Infrared Spectroscopy as Alternative to Wet Chemical Analysis to Characterize Eucalyptus globulus Pulps and Predict Their Ethanol Yield for a Simultaneous Saccharification and Fermentation Process

Bioethanol can be obtained from wood by simultaneous enzymatic saccharification and fermentation step (SSF). However, for enzymatic process to be effective, a pretreatment is needed to break the wood structure and to remove lignin to expose the carbohydrates components. Evaluation of these processes requires characterization of the materials generated in the different stages. The traditional analytical methods of wood, pretreated materials (pulps), monosaccharides in the hydrolyzated pulps, and ethanol involve laborious and destructive methodologies. This, together with the high cost of enzymes and the possibility to obtain low ethanol yields from some pulps, makes it suitable to have rapid, nondestructive, less expensive, and quantitative methods to monitoring the processes to obtain ethanol from wood. In this work, infrared spectroscopy (IR) accompanied with multivariate analysis is used to characterize chemically organosolv pretreated Eucalyptus globulus pulps (glucans, lignin, and hemicellulosic sugars), as well as to predict the ethanol yield after a SSF process. Mid (4,000–400 cm^?1) and near-infrared (12,500–4,000 cm^?1) spectra of pulps were used in order to obtain calibration models through of partial least squares regression (PLS). The obtained multivariate models were validated by cross validation and by external validation. Mid-infrared (mid-IR)/NIR PLS models to quantify ethanol concentration were also compared with a mathematical approach to predict ethanol yield estimated from the chemical composition of the pulps determined by wet chemical methods (discrete chemical data). Results show the high ability of the infrared spectra in both regions, mid-IR and NIR, to calibrate and predict the ethanol yield and the chemical components of pulps, with low values of standard calibration and validation errors (root mean square error of calibration, root mean square error of validation (RMSEV), and root mean square error of prediction), high correlation between predicted and measured by the reference methods values (R ² between 0.789 and 0.997), and adequate values of the ratio between the standard deviation of the reference methods and the standard errors of infrared PLS models relative performance determinant (RPD) (greater than 3 for majority of the models). Use of IR for ethanol quantification showed similar and even better results to the obtained with the discrete chemical data, especially in the case of mid-IR models, where ethanol concentration can be estimated with a RMSEV equal to 1.9 g?L^?1. These results could facilitate the analysis of high number of samples required in the evaluation and optimization of the processes.     

Quantitative aspects of near-infrared Fourier transform Raman spectroscopy

Three fundamental behaviors of vibrational spectroscopy data manipulation routinely associated with Fourier transform infrared (FTIR) spectroscopy are evaluated for near-infrared (NIR) Fourier transform Raman spectroscopy. Spectral reproducibility, spectral subtraction and sensitivity are examined relative to the NIR FT-Raman experiment. Quantitative predictive ability is compared for identical sets of samples containing mixtures of the three xylene isomers. Partial least-squares analysis is used to compare predictive ability. IR performance is found to be better than Raman, though the potential for method development using NIR FT-Raman is shown to be quite promising.     

Characterization of fossil Sequoioxylon wood using analytical instrumental techniques

In this study, fossil (Sequoioxylon) wood from the Oligocene–Miocene transition in İstanbul, Turkey was examined using non-destructive test methods to evaluate changes in anatomical and chemical structure. Molecular changes in the cell wall structure of the wood were determined using Fourier transform infrared (FTIR) and FT-Raman spectroscopy, along with the comparison to recent wood [Sequoiadendron giganteum (Lindl.)]. We found that the cell wall carbohydrates of the fossil wood were significantly more degraded compared with lignin; FT-Raman spectroscopy revealed the degradation in more detail compared with FTIR spectroscopy. FT-Raman spectra also demonstrated that hemicellulose and holocellulose were decreased in the fossil wood. Laser-induced breakdown spectroscopy (LIBS) analysis confirmed that the mass loss was due to the decreased H and O content of the fossil wood sample and was caused by decomposition. Light microscopy also showed that fossil and recent woods have similar anatomic structures, and that the micro-morphological structure of the fossil wood was well-preserved.     

A comparison of Fourier transform infrared and near-infrared Fourier transform Raman spectroscopy for quantitative measurements: An application in polymorphism

Polymorphism in cortisone acetate, a synthetic adrenocortical steroid, and in a compound from a heart disease project has been studied with near-infrared Fourier transform Raman (NIR FT-Raman) spectroscopy. For cortisone acetate similar quantitative precision was obtained with both Raman and diffuse reflection IR measurements. The Raman measurements of the heart disease compound gave a calibration with a standard error of prediction of better than 2.5%. The combination of excellent precision with very convenient measurement of powders makes NIR FT-Raman spectroscopy a valuable tool for quantitative measurements of polymorphism.     

Raman spectrometry and neural networks for the classification of wood types—1

In this work the coupling of near infrared (NIR) Fourier-transform (FT) Raman spectroscopy and neural computing for spectral feature extraction and classification of woods is reported. A NIR FT-Raman spectrometer operating at 1064 nm was used for all measurements; particular attention was paid to the effects of sample fluorescence and heating. It was demonstrated that fluorescence rejection is accomplished only for the lighter colored woods and that fluorescence was found to be severe for 10 of the 71 woods studied in this work even using excitation at 1064 nm. It was further found that hardwoods were no more or less susceptible to sample heating than softwoods. Feed-forward neural networks were used to extract the principal features of wood spectra at resolutions of 4, 8 and 16 cm⁻¹ and to classify spectra as either temperate hardwoods or temperate softwoods. Neural networks were constructed using zero and two processing elements in the hidden layer. It was shown that neural networks with two hidden processing elements perform near optimally, since each hidden layer processing element may function as either a hardwood or softwood feature detector. This work represents the first time that FT-Raman spectroscopy and neural network technology have been coupled for spectral feature extraction and classification.     

Monitoring the kappa number of bleached pulps based on FT-Raman spectroscopy

Cellulose - A new strategy was proposed to determine the Kappa number of bleached Eucalyptus globulus kraft pulps based on FT-Raman spectroscopy. Before modeling, smoothing (Savitzky-Golay),...     

Efficient total halogen-free photochemical bleaching of kraft pulps using alkaline hydrogen peroxide

Total halogen-free bleaching of kraft pulps was conducted by an oxidative photochemical process at room temperature using alkaline hydrogen peroxide. Selection of an appropriate wavelength of light was crucial for effective bleaching and avoiding degradation of cellulose. The wavelength of the light has to be selected so that the light is absorbed only by the colored compounds in the pulps and not by the bleaching reagents or the pulp itself. When a long-wavelength black-light fluorescent lamp was used in combination with aqueous hydrogen peroxide solution at pH 11, the bleaching efficiency for hardwood and softwood kraft pulps reached the same level as that obtained by conventional two-stage elemental chlorine-free processes.     

Fourier-transform Raman spectroscopic study of a Neolithic waterlogged wood assemblage

The use of Fourier-transform Raman spectroscopy for characterising lignocellulosics has increased significantly over the last twenty years. Here, an FT-Raman spectroscopic study of changes in the chemistry of waterlogged archaeological wood of Pinus sp. and Quercus sp. from a prehistoric assemblage recovered from northern Greece is presented. FT-Raman spectral features of biodeteriorated wood were associated with the depletion of lignin and/or carbohydrate polymers at various stages of deterioration. Spectra from the archaeological wood are presented alongside spectra of sound wood of the same taxa. A comparison of the relative changes in intensities of spectral bands associated with lignin and carbohydrates resulting from decay clearly indicated extensive deterioration of both the softwood and hardwood samples and the carbohydrates appear to be more deteriorated than the lignin. The biodeterioration of the archaeological timbers followed a pattern of initial preferential loss of carbohydrates causing significant loss of cellulose and hemicellulose, followed by the degradation of lignin.     

FT-Raman,FT-infrared and NIR spectroscopic characterization of oxygen-delignified kraft pulp treated with hydrogen peroxide under acidic and alkaline conditions

The effects of bleaching treatment of oxygen-delignified softwood kraft pulp with hydrogen peroxide under acidic and alkaline conditions were studied using standard technological techniques and spectroscopic analytical methods: near-infrared (NIR), Fourier-transform infrared (FTIR) and Fourier-transform (FT) Raman spectroscopies. Among the three tested spectroscopic techniques, NIR analysis appeared to be the most appropriate in terms of possible technological applications. The use of NIR spectroscopy combined with multivariate data analysis allowed to create models for pulp bleaching monitoring based on CIE L*a*b* measurements. Near-infrared and FTIR spectroscopic studies allowed differentiating between the effects of the acidic and alkaline peroxide bleaching stages, but failed in relation to the delignification process. The most representative bands in the FTIR and FT-Raman spectra in terms of delignification and chromophore removal exhibited no correlation with standard technological measurement results.     

Analytical pyrolysis study of biodelignification of cloned Eucalyptus globulus (EG) clone and Pinus pinaster Aiton kraft pulp and residual lignins

This study centred on the analysis of lignin in situ of cloned eucalypt and pine kraft pulps. Trametes versicolor laccase-violuric acid system (LMS) delignifications were performed on a softwood (Pinus pinaster) and a hardwood (Eucalyptus globulus) conventional kraft pulp with an initial kappa number of 34.5 and 15.5, respectively. The LMS treated pulps were then subjected to alkaline extraction stages (E). The kappa number data show that LMS is effective at biodelignifying both softwood and hardwood kraft pulps. However, under the conditions employed in this study, a greater level of biodelignification was obtained with LMS E. globulus (hardwood) than with LMS P. pinaster (softwood), but the amount of lignin removed was higher for the softwood pulp. The original milled wood samples, kraft pulps, biodelignified kraft pulps, and isolated residual lignin and milled wood lignins from the two wood samples have been characterized by pyrolysis-gas chromatography/mass spectrometry. The analysis of the pyrograms indicates that the lignin compositions of the two wood species and corresponding pulps are very different, as expected; however, the knowledge of the chemical mechanisms of delignification is very limited and requires additional work. Analytical pyrolysis is one the few degradative methods for the analysis of biopolymers that has shown a sufficient degree of success.     

Characterisation of dissolving pulp using designed process variables, NIR and NMR spectroscopy, and multivariate data analysis

Two processability variables, filter clogging and alkali resistance, were measured in a series of laboratorycooked viscose pulps. The pulps were also characterised by ¹³CCP/MAS solid state nuclear magnetic resonance (NMR) and near infrared (NIR) spectroscopy. Partial least squares (PLS) regression was used to investigate the information provided by the spectroscopic methods with respect to the processability measurements. The study showed that the alkali resistance, R18, of the pulp and the filter clogging value, Kw, of the laboratoryprepared viscose can be modelled by NIR and multivariate data analysis (MVA). The alkali resistance, R18, of the pulp can also be calculated by NMR and partial least squares (PLS) regression. Analysis of the loading values in the PLS model showed that pulps with high alkali resistance have higher crystallinity than pulps with low alkali resistance. Analysis of variables of the cooking conditions showed that the chemical charge (Na₂O) and pH should be kept low to give high alkali resistance, whereas high Na₂O gives low filter clogging values.     

Length determination of vessel elements in tree trunks used for water and nutrient transport by Fourier transform Raman spectroscopy

Length analysis of vessel elements in tree trunks used for water and nutrient transport is a lengthy, multistep procedure although it reflects environmental stresses on a tree. The feasibility of using FT-Raman spectroscopy for rapid determination of vessel element length in a tree was examined using wood powders of two Eucalyptus species, including samples of various ages and colors. The first-derivative transformation followed by the multiplicative scatter correction of Raman spectroscopic data and the partial least-squares regression revealed highly significant correlation between conventionally measured and Raman-predicted vessel element length with correlation coefficients (r) of 0.843 and 0.826, respectively, in the calibration (for known samples, n=186) and in the prediction (for unknown samples, n=40). FT-Raman spectroscopy coupled with multivariate data analysis will contribute to solving the interactions between emerging environmental issues and the anatomical structure of wood, which allow efficient management practices in growing forests to fix atmospheric CO₂ effectively.     

Sulfur-free dissolving pulps and their application for viscose and lyocell

In this study, the concept of multifunctional alkaline pulping has been approved to produce high-purity and high-yield dissolving pulps. The selective removal of hemicelluloses was achieved by either water autohydrolysis (PH) or alkaline extraction (E) both applied as pre-treatments prior to cooking. Alternatively, hemicelluloses were isolated after oxygen delignification in a process step denoted as cold caustic extraction (CCE). Eucalyptus globulus wood chips were used as the raw material for kraft and soda-AQ pulping. In all process modifications sulfur was successfully replaced by anthraquinone. By these modifications purified dissolving pulps were subjected to TCF bleaching and comprehensive viscose and lyocell application tests. All pulps met the specifications for dissolving pulps. Further more, CCE-pulps showed a significantly higher yield after final bleaching. Morphological changes such as ultrastructure of the preserved outer cell wall layers, specific surface area and lateral fibril aggregate dimension correlated with the reduced reactivity towards regular viscose processing. The residual xylan after alkali purification depicted a lower content of functional groups and a higher molecular weight and was obviously entrapped in the cellulose fibril aggregates which render the hemicelluloses more resistant to steeping in the standard viscose process. Simultaneously, the supramolecular structure of the cellulose is partly converted from cellulose I to cellulose II by the alkaline purification step which did not influence the pulps reactivity significantly. Nevertheless, these differences in pulp parameters did not affect the lyocell process due to the outstanding solubility of the pulps in NMMO. Laboratory spinning revealed good fiber strength for both, regular viscose and lyocell fibers. The high molecular weight xylan of the CCE-treated pulps even took part in fiber forming.     

Yb3+ as an origin of the strong anti-Stokes luminescence in NIR FT-Raman spectra of some lanthanide sesquioxides

Strong anti-Stokes bands observed in FT-Raman spectra of Y2O3, Gd2O3 and Lu2O3 are explained by NIR luminescence of Yb3+ impurities present in sesquioxides after the excitation with the 1064 nm line of an Nd:YAG laser. Samples of Y2O3:Yb, Ga2O3:Yb, CeO2:Yb, Gd2O3:Yb and Lu2O3:Yb were prepared by solution combustion synthesis procedure using urea. All materials were investigated by FT-Raman and FT-NIR spectroscopy and characterized by X-ray powder diffraction.     

Hydrogen peroxide bleaching of cellulose pulps obtained from brewer’s spent grain

Brewer’s spent grain (BSG) was evaluated for bleached pulp production. Two cellulose pulps with different chemical compositions were produced by soda pulping: one from the original raw material and the other from material pretreated by dilute acid. Both of them were bleached by a totally chlorine-free sequence performed in three stages, using 5% hydrogen peroxide in the two initial, and a 0.25 N NaOH solution in the last one. Chemical composition, kappa number, viscosity, brightness and yield of bleached and unbleached pulps were evaluated. The high hemicellulose (28.4% w/w) and extractives (5.8% w/w) contents in original BSG affected the pulping and bleaching processes. However, soda pulping of acid pretreated BSG gave a cellulose-rich pulp (90.4% w/w) with low hemicellulose and extractives contents (7.9% w/w and <3.4% w/w, respectively), which was easily bleached achieving a kappa number of 11.21, viscosity of 3.12 cp, brightness of 71.3%, cellulose content of 95.7% w/w, and residual lignin of 3.4% w/w. Alkaline and oxidative delignification of acid pretreated BSG was found as an attractive approach for producing high-purity, chlorine-free cellulose pulp.     

Evaluation of new organosolv dissolving pulps. Part II: Structure and NMMO processability of the pulps

The supermolecular structure of dissolving pulps produced from hardwood by the organosolv processes Acetosolv, Formacell, and Milox was characterized by physical methods (TEM, WAXS, SAXS, NMR) and compared with conventional Sulfite and standard commercial dissolving pulps. The suitability of the pulps for the NMMO technology was tested by spinning fibres and blowing films, whose structural and mechanical properties have also been determined. With TEM it was shown that the TCF-bleached organosolv pulps have only the primary (Formacell), the primary and S1 (Milox), or mainly the S1 (Acetosolv) layers exposed to the surface, whereas Sulfite pulping exposes the S2 cell wall layer. Especially for Milox and Acetosolv Eucalyptus wood pulps, a reduced degree of crystallinity was found, both with WAXS and NMR. The SAXS results indicate a lower pore intersection length for the new pulps as compared to conventional pulps. Unbleached organosolv pulps show a lower crystallinity, very low pore intersection lengths, and an average crystallite shape different from their bleached counterparts. The dissolution behaviour in NMMO and the processability of the bleached organosolv pulps was satisfactory so far. Fibres and films could be produced with structural and mechanical properties comparable with conventional Sulfite and standard commercial dissolving pulp products. However, unbleached organosolv pulps did not meet the requirements of the NMMO process.     

Practical uses of FTIR spectroscopy in wood science and technology

Based on own research activities this survey demonstrates the potential applications of FTIR spectroscopy in wood and wood-product research. This rapid method can be used e.g. with success for determination of lignin in woody materials and pulps. Crucial analytical data of lignins were also determined by quantitative evaluation of FTIR data. The degree of substitution of cellulose derivatives can be estimated. The course of delignification during pulping was monitored using transmission and circular ATR cells for the IR spectroscopy of the cooking liquors. Based on these spectra the Kappa number of pulps can be predicted.     

Rheology of nanofibrillated cellulose/acrylate systems for coating applications

In this work, the suitability of nanofibrillated cellulose (NFC) as a novel component for wood coatings has been evaluated. NFC was prepared from two different wood pulps with a high pressure homogeniser and a grinder, depending on the initial fibre size of the two pulps. The fibrillation process was monitored using viscosity measurements and scanning electron microscopy. Viscosity measurements were found to be a suitable, reliable and especially fast and easy method for process monitoring, optimization and quality assessment of the NFC fibrillation process. NFC was mixed with four different waterborne acrylic polymer emulsions and analysed regarding its rheological behaviour. The viscosity of the acrylate–NFC suspensions was dominated by the NFC, whereas the polymer type was of minor importance at the tested concentrations. The viscosity increased exponentially after NFC addition and consequently the viscosity of such suspensions would be precisely adjustable in the considered shear range. During accelerated storage at elevated temperatures, the general flow behaviour did not change; only a slight viscosity increase was observed. The study shows that rheology is an important issue that has to be taken into account when applying NFC as additive in water based coating systems and that NFC is suitable as component for coating applications.     

Pyrolysis-GC/MS and TG/MS study of mediated laccase biodelignification of Eucalyptus globulus kraft pulp

Biobleaching studies using laccase mediator system (LMS) were carried out, under optimized conditions, on two unbleached Eucalyptus globulus kraft pulps, one produced by conventional way, with kappa number of 16.1, and another with kappa number of 14.5, obtained by modified kraft procedure with a high liquor/wood ratio and with black liquor replacement in the middle of the cooking. The pulp properties before and after LMS and alkaline extraction were evaluated in terms of kappa number, hexeneuronic acid content, viscosity, brightness and acid insoluble lignin content.The original milled wood sample and the kraft pulps were characterized by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and thermogravimetry/mass spectrometry (TG/MS). Eucalypt wood lignin produces guaiacol and syringol derivatives during pyrolysis. These lignin products can be detected with high sensitivity using the selected ion chromatograms even in the bleached pulp of low lignin content (about 0.5%). Py-GC/MS revealed that the lignin moieties were similarly altered during biobleaching as during pulping, which is exemplified by the preferential removal of aldehyde groups from the alkyl side groups. Semi-quantitative analysis of the pyrograms indicates that the lignin content of the biobleached pulps is reduced by about half in comparison with the unbleached pulps. The TG/MS results show that the hemicellulose content of wood was strongly modified during pulping resulting in higher thermal stability.