydrogel. Lignin–agarose hydrogel could be prepared by using epichlorohydrin as the cross-linking agent. The cross-linking occurrence was recognized by FTIR. Physical and chemical properties of hydrogel were investigated. Gel strength of lignin–agarose hydrogel was characterized by texture personal analysis. The results demonstrated that the gel strength increased with increasing of lignin and epichlorohydrin (ECH) in agarose solutions. 5% lignin, 5% agarose and 10 mL ECH contributed the best gel formation and the great mechanical properties. The effect of cross-linking condition on the gel properties, for example, gel hardness and fracturability, was examined.     

Effect of some environmentally degradable materials on the pyrolysis of plastics II: influence of cellulose and lignin on the pyrolysis of complex mixtures

Pyrolysis of polymer mixtures with a composition similar to that of municipal plastic waste containing polyvinyl chloride (PVC) and of municipal plastic waste free of PVC was performed in the presence of components of biomass, namely lignin, cellulose, or both. The pyrolysis products were characterized by standard methods utilized in the petrochemical industry, i.e., paraffins-isoparaffinsolefins-naphthenes-aromatics analysis, proton nuclear magnetic resonance and infrared spectroscopy, and gas chromatography-mass spectrometry. Up to 3 wt% lignin, cellulose, or both in mixed polymers changed the material balance of pyrolysis by decreasing the amount of waxy products. The presence of both PVC and biomass components significantly changed the material balance by decreasing the waxy product yield and increasing the gas and coke yield. The composition of all pyrolysis products was also modified with the addition of PVC, components of biomass, or both.     

Solid-phase fluorescence spectroscopy to characterize organic wastes

The production of solid organic waste (SOW) such as sewage sludge (SS) or municipal solid waste (MSW) has been continuously increasing in Europe since the beginning of the 1990'. Today, the European Union encourages the stabilization of these wastes using biologic processes such as anaerobic digestion and/or composting to produce bio-energy and organic fertilizers. However, the design and management of such biologic processes require knowledge about the quantity and quality of the organic matter (OM) contained in the SOW. The current methods to characterize SOW are tedious, time-consuming and often insufficiently informative. In this paper, we assess the potential of solid-phase fluorescence (SPF) spectroscopy to quickly provide a relevant characterization of SOW. First, we tested well known model compounds (tryptophan, bovine serum albumin, lignin and humic acid) and biologic matrix (Escherichia coli) in three dimensional solid-phase fluorescence (3D-SPF) spectroscopy. We recorded fluorescence spectra from proteinaceous samples but we could not record the fluorescence emitted by lignin and humic acid powders. For SOW samples, fluorescence spectra were successfully recorded for MSW and most of its sub-components (foods, cardboard) but impossible for SS, sludge compost (SC) and ligno-cellulosic wastes. Based on visual observations and additional assays, we concluded that the presence of highly light-absorptive chemical structures in such dark-colored samples was responsible for this limitation. For such samples, i.e. lignin, humic acid, SS, SC and ligno-cellulosic wastes, we show that laser induced fluorescence (LIF) spectroscopy enables the acquisition of 2D fluorescence spectra.     

Mechanism and Characterization of Polyamide 4 Degradation by <Emphasis Type="Italic">Pseudomonas</Emphasis> sp.

We identified a biodegrading microorganism of polyamide (nylon) 4, a linear polymer of γ-aminobutyric acid (GABA). From activated sludge, the biodegrading bacteria strains of Pseudomonas sp. were isolated and identified by their taxonomic characteristics and nucleotide sequences of 16S rDNA. One strain, ND-11, was grown on a minimal medium containing polyamide 4 (PA4) as the sole carbon source. The strain produced GABA as a degradation intermediate, as identified by analyzing the NMR spectra of degraded products. The culture supernatant of strain ND-11 degraded the emulsified PA4 completely within one day. These results suggest that the ND-11 strain degraded PA4 using its extracellular enzymes to hydrolyze amide bonds.     

Relationships between analytical methods utilized as tools in the evaluation of landfill waste stability

In this study, the refuse from 12 landfills of various ages ranging from fresh refuse to material 11 years old was collected, and changes in the bio-stability parameters were determined. The parameters measured included cellulose, lignin, biochemical methane potential (BMP) and volatile solids, along with plastics. These parameters, along with the cellulose to lignin ratio were compared to determine which were most indicative of the bio-stability of the refuse. Lignin and volatile solids measurements were affected by plastics in refuse samples. Plastics increased both lignin and volatile solids measurements by approximately 10%. Cellulose and volatile solids measurements correlated well with age, each other, and with BMP measurements and were therefore considered the best parameters to determine stability. Data for the Riverbend landfill, a landfill with a moisture content of 48%, which is similar to that of bioreactor landfills, showed that degradation was nearly complete after 5 years as indicated by low values for cellulose and BMP.     

A Novel and Formaldehyde-Free Preparation Method for Lignin Amine and Its Enhancement for Soy Protein Adhesive

In this work, a novel two-step process to prepare primary lignin amine was developed. The lignin used in this study was obtained from the residue of cellulosic sugar fermentation for bioethanol (referred as “lignin”). The lignin was initially oxidized through Fenton oxidation. The oxidized lignin was further converted to lignin amine by reductive amination. Ammonia was used in the second step leading to give the highly active primary lignin amine. The oxidation and reduction exhibited relatively high yields of 80.0 and 91.2 % respectively. For comparison, lignin was partially depolymerized via mild hydrogenolysis and then the partial depolymerized lignin was also converted to lignin amine using the same method. The obtained lignin amines were characterized in detail using elemental analysis, proton nuclear magnetic resonance (¹H NMR), and Fourier transform infrared spectroscopy (FTIR). Further, modification of soy protein adhesive by lignin amine was exemplified in wood bonding, and the results indicated that addition of lignin amine greatly increased water resistance of soy protein adhesives.     

Selective organic compounds degradation under controlling composting conditions

Organic matter stabilization resulted from the decrease of cellulose, xylan, arabinan, acetyl groups, glucuronic acids, galacturonic acids (easily biodegradable fractions) and the increase of lignin (resistant compound) and humic substances coming from the initial wastes have been studied. A central composite experimental design was used to investigate the influence of environmental composting parameters (moisture, aeration and particle size) on organic matter evolution. The organic matter evolution was clearly influenced by the studied composting parameters. All results were concordant, with an increase of humic substances and lignin and a decrease of the rest of the cellulose and hemicellulose compounds. Lower cellulose, xylan, acetyl groups and glucuronic acids contents (higher degradation) have been observed under low particle size (1 cm) and higher moisture content (70%). However lower lignin and higher humic substances under medium (3 cm) to low particle size and low moisture content (40%) have been found.     

Feasibility of incorporating treated lignins in fiberboards made from agricultural waste

This paper studies the feasibility of incorporating treated lignins in fiberboards made from Vitis vinifera as an agricultural waste. The treated lignins are the purified Kraft lignin and the alkaline hydrolyzed Kraft lignin. V. vinifera raw material and its fibers were characterized in terms of chemical composition and the results were compared to other biomass species. The chemical composition of treated lignins shows that they have high purity compared to the lignin raw material. The lignin-V. vinifera fibreboards were produced on laboratory scale by adding powdered treated lignins to the material that had previously been steam exploded. Some of the important properties of fibreboards prepared using the treated lignins as natural adhesives were evaluated. These properties were density, thickness swelling, water absorption, modulus of elasticity, modulus of rupture, internal bond strength. The explored levels of treated lignins vary from 5% to 20%. The results showed that binderless fibreboards, fibreboards made from V. vinifera fibers and alkaline hydrolyzed Kraft lignin have weaker mechanical properties. However, the fibreboards obtained using purified Kraft lignin have good mechanical and water resistance properties which satisfy the requirements of the relevant standards specifications.     

Recent Industrial Applications of Lignin: A Sustainable Alternative to Nonrenewable Materials

Lignin represents a vastly under-utilized natural polymer co-generated during papermaking and biomass fractionation. Different types of lignin exist, and these differ with regard to isolation protocol and plant resource (i.e., wood type or agricultural harvesting residue). The incorporation of lignin into polymeric systems has been demonstrated, and this depends on solubility and reactivity characteristics. Several industrial utilization examples are presented for sulfur-free, water-insoluble lignins. These include materials for automotive brakes, wood panel products, biodispersants, polyurethane foams, and epoxy resins for printed circuit boards.     

Lignin-based Carbon Fibers: Effect of Synthetic Polymer Blending on Fiber Properties

Carbon fibers have been produced from hardwood lignin/synthetic polymer blend fibers. Hardwood kraft lignin was thermally blended with two recyclable polymers, poly(ethylene terephthalate) (PET) and polypropylene (PP). Both systems were easily spun into fibers. A thermostabilization step was utilized prior to carbonization to prevent fusion of individual fibers. For the lignin-based carbon fibers, careful control of heating rate was required. However, PET–lignin blend fibers can be thermostabilized under higher heating rates than the corresponding homofibers. Carbon fiber yield decreased with increasing incorporation of synthetic plastic. However, carbon fiber yield obtained for a 25% plastic blend fiber was still higher than that generally reported for petroleum pitch. Blend composition also affected surface morphology of the carbon fibers. Immiscible lignin–PP fibers resulted in a hollow and/or porous carbon fiber; whereas carbon fiber produced from miscible lignin–PET fibers have a smooth surface. Synthetic polymer blending also affected the mechanical properties of the fibers, especially MOE; lignin-based carbon fiber properties improved upon blending with PET.     

Injection-Molded Bioblends from Lignin and Biodegradable Polymers: Processing and Performance Evaluation

This paper investigates the effects of the incorporation of lignin and small quantities of epoxidized natural rubber (ENR) as an impact modifying agent on blends of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and poly(ε-caprolactone) (PCL). The addition of lignin resulted in a slight improvement of flexural strength and modulus of the ternary blending system. Incorporation of ENR into the blend resulted in an increase in notched Izod impact strength from 40 to 135% depending on the concentration of ENR. The addition of lignin into the blend resulted in an improvement of thermal stability of the ternary blend system. Morphological analysis showed a good dispersion of PHBV phases and lignin within the PCL matrix. Rheological characterization revealed that the presence of lignin resulted in increased storage modulus of the bioblend.     

The effect of lignin and sugars to the aerobic decomposition of solid wastes

A series of experimental runs were conducted from 1995 to 1999 in Madison (WI, USA) with the goal to investigate the biodegradation process of seven (7) solid waste components and mixtures of them under near optimal aerobic conditions. It was shown that substrates with high initial lignin contents or high initial HWSM contents were observed to have relatively low and high degradation extents, respectively. Two linear equations were derived that correlate degradation extent (as indicated by the volatile solids reduction) to initial lignin and initial HWSM contents separately. The lignin equation was compared to a similar equation previously developed for anaerobic environments by Chandler et al. (Predicting methane fermentation biodegradability. In: Biotechnology and Bioengineering Symposium No. 10 (1980) New York: John Wiley & Sons). With comparison to the Chandler formula, lignin was found to be less inhibitory to the overall substrate decomposition in aerobic environments compared to anaerobic ones. Cellulose loss contributed to a higher than 50% to the overall dry mass loss for all substrates studied. In addition, the cellulose to lignin (C/L) ratio appeared to be a relatively accurate compost maturity indicator, since it reduced to a value less than 0.5 for most substrates that had reached their degradation extent.     

Use of lignin degrading fungi in bioremediation

The use of lignin degrading fungi for decomposition of a wide variety of xenobiotics has become an area of intensive research. One distinct advantage of lignin degrading fungi over bacteria is that they do not require preconditioning to a particular pollutant prior to transformation. This degradative ability has been attributed to a nonspecific and nonstereoselective extracellular lignin-degrading enzymatic system (ligninase) which is induced by the fungi under nitrogen or carbon-limiting conditions (Reid, 1979). Ligninases (lignin-peroxidases) are responsible for the initial oxidative attack on lignin and other complex molecules via formation of a free radical thereby leading to depolymerization of complex molecular structures. Potential degradative ability of peroxidases may extend to include (1) sorbed contaminants, (2) high molecular-weight, hydrophobic contaminants, and (3) complex mixtures of chemicals typical of a contaminated site.     

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.     

Development of Lignin and Nanocellulose Enhanced Bio PU Foams for Automotive Parts

The green rigid polyurethane (PU) foam has been developed with 100 % soy polyol after optimization of formulation ingredients and lignin has been introduced and isocyanate content reduced in the green rigid PU foam. The cellulosic nanofibers have also been successfully incorporated and dispersed in green rigid PU foam to improve the rigidity. The influence of nano cellulose fiber modification (enzymatic treatment, hydrophobic modification with latex) on the foam density, open cell content, foam raise height, water vapor, and mechanical properties of rigid PU foam were studied. The foamed structures were examined using scanning electron microscopy to determine the cell size and shape due to the addition of cellulosic nanofibers. The odor test were performed to evaluate the odor concentration 100 % soyol based PU foam including lignin and nanofiber and compared to 100 % synthetic based polyol PU foam. The experimental results indicated that the compression and impact properties improved due to the modification of nano cellulosic fibers. The odor concentration level of nanofiber reinforced rigid PU foam reduced significantly compared to 100 % PU foam due to the replacing of isocyanate content. It can be said that with an appropriate combination of replacing isocyanate by lignin and addition of nanofiber, rigid PU foam properties could be improved.     

糙皮侧耳降解碱木素的动力学研究

对糙皮侧耳B1(白腐真菌的一种)降解碱木素的动力学进行了研究.基于Logistic方程,建立了糙皮侧耳B1在纯培养条件和碱木素存在条件下的生长动力学模型.动力学模型参数分别为0.94d-1和0.90d-1.该模型能够较好地模拟体系中生物量的变化,平均相对误差分别为3.2％和3.4％.糙皮侧耳B1对低浓度碱木素的降解存在...     

δ13C of Tree-Ring Lignin as an Indirect Measure of Climate Change

High-resolution paleoclimatic data are an essential requirement for testing numerical models of climate change and the global carbon cycle. If the long tree-ring chronologies, originally established for the purpose of dendrochronology, are to be fully exploited as an indirect measure of past climatic variability, additional techniques are required to obtain this information. The determination of the δ¹³C value of tree-ring cellulose has been used successfully to reconstruct past climates. However, under both aerobic and anaerobic conditions, the polysaccharide components of vascular plants (mainly cellulose and hemicelluloses) are more prone to rapid degradation than lignin. This has serious implications for the use of carbon isotope values of tree-ring cellulose as an indirect measure of past climates. An absolutely dated ring-width chronology was established for oaks (Quercus robur L.) growing at Sandringham Park in eastern England. Carbon isotope values were determined on α-cellulose and `Klason' lignin isolated from annual latewood samples over the period AD 1895–1999. The carbon isotope values of earlywood lignin are correlated with the latewood carbon isotope values of the previous year, supporting the theory that some of the carbon utilised in earlywood synthesis is assimilated in the previous year. The high-frequency variance in the carbon isotope indices of latewood lignin and cellulose is highly correlated with combined July and August environmental variables, indicating that they were formed at similar times. There was no evidence of secondary lignification. These resultsdemonstrate that the determination of carbon isotope values of latewood lignin offers the potential to obtain unambiguous proxy climatic data covering several millennia.