Band 65, Heft 4

No abstract available

The demand for biomass-derived fuels and fuel additives, particularly in the transportation sector, has stimulated intense research efforts in the chemistry of levulinic acid and levulinic acid secondary products over the past decade. Additionally, recent technological progress in lignocellulosic feedstock (LCF) chemistry has also increased attention in this regard. As a result, several oxygenating fuel additives with potential applications in both gasoline and diesel fuels have been identified. Some of the chemicals, such as ethyl valerate, appear to be viable alternatives to the currently used branched, short-chain ethers that are derived from side products of petrol refining. Cost-effective applications of lignocellulosic biomass are a crucial aspect of its feasibility. In consideration of the LCF biorefinery concept, the feasibility must also include the chemical pulping of LCF and the comprehensive utilisation of its main constituents cellulose, hemicelluloses, and lignin. The present study focuses on cellulose and hemicelluloses as viable sources for the production of biofuels and biofuel additives. Multifunctional catalysis, including hydrogenation and acid catalysis are the primary instruments used for the conversion of the monomeric carbohydrate building blocks, i.e., mainly C5 sugars, such as xylose and arabinose, and C6 sugars in the form of glucose and their respective secondary products, furfural and levulinic acid. Lignin utilisation is not addressed in this paper.

Steam refining was investigated as a pretreatment for enzymatic hydrolysis of poplar wood from a short rotation plantation. The experiments were carried out without debarking to use an economically realistic raw material. Steam refining conditions were varied in the range of 3–30 min and 170–220°C, according to a factorial design created with the software JMP from SAS Institute Inc., Cary, NC, USA. Predicted steaming conditions for highest glucose and xylose yields after enzymatic hydrolysis were at 210°C and 15 min. Control tests under the optimized conditions verified the predicted results. Further pretreatments without bark showed that the enzymes were not significantly inhibited by the bark. The yield of glucose and xylose was 61.9% of theoretical for the experiments with the whole raw material, whereas the yield for the experiments without bark was 63.6%. Alkaline extraction of lignin from the fibers before enzymatic hydrolysis resulted in an increase of glucose yields from mild pretreated fibers and a decrease for severe pretreated fibers. The extracted lignin had a high content of xylose of up to 14% after very mild pretreatments. On the other hand, molecular weights of the extracted lignin increased substantially after pretreatments with a severity factor above 4. Hence, alkaline extraction of the lignin seems only attractive in a narrow range of steaming conditions.

Sterilized pine wood strands were treated with the ascomycete Ophiostoma piliferum (Cartapip 97™) in an attempt to reduce aldehyde emissions through degradation of aldehyde-forming precursors. Wooden boards were then produced from the treated strands by means of a laboratory press. VOC emissions of these boards were characterized and the concentrations of seven major substances were followed for a period of 28 days in Markes μ-CTE micro-chambers employing Tenax-TDAS/GC/MS analytics. Boards made from treated strands showed a highly significant (P<0.001) reduction in aldehyde emissions by 70% compared to the control boards, while differences in the monoterpene emissions were not significant (P>0.05). Wood extractives from treated and untreated strands were also analyzed by GC/MS after milling and acetone/water extraction. A marked decrease of C18 unsaturated fatty acids was detected in agreement with the reduction of aldehyde emissions, and the monosaccharides as indicators of fungal growth were depleted and stilbenes and lignans were partially degraded.

Rice hulls are potential low-cost feedstocks for fuel ethanol production in many countries. Most of the relevant publications are devoted to homogenous (high quality) hulls generated in industrial mills. On the other hand, small-scale mills give rise to hulls containing grain fragments and bran. In the present work, the dilute-acid pretreatment of such heterogeneous rice hulls was investigated based on a central composite rotatable experimental design. The variables were: temperature (140–210°C), biomass load (5–20%), and sulfuric acid concentration (0.5–1.5% based on reaction mixture). A total of 16 experimental runs were carried out, including a 2 3 -plan, two replicates at the central point and six star points. Low temperatures were found to be favorable for the hydrolysis of xylan and of the easily hydrolyzable glucan fraction. High glucose formation (up to 15.3% of the raw material dry weight), attributable to starch hydrolysis, was detected in the hydrolysates obtained under the least severe pretreatment conditions. Several models were developed for predicting the effect of the operational conditions on the yield of pretreated solids, xylan and glucan conversion upon pretreatment, and on enzymatic convertibility of cellulose. The pretreatment temperature exerted the most significant effect on the conversion of the polysaccharides. Optimum results were predicted for the conversion of easily-hydrolyzable glucan in the material pretreated at 140.7°C, and for the enzymatic saccharification of cellulose in the material pretreated at 169°C. These results are interpreted that a two-step acid hydrolysis may be the best pretreatment strategy for heterogeneous rice hulls produced in small mills.

The chemoenzymatic modification of cellulosic pulps by the laccase-mediator system (LMS) consisting of laccase (EC 1.10.3.2) and the 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) has been investigated. The reaction proceeds under mild aqueous conditions (sodium citrate buffer pH 6, 30°C) and introduces primarily aldehyde groups into cellulose so that carboxyl groups amount to one-third to one-fifth of the carbonyl groups only. LMS treatment caused uniform oxidation of the material, also in the high-molecular weight area, which is a non-typical behavior compared to other chemical oxidations of cellulose. Treatment of the pulp only with TEMPO or only with laccase caused no changes whatsoever, whereas treatment with the TEMPO-derived oxoammonium ion (in the absence of laccase) introduced carbonyl groups into the pulp, but no carboxyls. This chemoenzymatic approach was compared to the well-known chemical approach by means of TEMPO and hypohalite. Both approaches yielded comparable distributions of functional groups at the low oxidation degrees studied, indicating a similar reaction mechanism with the TEMPO-derived oxoammonium ion being the actual oxidant. The laccase is able to generate this oxoammonium ion, which in turn oxidized the 6-hydroxymethyl group into the corresponding aldehyde.

The limitations of the current biorefinery process utilizing stirred-tank reactors for the enzymatic step include poor mixing in the case of high biomass loadings, additional steps for the product separation, and a long reaction time. In this study the hydrothermal pretreatment and the enzymatic hydrolysis of the lignocellulosic biomass were combined in one fixed-bed reactor. The influence of the shear forces during recirculation and enzyme stability at elevated temperatures were investigated. It has been shown that the shear forces resulting from pumping have a negligible effect on enzyme activity. However, large pressure drops reduce the enzyme activity significantly. Furthermore, the enzyme stability was significantly increased at elevated temperatures (60°C) by applying static pressures up to 200 bar (56% residual activity at 60°C after 24 h). This is beneficial for the process as a higher temperature accelerates the reaction. Further improvement of the overall process efficiency was achieved by increasing the solid-to-water ratio and circulation of the enzyme solution. At a biomass content of 7%, a glucose concentration of 61 g l -1 and a yield of 85% was achieved. The integrated process was first done on a laboratory scale (50 ml). At 100 bar, 60°C and 10% biomass loading an increased initial reaction rate was observed. However, this effect was followed by the stagnation of the glucose yield as one of the enzymes, Novozyme 188, showed no remarkable stabilization with pressure. Nevertheless, an overall glucose yield of 40% was achieved after 5.5 h, compared to 14 h under normal pressure and 50°C.

In a forest based biorefinery, pulp and paper are the main products, while side-streams are utilized for value-added products. One biorefinery concept is to remove hemicelluloses from wood by extraction prior to pulping and converting them into biofuels or chemicals. This study presents a concept of a larch wood based biorefinery and focuses on the mass balance of pre-extraction. Sugar rich extracts were obtained by hot water extraction of Siberian larch ( Larix sibirica Lebed.) wood chips at different temperatures and times. At 160°C and 60–90 min the extract contains 13–16% hemicelluloses (on wood). The composition of extracts and extracted wood has been determined to have a basis for mass balances. Fermentation of the hydrolyzed extract with Bacillus coagulans MXL-9 resulted in consumption of all C6 and C5 sugars and produced lactic acid in high yield. In an earlier work, it was demonstrated that water pre-extraction of larch chips followed by polysulfide-anthraquinone (PSAQ) pulping still produced a good papermaking pulp at a yield comparable to the corresponding non-extracted kraft pulp. Accordingly, the present results show that a larch wood based biorefinery has a potential for industrial application.

Pinewood was modified by vacuum impregnation with various aqueous lignin solutions of low concentration (0.5– 1.0%) and its decay resistance was tested by the standard procedure EN 113. Five lignin types were tested against three brown rot and one white rot fungi. The bio-durability of wood was considerably increased by the treatment. The highest effect of modification was for alkali, kraft, hydrolysis lignins and industrial lignosulfonate, when mass losses of wood for brown-rot fungi were negligible. The effect of the modification with certified lignosulfonates was insignificant. Chemical analysis revealed that phenols, which are leached from lignin and are adsorbed by wood in the impregnation process, could act as a biocide. The hydrophilic properties of wood either did not change (certified lignins) or were enhanced because of some change in the pore structure (industrial lignins). Further tests are needed to verify the positive effects of this technologically simple and environmentally friendly treatment.

A fraction of pyrolytic oils (PyO) – obtained by fast pyrolysis of alder ( Alnus incana ), ash-tree ( Fraxinus excelsior ) and aspen ( Populus tremula ) in a laboratory scale reactor – was precipitated in water. This hydrophobic moiety of PyO is called pyrolytic lignin (PyL). The composition of the volatile monomeric compounds of PyO and the PyL fraction was determined by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). It has been found that PyL has a high content of phenolic products (between 75% and 83%), which varies depending on the wood species. The antioxidant properties of the PyL fraction were studied and it was demonstrated that the antioxidant activity determined in different tests exceeded the corresponding activity of alkali lignin. The antioxidant properties of PyL are on the same level as those of the widely used antioxidants, such as rutin, trolox, curcumine, and tert -butylhydroquinone (TBHQ). A new method was developed for the extraction of a monomeric phenol fraction (Py-monPh) from PyO by means of the organic solvent methyl tert -butyl ether (MTBE). The Py-monPh can be considered as a promising source of antioxidants.

The implementation of biorefinery concepts into existing pulp and paper mills is a key step for a sustainable utilization of the natural resource wood. Water prehydrolysis of wood is an interesting process for the recovery of xylo-oligosaccharides and derivatives thereof, while at the same time cellulose is preserved to a large extent for subsequent dissolving pulp production. The recovery of value-added products out of autohydrolyzates is frequently hindered by extensive lignin precipitation, especially at high temperatures. In this study, a new high-temperature adsorption process (HiTAC process) was developed, where lignin is removed directly after the autohydrolysis, which enables further processing of the autohydrolyzates. The suitability of activated charcoals as a selective adsorbent for lignin under process-relevant conditions (150 and 170°C) has not been considered up to now, because former experiments showed decreasing efficiency of charcoal adsorption of lignin with increasing temperature in the range 20–80°C. In contrast to these results, we demonstrated that the adsorption of lignin at 170°C directly after autohydrolysis is even more efficient than after cooling the hydrolyzate to room temperature. The formation of lignin precipitation and incrustations can thus be efficiently prevented by the HiTAC process. The carbohydrates in the autohydrolysis liquor remain unaffected over a wide charcoal concentration range and can be further processed to yield valuable products.

Ionic liquids are able to dissolve polysaccharides and lignin, but there is only scarce knowledge about the dissolution of native wood. In the present paper, wood was dissolved by the ionic liquid 1-ethyl-3-methylimidazolium acetate (EMIMAc). A quantitative balance of the dissolved compounds is presented and the investigations are complemented by in situ microscopy of native wood in EMIMAc. The resulting dissolution kinetics in EMIMAc reveals distinct differences between spruce and beech. While particles of 0.1–0.5 mm of spruce dissolve slowly (up to 40% after 24 h), beech is dissolved more efficiently (75% after 24 h and 90% after 72 h). Wood chips of 10 mm length show similar dissolution kinetics and lignin yields of up to 10%. Microscopic studies reveal a disintegration of wood in EMIMAc into cells with large specific surface area, and differences in dissolution between spruce and beech were observed. These findings explain the size-independent dissolution of wood in EMIMAc and may open up new opportunities for the pretreatment of wood in ionic liquids.

The present study provides insight into the dissolution behavior of renewable materials in ionic liquids. Beech, spruce and rye straw were dissolved in 1-ethyl-3-methylimidazolium acetate as the ionic liquid of choice, which is currently one of the most frequently used cation-anion combinations among ionic liquids for biomaterial processing. The dissolution was followed by selective precipitation of cellulose, hemicelluloses, and lignin. The obtained lignin was analyzed with Curie-point pyrolysis gas chromatography/mass spectrometry (Cu-Py-GC/MS) and the separated cellulose/hemicellulose fractions with gel permeation chromatography (GPC). Time dependence of the dissolution process was studied on rye straw, eucalyptus kraft pulp and beech sulfite pulp. The results show a changing dissolution profile over time, which is due to progressing degradation of the cellulose in the ionic liquid.

Autohydrolysis of wood as a pretreatment stage before alkaline pulping is seen as an opportunity to approach the ideals of a forest biorefinery. In autohydrolysis the degradation products of primarily hemicelluloses and some other wood components are mainly dissolved (liquid phase) and they also escape partly as gas. In the present paper, birch was autohydrolysed at two intensity levels (characterised by P-factors of 200 and 1000) and the mass balances of autohydrolysis including solid, liquid, and gaseous phases were established. Approximately 10% and 25% of the total wood substance was transferred to the liquid phase at the two autohydrolysis intensities, respectively. In both cases about 50% of the degraded wood substance consisted of xylose-based material. The share of monomeric xylose was about 6% and 50% in the two samples, respectively. From the residual oligosaccharide fractions, 13% and 90% accounted for the DP2 to DP4 components in the P200 and P1000 samples, respectively. As expected, the weight-average molar mass of the components in the P1000 hydrolysate was substantially lower (0.4 kDa) than those in the corresponding P200 hydrolysate (2.1 kDa). Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) measurements revealed that relative to xylotriose the P1000 sample contained significantly fewer acidic pentosan fractions than the P200 sample. Xylooligosaccharides dissolved at both intensity levels remained highly acetylated, and some of these also carried 4-O-methylglucopyranosyluronic acid substituents.

Sequential extraction method was applied to lignins from hardwood and softwood isolated by kraft and VTT organosolv processes. Solvent extraction was found to fractionate lignin according to the molecular weight: small molecular weight lignin is dissolved in the organic solvents and the lignin with higher molecular weight is enriched into the residue. Isolated acetone fractions of lignin are more homogeneous with narrow molecular weight distributions. Based on the 31 P NMR results, both total hydroxyl content and the content of phenolic hydroxyl units are higher in the acetone fraction than in the residue. Pyrolysis-GC/MS of all lignins showed that p- hydroxy phenols are enriched to the residues. Preferential dissolution of syringyl type lignin in acetone was observed for hardwood kraft lignin, whereas the opposite behavior was seen for the hardwood organosolv lignin. Glass transition temperatures of all acetone soluble fractions were notably low compared to starting and residue lignins, which gives possibilities for future applications as a material with specific properties.

The objective of this study is to develop a process for conditioning spent liquor produced by SO 2 -ethanol-water (SEW) fractionation of spruce wood chips for fermentation to butanol, ethanol and acetone/isopropanol, i.e., by means of the so called acetone-butanol-ethanol (ABE) process using Clostridia bacteria. This study serves as part of an overall project aiming at the development of economic processes for producing chemicals and biofuels from mixed forest biomass via SEW fractionation and ABE fermentation technologies.

The overall target of this project, called Bioforest, is to develop an economic process for the production of commodity chemicals from mixed forest biomass, consisting of logging residues of hardwoods (HW) and softwoods (SW) and also from recycled fibers. The aim is to dissolve the biomass lignin and to produce monosugars based on hemicelluloses and hydrolyzed cellulose in high yield. The hydrolyzate could subsequently be converted into chemicals by modified acetone-butanol-ethanol fermentation. Here, the total mass balances of SO 2 -ethanol-water fractionation of different types of biomass feedstocks, such as SW and HW biomass, and deinked pulp are presented. Chemical composition of the feedstocks, solid residues (pulps) and spent liquors of fractionation were analyzed to gain more understanding about the fractionation procedure. The analysis was focused on carbohydrates, lignin, ash, acetyl groups and sugar degradation products. It was also examined if all feedstocks could be treated simultaneously in one digester because a larger feedstock supply within an economic transport radius improves the viability of the process. The fractionation approach was successful and it can be concluded that the method presented is very versatile for future applications in lignocellulosic biorefineries.

Oxidation of softwood and hardwood kraft lignins was observed under conditions of oxygen delignification (90°C and 110°C; 0.6 and 0.9 MPa) as a function of time by means of a number of analysis techniques and quantitative information was obtained on the degradation and formation of various compounds and structures. The decrease in reactor pressure was monitored during a 4-h reaction period. During the first 60 min, lignin reactivity was high, while a very intense stage took place during the first 20 min. The reactions decelerated after the first 60 min and after 120 min the reactions did not significantly advance. The oxygen consumption after 4-h reaction was 1.3–1.5 mole O 2 per 1 mole lignin depending on the conditions. In the first 20 min, 50%–60% of the oxygen was consumed and the consumption increased only slightly after 60 min. At 90°C, the changes in all observed quantities were smaller throughout the whole 4-h reaction period than at 110°C. Under the studied conditions, increasing the reaction temperature, rather than the pressure, had primary significance in the increasing rate of lignin degradation. Hardwood kraft lignin was more reactive than softwood kraft lignin. The results obtained in this study are the basis for the development of a mechanistic model for the oxygen delignification process of pulps to be published in subsequent papers.

Advanced analysis methods have been developed to follow the reactions of lignin during alkaline oxygen delignification conditions more comprehensively than before. This aim was attained by monitoring both the lignin macromolecule and the dissolved reaction products. Softwood (SW) and hardwood (HW) kraft spent liquor lignins were studied as substrates under various reaction conditions. The decrease in the contents of different types of free phenolic hydroxyl groups and the concurrent formation of carboxylic acids was followed by 31 P NMR of the phosphitylated products. In addition, the formation of acidic degradation products with low molecular weight was determined by capillary zone electrophoresis (CE). This way, it was possible to distinguish the carboxylic acids bound to the lignin macromolecule from the cleaved reaction products, even if they partly co-precipitated during sample preparation. Peak deconvolution was applied to get information on syringyl type phenolic structures and on C(5) condensed guaiacyl structures in hardwood lignin. Pyrolysis-GC/MS was applied to provide additional information about the distribution of guaiacyl/ s yringyl/ p- hydroxyphenyl (G/S/H) type lignin subunits, as well as changes in the phenylpropane side chain.

A detailed kinetic model for the lignin oxidation chemistry is presented. It is based mainly on the mechanisms and kinetics presented in the literature. Parameters that could not be found in the literature were regressed against the experimental data obtained from oxidation experiments with softwood kraft lignin. In addition to the detailed model for the chemistry, acid-base equilibrium reactions and gas-liquid mass transfer were modeled. Most of the experimental observations could be reproduced with the developed model. The reasons behind the behavior of guaiacyl and condensed phenols are discussed. The reaction routes affecting lignin solubilization and chemical consumption are presented. Model-ing of acid-base equilibria proved to be important because acid-base pairs of reactants react differently. Carbon dioxide buffers the pH and in this way affects the chemical reactions through the pH. A similar model could also be developed for other lignin treatments; for example, waste water purification or chemicals production in new biorefinery concepts. The developed reaction scheme will be used as a part of oxygen delignification model.

Determination of total lignin content in lignin samples and black liquors using methods with reduced or omitted acid hydrolysis has been compared to the standard method, and results show that the simplified methods yield equivalent results.

A novel alternative was investigated for elevating the xylan content of eucalyptus pulp through xylan deposition in the course of the oxygen delignification stage. The pH in the range of 10–13 was the only variable evaluated, while the other variables were kept constant in a range similar to industrial practice. Xylans were obtained from unbleached and bleached eucalyptus pulps by cold caustic extraction (CCE), giving rise to brown xylan liquor (BXL) and white xylan liquor (WXL), respectively. The liquors were added to a commercial brown pulp during oxygen delignification. The xylan-enriched pulps were subsequently bleached to 90% ISO with the D(EP)D sequence, beaten in a PFI mill and evaluated for their physical and mechanical properties. Xylan deposition occurred at variable degrees depending upon the pH. Pulp bleachability was not impaired by WXL xylan deposition but was slightly negatively affected by BXL xylan. Pulp beatability was improved by both WXL and BXL xylan deposition. The deposited xylan was more stable across bleaching and beating with the WXL xylan than the BXL xylan deposits. At low energy consumption, the deposited xylan improved pulp physical and mechanical properties. Xylan extraction by CCE with subsequent deposition in the oxygen delignification is an interesting technique to manufacture eucalypt pulps of high xylan content. The potential for industrial application is high as no significant modification of current pulp mill installations is needed.

In this project different aqueous based solvent systems were investigated for the dissolution of steam exploded (STEX) dissolving pulps prior to a coagulation step for preparation of textile fibers. The pulp samples studied could, to a large degree, be dissolved in a NaOH/urea/thiourea system, but there are always residuals, irrespective of the conditions. The dissolution process appeared to be kinetically controlled, as prolonged retention time decreased the amount of residuals. A pre-cooled NaOH/urea/thiourea system, and a retention time of 60 h generated the lowest amount (6%) of residuals of the STEX pretreated dissolving pulp studied. Some fundamental results are described and a model for dissolution of dissolving pulp fibers is proposed.

The bark of trees has a big potential as a source of green chemicals. The aim of the present work was to valorise the potential of deciduous tree species with this regard. Three widely spread trees in Europe (grey alder, ash tree, aspen) were in focus as a source of polyphenols, and the yields of polyphenolic compound in the extracts were considered as evaluation criteria. The highest yields of hydrophilic extractives were found in barks of grey alder and aspen (36.8 and 22.9%, respectively). In the former, the highest antioxidant activity was found towards free radicals (DPPH • and ABTS •+ ) and superoxide anion radical. Open chain diarylheptanoids, mainly oregonin, were identified as the major constituents of the grey alder hydrophilic extract. In addition to oregonin, the presence of 2 linear diarylheptanoids [platyphylloside and 1,7-bis-(3,4-dihydroxyphenyl)-heptane-5-O-β-D-glucopyranoside] was confirmed. For the first time, the compounds 1,7-bis-(3,4-dihydroxyphenyl)-3-hydroxyheptane-5-O-β-D-xylopyranoside and 1,7-bis-(3,4-dihydroxyphenyl)-heptane-3-one-5-O-β-D-glucopyranoside were detected in grey alder bark. The results of experiments in vitro and in vivo have shown the high potential for diarylheptanoids-containing extracts in prophylaxis and/or treatment of diseases due to the metabolic disorders and ageing. The biological activity of grey alder extract was confirmed in in vitro experiments by incubation of human blood samples. In vivo experiments with rats also showed positive results. The conclusion is that grey alder extracts have a high potential for prevention of ageing related pathologies. Besides diarylheptanoids, the bark contains condensed tannins in commercially available quantity (12.5%). Eco-friendly wood adhesives were obtained on a tannins basis. The bark left after polyphenols isolation can be used in soil melioration and as a sorbent for the removal of oil products from water surface. The investigation of the phenolic pool of grey alder could contribute to cluster technologies within the biorefinery-based bark processing.

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