BioResources

The potential supply of biomass feedstocks in the US and Canada is estimated using a static supply function approach. Estimated total biomass available at a price of $100 per metric ton is 568 million metric tons in the US and 123 million tons in Canada, which together can displace 23-45 billion gallons of gasoline. Sufficient biomass, mainly agricultural and mill residues, will be available at prices of around $50/ton to meet the advanced biofuel mandates of the US Energy Independence and Security Act of 2007. The estimates of agricultural residue supply are very sensitive to the assumed fraction of residues that can be sustainably removed from the field, and the potential of municipal solid waste as a feedstock depends on which components can be economically converted into liquid biofuels.

Smoothness of paper surface is an important property of paper from its printability viewpoint. A number of techniques are available for characterizing the topographical features of paper surface. These techniques have led to the development of smoothness testers of various types such as air-leak testers, optical contact testers, surface profilers, and a number of ink and liquid application apparatus to assess the smoothness. While all these methods are intended to serve the same purpose, they differ so greatly in their basic approach that the agreement between them cannot be taken for granted. In the present work, these methods have been applied to characterize the surface of handsheets of mechanical pulps. A comparison of these methods reveals that different methods grade these pulps differently confirming the multidimensional nature of the surface structure

Streptomyces sp. PG-08-3 was isolated from the desert of Rajasthan (India). The organism produced mannanase (15 Umg-1 protein) in the presence of 0.5% guar gum as a sole carbon source in minimal media by submerged fermentation (SmF). Enzyme production was enhanced by 7.3-fold when 0.5% soyabean meal and 0.25% of leucine were added to the minimal media. Increasing the guar gum concentration in the media by 0.1-1.0% resulted in linearly enhanced the production of mannanase.

Autohydrolysis of Eucalyptus globulus was conducted at three different intensity levels typical for prehydrolysis kraft pulping as utilized for manufacturing dissolving pulp grades. The objective was to establish for the autohydrolysis process a detailed mass balance comprising the chemical composition of all three phases: the autohydrolysate, the released gas, and the solid residue. Carbohydrate determination involved both acid methanolysis combined with gas chromatography (GC) and sulfuric acid total hydrolysis with high performance anion exchange chromatography (HPAEC) coupled with pulsed amperometric detection (PAD); this allowed reliable quantification of neutral as well as acidic sugar units in cellulosic and non-cellulosic polysaccharides. Uronic acids present in the Eucalyptus globulus wood were progressively degraded through decarboxylation, leading to substantial carbon dioxide formation. The degree of acetylation of xylan remaining in the wood residue was clearly reduced, while the amount of bound acetyl groups in dissolved xylo-oligosaccharides (XOS) stayed relatively constant as a function of autohydrolysis intensity. The bulk of the lignin that was dissolved during autohydrolysis could be attributed to the acid-soluble lignin content of the wood. Only small amounts of Klason lignin were dissolved.

This study concerns the structural change of lignin during auto-catalyzed ethanol-water pulping of aspen by 1H-NMR. The results showed that the linkages of alkyl-aryl ether of lignin, such as the α-ether linkages (α-O-4) and the β-ether linkages (β-O-4), were broken and the alkyl part formed carbenium at the Cα and Cβ of the aliphatic branch. Meanwhile, the aryl part of ether accepted one H+ and formed phenol. Because of the electronegative effect originating from the electron cloud of phenyl, partial carbenium of Cβ was rearranged. Due to its ether or hydroxyl linkage, rearranging to Cβ, the Cα was changed into carbenium and formed a new β-O-4 alkyl-aryl ether. The β-O-4 alkyl-aryl ether was not stable and broken further. So the large molecule of lignin was disintegrated into a smaller one and dissolved into ethanol. Finally, the α+ carbenium reformed α-O-4 linkages of ether with phenol.

In an effort to devise inexpensive and sustainable production of ethanol fuel, experiments were conducted to establish conditions for Pichia stipitis NRRL Y-7124 to ferment a membrane treated wood hydrolysate derived from sugar maple to produce ethanol. The degree of aeration required to effectively utilize xylose, produce ethanol, and minimize xylitol formation as well as the optimal hydrolysate concentration were the conditions examined. P. stipitis produced the highest concentrations of ethanol in shake flasks at 150 rpm (14.3 g/L in 71 h), and 50% hydrolysate maximized ethanol yield (12.4 g/L in 51.5 h). In the 50% hydrolysate cultures, P. stipitis produced ethanol at a rate of 0.24 g/Lh with a yield of 0.41 g ethanol/g wood-derived carbohydrate.

A series of comparable specimens of hornbeam wood were submitted to fungal and chemical pretreatments. Two strains of erosive white-rot fungi (P. chrysosporium and T. versicolor) and a lignin-selective fungus C. subvermispora were used. Chemical pretreatments were carried out with diluted sodium hydroxide, or sodium hydroxide and then by hydrogen peroxide, or per-acetic acid. Both biotic and abiotic pre-treatments modified the chemical composition of wood and were accompanied by its weight loss. The applied fungi apparently delignified the specimens, however at the expense of cellulose, especially when the erosive strains of fungi were used. The chemical pretreatments caused deep deacetyl-ation, and milder delignification of wood and did not cause an apparent loss of cellulose. Biotic pretreatments of hornbeam wood, despite their marked delignification effect, led to unexpected increase in the contents of residual lignin in the resulting kraft pulps. On the other hand, pulping of the chemically pre-treated chips yielded pulps with low contents of residual lignin and much higher brightness.

An experimental study was conducted to determine the abrasive wear behaviour of different weight percentage bamboo powder filled polyester composites under the multipass mode. The effect of bamboo powder concentration and sliding distance on the weight loss of composites has been analyzed. Worn surface have been analyzed to observe the mechanism of wear. The weight loss depends on bamboo powder concentration. The weight loss decreases with the increase of sliding distance. Samples having 20 weight percentage (wt%) of bamboo powder show the maximum weight loss during abrasion.

Various hydrophilic polyelectrolytes, including cationic starch products, are used by papermakers to promote inter-fiber bonding and increase paper’s dry-strength. Thus, papermakers can meet customer require-ments with a lower net cost of materials, more recycled fibers, or higher mineral content. In the absence of polymeric additives, key mechanisms governing bond development between cellulosic fibers include capillary action, three-dimensional mixing of macromolecules on facing surfaces, conformability of the materials, and hydrogen bonding. Dry-strength additives need to adsorb efficiently onto fibers, have a hydrophilic character, and have a sufficiently high molecular mass. Though it is possible to achieve significant strength gains by optimal usage of individual polyelectrolytes, greater strength gains can be achieved by sequential addition of oppositely charged polyelectrolytes. Superior strength can be achieved by in-situ formation of polyelectrolyte com-plexes, followed by deposition of those complexes onto fiber surfaces. Polyampholytes also hold promise as efficient dry-strength additives. Opportunities for further increases in performance of dry-strength agents may involve fiber surface modification, self-assembled layers, and optimization of the dry film characteristics of dry-strength polymers or systems of polymers.

We have developed a semi-empirical model to relate the tensile energy absorption (TEA) of paper sheets formed from high-consistency refined pulp to pulp properties, including water retention value (WRV), fibre length, and fibre curl. TEA is shown to be related to the normalized stretch (ratio of stretch to tensile strength) and the tensile strength of the pulp. Normalized stretch appears to be a function of fibre curl, whereas tensile strength for a given pulp is a function of the fibre length, fibre curl, and WRV. The manner in which these three pulp properties develop in a given refining operation determines the development of TEA.

Carboxylation of cotton linters was investigated relative to its use in ion exchange. The effects of different treatments of cotton linters, such as alkali, acid, and activating agents, e.g. LiCl, on the molecular structure and carboxylation of cotton linters were taken in our consideration. The absence or presence of a crosslinking was considered, and the efficiency of these prepared carboxylated cotton linters toward metal ions uptake, as well as thermal analysis of treated and carboxylated cotton linters, was investigated. It was found that treatment of cotton linters with alkali and activating agent decreased the crystallinity index (band intensity at 1425/band intensity at 890 cm-1). On the other hand, the prepared carboxylated cotton linters had lower crystallinity index than uncarboxylated linters. Thermal analysis of the treated and carboxylated cotton linters allowed calculation of the activation energy of thermally treated materials. It was found that the crosslinked and acid treated cotton linters had a higher activation.

Cellulose fibres from sugarcane bagasse were bleached and modified by zirconium oxychloride in order to improve the mechanical properties of composites with high density polyethylene (HDPE). The mechanical properties of the composites prepared from chemically modified cellulose fibres were found to increase compared to those of bleached fibres. Tensile strengths of the composites showed a decreasing trend with increasing filler content. However, the values for the chemically modified cellulose fibres/HDPE composites at all mixing ratios were found to be higher than that of neat HDPE. Results of water immersion tests showed that the water absorption affected the mechanical properties. The fracture surfaces of the composites were recorded using scanning electron microscopy (SEM). The SEM micrographs revealed that interfacial bonding between the modified filler and the matrix was significantly improved by the fibre modification.

Near infrared (NIR) spectroscopy method was introduced to measure the lignin content in Acacia species. Acid-soluble lignin, Klason lignin, and total lignin contents from 78 wood meal samples of Acacia spp. trees grown in Guangxi province with different ages, height, and families were measured by wet chemistry. NIR spectra were also collected using a Bruker MPA spectrometer within 4000-12500cm-1 of wavenumbers using a standard sample cup and split into calibration and prediction sets. Equations were developed using partial least squares (PLS) regression and cross validation for multivariate calibration in this study. High coefficients of determination (R2) and low root mean square errors of cross-validation (RMSECV) were obtained for Klason lignin (R2=0.94, RMSECV=0.398), acid-soluble lignin (R2=0.87, RMSECV=0.144), and total lignin (R2=0.91, RMSECV=0.448) from wood meal. High correlation coefficients were found between laboratory and predicted values for Klason lignin, acid-soluble lignin, and total lignin contents, with R2 and RMSEP values ranging from 0.67 to 0.94, and 0.19 to 0.526, respectively. The study showed that NIR analysis can be reliably used to predict lignin content in Acacia spp.

Bio-oil is a promising alternative source of energy produced from fast pyrolysis of biomass. Increasing the viscosity of bio-oil during storage is a major problem that can be controlled by the addition of methanol or other alcohols. This paper reports the results of our investigation of the reactions of short chain alcohols with aldehydes and acids in bio-oil. The reaction of methanol with hydroxyacetaldehyde (HA) to form the acetal was catalyzed by the addition of 7 x 10-4 M strong acids such as sulfuric, hydrochloric, p-toluene sulfonic acid, and methanesulfonic acid. HA formed 2,2-dimethoxyethanol (DME), and at 60 oC the equilibrium was reached in less than one hour. Smaller amounts of DME were formed in the absence of strong acid. HA, acetaldehyde, and propanal formed their corresponding acetals when reacted with methanol, ethanol, 1-propanol or 1-butanol. Esters of acetic acid and hydroxyacetic acid were observed from reactions with these same four alcohols. Other acetals and esters were observed by GC/MS analysis of the reaction products. The results from accelerated aging experiments at 90 oC suggest that the presence of methanol slows polymerization by formation of acetals and esters from low molecular weight aldehydes and organic acids.

The accessibility of cellulose samples having various degrees of crystallinity was studied with respect to molecules of water, lower primary alcohols, and lower organic acids. It was found that small water molecules have full access to non-crystalline domains of cellulose (accessibility coefficient α = 1). Molecules of the lowest polar organic liquids (methanol, ethanol, and formic acid) have partial access into the non-crystalline domains (α<1), and with increasing diameter of the organic molecules their accessibility to cellulose structure decreases. Accessibility of cellulose samples to molecules of various substances is a linear function of the coefficient α and the content of non-crystalline domains. The relationship between crystallinity (X) and accessibility (A) of cellulose to molecules of some liquids has been established as A = α (1-X). The water molecules were found to have greater access to cellulose samples than the molecules of the investigated organic liquids. The obtained results permit use of accessibility data to estimate the crystallinity of cellulose, to examine the structural state of non-crystalline domains, and to predict the reactivity of cellulose samples toward some reagents.

The “near neutral hemicellulose extraction process” involves extraction of hemicellulose using green liquor prior to kraft pulping. Ancillary unit operations include hydrolysis of the extracted carbohydrates using sulfuric acid, removal of extracted lignin, liquid-liquid extraction of acetic acid, liming followed by separation of gypsum, fermentation of C5 and C6 sugars, and upgrading the acetic acid and ethanol products by distillation. The process described here is a variant of the “near neutral hemicellulose extraction process” that uses the minimal amount of green liquor to maximize sugar production while still maintaining the strength quality of the final kraft pulp. Production rates vary between 2.4 to 6.6 million gallons per year of acetic acid and 1.0 and 5.6 million gallons per year of ethanol, depending upon the pulp production rate. The discounted cash flow rate of return for the process is a strong function of plant size, and the capital investment depends on the complexity of the process. For a 1,000 ton per day pulp mill, the production cost for ethanol was estimated to vary between $1.63 and $2.07/gallon, and for acetic acid between $1.98 and $2.75 per gallon depending upon the capital equipment requirements for the new process. To make the process economically attractive, for smaller mill sizes the processing must be simplified to facilitate reductions in capital cost.

A formic/acetic acid/water system was used in the ratios of 30:60:10, 20:60:20, and 30:50:20 separately for efficient hydrolysis and bioconversion of poplar chips, under the solid/liquid ratio of 1:12(g/ml), at 105 oC for 30, 45, 60, 75, and 90 min, respectively. The highest yield of 69.89% was at a formic/acetic acid /water ratio of 30:50:20(v/v/v), with solid/liquid in the ratio of 1:12(g/ml) at 105 oC for 90min. Lower kappa number and similar yield were achieved when hydrolytic residual woodchips were used for kraft pulping with over 2% Na2O and temperature 5 °C lower compared to untreated chips. Pulps from prehydrolysis-treated chips were easy to beat. But the tensile index, tear index, and burst index of the handsheets obtained from pulp with lowest kappa number from prehydrolysis-treated poplar chips were lower than those of the pulp from the untreated chips. Considerable xylose could be obtained from the prehydrolysis stage following kraft pulping under the same conditions for prehydrolysis-treated chips and untreated chips. However, by building on the mature kraft pulping and xylitol processes, large amounts of xylose from the hemicellulose were obtained in prehydrolysis, allowing production of high-valued products via biorefinery pathways. An economical balance of chemical dosage, energy consumption, pulp properties, and xylose value for prehydrolysis with organic acid should be reached with further investigation.

Bio-oil produced from fast pyrolysis of biomass contains various levels of acetic and formic acids derived from breakdown of cellulose and hemi-cellulose components. Removal of these organic acids from bio-oil was investigated for use as industrial chemicals as well as to improve the quality of recovered bio-oil as fuel in various applications. Calcium oxide and a quaternary ammonium anion-exchange resin were used to form acid salts of the organic acids, which were then separated, and the organic acids were generated by reacting with sulfuric acid. Both methods were found to be effective in limited ways and various difficulties encountered in this approach are discussed.

To enhance the bleaching efficiency, the activator of tetra acetyl ethylene diamine (TAED) was used in conventional H2O2 bleaching. The H2O2/TAED bleaching system can accelerate the reaction rate and shorten bleaching time at relative low temperature, which can reduce the production cost. In this research, the process with hydrogen peroxide activated by TAED bleaching of Populus nigra chemi-thermo mechanical pulp was optimized. Suitable bleaching conditions were confirmed as follows: pulp consistency 10%, bleaching temperature 70oC, bleaching time 60 min when the charge of H2O2 was 4%, NaOH charge 2%, and molar ratio of TAED to H2O2 0.3. The pulp brightness gain reached 23.6% ISO with the optimized bleaching conditions. FTIR analysis indicated that the H2O2/TAED bleaching system can decrease carbonyl group further than that of conventional H2O2 bleaching, which contributed to the higher bleaching efficiency and final brightness. The H2O2/TAED bleaching had stronger oxidation ability on lignin than that of H2O2 bleaching.

Flax fibre reinforced polypropylene composites were fabricated using a high speed mixer followed by injection moulding. Prior to composite production, the fibre was modified by acetylation in the presence of perchloric acid. The effect of acetylation of the fibre was assessed on the basis of moisture resistance and dielectric properties of the resulting composites. It was found that the moisture absorption and swelling properties of the composites were reduced respectively by 60% and 30% due to acetylation. Two different types of biocide were mixed with untreated flax fibre, and the samples were exposed to decay fungi for up to 3 months along with control polypropylene. The composites with acetylated fibres showed good protection against fungi, and biocide had less effect on biological resistance. The dielectric properties of the flax-polypropylene composites were also estimated as a function of aging period. The composites with modified fibre showed more improvement in dielectric properties compared to the composites with untreated fibres. The mechanical properties were investigated for those composites. Tensile and flexural strengths of composites were found to be increased following acetylation due to modification, and strength properties of both untreated and acetylated flax fibre reinforced polypropylene composites decreased with respect to aging period. The Charpy impact strengths of composites were found to increase with increasing aging periods.

The characteristics of enzymatic/mild acidolysis lignin (EMAL) isolated from moso bamboo were investigated using pyrolysis-gas chromato-graphy/mass spectrometry (Py-GC/MS). Pyrolysis temperature as a factor on products was studied, and the pyrolysis mechanism was inferred with respect to the dominating products. Research results showed that pyrolysis products derived from EMAL pyrolysis were mainly heterocyclic (2,3-dihydrobenzofuran), phenols, esters, and a minor amount of acetic acid. Pyrolysis temperature had a distinct impact on yields of pyrolysis products. As pyrolysis temperature increased, the yield of 2,3-dihydrobenzofuran rapidly decreased; however, yields of phenols increased smoothly. It can be obtained that, at the low temperatures (250-400oC), pyrolysis products were mainly 2,3-dihydrobenzofuran, and the highest yield was 66.26% at 320oC; at the high temperatures (400-800oC), pyrolysis products were mainly phenols, and yields hit their highest level of 56.43% at 600 oC. A minor amount of acetic acid only emerged at 800°C. Knowledge of pyrolysis products releasing from EMAL and the pyrolysis mechanism could be basic and essential to the understanding of thermochemical conversion of EMAL to chemicals or high-grade energy.

The applicability of a special pilot-scale installation (Short Circulation Device) was studied for demonstrating the enrichment of selected resin and fatty acids in process waters when increasing water reuse during the manufacture of paper. The traditional gas chromatography with flame ionization detection (GC-FID), turbidity, and online sample enrichment (solid phase extraction, SPE) for atmospheric pressure chemical ionization-mass spectrometry (APCI-MS) measurements were used for the analysis of the resin and fatty acids. The data from all the measurements with unbleached thermomechanical pulp (TMP) process waters were in a good agreement, and correlation coefficients (R2) > 0.9 were obtained in each case. Rapid information about the levels of wood extractives in papermaking process waters is of great importance, and it offers a suitable way to predict oncoming pitch problems. It was concluded that the routine control of the extractives level in papermaking process waters is possible by all these methods.

Pectins are important structural elements in spruce fibres. Alkaline peroxide bleaching of spruce thermomechanical pulp (TMP) causes degradation and demethylation of pectins, yielding high-charge-density pectic acids. The pectic acids in fibres contribute strongly to the negative fibre charge, and the dissolved pectic acids increase the cationic demand of bleached TMP water. In this study, a method to isolate pectic acids from peroxide-bleached TMP pulp water is presented. The pectic acids were isolated and purified in good yield using a polyacrylate resin to remove lignin, a cellulose filter to remove galactoglucomannans (GGM), and an anion exchange resin to separate pectic acids from neutral carbohydrates. Salts and residual low-molar-mass carbohydrates were further removed from the isolated pectic acids by dialysis. The isolated pectic acids (>80% purity) had a low molar mass and a wide polydispersity (5.9 kDa, MW/MN 3.3). The aggregation and precipitation of the isolated pectic acids, as well as citrus fruit pectic acids with well-defined molar masses, by Ca2+-ions were studied. The molar mass of pectic acids was a key factor determining the precipitation of Ca2+-pectates. Pectic acids below 6 kDa were not precipitated by Ca2+, while higher molar masses led first to partial and then to complete precipitation. The precipitated Ca2+-pectates may impair paper machine runnability and paper quality.

Defining and quantifying amino acid requirements will become an important consideration in the next generation of feeding schemes for dairy cattle beyond the current emphasis on identification of limiting amino acids. In this context different amino acid profiles of untreated, urea treated, fungal treated, and urea plus fungal treated lignocellulosic feed by both P. ostreatus wild and its two cellulase-minus/ less lignolytic mutants were analyzed. Cellulase-free mutant strains were obtained after 20 minutes of exposure to UV light and 0.4 seconds to X-rays. A UV mutant of P. ostreatus (POM1) exhibited better performance than the X-ray mutant (POM2) in terms of production of less cellulolytic and more lignolytic enzymes. Urea treatment of straw enhanced the total amino acid content by less than a factor of two, while the fungal treatment improved it by 13-14 times. Fungal treatment of urea-treated straw improved the total amino acid content by a factor of 15, indicating the importance of urea in the straw. Further, the fungal treatment of urea-treated straw enhanced the quantity of amino acids such as glutamine, glycine, aspergine, etc. by 15-20 times. The quantity of limiting amino acids such as methionine, lysine, and histidine was also enhanced by 8 to 10 times through the fungal treatment. Maximum amounts of all the amino acids were found in urea plus fungal (POM1) treated paddy straw than in only fungal treated and only urea treated paddy straws.

The graft copolymerization of acrylamide, N-vinyl-2-pyrralidone and N, N’-methylene-bis-acrylamide was carried out to modify the sisal fiber to improve its mechanical and thermal stability. The grafting of poly-(acrylamide-co-N-vinyl-2-pyrrolidone) on sisal fiber surfaces facilitated the loading of Ag(I) ions and Ag(0) nanoparticles. Surface microstructure of the surface modified sisal fiber confirmed the grafting of the copolymer. The XRD and FTIR graphs also showed changes on grafting and on Ag(I) ions and the loading of Ag(0) nanoparticles. It is evident from the DSC curves that the initial thermal stability was improved by delaying the hemicellulose decomposition on grafting and silver ion loading.