Enhanced Removal of Brine From Porous Structures by Supercritical CO2.

Supercritical CO2 (sCO2) removes water from brine held in pumice stone at levels well above the solubility of water in sCO2. The higher water removal results from a combination of passive emulsification of water in sCO2 and viscous fingering of sCO2 through the saturated pumice. This leads to higher levels of salt deposition than that expected from solubility considerations alone. These deposits could impact the injectivity of sCO2 as well as its movement in the subsurface. The finding that the water concentration in sCO2 is not necessarily capped at the solubility limit should influence the parametrization of injection models.

Comparison of various chemometric methods on visible and near-infrared spectral analysis for wood density prediction among different tree species and geographical origins.

Visible and near-infrared (Vis-NIR) spectroscopy has been widely applied in many fields for the qualitative and quantitative analysis. Chemometric techniques including pre-processing, variable selection, and multivariate calibration models play an important role to better extract useful information from spectral data. In this study, a new de-noising method (lifting wavelet transform, LWT), four variable selection methods, as well as two non-linear machine learning models were simultaneously analyzed to compare the impact of chemometric approaches on wood density determination among various tree species and geographical locations. In addition, fruit fly optimization algorithm (FOA) and response surface methodology (RSM) were employed to optimize the parameters of generalized regression neural network (GRNN) and particle swarm optimization-support vector machine (PSO-SVM), respectively. As for various chemometric methods, the optimal chemometric method was different for the same tree species collected from different locations. FOA-GRNN model combined with LWT and CARS deliver the best performance for Chinese white poplar of Heilongjiang province. In contrast, PLS model showed a good performance for Chinese white poplar collected from Jilin province based on raw spectra. However, for other tree species, RSM-PSO-SVM models can improve the performance of wood density prediction compared to traditional linear and FOA-GRNN models. Especially for Acer mono Maxim, when compared to linear models, the coefficient of determination of prediction set ( R p 2 ) and relative prediction deviation (RPD) were increased by 47.70% and 44.48%, respectively. And the dimensionality of Vis-NIR spectral data was decreased from 2048 to 20. Therefore, the appropriate chemometric technique should be selected before building calibration models.

Hispolon Cyclodextrin Complexes and Their Inclusion in Liposomes for Enhanced Delivery in Melanoma Cell Lines.

Hispolon, a phenolic pigment isolated from the mushroom species Phellinus linteus, has been investigated for anti-inflammatory, antioxidant, and anticancer properties; however, low solubility and poor bioavailability have limited its potential clinical translation. In this study, the inclusion complex of hispolon with Sulfobutylether-ß-cyclodextrin (SBEßCD) was characterized, and the Hispolon-SBEßCD Complex (HSC) was included within the sterically stabilized liposomes (SL) to further investigate its anticancer activity against melanoma cell lines. The HSC-trapped-Liposome (HSC-SL) formulation was investigated for its sustained drug delivery and enhanced cytotoxicity. The inclusion complex in the solid=state was confirmed by a Job's plot analysis, molecular modeling, differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), Proton nuclear magnetic resonance (NMR) spectroscopy, and scanning electron microscopy (SEM). The HSC-SL showed no appreciable deviation in size (<150 nm) and polydispersity index (<0.2) and improved drug encapsulation efficiency (>90%) as compared to control hispolon liposomes. Individually incorporated hispolon and SBEßCD in the liposomes (H-CD-SL) was not significant in loading the drug in the liposomes, compared to HSC-SL, as a substantial amount of free drug was separated during dialysis. The HSC-SL formulation showed a sustained release compared to hispolon liposomes (H-SLs) and Hispolon-SBEßCD liposomes (H-CD-SLs). The anticancer activity on melanoma cell lines (B16BL6) of HSC and HSC-SL was higher than in H-CD-SL and hispolon solution. These findings suggest that HSC inclusion in the HSC-SL liposomes stands out as a potential formulation approach for enhancing drug loading, encapsulation, and chemotherapeutic efficiency of hispolon and similar water insoluble drug molecules.

Fast Pyrolysis Bio-Oil-Based Epoxy as an Adhesive in Oriented Strand Board Production.

The objectives of this study were to utilize bio-oil-based epoxy resin in oriented strand board (OSB) production and investigate the effect of bio-oil substitution in epoxy resin as an adhesive for OSB production. Bio-oil was produced by the fast pyrolysis (FP) process using southern yellow pine (Pinus spp.). Bio-oil-based epoxy resin was synthesized by the modification of epoxy resin with FP bio-oil at various substitution levels. Acetone extraction using a Soxhlet process indicated a superior cured reaction of bio-oil and epoxy resin at 20% bio-oil substitution. FTIR spectra corroborated the Soxhlet extraction with the removal of the epoxide peak signature within the cross-linked polymer. Images from the scanning electron microscopy suggested bulk phase homogeneity. OSB panels were tested according to ASTM D1037-12. The modulus of rupture (MOR), modulus of elasticity (MOE), internal bond strength, and water resistance (thickness swell and water absorption) properties of the OSB panels were feasible at bio-oil substitution up to 30% in the epoxy resin system.

The Effect of Cellulose Nanocrystal Suspension Treatment on Suspension Viscosity and Casted Film Property.

Cellulose nanocrystals (CNCs) have attracted significant interest in different industrial sectors. Many applications have been developed and more are being explored. Pre-treatment of the suspension plays a critical role for different applications. In this study, different pre-treatment methods, including homogenization, ultrasonication, and mixing with a magnetic stirrer were applied to a CNC suspension. After treatment, the rheological behaviors of the treated CNC suspensions were characterized using a rotational viscometer. The treated suspensions were then used to cast films for characterization by ultraviolet-visible (UV-Vis) and Fourier transform near-infrared spectroscopy (FT-NIR). All the CNC suspensions demonstrated a shear thinning phenomena. Homogenization or ultrasonication significantly decreased the suspension viscosity compared with the suspension mixed by a magnetic stirrer. The viscosity of CNC suspension changed with time after treatment and settlement of treated CNC suspensions in room conditions increased the viscosity dramatically with time. Different UV and visible light interferences were observed for the CNC films generated from suspensions treated by different methods. The degree of crystallinity of the CNC films evaluated by FT-NIR showed that the film from suspension treated by homogenization and ultrasonication has the highest degree of crystallinity. Pre-treatments of CNC suspension affected the suspension viscosities and formed film properties.

Displacement dewatering of sludge with supercritical CO2.

Supercritical CO2 (sCO2) displaces water from wastewater, alum, and papermill sludge. The sCO2 appears to enter the sludge matrix through viscous fingering through the entrained water. Because the water removed far exceeds the solubility of water in sCO2, it must be displaced by the sCO2 rather than dissolved out. Adding a small amount of soap to the sludge converts some of the bound water into free water, which can then be displaced by sCO2. Application of the sCO2 in multiple stages greatly enhances dewatering as compared to a single stage process. Approximately 70, 70 and 85% of the initial water can be removed from alum, wastewater and paper sludges, respectively, through a five-stage process. Staged application of sCO2 doubles the efficiency of water removal over a single-stage process of the same duration. It is proposed that when the sCO2 entrained in the sludge is decompressed between stages some of the water is explosively displaced by the expanding CO2.

Lifting wavelet transform for Vis-NIR spectral data optimization to predict wood density.

Visible and near infrared (Vis-NIR) spectroscopy is a mature analytical tool for qualitative and quantitative analysis in various sectors. However, in the face of "curse of dimensionality" due to thousands of wavelengths for a Vis-NIR spectrum of a sample, the complexity of computation and memory will be increased. Additionally, variable optimization technique can be used to improve prediction accuracy through removing some irrelevant information or noise. Wood density is a critical parameter of wood quality because it determines other important traits. Accurate estimation of wood density is becoming increasingly important for forest management and end uses of wood. In this study, the performance of two-dimensional (2D) correlation spectroscopy between wavelengths of various spectral transformations, i.e., reflectance spectra (R), reciprocal (1/R), and logarithm spectra (log (1/R)), were analyzed before optimizing spectral variable. The spectra of optimal transformation were decomposed using biorthogonal wavelet family from 3rd to 8th decomposition level based on lifting wavelet transform (LWT). The optimal wavelet coefficients of LWT were selected based on the performance of calibration set using partial least squares (PLS). Two frequent variable selection methods including uninformative variable elimination (UVE) and competitive adaptive reweighted sampling (CARS) were also compared. The results showed that the dimensionality of spectral matrix was reduced from 2048 to 16 and the best density prediction results of Siberian elm (Ulmus pumila L.) were obtained (Rp2R = 0.899, RMSEP = 0.016) based on LWT.

Lifting Wavelet Transform De-noising for Model Optimization of Vis-NIR Spectroscopy to Predict Wood Tracheid Length in Trees.

The data analysis of visible-near infrared (Vis-NIR) spectroscopy is critical for precise information extraction and prediction of fiber morphology. The objectives of this study were to discuss the de-noising of Vis-NIR spectra, taken from wood, to improve the prediction accuracy of tracheid length in Dahurian larch wood. Methods based on lifting wavelet transform (LWT) and local correlation maximization (LCM) algorithms were developed for optimal de-noising parameters and partial least squares (PLS) was employed as the prediction method. The results showed that: (1) The values of tracheid length in the study were generally high and had a great positive linear correlation with annual rings (R = 0.881), (2) the optimal de-noising parameters for larch wood based Vis-NIR spectra were Daubechies-2 (db2) mother wavelet with 4 decomposition levels while using a global fixed hard threshold based on LWT, and (3) the Vis-NIR model based on the optimal LWT de-noising parameters ( R c 2 = 0.834, RMSEC = 0.262, RPD c = 2.454) outperformed those based on the LWT coupled with LCM algorithm (LWT-LCM) ( R c 2 = 0.816, RMSEC = 0.276, RPD c = 2.331) and raw spectra ( R c 2 = 0.822, RMSEC = 0.271, RPD c = 2.370). Thus, the selection of appropriate LWT de-noising parameters could aid in extracting a useful signal for better prediction accuracy of tracheid length.

Chemometric modeling of thermogravimetric data for the compositional analysis of forest biomass.

The objective of this study was to investigated the use of chemometric modeling of thermogravimetric (TG) data as an alternative approach to estimate the chemical and proximate (i.e. volatile matter, fixed carbon and ash contents) composition of lignocellulosic biomass. Since these properties affect the conversion pathway, processing costs, yield and / or quality of products, a capability to rapidly determine these for biomass feedstock entering the process stream will be useful in the success and efficiency of bioconversion technologies. The 38-minute long methodology developed in this study enabled the simultaneous prediction of both the chemical and proximate properties of forest-derived biomass from the same TG data. Conventionally, two separate experiments had to be conducted to obtain such information. In addition, the chemometric models constructed with normalized TG data outperformed models developed via the traditional deconvolution of TG data. PLS and PCR models were especially robust in predicting the volatile matter (R2-0.92; RPD- 3.58) and lignin (R2-0.82; RPD- 2.40) contents of the biomass. The application of chemometrics to TG data also made it possible to predict some monomeric sugars in this study. Elucidation of PC loadings obtained from chemometric models also provided some insights into the thermal decomposition behavior of the chemical constituents of lignocellulosic biomass. For instance, similar loadings were noted for volatile matter and cellulose, and for fixed carbon and lignin. The findings indicate that common latent variables are shared between these chemical and thermal reactivity properties. Results from this study buttresses literature that have reported that the less thermally stable polysaccharides are responsible for the yield of volatiles whereas the more recalcitrant lignin with its higher percentage of elementary carbon contributes to the yield of fixed carbon.

Preparation and Characterization of Epoxy Resin Cross-Linked with High Wood Pyrolysis Bio-Oil Substitution by Acetone Pretreatment.

The use of cost effective solvents may be necessary to store wood pyrolysis bio-oil in order to stabilize and control its viscosity, but this part of the production system has not been explored. Conversely, any rise in viscosity during storage, that would occur without a solvent, will add variance to the production system and render it cost ineffective. The purpose of this study was to modify bio-oil with a common solvent and then react the bio-oil with an epoxy for bonding of wood without any loss in properties. The acetone pretreatment of the bio-oil/epoxy mixture was found to improve the cross-linking potential and substitution rate based on its mechanical, chemical, and thermal properties. Specifically, the bio-oil was blended with epoxy resin at weight ratios ranging from 2:1 to 1:5 and were then cured. A higher bio-oil substitution rate was found to lower the shear bond strength of the bio-oil/epoxy resins. However, when an acetone pretreatment was used, it was possible to replace the bio-oil by as much as 50% while satisfying usage requirements. Extraction of the bio-oil/epoxy mixture with four different solvents demonstrated an improvement in cross-linking after acetone pretreatment. ATR-FTIR analysis confirmed that the polymer achieved a higher cross-linked structure. DSC and TGA curves showed improved thermal stability with the addition of the acetone pretreatment. UV-Vis characterization showed that some functional groups of the bio-oil to epoxy system were unreacted. Finally, when the resin mixture was utilized to bond wood, the acetone pretreatment coupled with precise tuning of the bio-oil:epoxy ratio was an effective method to control cross-linking while ensuring acceptable bond strength.

Simultaneous Moisture Content and Mass Flow Measurements in Wood Chip Flows Using Coupled Dielectric and Impact Sensors.

An 8-electrode capacitance tomography (ECT) sensor was built and used to measure moisture content (MC) and mass flow of pine chip flows. The device was capable of directly measuring total water quantity in a sample but was sensitive to both dry matter and moisture, and therefore required a second measurement of mass flow to calculate MC. Two means of calculating the mass flow were used: the first being an impact sensor to measure total mass flow, and the second a volumetric approach based on measuring total area occupied by wood in images generated using the capacitance sensor's tomographic mode. Tests were made on 109 groups of wood chips ranging in moisture content from 14% to 120% (dry basis) and wet weight of 280 to 1100 g. Sixty groups were randomly selected as a calibration set, and the remaining were used for validation of the sensor's performance. For the combined capacitance/force transducer system, root mean square errors of prediction (RMSEP) for wet mass flow and moisture content were 13.42% and 16.61%, respectively. RMSEP using the combined volumetric mass flow/capacitance sensor for dry mass flow and moisture content were 22.89% and 24.16%, respectively. Either of the approaches was concluded to be feasible for prediction of moisture content in pine chip flows, but combining the impact and capacitance sensors was easier to implement. In situations where flows could not be impeded, however, the tomographic approach would likely be more useful.

Rapid Quantitative Analysis of Forest Biomass Using Fourier Transform Infrared Spectroscopy and Partial Least Squares Regression.

Fourier transform infrared reflectance (FTIR) spectroscopy has been used to predict properties of forest logging residue, a very heterogeneous feedstock material. Properties studied included the chemical composition, thermal reactivity, and energy content. The ability to rapidly determine these properties is vital in the optimization of conversion technologies for the successful commercialization of biobased products. Partial least squares regression of first derivative treated FTIR spectra had good correlations with the conventionally measured properties. For the chemical composition, constructed models generally did a better job of predicting the extractives and lignin content than the carbohydrates. In predicting the thermochemical properties, models for volatile matter and fixed carbon performed very well (i.e., R2 > 0.80, RPD > 2.0). The effect of reducing the wavenumber range to the fingerprint region for PLS modeling and the relationship between the chemical composition and higher heating value of logging residue were also explored. This study is new and different in that it is the first to use FTIR spectroscopy to quantitatively analyze forest logging residue, an abundant resource that can be used as a feedstock in the emerging low carbon economy. Furthermore, it provides a complete and systematic characterization of this heterogeneous raw material.

Identifying Plant Part Composition of Forest Logging Residue Using Infrared Spectral Data and Linear Discriminant Analysis.

As new markets, technologies and economies evolve in the low carbon bioeconomy, forest logging residue, a largely untapped renewable resource will play a vital role. The feedstock can however be variable depending on plant species and plant part component. This heterogeneity can influence the physical, chemical and thermochemical properties of the material, and thus the final yield and quality of products. Although it is challenging to control compositional variability of a batch of feedstock, it is feasible to monitor this heterogeneity and make the necessary changes in process parameters. Such a system will be a first step towards optimization, quality assurance and cost-effectiveness of processes in the emerging biofuel/chemical industry. The objective of this study was therefore to qualitatively classify forest logging residue made up of different plant parts using both near infrared spectroscopy (NIRS) and Fourier transform infrared spectroscopy (FTIRS) together with linear discriminant analysis (LDA). Forest logging residue harvested from several Pinus taeda (loblolly pine) plantations in Alabama, USA, were classified into three plant part components: clean wood, wood and bark and slash (i.e., limbs and foliage). Five-fold cross-validated linear discriminant functions had classification accuracies of over 96% for both NIRS and FTIRS based models. An extra factor/principal component (PC) was however needed to achieve this in FTIRS modeling. Analysis of factor loadings of both NIR and FTIR spectra showed that, the statistically different amount of cellulose in the three plant part components of logging residue contributed to their initial separation. This study demonstrated that NIR or FTIR spectroscopy coupled with PCA and LDA has the potential to be used as a high throughput tool in classifying the plant part makeup of a batch of forest logging residue feedstock. Thus, NIR/FTIR could be employed as a tool to rapidly probe/monitor the variability of forest biomass so that the appropriate online adjustments to parameters can be made in time to ensure process optimization and product quality.

The effect of ethanol on hydroxyl and carbonyl groups in biopolyol produced by hydrothermal liquefaction of loblolly pine: (31)P-NMR and (19)F-NMR analysis.

The goal of this study was to investigate the role of ethanol and temperature on the hydroxyl and carbonyl groups in biopolyol produced from hydrothermal liquefaction of loblolly pine (Pinus spp.) carried out at 250, 300, 350 and 390°C for 30min. Water and water/ethanol mixture (1/1, wt/wt) were used as liquefying solvent in the HTL experiments. HTL in water and water/ethanol is donated as W-HTL and W/E-HTL, respectively. It was found that 300°C and water/ethanol solvent was the optimum liquefaction temperature and solvent, yielding up to 68.1wt.% bio-oil and 2.4wt.% solid residue. (31)P-NMR analysis showed that biopolyol produced by W-HTL was rich in phenolic OH while W/E-HTL produced more aliphatic OH rich biopolyols. Moreover, biopolyols with higher hydroxyl concentration were produced by W/E-HTL. Carbonyl groups were analyzed by (19)F-NMR, which showed that ethanol reduced the concentration of carbonyl groups.

Characterization of Epoxy Composites Reinforced with Wax Encapsulated Microcrystalline Cellulose.

The effect of paraffin wax encapsulated microcrystalline cellulose (EMC) particles on the mechanical and physical properties of EMC/epoxy composites were investigated. It was demonstrated that the compatibility between cellulose and epoxy resin could be maintained due to partial encapsulation resulting in an improvement in epoxy composite mechanical properties. This work was unique because it was possible to improve the physical and mechanical properties of the EMC/epoxy composites while encapsulating the microcrystalline cellulose (MCC) for a more homogeneous dispersion. The addition of EMC could increase the stiffness of epoxy composites, especially when the composites were wet. The 1% EMC loading with a 1:2 ratio of wax:MCC demonstrated the best reinforcement for both dry and wet properties. The decomposition temperature of epoxy was preserved up to a 5% EMC loading and for different wax:MCC ratios. An increase in wax encapsulated cellulose loading did increase water absorption but overall this absorption was still low (<1%) for all composites.

Classification and Identification of Plant Fibrous Material with Different Species Using near Infrared Technique-A New Way to Approach Determining Biomass Properties Accurately within Different Species.

Plant fibrous material is a good resource in textile and other industries. Normally, several kinds of plant fibrous materials used in one process are needed to be identified and characterized in advance. It is easy to identify them when they are in raw condition. However, most of the materials are semi products which are ground, rotted or pre-hydrolyzed. To classify these samples which include different species with high accuracy is a big challenge. In this research, both qualitative and quantitative analysis methods were chosen to classify six different species of samples, including softwood, hardwood, bast, and aquatic plant. Soft Independent Modeling of Class Analogy (SIMCA) and partial least squares (PLS) were used. The algorithm to classify different species of samples using PLS was created independently in this research. Results found that the six species can be successfully classified using SIMCA and PLS methods, and these two methods show similar results. The identification rates of kenaf, ramie and pine are 100%, and the identification rates of lotus, eucalyptus and tallow are higher than 94%. It is also found that spectra loadings can help pick up best wavenumber ranges for constructing the NIR model. Inter material distance can show how close between two species. Scores graph is helpful to choose the principal components numbers during the model construction.

Multivariate Calibration and Model Integrity for Wood Chemistry Using Fourier Transform Infrared Spectroscopy.

This research addressed a rapid method to monitor hardwood chemical composition by applying Fourier transform infrared (FT-IR) spectroscopy, with particular interest in model performance for interpretation and prediction. Partial least squares (PLS) and principal components regression (PCR) were chosen as the primary models for comparison. Standard laboratory chemistry methods were employed on a mixed genus/species hardwood sample set to collect the original data. PLS was found to provide better predictive capability while PCR exhibited a more precise estimate of loading peaks and suggests that PCR is better for model interpretation of key underlying functional groups. Specifically, when PCR was utilized, an error in peak loading of ±15 cm(-1) from the true mean was quantified. Application of the first derivative appeared to assist in improving both PCR and PLS loading precision. Research results identified the wavenumbers important in the prediction of extractives, lignin, cellulose, and hemicellulose and further demonstrated the utility in FT-IR for rapid monitoring of wood chemistry.

Prediction of mixed hardwood lignin and carbohydrate content using ATR-FTIR and FT-NIR.

This study used Attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and Fourier transform near-infrared (FT-NIR) spectroscopy with principal component regression (PCR) and partial least squares regression (PLS) to build hardwood prediction models. Wet chemistry analysis coupled with high performance liquid chromatography (HPLC) was employed to obtain the chemical composition of these samples. Spectra loadings were studied to identify key wavenumber in the prediction of chemical composition. NIR-PLS and FTIR-PLS performed the best for extractives, lignin and xylose, whose residual predictive deviation (RPD) values were all over 3 and indicates the potential for either instrument to provide superior prediction models with NIR performing slightly better. During testing, it was found that more accurate determination of holocellulose content was possible when HPLC was used. Independent chemometric models, for FT-NIR and ATR-FTIR, identified similar functional groups responsible for the prediction of chemical composition and suggested that coupling the two techniques could strengthen interpretation and prediction.

Effect of liquefaction temperature on hydroxyl groups of bio-oil from loblolly pine (Pinus taeda).

Loblolly pine was liquefied with ethylene glycol at 100, 150, 200 and 250 °C in order to analyze the effect of liquefaction temperature on hydroxyl groups of bio-oil, and to determine the source and variation of hydroxyl groups. The optimum temperature was found to be 150-200 °C. Hydroxyl number (OHN) of the bio-oil was ranged from 632 to 1430 mg KOH/g. GC-MS analysis showed that 70-90% of OHN was generated from unreacted EG. (31)P NMR analysis showed that the majority of hydroxyl groups were aliphatic, and none of the bio-oil exhibited any detectable hydroxyl groups from phenolic sources. Finally, it was found that all bio-oils were stable in terms of OHN for 2 months when stored at -10 °C.

Near infrared spectroscopy calibration for wood chemistry: which chemometric technique is best for prediction and interpretation?

This paper addresses the precision in factor loadings during partial least squares (PLS) and principal components regression (PCR) of wood chemistry content from near infrared reflectance (NIR) spectra. The precision of the loadings is considered important because these estimates are often utilized to interpret chemometric models or selection of meaningful wavenumbers. Standard laboratory chemistry methods were employed on a mixed genus/species hardwood sample set. PLS and PCR, before and after 1st derivative pretreatment, was utilized for model building and loadings investigation. As demonstrated by others, PLS was found to provide better predictive diagnostics. However, PCR exhibited a more precise estimate of loading peaks which makes PCR better for interpretation. Application of the 1st derivative appeared to assist in improving both PCR and PLS loading precision, but due to the small sample size, the two chemometric methods could not be compared statistically. This work is important because to date most research works have committed to PLS because it yields better predictive performance. But this research suggests there is a tradeoff between better prediction and model interpretation. Future work is needed to compare PLS and PCR for a suite of spectral pretreatment techniques.