Production of single-component cellulose-based hydrogel and its utilization as adsorbent for aqueous contaminants.

The growing concern for the environment has resulted in renewed interest in bio-based resources. This study aims to produce a hydrogel adsorbent from cellulose and examine its adsorption performance. In pursuit of this goal, we report a simple one-pot synthesis of cellulose acetate sulfate (CAS), followed by the formation of CAS hydrogels and their subsequent adsorption performances. The CAS includes both hydrophilic and hydrophobic functional groups, enable the formation of a single-component hydrogel through intermolecular interactions in deionized water. The thermal reversibility of CAS hydrogels makes them easily processable into various shapes. The durability of the CAS hydrogel adsorbents can be improved by introducing divalent cations (e.g., Ca2+), which create ionically crosslinked hydrogels. The ionically a crosslinked CAS hydrogel adsorbent exhibits a maximum adsorption capacity of 245 mg/g for methylene blue (MB) at 23 °C and a pH of 7. The adsorption behavior of MB on the CAS hydrogel follows both the pseudo-second-order model and the Langmuir adsorption isotherm model. Furthermore, the CAS hydrogel adsorbent maintains a 70 % removal ratio after five cycles. The simplicity of synthesis and hydrogel formation opens up new possibilities for producing and utilizing cellulose-based hydrogels as adsorbents for aqueous contaminants.

Effective toluene removal from aqueous solutions using fast pyrolysis-derived activated carbon from agricultural and forest residues: Isotherms and kinetics study.

In this study, the production and characterization of activated carbons (ACs) from agricultural and forest residue using physical activation are discussed. Biomass-based biochars produced during fast pyrolysis process is introduced as alternative precursors to produce AC and the integrated process for the co-production of porous adsorbent materials from biochar via the fast pyrolysis process is suggested. Moderate surface areas and good adsorption capacities were obtained from switchgrass (SWG) and pine tops (PT) based AC. The surface areas were 959 and 714 m2/g for SWG- and PT-based AC, respectively. The adsorption capacities using toluene as pollutant for two model systems of 180 and 300 ppm were measured and ranged between 441-711 and 432-716 mg/g for SWG-based and PT-based AC, respectively. The nitrogen adsorptive behavior, Lagergren pseudo-second-order kinetic (PSOK) model and kinetics isotherms studies describe a heterogeneous porous system, including a mesoporous fraction with the existence of a multilayer adsorption performance. The presence of micropores and mesopores in SWG- and PT-based AC suggests potential commercial applications for using pyrolytic biochars for AC production.

At-Line Sampling and Characterization of Pyrolytic Vapors from Biomass Feedstock Blends Using SPME-GC/MS-PCA: Influence of Char on Fast Pyrolysis.

Solid-phase microextraction (SPME) coupled with gas chromatography-mass spectrometry (GC-MS) analysis was used for the at-line sampling of pyrolytic vapors produced during the fast pyrolysis of biomass. The pure and binary blends of switchgrass (SWG) and pine harvest residues (PT6) were used as biomass feedstocks. Sequential SPME sampling allowed for monitoring of changes in the pyrolysis vapors as char accumulated in the fluid bed. The relative concentration and composition of the pyrolysis vapors desorbed from the SPME fibers were investigated using GC-MS, and the resulting chromatograms were analyzed using principal component analysis (PCA) to compare the composition of the pyrolysis vapors over the course of the pyrolysis run. The chemical compositions of both carbohydrate and lignin fragments varied as the char builds up in the reactor bed. Fragments derived from cellulose and hemicelluloses included anhydrosugars, furans, and light-oxygenated compounds. Lignin fragments included methoxyphenols, phenolic ketones, aldehydes, and low-molecular-weight aromatics. The composition of the carbohydrate fragments changed more than those of the lignin fragments as the char built up in the fluid bed. This combination of SPME-GC/MS-PCA was a novel, easy, and effective method for measuring the composition and changes in the composition of pyrolysis vapors during the fast pyrolysis process. This work also highlighted the effect of char build-up on the composition of the overall pyrolysis vapors.

Dynamic life-cycle carbon analysis for fast pyrolysis biofuel produced from pine residues: implications of carbon temporal effects.

BACKGROUND: Woody biomass has been considered as a promising feedstock for biofuel production via thermochemical conversion technologies such as fast pyrolysis. Extensive Life Cycle Assessment studies have been completed to evaluate the carbon intensity of woody biomass-derived biofuels via fast pyrolysis. However, most studies assumed that woody biomass such as forest residues is a carbon-neutral feedstock like annual crops, despite a distinctive timeframe it takes to grow woody biomass. Besides, few studies have investigated the impacts of forest dynamics and the temporal effects of carbon on the overall carbon intensity of woody-derived biofuels. This study addressed such gaps by developing a life-cycle carbon analysis framework integrating dynamic modeling for forest and biorefinery systems with a time-based discounted Global Warming Potential (GWP) method developed in this work. The framework analyzed dynamic carbon and energy flows of a supply chain for biofuel production from pine residues via fast pyrolysis. RESULTS: The mean carbon intensity of biofuel given by Monte Carlo simulation across three pine growth cases ranges from 40.8-41.2 g CO2e MJ-1 (static method) to 51.0-65.2 g CO2e MJ-1 (using the time-based discounted GWP method) when combusting biochar for energy recovery. If biochar is utilized as soil amendment, the carbon intensity reduces to 19.0-19.7 g CO2e MJ-1 (static method) and 29.6-43.4 g CO2e MJ-1 in the time-based method. Forest growth and yields (controlled by forest management strategies) show more significant impacts on biofuel carbon intensity when the temporal effect of carbon is taken into consideration. Variation in forest operations and management (e.g., energy consumption of thinning and harvesting), on the other hand, has little impact on the biofuel carbon intensity. CONCLUSIONS: The carbon temporal effect, particularly the time lag of carbon sequestration during pine growth, has direct impacts on the carbon intensity of biofuels produced from pine residues from a stand-level pine growth and management point of view. The carbon implications are also significantly impacted by the assumptions of biochar end-of-life cases and forest management strategies.

Techno-economic analysis of producing xylo-oligosaccharides and cellulose microfibers from lignocellulosic biomass.

This study assesses the economic performance of a biorefinery producing xylo-oligosaccharides (XOS) from miscanthus by autohydrolysis and purification based on a rigorous model developed in ASPEN Plus. Varied biorefinery capacities (50-250 oven dry metric ton (ODMT)/day) and three XOS content levels (80%, 90%, 95%) are analyzed. The XOS minimum selling price (XOS MSP) is varied between $3,430-$7,500, $4,030-$8,970, and $4,840-$10,640 per metric ton (MT) for 80%, 90%, and 95% content, respectively. The results show that increasing biorefinery capacity can significantly reduce the XOS MSP and higher purity leads to higher XOS MSP due to less yield, and higher capital and operating costs. This study also explores another system configuration to produce high-value byproducts, cellulose microfiber, by utilizing the cellulose to produce microfiber instead of combusting for energy recovery. The XOS MSP of cellulose microfiber case is $2,460-$7,040/MT and thus exhibits potential economic benefits over the other cases.

Design strategies, properties and applications of cellulose nanomaterials-enhanced products with residual, technical or nanoscale lignin-A review.

With the increasing demand for greener alternatives to fossil-derived products, research on cellulose nanomaterials (CNMs) has rapidly expanded. The combination of nanoscale properties and sustainable attributes makes CNMs an asset in the quest for a sustainable society. However, challenges such as the hydrophilic nature of CNMs, their low compatibility with non-polar matrices and modest thermal stability, slow the development of end-uses. Combination of CNMs with amphiphilic lignin can improve the thermal stability, enhance the compatibility with non-polar matrices and, additionally, endow CNMs with new functionalities e.g., UV shielding or antioxidative properties. This article comprehensively reviews the different design strategies and their influence on properties and applications of CNMs containing lignin in various forms; either as residual lignin, added technical lignin, or nanoscale particles. The review focuses especially on the synergy created between CNMs and lignin, paving the way for new production routes and use of CNM/lignin materials in high-performance applications.

Steam torrefaction of Eucalyptus globulus for producing black pellets: A pilot-scale experience.

Steam torrefaction of Eucalyptus globulus was performed at temperatures between 245°C and 265°C in a 100kg/h pilot plant. Torrefied biomass was then pelletized in a 300kg/h unit and the pellets were subject to durability, density and combustion tests. The structural changes measured with FTIR were studied along with the combustion behavior of the materials. Compositional analysis showed that increasing the torrefaction temperature reduced both hemicellulose fraction and overall mass yield (MY). Furthermore, there was a linear relationship between the energy yield (EY) and mass yield (EY=[1.04-0.9(1-MY)]) for these samples. The ignition and comprehensive indexes confirmed that the stability of the torrefied biomass in a combustion environment was higher than for untreated biomass. Finally, pellets showed high durability (98%), and had an energy density (13-14GJ/m3), which is comparable to low-rank coals.

Lignin-Based Thermoplastic Materials.

Lignin-based thermoplastic materials have attracted increasing interest as sustainable, cost-effective, and biodegradable alternatives for petroleum-based thermoplastics. As an amorphous thermoplastic material, lignin has a relatively high glass-transition temperature and also undergoes radical-induced self-condensation at high temperatures, which limits its thermal processability. Additionally, lignin-based materials are usually brittle and exhibit poor mechanical properties. To improve the thermoplasticity and mechanical properties of technical lignin, polymers or plasticizers are usually integrated with lignin by blending or chemical modification. This Review attempts to cover the reported approaches towards the development of lignin-based thermoplastic materials on the basis of published information. Approaches reviewed include plasticization, blending with miscible polymers, and chemical modifications by esterification, etherification, polymer grafting, and copolymerization. Those lignin-based thermoplastic materials are expected to show applications as engineering plastics, polymeric foams, thermoplastic elastomers, and carbon-fiber precursors.

Wood Extractives Promote Cellulase Activity on Cellulosic Substrates.

Deposition of hydrophobic wood extractives and representative model compounds, on the surface of cellulose prior to enzymatic hydrolysis was found to either enhance or inhibit the action of cellulase enzymes. The effect of these compounds was correlated with their chemical structure, which may in part explain the differential effects observed between softwood and hardwood extractives. Specifically, the addition of sterol, enhanced enzymatic hydrolysis of microcrystalline cellulose by 54%, whereas the addition of a triglyceride could inhibit the hydrolysis by 49%. The effects of the different extractives' could be explained by considering their Hansen solubility parameters. The amphiphilic and/or hydrophobic character of model extractives was found to be the variable that affected the deposition of extractives on cellulose surfaces and the eventual adsorption of cellulolytic enzymes on it. The observed beneficial effects of extractives are likely related to a reduction in the irreversible binding of the enzymes on the cellulose surface.

Determination of molecular weight distributions in native and pretreated wood.

The analysis of native wood components by size-exclusion chromatography (SEC) is challenging. Isolation, derivatization and solubilization of wood polymers is required prior to the analysis. The present approach allowed the determination of molecular weight distributions of the carbohydrates and of lignin in native and processed woods, without preparative component isolation steps. For the first time a component selective SEC analysis of sawdust preparations was made possible by the combination of two selective derivatization methods, namely; ionic liquid assisted benzoylation of the carbohydrate fraction and acetobromination of the lignin in acetic acid media. These were optimized for wood samples. The developed method was thus used to examine changes in softwood samples after degradative mechanical and/or chemical treatments, such as ball milling, steam explosion, green liquor pulping, and chemical oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). The methodology can also be applied to examine changes in molecular weight and lignin-carbohydrate linkages that occur during wood-based biorefinery operations, such as pretreatments, and enzymatic saccharification.

NIR and Py-mbms coupled with multivariate data analysis as a high-throughput biomass characterization technique: a review.

Optimizing the use of lignocellulosic biomass as the feedstock for renewable energy production is currently being developed globally. Biomass is a complex mixture of cellulose, hemicelluloses, lignins, extractives, and proteins; as well as inorganic salts. Cell wall compositional analysis for biomass characterization is laborious and time consuming. In order to characterize biomass fast and efficiently, several high through-put technologies have been successfully developed. Among them, near infrared spectroscopy (NIR) and pyrolysis-molecular beam mass spectrometry (Py-mbms) are complementary tools and capable of evaluating a large number of raw or modified biomass in a short period of time. NIR shows vibrations associated with specific chemical structures whereas Py-mbms depicts the full range of fragments from the decomposition of biomass. Both NIR vibrations and Py-mbms peaks are assigned to possible chemical functional groups and molecular structures. They provide complementary information of chemical insight of biomaterials. However, it is challenging to interpret the informative results because of the large amount of overlapping bands or decomposition fragments contained in the spectra. In order to improve the efficiency of data analysis, multivariate analysis tools have been adapted to define the significant correlations among data variables, so that the large number of bands/peaks could be replaced by a small number of reconstructed variables representing original variation. Reconstructed data variables are used for sample comparison (principal component analysis) and for building regression models (partial least square regression) between biomass chemical structures and properties of interests. In this review, the important biomass chemical structures measured by NIR and Py-mbms are summarized. The advantages and disadvantages of conventional data analysis methods and multivariate data analysis methods are introduced, compared and evaluated. This review aims to serve as a guide for choosing the most effective data analysis methods for NIR and Py-mbms characterization of biomass.

Development of Langmuir-Schaeffer cellulose nanocrystal monolayers and their interfacial behaviors.

Model cellulose surfaces based on cellulose nanocrystals (CNs) were prepared by the Langmuir-Schaeffer technique. Cellulose nanocrystals were obtained by acid hydrolysis of different natural fibers, producing rodlike nanoparticles with differences in charge density, aspect ratio, and crystallinity. Dioctadecyldimethylammonium bromide (DODA-Br) cationic surfactant was used to create CN-DODA complexes that allowed transfer of the CNs from the air/liquid interface in an aqueous suspension to hydrophobic solid substrates. Langmuir-Schaeffer horizontal deposition at various surface pressures was employed to carry out such particle transfer that resulted in CN monolayers coating the substrate. The morphology and chemical composition of the CN films were characterized by using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). Also, their swelling behavior and stability after treatment with aqueous and alkaline solutions were studied using quartz crystal microgravimetry (QCM). Overall, it is concluded that the Langmuir-Schaeffer method can be used to produce single coating layers of CNs that were shown to be smooth, stable, and strongly attached to the solid support. The packing density of the films was controlled by selecting the right combination of surface pressure during transfer to the solid substrate and the amount of CNs available relative to the cationic charges at the interface.

Biomimetic oxidative treatment of spruce wood studied by pyrolysis-molecular beam mass spectrometry coupled with multivariate analysis and 13C-labeled tetramethylammonium hydroxide thermochemolysis: implications for fungal degradation of wood.

In this work, pyrolysis-molecular beam mass spectrometry analysis coupled with principal components analysis and (13)C-labeled tetramethylammonium hydroxide thermochemolysis were used to study lignin oxidation, depolymerization, and demethylation of spruce wood treated by biomimetic oxidative systems. Neat Fenton and chelator-mediated Fenton reaction (CMFR) systems as well as cellulosic enzyme treatments were used to mimic the nonenzymatic process involved in wood brown-rot biodegradation. The results suggest that compared with enzymatic processes, Fenton-based treatment more readily opens the structure of the lignocellulosic matrix, freeing cellulose fibrils from the matrix. The results demonstrate that, under the current treatment conditions, Fenton and CMFR treatment cause limited demethoxylation of lignin in the insoluble wood residue. However, analysis of a water-extractable fraction revealed considerable soluble lignin residue structures that had undergone side chain oxidation as well as demethoxylation upon CMFR treatment. This research has implications for our understanding of nonenzymatic degradation of wood and the diffusion of CMFR agents in the wood cell wall during fungal degradation processes.

Use of NIR and pyrolysis-MBMS coupled with multivariate analysis for detecting the chemical changes associated with brown-rot biodegradation of spruce wood.

Near infrared (NIR) spectroscopy and pyrolysis-molecular beam mass spectrometry (py-MBMS) analysis can be used in conjunction with multivariate regression and principal components analysis to differentiate brown-rot-degraded wood from non-degraded spruce and to follow the temporal changes in wood undergoing brown-rot degradation. Regression of NIR test results vs. percent weight loss for Postia placenta- and Gloeophyllum trabeum-infected spruce wood blocks yielded a correlation coefficient of 0.96. Regression of MBMS test results for the same samples yielded a correlation coefficient of 0.96. Principle components analysis was used to differentiate non-infected wood and P. placenta- and G. trabeum-infected wood. These techniques may be used to detect different types of biodegradation and to develop a better understanding of the chemical changes that the wood undergoes when it is subjected to brown-rot biodegradation.