Ali Hussain Motagamwala

Lignin monomer production integrated into the γ-valerolactone sugar platform

We demonstrate an experimental approach for upgrading lignin that has been isolated from corn stover via biomass fractionation using γ-valerolactone (GVL) as a solvent. This GVL-based approach can be used in parallel with lignin upgrading to produce soluble carbohydrates at high yields (≥70%) from biomass without the use of enzymes, ionic liquids, or concentrated acids. The lignin was isolated after an initial hydrolysis step in which corn stover was treated in a high-solids batch reactor at 393 K for 30 min in a solvent mixture consisting of 80 wt% GVL and 20 wt% water. Lignin was isolated by precipitation in water and characterized by 2D HSQC NMR, showing that the extracted lignin was similar to native lignin, which can be attributed to the low acid level and the low extraction temperatures that are achievable using GVL as a solvent. This lignin was upgraded using a two-stage hydrogenolysis process over a Ru/C catalyst. The isolated lignin was first dissolved to form a mixture of 10% lignin, 80% THF, 8.5% H3PO4 and 1.5% H2O, and treated at 423 K under hydrogen. The THF was removed by evaporation and replaced with heptane, forming a biphasic mixture. This mixture was then treated at 523 K in the presence of Ru/C and H2. The resulting heptane phase contained soluble lignin-derived monomers corresponding to 38% of the carbon in the original lignin. By adding 5% methanol during the second catalytic step, we produced additional monomers containing methyl esters and increased carbon yields to 48%. This increase in yield can be attributed to stabilization of carboxylic acid intermediates by esterification. The yield reported here is comparable to yields obtained with native lignin and is much higher than yields obtained with lignin isolated by other processes. These results suggest that GVL-based biomass fractionation could facilitate the integrated conversion of all three biomass fractions.

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

An engineered solvent system for sugar production from lignocellulosic biomass using biomass derived γ-valerolactone

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

Functionality and molecular weight distribution of red oak lignin before and after pyrolysis and hydrogenation

γ-Valerolactone (GVL) is a biomass-derived solvent which completely solubilizes all fractions of lignocellulosic biomass, leading to the recovery of polysaccharides (cellulose and hemicellulose) as soluble carbohydrates at high yields (>70%) without the use of expensive reagents, like enzymes and ionic liquids. Biological upgrading of carbohydrates to biofuels or bio-based chemicals requires that the carbohydrates are separated from GVL. We demonstrate that an engineered solvent system consisting of GVL, water and an organic co-solvent is mono-phasic at the temperatures used for biomass fractionation (e.g., 160 °C) and is bi-phasic at lower temperatures (e.g., room temperature). The advantage of using this engineered solvent system is that the carbohydrates are spontaneously separated from organic solvent components into an aqueous hydrolysate stream, thereby avoiding the need for expensive and potentially hazardous separation processes, such as operation at elevated pressures required for separation using liquid CO2. We also show that the organic co-solvent can be selected from an array of organic components, leading to a trade-off between the efficacy of carbohydrate separation and the ‘greenness’ of the solvent. We show further that toluene is a promising co-solvent component, and techno-economic analyses of the process, wherein toluene is used as a co-solvent, lead to a minimum selling price of ethanol of

Analysis of reaction schemes using maximum rates of constituent steps

3.10 per gallon of gasoline equivalent.

Toward biomass-derived renewable plastics: Production of 2,5-furandicarboxylic acid from fructose

Three red oak derived lignin samples: 1. lignin extracted from red oak chips using γ-valerolactone (GVL lignin), 2. lignin extracted from the pyrolysis oil of red oak chips by fractionation and water extraction (pyrolytic lignin) and 3. pyrolytic lignin hydrogenated over Ru/C (hydrogenated pyrolytic lignin), were analyzed by FT-ICR MS, NMR, and GPC. More than 1100 distinct molecular weights were observed by FT-ICR MS of the lignin streams while changes in the O/C and H/C ratios suggested the dehydration of hydroxylated sidechains from pyrolysis and partial saturation of the compounds from hydrogenation. The relative average molecular weight of the lignin determined by GPC decreased five-fold after pyrolysis. Quantitative 13C, HSQC, and HMBC NMR revealed a decrease in the C–O aliphatics from pyrolysis potentially forming alkane, alkene, and carbonyl functionalities. The aldehydes and ketones were highly reactive during hydrogenation and may potentially be responsible for coke formation.

A co-solvent hydrolysis strategy for the production of biofuels: process synthesis and technoeconomic analysis

Significance The design of active and selective catalysts is essential for a wide range of industrial applications and societal issues. A fundamental approach is to identify the key elementary steps and to elucidate the predicted reaction kinetics for potential reaction mechanisms. We present a methodology to analyze analytically the performance of catalytic reaction schemes by calculation of the maximum rates of the constituent steps. This proposed methodology can be used to identify the important transition states and adsorbed species, such that more detailed calculations can be carried out for these species, whereas more approximate methods can be used for the remaining species, thereby substantially reducing the computational time required to elucidate how catalyst performance is controlled by the fundamental surface chemistry. We show that the steady-state kinetics of a chemical reaction can be analyzed analytically in terms of proposed reaction schemes composed of series of steps with stoichiometric numbers equal to unity by calculating the maximum rates of the constituent steps, rmax,i, assuming that all of the remaining steps are quasi-equilibrated. Analytical expressions can be derived in terms of rmax,i to calculate degrees of rate control for each step to determine the extent to which each step controls the rate of the overall stoichiometric reaction. The values of rmax,i can be used to predict the rate of the overall stoichiometric reaction, making it possible to estimate the observed reaction kinetics. This approach can be used for catalytic reactions to identify transition states and adsorbed species that are important in controlling catalyst performance, such that detailed calculations using electronic structure calculations (e.g., density functional theory) can be carried out for these species, whereas more approximate methods (e.g., scaling relations) are used for the remaining species. This approach to assess the feasibility of proposed reaction schemes is exact for reaction schemes where the stoichiometric coefficients of the constituent steps are equal to unity and the most abundant adsorbed species are in quasi-equilibrium with the gas phase and can be used in an approximate manner to probe the performance of more general reaction schemes, followed by more detailed analyses using full microkinetic models to determine the surface coverages by adsorbed species and the degrees of rate control of the elementary steps.

Microkinetic Analysis and Scaling Relations for Catalyst Design

A process for converting fructose to 2,5-furandicarboxylic acid, a monomer used in the production of a renewable plastics. We report a process for converting fructose, at a high concentration (15 weight %), to 2,5-furandicarboxylic acid (FDCA), a monomer used in the production of polyethylene furanoate, a renewable plastic. In our process, fructose is dehydrated to hydroxymethylfurfural (HMF) at high yields (70%) using a γ-valerolactone (GVL)/H2O solvent system. HMF is subsequently oxidized to FDCA over a Pt/C catalyst with 93% yield. The advantage of our system is the higher solubility of FDCA in GVL/H2O, which allows oxidation at high concentrations using a heterogeneous catalyst that eliminates the need for a homogeneous base. In addition, FDCA can be separated from the GVL/H2O solvent system by crystallization to obtain >99% pure FDCA. Our process eliminates the use of corrosive acids, because FDCA is an effective catalyst for fructose dehydration, leading to improved economic and environmental impact of the process. Our techno-economic model indicates that the overall process is economically competitive with current terephthalic acid processes.

An “ideal lignin” facilitates full biomass utilization

We develop an integrated strategy for the production of ethanol from lignocellulosic biomass. Cellulose and hemicellulose fractions are first hydrolyzed into sugars using a mixture of γ-valerolactone (GVL), water, and toluene as a solvent containing dilute sulfuric acid as a catalyst, and the sugars are then co-fermented into ethanol over engineered yeast strains. Separation subsystems are designed to effectively recover GVL and toluene for reuse in biomass hydrolysis and to recover lignin and humins for heat and power generation. We also develop an alternative process, in which we recover sugars and GVL from the residual biomass. To minimize utility requirements, we conduct heat integration, which allows us to meet all heating requirements using biomass residues. Finally, we perform a range of system-level analyses to identify the major cost and technological drivers. The proposed strategy is shown to be cost-competitive with other strategies.

Enhanced Furfural Yields from Xylose Dehydration in the γ-Valerolactone/Water Solvent System at Elevated Temperatures

Microkinetic analysis plays an important role in catalyst design because it provides insight into the fundamental surface chemistry that controls catalyst performance. In this review, we summarize the development of microkinetic models and the inclusion of scaling relationships in these models. We discuss the importance of achieving stoichiometric and thermodynamic consistency in developing microkinetic models. We also outline how analysis of the maximum rates of elementary steps can be used to determine which transition states and adsorbed intermediates are kinetically significant, allowing the derivation of general reaction kinetics rate expressions in terms of changes in binding energies of the relevant transition states and intermediates. Through these analyses, we present how to predict optimal surface coverages and binding energies of adsorbed species, as well as the extent of potential rate improvement for a catalytic system. For systems in which the extent of potential rate improvement is small because of limitations imposed by scaling relations, different approaches, including the addition of promoters and formation of catalysts containing multiple functionalities, can be used to break the scaling relations and obtain further rate enhancement.