Graft copolymers of lignin from straw with 1‐ethenylbenzene: Synthesis and characterization

The synthesis of copolymers between lignin from steam‐exploded straw and 1‐ethenylbenzene is described. Beforehand, lignin from steam‐exploded straw was fully characterized by using elemental analysis, ultraviolet spectroscopy, gel permeation chromatography (GPC), Fourier transform infrared (FTIR), and both ¹H and ¹³C nuclear magnetic resonance (NMR) spectroscopy. Using a previously described procedure utilizing calcium chloride and hydrogen peroxide as reagents the synthesis of the copolymers was performed. FTIR of the copolymers showed the presence of both lignin and polystyrene. GPC analysis showed the presence of a fraction with high molecular weights. These results were confirmed from both viscosity data and differential calorimetry. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 72–79, 2001     

Polyurethanes and polyesters from lignin

Lignin, obtained through steam explosion from straw, was completely characterized via elemental analysis, gel permeation chromatography, ultraviolet and infrared spectroscopy, and ¹³C and ¹H nuclear magnetic resonance spectrometry. Polyurethanes were obtained by treating steam‐exploded lignin from straw with 4,4′‐methylenebis(phenylisocyanate), 4,4′‐methylenebis(phenylisocyanate) –ethandiol, and poly(1,4‐butandiol)tolylene‐2,4‐diisocyanate terminated. The obtained materials were characterized by using gel permeation chromatography, infrared spectroscopy, and scanning electron microscopy. Differential scanning calorimetry analysis showed a T_g at ?6°C, assigned to the glass transition of the poly(1,4‐butandiol) chains. The presence of ethylene glycol reduced the yields of the polyurethanes. The use of the prepolymer gave the best results in polyurethane formation. Steam‐exploded lignin was used as the starting material in the synthesis of polyesters. Lignin was treated with dodecanoyl dichloride. The products were characterized by using gel permeation chromatography, infrared spectroscopy, ¹³C and ¹H nuclear magnetic resonance spectrometry, and scanning electron microscopy. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1451–1456, 2005     

Enhancing water resistance of welded dowel wood joints by acetylated lignin

Low molecular mass acetylated organosolv lignin from wheat straw and from depolymerised low sulphur organosolv wood lignin have been shown to markedly improve both the water resistance and the mechanical performance of welded dowel wood joints. The acetylated oligomers distribution and extent of acetylation of the two lignins were determined by Matrix assisted laser desorption ionization-time-of-flight mass spectrometry. Extensive acetylation was confirmed by CP-MAS ¹³C NMR spectrometry. Force–displacement measurements on welded dowel joints to which acetylated wood lignins were added showed a ductile behaviour. This is due to the interpenetration of the elastic acetylated lignin network into the more rigid composite network of the welded interphase.     

Influence of steaming pressure on steam explosion pretreatment of Lespedeza stalks (Lespedeza cyrtobotrya). II. Characteristics of degraded lignin

Lignin fractions obtained by steam explosion pretreatment and subsequent alkaline ethanol solution post‐treatment from Lespedeza cyrtobotrya stalks were studied in terms of chemical characteristics, to reflect the influence of elevating steam pressure from 15 to 25 kg/m². Because of the remarkable selectivity with respect to lignin, the post‐treatment with 60% ethanol solution containing 1% NaOH yielded 8.3, 13.0, 16.0, 16.4, and 17.8% lignin fractions from the samples steam‐exploded at 15, 17.5, 20, 22.5, and 25 kg/m² for 4 min, respectively, comparing to 7.7% lignin removal from the raw material. Steam explosion pretreatment, not only obviously cleaved the linkage between carbohydrates and lignin resulting in the significantly decrease of the associated hemicelluloses in lignin fractions, but also broke the β‐O‐4 bond between lignins to some degrees. In particular, slightly more guaiacyl moieties than syringyl units were affected. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Investigation of oil palm based Kraft and auto-catalyzed organosolv lignin susceptibility as a green wood adhesives

The aim of this study is to highlight the application and potentiality of oil palm based lignins in the synthesis of green phenolic resins. The delignification processes were conducted using Kraft and auto-catalyzed ethanol–water pulping processes. The extracted lignins were characterized using elemental analysis, Fourier transform-infrared, ¹H and ¹³C nuclear magnetic resonance (NMR) spectroscopy, molecular weight distribution (M_n, M_w and polydispersity), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The obtained FTIR results revealed that the Kraft lignin contained substantial amounts of guaiacyl units with smaller amounts of syringyl units. The molecular weight of Kraft lignin was 1564 g mol⁻¹ which is higher than organosolv lignin at 1231 g mol⁻¹. The activated free ring position (2.99%) of Kraft lignin was comparatively higher than that of organosolv lignin (2.06%) which was measured using Mannich reactivity analysis. Thermal analysis of Kraft lignin showed higher thermal stability compared to organosolv lignin. The structural and thermal characteristics implied that Kraft lignin had higher potential for the production of green phenolic resins when compared with organosolv lignin.     

Oxypropylation of Lignins and Preparation of Rigid Polyurethane Foams from the Ensuing Polyols

Summary: Different lignins were converted into polyols by a chain extension reaction with propylene oxide ( PO ). Thus, soda lignin from Alfa (Stipa tenacissima) ( SL ), organosolv lignin from hardwoods ( OL ), kraft lignin ( KL ) from softwood and oxidized organosolv lignin ( OOL ) were oxypropylated in a batch reactor at 180 °C in the presence of KOH as catalyst. The ensuing polyols were characterized by FTIR and ¹H NMR spectroscopy, which showed that they had incorporated poly(propylene oxide) grafts into their structure. Their viscosity varied from 5 mPa · s to infinity, depending on the Lignin / PO ratio and their hydroxy index was in the range of 100–200, which made them suitable for rigid polyurethane foam (RPU) formulations. The RPUs thus obtained had a T_g of ca. 60 °C and a thermal conductivity of ≈20 mW/m · K before ageing and ≈25 mW/m · K after accelerated ageing for 10 d at 70 °C. The analyses of the gases inside the cells showed that these were mostly closed, since the partial pressure did not decrease significantly with ageing.

Photograph of polyurethane foam made from OLOP .     

Enhanced ethanol production from enzymatically treated steam‐exploded rice straw using extractive fermentation

Alcohol fermentation of an enzymatic hydrolyzate of exploded rice straw was studied experimentally. Rice straw was treated under variable conditions, such as steam pressure and steaming time. The exploded rice straw was separated into water‐soluble material, methanol‐soluble lignin, Klason lignin, and a mixture of cellulose and a low molecular weight substance. The effects of steam explosion on the characteristics of the exploded rice straw were clarified from the point of view of the amounts of extractive components. Steam explosion was found to be effective for the delignification of rice straw and for increasing its susceptibility to enzyme hydrolysis and alcohol fermentation. The polysaccharides (cellulose and hemicellulose) in the rice straw treated at a steam pressure of 3.5 MPa with a steaming time of 2 min were hydrolyzed almost completely into monosaccharides, (ie glucose and xylose) by a mixture of Trichoderma viride cellulase (Meicelase) and Aspergillus aculeatus cellulase (Acucelase). The enzymatic hydrolyzate of exploded rice straw was converted into ethanol efficiently by Pichia stipitis and the ethanol yield from sugar was about 86%(w/w) of the theoretical value. The ethanol concentration in a membrane bioreactor coupled with a pervaporation system reached 50 gdm^?3 and was about five times higher than that in the culture broth. The energy efficiency (ratio of combustion energy of ethanol produced to energy for steam explosion) reached a maximum value at a pressure of 3.5 MPa for 2 min. © 2001 Society of Chemical Industry     

Coconut husk lignin. II. Characterization by infrared and nuclear magnetic resonance spectroscopy

Results of the characterization of coconut husk lignin by infrared (IR) and proton nuclear magnetic resonance (H-NMR) spectroscopy are presented. Lignin was extracted with both alkaline and organosolv liquors. The IR spectra of dioxane lignin were very similar to those reported for hardwood lignins. Furthermore, these results combined with those obtained from the H-NMR studies suggest that coconut husk lignin can be classified into the Lm-type lignins. These lignins are characteristic of the monocotyledon class, of which the coconut palm is a member. The H-NMR studies showed that anthraquinone significantly inhibited the occurrence of lignin condensation during the alkaline extraction with sodium hydroxide solutions. This inhibition was more intense in the lignin extracted at 150°C than in that extracted at 100°C.     

Extraction,Characterization and Utilization of Organosolv Miscanthus Lignin for the Conception of Environmentally Friendly Mixed Tannin/Lignin Wood Resins

Lignin was extracted from Miscanthus × giganteus using two procedures: an aqueous-ethanol organosolv treatment and a two-step process involving a dilute acid pre-soaking step followed by an aqueous-ethanol organosolv treatment. The organosolv lignin was subjected to a comprehensive structural characterization by ¹³C and MALDI-TOF MS and used for the formulation of a green wood adhesive prepared with 100% natural resins. The best formulation was composed of 60% of mimosa tannin and 40% of glyoxalated lignin extracted using a 1-step organosolv treatment. This formulation, when applied to wooden test panels yielded good internal bond strength results, which was good enough to pass relevant international standard specifications for interior-grade panels.     

Structural characterization of residual lignins isolated with cyanamide-activated hydrogen peroxide from various organosolvs pretreated wheat straw

The posttreatment of various organosolvs pretreated wheat straw with cyanamide-activated hydrogen peroxide was studied. About 44–80% of the total residual lignin and 38–85% of the total residual hemicelluloses were released or degraded during the posttreatment with 1.8% H₂O₂–0.18% cyanamide at 50°C under pH 10.0 for 4 h from different aqueous organic acids or alcohols pretreated straw. The seven degraded residual lignin preparations were subjected to a comprehensive physicochemical and structural characterization by UV, FTIR, and ¹H and ¹³NMR spectroscopy, and GPC. The nitrobenzene oxidation method was also applied to the in situ lignins. It was found that the seven residual lignin preparations contained large amounts of noncondensed syringyl and guaiacyl units, together with fewer noncondensed p-hydroxyphenyl units, esterified p-coumaric acid, and mainly etherified ferulic acid. All of the lignin fractions are free of associated polysaccharides and had molecular-average weights ranging between 2980 and 3820 g mol⁻¹. Analysis of these low molecular weight degradation products revealed an oxidation of residual lignin had occurred. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of ultrasound on the physicochemical properties of organosolv lignins from wheat straw

The extractability and physicochemical properties of the wheat straw lignins were comparatively studied by using extraction methods with 0.5M NaOH in 60% aqueous methanol with and without application of ultrasonic irradiation. The results showed that applying sonication for 5, 10, 15, 20, 25, 30, and 35 min solubilized 67.4, 68.6, 74.4, 77.3, 77.3, 77.9, and 78.5% of the original lignin, whereas the treatment with 0.5M NaOH in 60% aqueous methanol at 60°C for 2.5 h without ultrasound assistance released 61.0% of the original lignin. The lignin preparations isolated by ultrasound‐assisted extractions showed slightly lower molecular weights, associated polysaccharides, and thermal stabilities during the initial stage of decomposition. More important, there were no significant differences in the primary structural features between the lignin preparations. Ultrasound‐assisted extractions under the alkaline organosolv extractions did not affect the overall structure of the lignin from wheat straw. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2512–2522, 2002     

Quantitative Phosphorus-31 NMR Analysis of Six Soluble Lignins

By using a set of lignin samples, which have been subjected to thorough analyses by the international wood chemistry community, the recently developed quantitative method of ³¹P NMR spectroscopy was comprehensively examined. The values of total phenolic hydroxyl groups and those of total hydroxyl groups were found to favourably compare with those obtained by other laboratories, applying independent methods of analysis. Furthermore, the application of quantitative ³¹P NMR spectroscopy offered additional detailed structural information for the examined lignins which was in accord with literature accounts for similar wood species and lignin preparations. More specifically, the steam explosion lignins from aspen and yellow poplar woods and that produced by ball milling/enzyme hydrolysis of cottonwood were found to contain relatively high amounts of β-O-4 structures. In contrast, the kraft, organosolv, and the acid hydrolysis processes were found to induce significant chain scission on the resulting lignins. Ball milled cottonwood lignin contained the highest frequency of β-O-4 bonds and the lowest amount of free phenolic hydroxyls. The erythro form of β-O-4 structures were invariably predominant in the lignins from aspen, yellow poplar and cottonwood, in accord with the conclusions of previous reports on hardwood lignins. Thus, the application of quantitative ³¹P NMR spectroscopy offered the detailed chemical composition of the examined lignins.     

Structural Variation of Bamboo Lignin before and after Ethanol Organosolv Pretreatment

In order to make better use of lignocellulosic biomass for the production of renewable fuels and chemicals, it is necessary to disrupt its recalcitrant structure through pretreatment. Specifically, organosolv pretreatment is a feasible method. The main advantage of this method compared to other lignocellulosic pretreatment technologies is the extraction of high-quality lignin for the production of value-added products. In this study, bamboo was treated in a batch reactor with 70% ethanol at 180 °C for 2 h. Lignin fractions were isolated from the hydrolysate by centrifugation and then precipitated as ethanol organosolv lignin. Two types of milled wood lignins (MWLs) were isolated from the raw bamboo and the organosolv pretreated residue separately. After the pretreatment, a decrease of lignin (preferentially guaiacyl unit), hemicelluloses and less ordered cellulose was detected in the bamboo material. It was confirmed that the bamboo MWL is of HGS type (p-hydroxyphenyl (H), vanillin (G), syringaldehyde (S)) associated with a considerable amount of p-coumarate and ferulic esters of lignin. The ethanol organosolv treatment was shown to remove significant amounts of lignin and hemicelluloses without strongly affecting lignin primary structure and its lignin functional groups.     

Production of H2 and medium heating value gas via steam gasification of lignins in fixed‐bed reactors

In this work, steam gasification of Alcell and Kraft lignins were carried out in a fixed‐bed reactor in order to produce H₂ and medium heating value gas. The conversion of lignins increased from a low of 64 wt% for Alceil lignin to a high of 88 wt% for Kraft lignin with increasing steam flow rate and temperature. Maximum H₂ production of 60.7 mol% was obtained at 800°C and at a steam flow rate of 15 g/h/g of Kraft lignin, whereas maximum heating value of 18000 kl/m³ of the product gas was obtained at 650°C and at 5 g/h/g of Alcell lignin. Also, the performance of a Ni‐based steam reforming catalyst for the production of H₂ was studied for both types of lignin in a dual fixed‐bed reaction system. A maximum H₂ production of 63 mol% was obtained at a catalyst bed temperature of 750°C and at a catalyst loading of 0.3 g for Alcell lignin. The sulfur present in Kraft lignin had detrimental effect on the catalyst performance.     

Condensation Reactions of Lignin During Oxygen Delignification Under Acidic Conditions

Spruce wood (Picea abies) has been subjected to delignification by oxygen under acidic conditions using different solvent media. The residual and removed lignins were submitted to permanganate oxidation and the products analyzed by GC and GC-MS. Results from the analysis of the residual lignins indicate that lignin “condensation” depends on the nature of oxidation medium. It was found that the addition of acetone to the aqueous liquor decreases both acid catalyzed and radical side reactions. Lignin “condensation” in water containing media is dominated by radical reactions. Results from the analysis of the lignin removed during oxygen delignification in an acetone/water medium indicate that significant amounts of “condensed” structures are present, which are relatively stable towards oxidation. The presence of diphenylmethane, diarylether and biphenyl type structures in the removed lignin was confirmed by CP-MAS ¹³C NMR spectroscopy.     

Miscanthus sinensis fractionation by different reagents

Miscanthus sinensis L. was fractionated by different reagents (ethanol, soda and soda–ethanol) in order to obtain cellulose, hemicelluloses and lignin. Characterization of original M. sinensis fibres (66.6% holocellulose, 36.1% α-cellulose, and 15.5% lignin) was done and compared with other biomass species chemical composition (alternative raw materials, agriculture residues, coniferous and leafy plants). Obtained solid fractions were chemically characterized and compared with solid fractions from other biomass products (palm oil empty fruit bunches (EFB) and rice straw) generated by similar fractionation processes (soda and organosolv). Soda process produced the solid fraction with the highest content in α-cellulose and lowest content in lignin revealing a strong fractionation effect. On the contrary, soda–ethanol process was found to present low fractionation capability. Obtained cellulose samples were characterized by FTIR to complete the chemical structure analysis. Lignin samples isolated from the liquid fractions were submitted to FTIR, ¹H NMR, GPC, DSC and TGA in order to suggest suitable applications for the products based on their properties.     

Molecular Weight Distribution of (Semi-) Commercial Lignin Derivatives

Absolute molecular weights of several commercially and semi-commercially available lignins were determined by gel permeation chromatography (GPC with a differential viscosity detector (DV). Solubility in THF was assured by acetylation. Polystyrene molecular weight standards were used for establishing a universal calibration curve. The lignins included those from hardwood, softwood, and sugar cane bagasse; and these were isolated by the kraft or organosolv pulping process, or by steam explosion/autohydrolysis. All lignins exhibited more or less uniform distributions with weight average molecular weights (M_w) between 3, 000 and 20, 000; with polydispersities (M_w/M_n)between 2 and 12; with Mark-Houwink-Sakurada exponential factors (α) between 0.17 and 0.35; and with intrinsic viscosities between 0.037 and 0.08 dLg^?1. A significant relationship between M_w/M_n and M_w was discovered that had a correlation factor of 0.92. This relationship has the form of M_w/M_n = 0.45 (M_w 10^?3 + 0.85.     

Engineering Plastics from Lignin XIV. Characterization of Chain-Extended Hydroxypropyl Lignins

Abstract

Three series of chain-extended hydroxypropyl lignins (CEEQLs), prepared fran oqanosolv and kraft lignin, were examined regarding their chemical, molecular weight and them1 characteristics. Results showed that the molar substitution (MS) of propylene oxide, which was defined as the number of propoxy repeat units which comprise the chain attached to a single reactive site on lignin, varied and affected copolymer properties. As the MS increased from 1 to 7.2, the number average molecular weight (M_g) increased while the glass transition temperature (T_g) decreased. The actual M_g observed by GPC exceeded however that expected on the basis of mass gain by derivatization. This was attributed to changes in the apparent hydrodynamic volume in relation to MS. The change in T_g with increasing MS followed the Gordon-Taylor relationship. Differences in the chemical composition of the original lignin (organosolv or Kraft) were not obvious as the lignin content of the copolymer decreased below 50%.     

Catalytic organosolv fractionation of willow wood and wheat straw as pretreatment for enzymatic cellulose hydrolysis

BACKGROUND: Ethanol‐based organosolv fractionation of lignocellulosic biomass is an effective pretreatment technology for enzymatic cellulose hydrolysis to produce sugars and lignin within a biorefinery. This study focuses on the catalytic effect of H₂SO₄, HCl, and MgCl₂ on organosolv pretreatment of willow wood and wheat straw. RESULTS: The use of catalysts improved fractionation of both feedstocks. The maximum enzymatic cellulose digestibility obtained was 87% for willow wood (using 0.01 mol L^?1 H₂SO₄ as catalyst) and 99% for wheat straw (0.02 mol L^?1 HCl). Non‐catalytic organosolv fractionation at identical conditions resulted in 74% (willow wood) and 44% (wheat straw) glucose yield by enzymatic hydrolysis. Application of catalysts in organosolv pretreatment was particularly effective for wheat straw. The influence of the acid catalysts was found to be primarily due to their effect on the pH of the organosolv liquor. Acid catalysts particularly promoted xylan hydrolysis. MgCl₂ was less effective than the acid catalysts, but it seemed to more selectively improve delignification of willow wood. CONCLUSION: Application of catalysts in organosolv pretreatment of willow wood and wheat straw was found to substantially improve fractionation and enzymatic digestibility. The use of catalysts can contribute to achieving maximum utilization of lignocellulosic biomass in organosolv‐based biorefineries. Copyright © 2011 Society of Chemical Industry     

有机溶剂型木质素提取方法探索

本文采用有机溶剂法对汽爆稻壳中木质素的提取工艺进行了探索，通过正交分析提出了合适的提取方法以及最优的工艺条件，并对木质素产品的理化指标及结构特点进行了表征。结果表明，有机溶剂型木质索（organosolv lignin）与传统木质素产品相比具有灰分、残糖含量低，分子量大小和分布适中以及活性基团丰富等优点，在高分子材料的合成和改性领域有广阔的应用前景。