How chip size impacts steam pretreatment effectiveness for biological conversion of poplar wood into fermentable sugars

Background Woody biomass is highly recalcitrant to enzymatic sugar release and often requires significant size reduction and severe pretreatments to achieve economically viable sugar yields in biological production of sustainable fuels and chemicals. However, because mechanical size reduction of woody biomass can consume significant amounts of energy, it is desirable to minimize size reduction and instead pretreat larger wood chips prior to biological conversion. To date, however, most laboratory research has been performed on materials that are significantly smaller than applicable in a commercial setting. As a result, there is a limited understanding of the effects that larger biomass particle size has on the effectiveness of steam explosion pretreatment and subsequent enzymatic hydrolysis of wood chips. Results To address these concerns, novel downscaled analysis and high throughput pretreatment and hydrolysis (HTPH) were applied to examine whether differences exist in the composition and digestibility within a single pretreated wood chip due to heterogeneous pretreatment across its thickness. Heat transfer modeling, Simons’ stain testing, magnetic resonance imaging (MRI), and scanning electron microscopy (SEM) were applied to probe the effects of pretreatment within and between pretreated wood samples to shed light on potential causes of variation, pointing to enzyme accessibility (i.e., pore size) distribution being a key factor dictating enzyme digestibility in these samples. Application of these techniques demonstrated that the effectiveness of pretreatment of Populus tremuloides can vary substantially over the chip thickness at short pretreatment times, resulting in spatial digestibility effects and overall lower sugar yields in subsequent enzymatic hydrolysis. Conclusions These results indicate that rapid decompression pretreatments (e.g., steam explosion) that specifically alter accessibility at lower temperature conditions are well suited for larger wood chips due to the non-uniformity in temperature and digestibility profiles that can result from high temperature and short pretreatment times. Furthermore, this study also demonstrated that wood chips were hydrated primarily through the natural pore structure during pretreatment, suggesting that preserving the natural grain and transport systems in wood during storage and chipping processes could likely promote pretreatment efficacy and uniformity

Constellation Modelling, Performance Prediction and Operations Management for the Spire Constellation

The operational complexity of managing the Spire constellation continually increases with the routine introduction of additional satellites and new capabilities. The heterogeneous nature of the satellites, payloads, and ground station configurations compounds the difficulty of strategic planning and operational scheduling. In order to efficiently operate this diverse network of assets, Spire developed a suite of bespoke constellation modeling and management tools that are designed to support existing demand and to scale for future needs. The modeling tools enable Spire to accurately simulate and optimize the performance of various constellation configurations prior to deployment. The operational tools required to harness the full potential of the constellation incorporate complex techniques in order to schedule payload operations, maximize data collection, and monitor performance. These tools are developed in a modular and scalable fashion to ensure that new capabilities, such as the introduction of inter-satellite links, can be readily integrated into the planning system. In addition to these internal tools, Spire also offers a suite of standardized APIs and user services through which both internal and external customers can seamlessly integrate payloads and software with the Spire constellation, enabling secure access to development and simulation environments, scheduling, and data pipeline tools. The constellation modeling, performance prediction, and operational management tools developed at Spire are essential to ensure efficient and optimized production in an increasingly complex system

Evaluating lignin valorization via pyrolysis and vapor-phase hydrodeoxygenation for production of aromatics and alkenes

Lignin valorization to chemicals is an important component of creating economically viable biofuels production from lignocellulosic biomass. Any such strategy should aim at producing chemicals used at scales that can appropriately match lignin availability. Herein, a combined pyrolysis and low-pressure hydrodeoxygenation (HDO) process configuration is proposed to achieve total oxygen removal and obtain hydrocarbon (aromatic and alkene) products. This approach is tested for its robustness for lignin feedstocks obtained from a variety of sources and extracted using different procedures. The experimental results demonstrate that regardless of the lignin source, the HDO process using a MoO3 catalyst was able to funnel the complex mixture of pyrolysis vapors to mono-aromatics (17–29 C%), as well as alkenes and alkanes. The formation of char from lignin pyrolysis retains more than 50% of the feed carbon in the pyrolyzer, allowing only a portion of carbon to volatilize and be converted to products. A partial depolymerization technique is employed on one of the lignin samples prior to pyrolysis as an example of how the amount of char can be drastically reduced leading to an increased yield of aromatics (53–55 C%). Techno-economic analysis based on the experimental results suggest significant economic benefit of this strategy compared to using lignin as simply a boiler feed

Correlated mechanochemical maps of Arabidopsis thaliana primary cell walls using atomic force microscope infrared spectroscopy

Spatial heterogeneity in composition and organisation of the primary cell wall affects the mechanics of cellular morphogenesis. However, directly correlating cell wall composition, organisation and mechanics has been challenging. To overcome this barrier, we applied atomic force microscopy coupled with infrared (AFM-IR) spectroscopy to generate spatially correlated maps of chemical and mechanical properties for paraformaldehyde-fixed, intact Arabidopsis thaliana epidermal cell walls. AFM-IR spectra were deconvoluted by non-negative matrix factorisation (NMF) into a linear combination of IR spectral factors representing sets of chemical groups comprising different cell wall components. This approach enables quantification of chemical composition from IR spectral signatures and visualisation of chemical heterogeneity at nanometer resolution. Cross-correlation analysis of the spatial distribution of NMFs and mechanical properties suggests that the carbohydrate composition of cell wall junctions correlates with increased local stiffness. Together, our work establishes new methodology to use AFM-IR for the mechanochemical analysis of intact plant primary cell walls

Cyclic, tethered and nanoparticulate silicones for material modification

I have examined three different topological forms of a material modifier. The modifier is silicone and the three topological forms are cyclic, linear tethers and networked siloxane bonds in the form of a nanoparticulate. Often silicones, or siloxanes, are added to a material because of its unique properties that are related to its inorganic or inorganic-organic hybrid character. This dissertation addresses either the synthesis of silicones for material modification or the effect of the adding silicones to a variety of substrates and polymeric systems. Chapters 2 and 3 present research focused on the first topological form, cyclic PDMS. The synthesis of cyclic polymers is very important to the synthesis and subsequent characterization of cyclic containing multi-component materials. Cyclic PDMS is formed via ring-chain depolymerization and bimolecular coupling and the unique issues associated with the formation, purification and analysis of cyclic polymer topologies. The goal of the work described in these chapters was to find a straightforward high-yield route to form large cycles of PDMS in a relatively high purity. Chapter 4 focuses on the modification of the next topological form, linear polymers as tethers for surface modification and presents a novel concept for surface-modifying compounds; the incorporation of an ionic-reactive functionality into PDMS is presented. The idea being its ionic character will increase affinity for the surface, surface coverage and levelness, while the subsequent reactive fixation will permanently modify the surface to improve retention and fastness. The use of such chemistry has not been applied for surface modification protocols. Chapters 5, 6 and 7 discuss the characterization of systems with the third topological form incorporated. They include differences in the viscoelastic behavior of PVAc/silica nanocomposites and the neat PVAc matrix, relating those differences to polymer dynamics and structure as determined by several solid-state NMR experiments. The latter two chapters pertain to PVAc/silica nanocomposites with PDMS surface treatments. Specifically, evaluating how polymer dynamics and structure changes particularly at the interfaceinterphase with various PDMS surface treatments having different topologies at the surface.Ph.D.Committee Chair: Dr. Haskell W. Beckham; Committee Member: Dr. Anselm Griffin; Committee Member: Dr. Johannes Leisen; Committee Member: Dr. Sankar Nair; Committee Member: Dr. Uwe Bun

Cellulose Isolation Methodology for NMR Analysis of Cellulose Ultrastructure

In order to obtain accurate information about the ultrastructure of cellulose from native biomass by 13C cross polarization magic angle spinning (CP/MAS) NMR spectroscopy the cellulose component must be isolated due to overlapping resonances from both lignin and hemicellulose. Typically, cellulose isolation has been achieved via holocellulose pulping to remove lignin followed by an acid hydrolysis procedure to remove the hemicellulose components. Using 13C CP/MAS NMR and non-linear line-fitting of the cellulose C4 region, it was observed that the standard acid hydrolysis procedure caused an apparent increase in crystallinity of ~10% or less on the cellulose isolated from Populus holocellulose. We have examined the effect of the cellulose isolation method, particularly the acid treatment time for hemicellulose removal, on cellulose ultrastructural characteristics by studying these effects on cotton, microcrystalline cellulose (MCC) and holocellulose pulped Populus. 13C CP/MAS NMR of MCC indicated that holocellulose pulping and acid hydrolysis has little effect on the crystalline ultrastructural components of cellulose. Although any chemical method to isolate cellulose from native biomass will invariably alter substrate characteristics, especially those related to regions accessible to solvents, we found those changes to be minimal and consistent in samples of typical crystallinity and lignin/hemicellulose content. Based on the rate of the hemicellulose removal, as determined by HPLC-carbohydrate analysis and magnitude of cellulose ultrastructural alteration, the most suitable cellulose isolation methodology utilizes a treatment of 2.5 M HCl at 100 °C for a standard residence time between 1.5 and 4 h. However, for the most accurate crystallinity results this residence time should be determined empirically for a particular sample

Cellulose Isolation Methodology for NMR Analysis of Cellulose Ultrastructure

In order to obtain accurate information about the ultrastructure of cellulose from native biomass by 13C cross polarization magic angle spinning (CP/MAS) NMR spectroscopy the cellulose component must be isolated due to overlapping resonances from both lignin and hemicellulose. Typically, cellulose isolation has been achieved via holocellulose pulping to remove lignin followed by an acid hydrolysis procedure to remove the hemicellulose components. Using 13C CP/MAS NMR and non-linear line-fitting of the cellulose C4 region, it was observed that the standard acid hydrolysis procedure caused an apparent increase in crystallinity of ~10% or less on the cellulose isolated from Populus holocellulose. We have examined the effect of the cellulose isolation method, particularly the acid treatment time for hemicellulose removal, on cellulose ultrastructural characteristics by studying these effects on cotton, microcrystalline cellulose (MCC) and holocellulose pulped Populus. 13C CP/MAS NMR of MCC indicated that holocellulose pulping and acid hydrolysis has little effect on the crystalline ultrastructural components of cellulose. Although any chemical method to isolate cellulose from native biomass will invariably alter substrate characteristics, especially those related to regions accessible to solvents, we found those changes to be minimal and consistent in samples of typical crystallinity and lignin/hemicellulose content. Based on the rate of the hemicellulose removal, as determined by HPLC-carbohydrate analysis and magnitude of cellulose ultrastructural alteration, the most suitable cellulose isolation methodology utilizes a treatment of 2.5 M HCl at 100 °C for a standard residence time between 1.5 and 4 h. However, for the most accurate crystallinity results this residence time should be determined empirically for a particular sample