Omid Hosseinaei

Increasing the revenue from lignocellulosic biomass: Maximizing feedstock utilization

Replacing petroleum by biomass can be economically feasible by generating revenue from the three primary biomass constituents. The production of renewable chemicals and biofuels must be cost- and performance- competitive with petroleum-derived equivalents to be widely accepted by markets and society. We propose a biomass conversion strategy that maximizes the conversion of lignocellulosic biomass (up to 80% of the biomass to useful products) into high-value products that can be commercialized, providing the opportunity for successful translation to an economically viable commercial process. Our fractionation method preserves the value of all three primary components: (i) cellulose, which is converted into dissolving pulp for fibers and chemicals production; (ii) hemicellulose, which is converted into furfural (a building block chemical); and (iii) lignin, which is converted into carbon products (carbon foam, fibers, or battery anodes), together producing revenues of more than

Integrating Separation and Conversion—Conversion of Biorefinery Process Streams to Biobased Chemicals and Fuels

500 per dry metric ton of biomass. Once de-risked, our technology can be extended to produce other renewable chemicals and biofuels.

Effect of hemicellulose extraction on physical and mechanical properties and mold susceptibility of flakeboard.

The concept of the integrated biorefinery is critical to developing a robust biorefining industry in the USA. Within this model, the biorefinery will produce fuel as a high-volume output addressing domestic energy needs and biobased chemical products (high-value organics) as an output providing necessary economic support for fuel production. This paper will overview recent developments within two aspects of the integrated biorefinery—the fractionation of biomass into individual process streams and the subsequent conversion of lignin into chemical products. Solvent-based separation of switchgrass, poplar, and mixed feedstocks is being developed as a biorefinery “front end” and will be described as a function of fractionation conditions. Control over the properties and structure of the individual biomass components (carbohydrates and lignin) can be observed by adjusting the fractionation process. Subsequent conversion of the lignin isolated from this fractionation leads to low molecular weight aromatics from selective chemical oxidation. Together, processes such as these provide examples of foundational technology that will contribute to a robust domestic biorefining industry.

Effects of organosolv fractionation time on thermal and chemical properties of lignins

Hemicellulose is the most hydrophilic polymer of wood, and as a polysaccharide, it has potential applications in conversion to biofuels. The objective of this study was to enhance properties of flakeboard by extracting hemicellulose. Hot-water pretreatment was performed to extract hemicellulose under different temperatures (140°C, 155°C, and 170°C) and times (30 and 60 min). The flakes were blended with 5 percent liquid phenol-formaldehyde resin and 1 percent wax emulsion. The mat was pressed at 200°C for 5 minutes. The physical and mechanical properties and the susceptibility of flakeboard to mold were studied. Panels made from the hemicellulose-extracted flakes showed remarkable decreases in water absorption and thickness swelling without a decrease in mechanical properties. Resistance of the panels to the mold growth also increased with increasing mass loss due to extraction. The most severe condition of extraction (170°C, 60 min), in addition to having the lowest water absorption a...

Improving Processing and Performance of Pure Lignin Carbon Fibers through Hardwood and Herbaceous Lignin Blends

Organosolv fractionation is a promising pathway to separate cellulosic biomass into high purity cellulose, hemicelluloses, and lignin. This work specifically investigates the properties of lignins isolated at specific time points as fractionation progressed, with the intent of correlating fractionation time with lignin purity, yield, thermal and chemical properties. Yellow poplar (Liriodendron tulipifera) was fractionated using a mixture of methyl isobutyl ketone, ethanol, and water with sulfuric acid as catalyst at 140 °C over a two-hour period. Aliquots of the liquor were collected by sampling every 15 min during the fractionation to generate a series of lignins. The results showed that with increased fractionation time, lignin purity improved from 90.3 to 94.6% and the glass transition temperature increased from 117 to 137 °C. The loss of aliphatic OH and increase of phenolic OH with fractionation time led to an increase in condensed structures and increased polydispersity at times greater than 90 min. Principal component analysis of Fourier transform infrared spectroscopic data confirmed the shift to higher purity and more condensed chemical structures with increasing fractionation time. Overall, this study demonstrates that thermal and chemical properties of lignin change with the organosolv fractionation time.

Cellulose nanocrystal (CNC)-based nanocomposites for UV curable high-solid coating systems

Lignin/lignin blends were used to improve fiber spinning, stabilization rates, and properties of lignin-based carbon fibers. Organosolv lignin from Alamo switchgrass (Panicum virgatum) and yellow poplar (Liriodendron tulipifera) were used as blends for making lignin-based carbon fibers. Different ratios of yellow poplar:switchgrass lignin blends were prepared (50:50, 75:25, and 85:15 w/w). Chemical composition and thermal properties of lignin samples were determined. Thermal properties of lignins were analyzed using thermogravimetric analysis and differential scanning calorimetry. Thermal analysis confirmed switchgrass and yellow poplar lignin form miscible blends, as a single glass transition was observed. Lignin fibers were produced via melt-spinning by twin-screw extrusion. Lignin fibers were thermostabilized at different rates and subsequently carbonized. Spinnability of switchgrass lignin markedly improved by blending with yellow poplar lignin. On the other hand, switchgrass lignin significantly improved thermostabilization performance of yellow poplar fibers, preventing fusion of fibers during fast stabilization and improving mechanical properties of fibers. These results suggest a route towards a 100% renewable carbon fiber with significant decrease in production time and improved mechanical performance.

A Fundamental Tandem Mass Spectrometry Study of the Collision‐Activated Dissociation of Small Deprotonated Molecules Related to Lignin

Demand for durable clear wood coatings is on the rise. Cellulose nanocrystals (CNC) constitute an organic nanomaterial widely studied in polymer composites for its reinforcing effect. In this study, CNC was used to enhance the performance of a UV curable high-solid content coating system intended for indoor environments. The CNC surface was modified by a cationic surfactant since the coating system was hydrophobic resin-based requiring hydrophobic nanomaterial reinforcement. Modified CNC was mixed with the coating system using a high-speed mixer and the ultrasonication technique. Mechanical, thermal and morphological properties and curing behavior of the newly developed UV-curing coatings were assessed. Inclusion of CNC in the coating increased the mechanical properties (hardness and reduced modulus) of the coating system to a large extent. Thermal stability of the coating system was also improved by CNC addition. The CNC did not affect the curing behavior of the coating, in contrast to most inorganic nanomaterials. The CNC dispersed well in the matrix at 1% loading. Results of this study show that CNC can be used successfully with high-solid content coating systems.

Mechanical Properties of Secondary Wall and Compound Corner Middle Lamella near the Phenol-Formaldehyde (PF) Adhesive Bond Line Measured by Nanoindentation

The collision-activated fragmentation pathways and reaction mechanisms of 34 deprotonated model compounds representative of lignin degradation products were explored experimentally and computationally. The compounds were evaporated and ionized by using negative-ion mode electrospray ionization doped with NaOH to produce abundant deprotonated molecules. The ions were isolated and subjected to collision-activated dissociation (CAD). Their fragment ions were then isolated and also subjected to CAD. This was repeated until no further fragmentation was observed (up to MS6 ). This approach enabled the identification of characteristic reaction pathways and delineation of reasonable fragmentation mechanisms for deprotonated molecules containing various functional groups. The varying fragmentation patterns observed for different types of compounds allow for the identification of the functionalities in these compounds. This information was utilized to identify the presence of specific functionalities and their combinations in molecules in an organosolv lignin sample.

Effects of nanocrystalline cellulose on the micro-creep properties of phenol formaldehyde resin

To find out the penetration of PF into the wood cell wall and its effects onthe mechanical properties in the cellular level, the elastic modulus and hardness of secondary wall (S2 layer) and compound corner middle lamella (CCML) near PF bond line region were determined by nanoindentation. Compare to the reference cell walls (unaffected by PF), PF penetration into the wood tissues showed improved elastic modulus and hardness. And the mechanical properties decreased slowly with the increasing the distance from the bond line, which are attributed to the effects of PF penetration into S2 layer and CCML. The reduced elastic modulus variations were from18.8 to 14.4 GPa for S2 layer, and from10.1 to 7.65 GPa for CCML. The hardness was from 0.67 to 0.52 GPa for S2 layer, and from 0.65 to 0.52 GPa for CCML. In each test viewpoint place, the average hardness of CCML was almost as high as that of S2 layer, but the reduced elastic modulus was about 50% less than that of S2 layer. But the increase ratio of mechanical properties was close. All the results showed PF penetrates into the CCML. The penetration behavior and penetration depth from bond line were similar in both S2 layer and CCML.

Analysis of gas chromatography/mass spectrometry data for catalytic lignin depolymerization using positive matrix factorization

The use of nanocrystalline cellulose (NCC) has become increasingly prevalent in recent years, with limited studies on the the time-dependent characteristics of wood-adhesive composite reinforced by it. To analyze the viscoelasticity of control phenol formaldehyde (PF) resin and wood-resin composites added with three types of NCC, the micro-creep properties of control phenol formaldehyde (PF) resin and PF resin with cellulose nanofibrils (CNF), cellulose microfibrils (CMF), and cellulose nanocrystals (CNC) were investigated by nanoindentation (NI). The sample creep curves proved that adding CNC, CMF, and CNF into the PF resin remarkably impacted the creep properties of the wood-resin sample interface. The cured resin sample had the lowest strength and the most deformation, and the pure wood sample performed slightly better. Among the three NCC-added wood-resin samples, the CNF-added wood-resin sample has the least deformation in the same load and the least permanent deformation after unloading followed by CMF-added and CNC-added wood-resin samples. In the derivative of creep curve function, the depth tendency of CNC-added and CNF-added wood-resin samples showed a gently increasing slope with time in contrast to CMF-added ones. Furthermore, scanning probe microscopy (SPM) images supported that PF resin had filled up the pores of the wood microstructures and strengthened the wood-resin sample in the company of NCC, which was then able to carry the load.