Ultrasonically assisted liquefaction of lignocellulosic materials

In our research, we have utilized high energy ultrasound for the liquefaction of different lignocellulosic materials, wood wastes in particular. We developed a highly efficient way of transforming this biomass waste into valuable chemicals. It was found, that the reaction yield in all experiments was high and that the reaction times were shortened up to nine times when using the ultrasound process with smaller residual particles and with no influence on the hydroxyl number of the final products. The use of the ultrasound process inhibits the formation of the large molecular structures during the liquefaction from the degradation products, by keeping the reactive segments apart and due to such a short reaction time being used. The short reaction time and subsequent low energy consumption for the liquefaction reaction leads to the creation of the new method for the transformation of the wood waste materials into valuable chemicals.     

Potential yields and properties of oil from the hydrothermal liquefaction of microalgae with different biochemical content

A range of model biochemical components, microalgae and cyanobacteria with different biochemical contents have been liquefied under hydrothermal conditions at 350 °C, ∼200 bar in water, 1 M Na₂CO₃ and 1 M formic acid. The model compounds include albumin and a soya protein, starch and glucose, the triglyceride from sunflower oil and two amino acids. Microalgae include Chlorella vulgaris,Nannochloropsis occulata and Porphyridium cruentum and the cyanobacteria Spirulina. The yields and product distribution obtained for each model compound have been used to predict the behaviour of microalgae with different biochemical composition and have been validated using microalgae and cyanobacteria. Broad agreement is reached between predictive yields and actual yields for the microalgae based on their biochemical composition. The yields of bio-crude are 5-25 wt.% higher than the lipid content of the algae depending upon biochemical composition. The yields of bio-crude follow the trend lipids > proteins > carbohydrates.     

Gill-symbiosis in mytilidae associated with wood fall environments

Bivalves belonging to the genera Idas and Adipicola were collected from wood fall environments in the west Pacific (Vanuatu islands) between 300 and 890 m depths in 2004. Bacterial symbionts were checked by three complementary techniques: histological and DAPI staining, in situ hybridization (FISH), and TEM. No bacteria were detected inside the gills of the two species, rejecting the endosymbiosis hypothesis. However, results from our study demonstrated the existence of ectosymbionts colonizing microvilli differentiated at the apical surface of the cells constituting the lateral zone of gill filaments. These ectosymbionts are γ-Proteobacteria due to their strong hybridization with the specific probe GAM42; in contrast no hybridization was obtained from either gills or other host tissues by using the oligonucleotide probes specific to α- β- and δ-Proteobacteria. Based on TEM observations, these Gram-negative bacterial symbionts are not methanotrophic due to the lack of concentric stacking of intracellular membranes in their cytoplasm. Such ectosymbionts may represent thioautotrophic bacteria as already described in various Mytilidae from hydrothermal vents and cold seeps. Unfortunately, no phylogenetic analysis could be done in this study to compare their DNA sequence to that of other marine invertebrate symbionts described to date.     

Effects of chemical inhomogeneity of corn stalk on solvolysis liquefaction

Structural characterization of corn stalk (CS) factions including whole stalk, ear husk, leaf blade, stem bark and stem pith was conducted. Different fractions were liquefied by solvolysis liquefaction method. Acid number, hydroxyl number and insoluble residues ratios (IRR) of liquefied products from CS factions were monitored. Results showed chemical compositions of CS fractions had remarkable difference. Cellulose, hemicellulose and lignin accounted for 36.9-41.43%, 21.77-37.3% and 3.38-7.52% of the raw material, respectively. Acid numbers increased with increasing time from 30 to 90 min, whereas hydroxyl numbers decreased gradually, IRR decreased and then increased. However, properties of liquefied products differed remarkably. Higher acid number, higher hydroxyl number, and lower IRR were detected from ear husk liquefied products. This is coincident with the higher content of hemicelluloses in ear husk. This work proved that whole utilization process is unsatisfactory in solvolysis liquefaction and different fractions of CS should be given themselves optimum applications.     

Relationship between wood anatomy,tree-ring widths and wood density of Pinus sylvestris L. and climate at high latitudes in northern Sweden

In this study, wood anatomy, tree-ring width and wood density of Pinus sylvestris at the northern timberline in Fennoscandia were used to identify relationships among the parameters and to screen them for their climatic signals. Furthermore we investigated the influence of the juvenile wood section for all parameters developed. The measurements of wood anatomy were conducted with confocal laser scanning microscopy (CLSM) while the density profiles were produced using an Itrax MultiScanner. We developed chronologies of ring width, wood density and anatomy for a period between 1940 and 2010. Correlations between wood density and wood anatomy were strong in the latewood part. For some wood anatomy and density chronologies youth trends were found in the juvenile part. Wood density decreased from the pith up to the 9th ring and stabilized afterwards, while cell lumen diameter and lumen area increased simultaneously up to the 15th ring. All chronologies contained strong summer temperature signals. The wood anatomical variables provided additional information about seasonal precipitation which could not be found in wood density and tree-ring widths. Our study confirmed previous results stating that the parameter maximum density contains the strongest climate signal, that is, summer temperatures at the northern timberline. Nevertheless, the intra-annual data on tracheid dimensions showed good potential to supply seasonal climatic information and improve our understanding of climatic effects on tree growth and wood formation.     

SO3H-functionalized ionic liquid: efficient catalyst for bagasse liquefaction

Liquefaction is a process for the production of biofuel or value-added biochemicals from non-food biomass. SO₃H-, COOH-functionalized and HSO₄-paired imidazolium ionic liquids were shown to be efficient catalysts for bagasse liquefaction in hot compressed water. Using SO₃H-functionalized ionic liquid, 96.1% of bagasse was liquefied and 50.6% was selectively converted to low-boiling biochemicals at 543 K. The degree of liquefaction and selectivity for low-boiling products increased and the average molecular weight of the tetrahydrofuran soluble products decreased with increasing acidic strength of ionic liquids. Analysis of products and comparative characterization of raw materials and residues suggested that both catalytic liquefaction and hydrolysis processes contribute to the high conversion of bagasse. A possible liquefaction mechanism based on the generation of 3-cyclohexyl-1-propanol, one of the main products, is proposed.     

Comparative wood anatomy ofCoriaria

Wood anatomy ofCoriaria was surveyed to clarify generic features on the basis of 14 species collected from various regions of the World to cover the whole range of geographic distribution and habitual variation. Wood anatomy ofcoriaria is considerably uniform, and the species share a combination of the following features: 1) pores are thin-walled, polygonal in outline and mostly in multiples; 2) vessel elements and libriform fibers are very short; 3) perforation plates are exclusively simple; 4) intervessel pits are alternate; 5) vascular tracheids are present; 6) wood parenchyma is vasicentric and sometimes confluent; 7) rays are heterogeneous and large. Its species differ in several characters, such as distinctness of growth rings, pore size, pore patterns, type and abundance of wood parenchyma, and distinctness of storied structure. Comparisons among species indicate that the species of the Northern Hemisphere show a tendency toward having semi-ring porosity, while those of the Southern and Western Hemisphere have diffuse porosity. The other infrageneric variations appear to be related to different habits of the species rather than to geographic distribution. Small trees mostly have confluent and vasicentric parenchyma composed of fusiform cells and distinctly storied tissues, while shrubs and herbs have less abundant parenchyma which is vasicentric and comprises strands of two to four cells and indistinctly storied tissues.     

Production and characterization of biopolyols and polyurethane foams from crude glycerol based liquefaction of soybean straw

The feasibility of using crude glycerol to liquefy soybean straw for the production of biopolyols and polyurethane (PU) foams was investigated in this study. Liquefaction conditions of 240 °C, >180 min, 3% sulfuric acid loading, and 10-15% biomass loading were preferred for the production of biopolyols with promising material properties. Biopolyols produced under preferential conditions showed hydroxyl numbers from 440 to 540 mg KOH/g, acid numbers below 5 mg KOH/g, and viscosities from 16 to 45 Pa.s. PU foams produced under preferential conditions showed densities from 0.033 to 0.037 g/cm³ and compressive strength from 148 to 227 kPa. These results suggest that crude glycerol can be used as an alternative solvent for the liquefaction of lignocellulosic biomass such as soybean straw for the production of biopolyols and PU foams. The produced biopolyols and PU foams showed material properties comparable to their analogs from petroleum solvent based liquefaction processes.     

Development of environmentally-benign wood preservatives based on the combination of organic biocides with antioxidants and metal chelators

Wood extractives can be envisaged to protect heartwood by at least three different mechanisms, i.e. fungicide, free radical scavengers/antioxidants and as metal chelators. In short-term laboratory decay tests using two different wood species and decay fungi, the combination of different organic fungicides with various antioxidants and/or metal chelators gave enhanced activity as compared to the organic biocide alone, with the best results usually obtained with all three compounds. Outdoor ground-contact stakes treated with a biocide and antioxidant combination and exposed for 30 months also gave enhanced protection against both decay fungi and termites. It was concluded that the combination of an organic biocide with metal chelating and/or antioxidant additives gives enhanced protection to wood against fungi as compared to the biocide alone and, consequently, it may be possible to develop environmentally-benign wood preservative systems based on this idea.     

Quantitative evaluation of heavy metals' pollution hazards in liquefaction residues of sewage sludge

Liquefaction residues (LR) are the main by-products of sewage sludge (SS) liquefaction. This study quantitatively evaluates the potential ecological risk and pollution degrees of heavy metals (Pb, Zn, Cu, Cd, Cr and Ni) in LR versus SS. The leaching rates (R1) of heavy metals in LR were much lower than those in SS, revealing that the mobility/leachability of heavy metals was well suppressed after liquefaction. Geo-accumulation index (Igeo) indicated that the liquefaction process significantly weakened the contamination degrees of heavy metals. Potential ecological risk index (RI) demonstrated that overall risks caused by heavy metals were obviously lowered from 1093.56 (very high risk) in SS to 4.72 and 1.51 (low risk) in LR1 and LR2, respectively. According to the risk assessment code (RAC), each tested heavy metal had no or low risk to the environments after liquefaction. In a word, the pollution hazards of heavy metals in LR were markedly mitigated.     

Total concentrations and chemical speciation of heavy metals in liquefaction residues of sewage sludge

The risk (including bioavailability and eco-toxicity) of heavy metals (Pb, Zn, Cu, Cd, Cr and Ni) in liquefaction residues (LR) of sewage sludge (SS) was estimated, according to both the speciation of heavy metals and the local environmental characteristics. The amount of organic matters in LR was lower than that in SS, resulting in a smaller calorific value, while the total content of heavy metals in LR nearly doubled. High residual rates of heavy metals (about 80%) indicated that the heavy metals in SS were concentrated into LR after liquefaction. The comparisons of sequential extraction results between SS and LR showed that after liquefaction, the mobile and easily available heavy metal fractions (acid soluble/exchangeable and reducible fractions) were mainly transformed into the relatively stable heavy metal fractions (oxidizable and residual fractions). The bioavailability and eco-toxicity of heavy metals in LR were relieved, though the total concentrations of heavy metals increased.     

Comparative study of liquefaction process and liquefied products from bamboo using different organic solvents

The effects of various solvents, including phenol, ethylene glycol (EG) and ethylene carbonate (EC), and different liquid ratios on the liquefaction of bamboo, have been studied systematically in this paper. The processes were catalyzed by hydrochloride acid at 180 °C in autoclaves for different reaction times. The results show that phenol is the optimum solvent for bamboo liquefaction with a yield up to 99%. The Fourier transform-infrared (FT-IR) analyses of the residues show that cellulose, hemicelluloses and lignin are almost decomposed when using phenol as solvent. The gel permeation chromatography (GPC) results of the liquid products show that the high molecular weight of bamboo decreases significantly to around 1800 g mol⁻¹ after liquefaction. The gas chromatography and mass spectrometry (GC–MS) analysis shows that low boiling point products of liquefied bamboo are similar regardless of the type of solvent used.     

Gas diffusion through wood: implications for oxygen supply

Living tissue in tree stems has to be supplied with oxygen, which can be transported upwards with the transpiration stream; but in times of zero sapflow, the only source is the oxygen stored or diffusing radially through bark and xylem. We measured radial and axial diffusion of oxygen against nitrogen gas in wood of coniferous (Picea abies (L.) Karst. and Taxus baccata L.), ring-porous (Quercus robur L. and Fraxinus excelsior L.) and diffuse-porous (Fagus sylvatica L. and Carpinus betulus L.) trees at different water and gas contents in the laboratory. The diffusion coefficient (D) in radial direction was mostly between 10⁻¹¹ and 10⁻⁷ m² s⁻¹ and was strongly related to the gas content. At 40% gas volume, D increased 5–13-fold in Picea, Taxus and Quercus, 36-fold in Fraxinus, and about 1000-fold in Carpinus and Fagus relative to D at 15% gas volume. In the axial direction, diffusion was 1 or 2 orders of magnitude faster. Between-species differences in diffusion velocities can largely be explained by wood structure. In general, D was lowest in conifers, highest in diffuse-porous and intermediate in ring-porous hardwoods, where the large vessels were mostly blocked by tyloses. Model calculations showed that at very high water content, radial diffusion can be too low to ensure the supply of respiring sapwood with sufficient oxygen and an important function of gas in living stems appears to be the supply of oxygen through storage and diffusion.     

Activity of dehydroabietic acid derivatives against wood contaminant fungi

The antifungal activity of 10 dehydroabietic acid derivatives with different configuration in A and B rings (cis/trans A/B junction) and different substituents and/or functionalities was evaluated in bioassays in vitro and in situ (pine wood blocks).

The test compounds dissolved in acetone were assayed at several concentrations w/w (test compound/culture medium) against the fungi. The Relative Inhibition (RI) was determined by measuring the radial growth of colonies of the fungi treated with the test compounds by comparison with those of control cultures; the results are expressed as EC₅₀.

The results of bioassays in vitro have shown that hydroxyl and aldehyde functions are required for antifungal activity in this group of compounds and deisopropylation can increase the activity. Our assay of antifungal activity in situ (in pine wood blocks) provides a means to investigate the preservative activities of these antifungal compounds under actual conditions of use.

The dehydroabietic acid derivative cis-deisopropyldehydroabietanol (10) inhibited the growth of several of the fungi tested, in vitro and in situ.

The results obtained in situ with the test compound (10) at 6% and 8% were not significantly different from the reference products and a good level of protection of the wood against the organisms tested was achieved.

The results in wood bioassays present new possibilities in the search for natural new compounds in the wood protection, as an alternative to conventional fungicides.     

光频微波对黄曲霉的杀灭试验

黄曲霉是污染粮食、食品、中药材和烟丝的常见霉菌。由于黄曲霉的产物黄曲霉毒素具有很强的致癌作用。因此 ,从这些食品或物品中消除黄曲霉可减少甚至消除黄曲霉毒素的危害。报告了微波辐射杀灭烟丝中黄曲霉的效果。光频微波对烟丝上的黄曲霉菌具有良好的杀灭作用 ,微波辐射 30s后菌落数明显减少 ,经 4 5s作用后可完全杀灭黄曲霉的细胞 (包括菌丝和孢子 )。应用光频微波辐射杀灭黄曲霉具有经济、方便和高效的优点 ,既可以用于大规模工业生产 ,亦可在家庭生活中使用。     

Sorption and desorption of chromate by wood shavings impregnated with iron or aluminum oxide

This study examined the impregnation of hybrid poplar shavings with Fe or Al oxide and their reactivity with Cr(VI). The shavings were impregnated with an average of 1.24 ± 0.18 mmol Fe g⁻¹ or 1.51 ± 0.17 mmol Al g⁻¹, and the impregnated Fe or Al oxide was highly amorphous. Capacity of Cr(VI) sorption by impregnated shavings was high and rate of the sorption was rapid. While the freshly sorbed Cr on the Fe oxide-shavings was readily desorbed in 0.1M NaOH, nine weeks of ageing reduced the desorbability to only 6.5% of the sorbed Cr. Extraction with 0.1 M NaOH remained feasible to recover most sorbed Cr from the Al oxide-shavings over the same ageing period. Impregnation of the shavings with Fe or Al oxide turns the wood waste into a product for removing Cr(VI) or other oxyanions from wastewater.     

Laccase production and wood degradation by a white-rot fungus Daedalea flavida

A comparative study has been conducted on seven white rot fungi to investigate their abilities to produce laccase and selectively degrade lignin. Laccase was produced constitutively on the different media tested. Of the different lignins, phenolic compounds and sugars involved, the highest laccase yield was obtained on indulin AT. Salicylic acid inhibited enzyme activity. A temperature of 20°C and 0.2% of indulin AT were found to be optimum for enzyme activity. No correlation was found between the amount of enzyme and fungal mass produced. During semisolid degradation of angiospermic wood sawdust, Daedalea flavida caused a total weight loss of 11%, with a lignin loss of 15.77% during two months of decay. Lignin removal was comparatively selective during the first month, during which time laccase production was also higher, indicating its probable role in lignin degradation.     

Fungal resistance of rubber wood modified by fatty acid chlorides

Decay resistance of Rubber wood (Hevea brasiliensis) esterified with three fatty acid chlorides (hexanoyl chloride (C6), decanoyl chloride (C10) and tetra-decanoyl chloride (C14)) was evaluated. Unmodified and modified wood samples were exposed to a brown rot (Polyporus meliae) and a white rot (Coriolus versicolor) fungus for 12 weeks. Unmodified rubber wood was severely decayed by P. meliae and C. versicolor, which was indicated by significant weight loss. The rate of decay by brown rot was higher than white rot. Modified wood samples exhibited very good resistant to brown and white-rot fungi. The degree of protection increased with increase in degree of modification. P. meliae, a brown rot fungus, removed structural carbohydrate component in unmodified wood selectively whereas, C. vesicolor showed preference to lignin. The FTIR spectra of modified wood exposed to fungi show no significant changes in relative peak intensities of lignin/carbohydrates indicating effectiveness of chemically modified wood in restricting chemical degradation. Chemical modification occurred more efficiently at carbohydrate portion of the wood. Therefore, it is more effective in retarding decay due to P. meliae.