Application of off-line pyrolysis with dynamic solid-phase microextraction to the GC–MS analysis of biomass pyrolysis products

Pyrolysis coupled with dynamic solid-phase micro extraction (Py-SPME) followed by GC–MS analysis was applied to the determination of volatile compounds evolved by a micro-scale off-line pyrolysis apparatus, in order to extend the information affordable with this type of analytical equipment. The Py-SPME method with a carboxen/PDMS fiber working in the retracted mode was tested on four biomass samples (switchgrass, sweet sorghum, corn stalk and poplar) for qualitative analysis of semi-volatile pyrolysis products and quantitative determination of main volatiles (C₁–C₄) pyrolysis products. The developed procedure allowed capturing and analysis of all GC analyzable compounds, without memory effects and with good peak resolution also for early GC-eluting compounds. Twelve main volatile pyrolysis products, including hydroxyacetaldehyde and acetic acid, were successfully quantified; in spite of the intrinsic variability introduced by dynamic SPME sampling, results were relatively accurate and consistent with literature data on bench pyrolysis reactors.     

The Mesomeric Effect of Thiazolium on non‐Kekulé Diradicals in Pichia stipitis Transketolase

It is theoretically plausible that thiazolium mesomerizes to congeners other than carbene in a low effective dielectric binding site; especially given the energetics and uneven electronegativity of carbene groups. However, such a phenomenon has never been reported. Nine crystal structures of transketolase obtained from Pichia stipitis (TKps) are reported with subatomic resolution, where thiazolium displays an extraordinary ring‐bending effect. The bent thiazolium congeners correlate with non‐Kekulé diradicals because there is no gain or loss of electrons. In conjunction with biophysical and biochemical analyses, it is concluded that ring bending is a result of tautomerization of thiazolium with its non‐ Kekulé diradicals, exclusively in the binding site of TKps. The chemophysical properties of these thiazolium mesomers may account for the great variety of reactivities carried out by thiamine–diphosphate‐containing (ThDP) enzymes. The stability of ThDP in living systems can be regulated by the levels of substrates, and hydration and dehydration, as well as diradical‐mediated oxidative degradation.     

On fermentability of nafion catalyzed hemicellulose hydrolyzates

Applied Biochemistry and Biotechnology -     

Application of fentonś reaction to steam explosion prehydrolysates from poplar biomass

The application of Fenton’s reaction to enhance the fermentability of prehydrolysates obtained from steam explosion pretreatment of poplar biomass was studied. Reaction conditions of temperature and H₂O₂ and Fe(II) concentrations were studied. The fermentability of prehydrolysate treated by Fenton’s reaction was tested by using different inoculum sizes of thermotolerant strain Kluyveromyces marxianus CECT 10875. The highest percentages of toxic compound degradation (ranging from 71 to 93% removal) were obtained at the highest H₂O₂ concentration tested (50 mM). However, a negative effect on fermentability was observed at this H₂O₂ concentration at the lower inoculum loading. An increase in inoculum size to 0.6 g/L resulted in an enhanced ethanol fermentation yield of 95% relative to control.     

Amazonian lignocellulosic materials-V

A plate-agar technique for fungal screening was applied to evaluate the xylanolytic activities of 18Penicillium janthinellum and 10Aspergillus sydowi species from the Amazon region. In order to compare these genera with those of other regions, oneAspergillus sp., one P.janthinellum, and 12 unknown genera from the southern region of Chile were studied. From these fungi strain,A. sydowi (56 strain) (25.2 IU/mL),P. janthinellum (671 strain) (47.3 IU/mL) from Amazonia,P. janthinellum (X4Z2 strain) (9.5 IU/mL), and anAspergillus sp. (X2M1 strain) (33.3 IU/mL) from the southern region of Chile were identified.     

Milling of lignocellulosic biomass

Ethanol is being considered as an attractive alternative transportation fuel for the future. One method of producing ethanol from lignocellulose involves reducing the size of biomass to smaller particles, and using acid or enzyme treatments to hydrolyze the biomass to sugars. The size-reduction step is necessary to eliminate mass- and heat-transfer limitations during the hydrolysis reactions. However, milling to small size consumes large amounts of energy, and reducing the energy usage is critical to the overall process economics. In this study, the energy requirements and size distribution for milling wood were measured for various pilot-scale size-reduction equipment. Hammer milling used less energy than disk milling, but produced particles with a larger-size distribution. Additionally, energy requirements were measured for shredding paper and switchgrass.     

Critical conditions for improved fermentability during overliming of acid hydrolysates from spruce

Bioethanol can be produced from wood via acid hydrolysis, but detoxification is needed to achieve good fermentability. Overliming was investigated in a factorial designed experiment, in which pH and temperature were varied. Degradation of inhibitory furan aldehydes was more extensive compared to monosaccharides. Too harsh conditions led to massive degradation of sugars and formation of inhibiting acids and phenols. The ethanol productivity and yield after optimal overliming reached levels exceeding reference fermentations of pure glucose. A novel metric, the balanced ethanol yield, which takes both ethanol production and losses of fermentable sugars into account, was introduced and showed the optimal conditions within the investigated range. The findings allow process technical and economical considerations to govern the choice of conditions for overliming.     

Kinetics of thermochemical pretreatment of lignocellulosic materials

The results of an experimental study of the acid hydrolysis of hardwood are presented in the form of values for the three parameters, activation energy, power on the acid concentration, and pre-exponen-tial factor, of the first order kinetic constants for each of the following reaction participants: xylan remaining, glucan remaining, xylose formed, and xylose decomposed. These are used as a base for a quantitative theory to predict the temperature, time, and acid concentrations needed for effective pretreatment of the substrate for subsequent enzymatic hydrolysis of the glucan. This theory is based on the assumption that successful pretreatment requires >90% removal of the xylan, <10% removal of the glucan, and >80% xylose yield. This theory is compared with selected published data.     

HPLC characterization of phenolics in lignocellulosic materials

Summary The application of HPLC with an electrochemical detector for the determination of phenolics in lignocellulosic materials is reported. The separation of phenolic acids and aldehydes (gallic acid, p-hydroxybenzoic acid, vanillic acid, p-coumaric acid, syringic acid, ferulic acid, vanillin, syringaldehyde and p-hydroxybenzaldehyde) on two different columns (reversed phase C6 and styrene-divinylbenzene PLRP-S) is shown. Chromatograms of phenolic compounds in neutral, basic and oxidative extracts of wheat straw treated with NaOH and white rot fungusStropharia rugosoannulata are reported along with quantitative results.     

Thermal properties of lignocellulosic filler-thermoplastic polymer bio-composites

Summary In the TG analysis of the bio-composites, their thermal stability was found to slightly decrease and the ash content to increase as the lignocellulosic filler loading increased. This is a logical consequence of the lower thermal stability of the lignocellulosic filler compared to that of the matrix polymer. The dispersion and interfacial adhesion between the lignocellulosic filler and thermoplastic polymer were important factors affecting the thermal stability of the composite system. In order to improve their compatibility and interfacial adhesion, the incorporation of a compatibilizing agent into the lignocellulosic material-thermoplastic polymer composites is recommended. In the TMA analysis, the thermal expansion of the composites was found to decrease with increasing filler loading and incorporating compatibilizing agent. Lignocellulosic filler is a suitable material for preventing the thermal expansion of the composite materials caused by atmospheric changes.     

Anaerobic digestion of lignocellulosic biomass and wastes

Anaerobic digestion represents one of several commercially viable processes to convert woody biomass, agricultural wastes, and municipal solid wastes to methane gas, a useful energy source. This process occurs in the absence of oxygen, and is substantially less energy intensive than aerobic biological processes designed for disposal purposes. The anaerobic conversion process is a result of the synergistic effects of various microorganisms, which serve as a consortium. The rate-limiting step of this conversion process has been identified as the hydrolysis of cellulose, the major polymeric component of most biomass and waste feedstocks. Improvements in process economics therefore rely on improving the kinetic and physicochemical characteristics of cellulose degrading enzymes. The most thoroughly studied cellulase enzymes are produced by aerobic fungi, namely Trichoderma reesei. However, the pH and temperature optima of fungal cellulases make them incompatible for use in anaerobic digestion systems, and the major populations of microorganisms involved in cellulase enzyme production under anaerobic digestion conditions are various bacterial producers. The current state of understanding of the major groups of bacterial cellulase producers is reviewed in this paper. Also addressed in this review are recently developed methods for the assessment of actual cellulase activity levels, reflective of the digester "hydrolytic potential," using a series of detergent extractive procedures.     

Extraction of Proteins from Switchgrass Using Aqueous Ammonia within an Integrated Biorefinery

Switchgrass (Panicum vergatum) is a potential feedstock for future cellulosic biorefineries. Such a feedstock may also provide protein, most likely for use as an animal feed. In this paper, we present a potential scheme for integrating fiber processing with extractions to obtain both sugar and protein products from switchgrass pretreated using Ammonia Fiber Expansion (AFEX). Solutions of 3% aqueous ammonia at pH 10.5 provided optimal extraction of proteins. Addition of the nonionic surfactant Tween-80 improved protein recovery for AFEX-treated materials. It was determined that an extraction following AFEX solubilized approximately 40% of the protein, while a subsequent hydrolysis solubilized much of the remaining protein while producing 325 g sugar per kg biomass. The remaining insoluble residue contained very little protein or ash, making it ideal for heat and power production. In contrast, an extraction following hydrolysis solubilized only 68% of the original protein in the biomass, while obtaining slightly higher sugar yields.     

Surface properties of lignocellulosic fibers bearing carboxylic groups

Fibers with various amounts of carboxylic acid functionalities as determined with FTIR and conductometric titration were prepared by chemical modification of high bleached kraft pulp (CP) and chemical thermomechanical pulp (CTMP) with succinic anhydride. The degree of the modification was dependent on reaction time and the type of fiber used. The modification levelled off after 15h of reaction, and this effect was similar for both fiber substrates. The amount of carboxylic acid attached to CTMP, determined by weight gain, was however less than half of the amount of carboxylic moieties introduced to CP fibers at any reaction time. ESCA characterization of the succinylated fibers indicates that the carboxylic acid functionalities are predominantly introduced at the fiber surface. The wettability in water, measured as contact angle, of the succinylated CTMP fibers was significantly improved by the modification, whereas the wettability of CP fibers was slightly decreased. The differences in wettability are caused by the dispersive and polar characteristics of succinic acid attached to the fiber surface and its interaction with the fiber surface. The character of the linkage group in the anhydride used for modification as well as the composition of the cellulose fiber surface are suggested to play a crucial role in the surface energy of the modified fibers and hence their wetting properties.     

Hybrid process for the conversion of lignocellulosic materials

Because of the recalcitrant nature of lignocellulosic materials, it is important to pretreat the biomass in order to obtain a suitable material for the bioconversion. In this study, two different types of pretreatments were performed. The first experiment used a 2-gal Parr reactor operated at 140, 150,160, and 170‡C with sulfuric acid concentrations varying from 0.5 to 2%. A second pretreatment was performed with a two-stage low-temperature process. The first-stage pretreatment was performed at 100 or 120‡C with sulfuric acid concentrations of 0.5, 2, and 5% followed by a secondstage pretreatment at 120‡C with 2% acid concentration. The best residues for enzymatic hydrolysis and simultaneous saccharification and fermentations (SSF) came from the higher temperature pretreatment with the Parr reactor. However, a large portion of the xylose fraction was degraded to furfural and glucose was degraded to HMF. On the contrary, the two-stage low temperature pretreatment resulted in a very low percentage of xylose degradation, and no glucose degradation. The residues from this two-stage pretreatment performed satisfactorily toward the production of ethanol by SSFs. This study discusses the results obtained from these experiments.     

Surface modification of lignocellulosic fibers using high-frequency ultrasound

Enzymatic and chemical oxidation of fiber surfaces has been reported in the literature as a method for producing medium density fiberboards without using synthetic adhesives. This work focuses on modifying the surface properties of wood fibers by the generation of free radicals using high-frequency ultrasound. A sonochemical reactor operating at 610 kHz is used to sonicate the aqueous suspensions of thermomechanical pulp fibers (TMP). TMP is analyzed using FTIR-transmission, FTIR-ATR spectroscopy and inverse gas chromatography (IGC). The non-conjugated carbonyl groups in TMP are represented by the peak area ratio A₁₇₃₆/A₁₅₁₁ in the FTIR-transmission spectra and by A₁₇₂₈/A₁₅₀₉ in the FTIR-ATR spectra. The increase in these ratios suggests that there is an increase in the number of non-conjugated carbonyl groups in TMP after sonication. To further investigate, sonication of the hydrolytic lignin was also carried out and analyzed using UV, UV-ionization and FTIR-transmission spectroscopy. The changes in the surface properties of the fibers are analyzed using IGC which showed an increase in the surface free energy of fibers. The effect of operating parameters such as power of ultrasound and sonication time is also studied.     

Thermal characterization of lignocellulosic residue from different sugarcanes

Bagasse samples from four different sugarcane were directly collected as the residues of milling in a processing plant. The samples were dried at 105 °C, compressed to small granules and then their TG/DTA and DSC curves in synthetic air were recorded. Similar thermogravimetric curves were obtained for the different samples and they exhibited four mass loss steps. However, the analysis of the exotherm DSC peaks showed that the oxidation of the organic matter resulted different enthalpy values (ΔH/kJ g⁻¹).     

Sorption capacity of lignocellulosic materials toward humic acids

Russian Chemical Bulletin - Sorption capacity toward humic acids was studied for a number of lignocellulosic materials with different structures and chemical compositions. The values of sorption...     

Processing of lignocellulosic polymer wastes using microwave irradiation

Lignin and mixed lignocellulosic natural polymer wastes have been accumulated in landfills over the past hundred years. These wastes should be processed to produce added- value chemicals and materials. This mini-review presents a brief literature survey related to state-of-the-art methods developed recently by the world research community to solve the problem of rational conversion of lignocellulosic polymer wastes, including production of hydrogen, synthesis gas, phenols, and monomers. The focus is made on microwave and plasma technologies used for lignocellulosic wastes processing.     

Catalytic role of lignocellulosic materials in triacylglycerol cracking

Cracking of vegetable oils and animal fats carried out with a view to preparing fuels or fuel components for diesel engines is one of the options of reducing high molecular weight and viscosity of natural triacylglycerols (TAG). We have found out that lignocellulose shows a surprisingly high catalytic activity in TAG cracking comparable and equivalent to that achieved with zeolite catalysts NaY and clinoptilolite. This paper presents results obtained from cracking of rapeseed, sunflower, soybean and jatropha oils, lard and used cooking oils in the presence of woody sawdust, cereal straw and waste paper used as catalysts. The yield of liquid products in the feedstock was 80-90% relative to the feedstock TAG at temperatures of 350-440 °C applied for a period of 20-30 min. The yield of treated condensates having properties similar to those of fossil diesel reached, after water separation and evaporation of the volatile fraction up to 190 °C, 70-80% of the feedstock TAG. The type of the TAG and the lignocellulosic catalyst used had no significant effect on the product yield and its parameters. Liquid condensates obtained via catalysis with lignocellulosic catalysts had similar composition and properties as condensates produced by zeolite-catalyzed cracking. Blends of treated condensates of 5-10 vol.% with fossil diesel are compliant with the EN 590 standard and can thus be used as fuels for diesel engines.     

Alkali (NaOH) Pretreatment of Switchgrass by Radio Frequency-based Dielectric Heating

Radio-frequency (RF)-based dielectric heating was used in the alkali (NaOH) pretreatment of switchgrass to enhance its enzymatic digestibility. Due to the unique features of RF heating (i.e., volumetric heat transfer, deep heat penetration of the samples, etc.), switchgrass could be treated on a large scale, high solid content, and uniform temperature profile. At 20% solid content, RF-assisted alkali pretreatment (at 0.1 g NaOH/g biomass loading and 90°C) resulted in a higher xylose yield than the conventional heating pretreatment. The enzymatic hydrolysis of RF-treated solids led to a higher glucose yield than the corresponding value obtained from conventional heating treatment. When the solid content exceeded 25%, conventional heating could not handle this high-solid sample due to the loss of fluidity, poor mixing, and heating transfer of the samples. As a result, there was a significantly lower sugar yield, but the sugar yield of the RF-based pretreatment process was still maintained at high levels. Furthermore, the optimal particle size and alkali loading in the RF pretreatment was determined as 0.25–0.50 mm and 0.25 g NaOH/g biomass, respectively. At alkali loading of 0.20–0.25 g NaOH/g biomass, heating temperature of 90^oC, and solid content of 20%, the glucose, xylose, and total sugar yield from the combined RF pretreatment and the enzymatic hydrolysis were 25.3, 21.2, and 46.5 g/g biomass, respectively.