Products properties from fast pyrolysis of enzymatic/mild acidolysis lignin

The conversion of enzymatic/mild acidolysis lignin (EMAL) isolated from moso bamboo to aromatic chemicals by fast pyrolysis were investigated under nitrogen atmosphere and atmospheric pressure. The experiment of EMAL pyrolyzing was set on a tubular reactor furnace at the temperature levels of 400, 500, 600, 700, 800 and 900 °C, and the products derived from EMAL pyrolyzing were classified into three-phase of gas, condensed liquid (tar), and solid (char). The chemical structure and surface morphology of solid product were characterized by fourier transforms infrared spectroscopy (FTIR) and scanning electron microscopy (SEM), and the ingredients of gas product and liquid (tar) were analyzed with gas chromatography (GC) and gas chromatography/mass spectrometer (GC/MS). The analysis results indicated that the yield of char decreased rapidly from 43% to 28% with an increase of temperature, and the yield of gas product increased gradually from 6% to 26%, and the yield of tar attained a maximum at 700 °C. SEM showed that char took on lots of vesicles that resulted from the gas release from EMAL pyrolyzing. The ingredients of gas product were comprised of H₂, CO, CO₂ and light hydrocarbons (CH₄, C₂H₄ and C₂H₆), and the amount of H₂, CO were high. Besides a huge amount of phenols, the tar contained aromatic hydrocarbons, chain hydrocarbons, monoaromatic aromatic hydrocarbons and some ketones, and the carbon number of chemical compounds were C₆–C₁₀.     

EXAFS Study on Structural Change of Charcoal-supported Ruthenium Catalysts during Lignin Gasification in Supercritical Water

Lignin gasification in supercritical water over charcoal supported ruthenium trivalent salts was studied using a batch reactor at 673 K. Ruthenium (III) nitrosyl nitrate on charcoal (Ru(NO)(NO₃)₃/C) was more active than ruthenium (III) chloride on charcoal (RuCl₃/C) for the gasification reaction. EXAFS analysis revealed that ruthenium metal particles were formed in both RuCl₃/C and Ru(NO)(NO₃)₃/C catalysts during the lignin gasification and that the size of ruthenium metal in Ru(NO)(NO₃)₃/C was smaller than that in RuCl₃/C. It was concluded that well-dispersed ruthenium metal particles were active for the lignin gasification in supercritical water.     

Decomposition of Bt and Non-Bt Corn Hybrid Residues in the Field

Results of a previous laboratory study indicated that six transgenic crops expressing the Cry1Ab insecticidal protein from Bacillus thuringiensis (Bt) decomposed at a slower rate than their respective non-Bt isolines. Consequently, litter decomposition rates, nitrogen cycling, and carbon pools may change in agricultural systems as the result of the widespread use of Bt crops. In this study, we assessed the decomposition rates and chemical composition of commonly grown hybrids of Bt and non-Bt isolines of corn (Zea mays L.) in the field. Leaves, stalks, and cobs from two Bt corn hybrids (Pioneer 34N44 Bt and NC+ 4990 Bt) and their non-Bt isolines (Pioneer 34N43 and NC+ 4880) were analyzed for biomass fractions (soluble, hemicellulose, cellulose, and lignin) and total C and N content. Litterbags containing these residues were buried at a depth of 10 cm in a Holdrege silt loam (fine-silty, mixed, mesic Typic Argiustolls) soil and recovered 5, 11, 17, and 23 months after placement in the field. There were no differences in the rates of decomposition and mass of C remaining over time between the Bt and non-Bt corn residues. Plant parts differed in decomposition rates where leaves > stalks > cobs. There were differences in total C, total N, biomass fractions, and C:N ratios between initial Bt and non-Bt corn residues, and between companies (NC+ and Pioneer), however, these differences did not result in differences in their rates of decomposition or mass of C remaining over time. For each plant part, there were no differences in lignin content between the Bt and non-Bt residues. These data suggest that the Bt and non-Bt corn hybrids used in this study should not cause differences in carbon sequestration when their residues decompose under similar environmental conditions.     

Comparative antioxidant activity of nanoscale lignin prepared by a supercritical antisolvent (SAS) process with non-nanoscale lignin

Nowadays, lignin antioxidant study is a hot spot. But some properties of lignin make it hard for a wide range of application. To improve lignin antioxidant activity, we employed supercritical antisolvent (SAS) method for preparation of nanoscale lignin (0.144 ± 0.03 μm) using acetone as a solvent and supercritical carbon dioxide as an antisolvent. The nanoscale lignin was characterised by Scanning Electron Microscopy (SEM), Fourier-Transform Infrared Spectroscopy (FTIR) and X-ray Diffraction (XRD). The results showed that SAS process did not result in lignin degradation or chemical structure change. Due to solubility increase, many antioxidant parameters of the nanoscale lignin were obviously enhanced, including DPPH radical scavenging activity, superoxide radical scavenging activity and reducing power. As an antioxidant, the nanoscale lignin was a better material than the non-nanoscale lignin. Our study was to promote the lignin application in animal husbandry, pharmaceutical and food processing industries.     

木质素的高值化利用研究进展

目前国内外所开发的木质素产品已经有数百种,但是,由于木质素本身结构非常复杂且种类繁多,使得开发木质素产品存在一定的盲目性。文章结合近年来木质素产品的研究及开发,介绍了木质素结构与功能之间的联系,以期能够充分利用木质素的结构特点来改进和生产木质素产品,以得到具有工业应用价值的产品,不仅具有环保意义,更具有经济意义。     

The Cost Evaluation of Advanced Oxidation Processes in Laboratory and Pilot-Scale Experiments

The present level of the development of water/wastewater treatment methods, including advanced oxidation processes, allows removal of pollutants of wide spectrum under no question. However, the overall process cost and, especially, associated energy consumption are of increased importance. The present review presents the energy cost calculations made for the pollutants removal reported in more than forty publications for over the last four decades. Phenol, glycols, methyl-tert-butyl ether (MTBE), aliphatic unsaturated compounds, humic acids and lignin were considered as water pollutants for economic evaluation of their removal. Two oxidation processes, ozonation and Fenton reaction, were chosen as water treatment methods.     

Lignin Depolymerization and Conversion: A Review of Thermochemical Methods

The structure of lignin suggests that it can be a valuable source of chemicals, particularly phenolics. However, lignin depolymerization with selective bond cleavage is the major challenge for converting it into value‐added chemicals. Pyrolysis (thermolysis), gasification, hydrogenolysis, chemical oxidation, and hydrolysis under supercritical conditions are the major thermochemical methods studied with regard to lignin depolymerization. Pyrolytic oil and syngases are the primary products obtained from pyrolysis and gasification. A significant amount of char is also produced during pyrolysis. Thermal treatment in a hydrogen environment seems very promising for converting lignin to liquid fuel and chemicals like phenols, while oxidation can produce phenolic aldehydes. Reaction severity, solvents, and catalysts are the factors of prime importance that control yield and composition of the product.     

A Method for Evaluating Lignin Mobility Distributions Obtained by Capillary Zone Electrophoresis

Abstract

The profile of the mobility distribution of lignin-containing samples depends on type of sample. To facilitate comparison, a procedure for determining the average mobility (μ_av), i.e. the average charge density, of lignin is presented. The procedure is applied to black liquor (Sb), isolated dissolved lignin (Sd) and isolated residual (Sr) lignin samples, obtained from flow-through kraft cooks of softwood. The μ_av of the isolated lignin samples is compared with the concentration of phenol and carboxyl groups and relative molecular size. As the cook proceeds the μ_av for a particular type of lignin sample increases, reflecting an increase in average charge density. The μ_av, measured at pH 12, decreases in the order Sd>Sb>Sr, except at the end of the cook, when the average charge densities of the Sb and Sr samples are similar. Associations between lignin and carbohydrate fragments are proposed to cause the lower mobility of black liquor compared to isolated dissolved lignin. Characterisations performed at pH 10 indicate that the isolated dissolved lignin samples may have a higher pK_a in the middle of the cook than the other samples.     

Supercritical water gasification of biomass for hydrogen production

Hydrogen from waste biomass is considered to be a clean gaseous fuel and efficient for heat and power generation due to its high energy content. Supercritical water gasification is found promising in hydrogen production by avoiding biomass drying and allowing maximum conversion. Waste biomass contains cellulose, hemicellulose and lignin; hence it is essential to understand their degradation mechanisms to engineer hydrogen production in high-pressure systems. Process conditions higher than 374 °C and 22.1 MPa are required for biomass conversion to gases. Reaction temperature, pressure, feed concentration, residence time and catalyst have prominent roles in gasification. This review focuses on the degradation routes of biomass model compounds such as cellulose and lignin at near and supercritical conditions. Some homogenous and heterogeneous catalysts leading to water–gas shift, methanation and other sub-reactions during supercritical water gasification are highlighted. The parametric impacts along with some reactor configurations for maximum hydrogen production and technical challenges encountered during hydrothermal gasification processes are also discussed.