Catalytic fast pyrolysis (CFP) has emerged as an attractive process for the conversion of lignocellulosic biomass into renewable fuels and products. Considerable research and development has focused on using circulating-bed reactors with zeolite catalysts (e.g., HZSM-5) for CFP because of their propensity to form gasoline-range aromatic hydrocarbons. However, the high selectivity for aromatics comes at the expense of low carbon yield, a key economic driver for this process. In this contribution, we evaluate non-zeolite catalysts in a fixed-bed reactor configuration for an integrated CFP process to produce fuel blendstocks from lignocellulosic biomass. These experimental efforts are coupled with technoeconomic analysis (TEA) to benchmark the process and guide research and development activities to minimize costs. The results indicate that CFP bio-oil can be produced from pine with improved yield by using a bifunctional metal-acid 2 wt% Pt/TiO₂ catalyst in a fixed-bed reactor operated with co-fed H₂ at near atmospheric pressure, as compared to H-ZSM5 in a circulating-bed reactor. The Pt/TiO₂ catalyst exhibited good stability over 13 reaction-regeneration cycles with no evidence of irreversible deactivation. The CFP bio-oil was continuously hydrotreated for 140 h time-on-stream using a single-stage system with 84 wt% of the hydrotreated product having a boiling point in the gasoline and distillate range. This integrated biomass-to-blendstock process was determined to exhibit an energy efficiency of 50% and a carbon efficiency of 38%, based on the experimental results and process modelling. TEA of the integrated process revealed a modelled minimum fuel selling price (MFSP) of $4.34 per gasoline gallon equivalent (GGE), which represents a cost reduction of $0.85 GGE⁻¹ compared to values reported for CFP with a zeolite catalyst. TEA also indicated that catalyst cost was a significant factor influencing the MFSP, which informed additional CFP experiments in which lower-cost Mo₂C and high-dispersion 0.5 wt% Pt/TiO₂ catalysts were synthesized and evaluated. These materials demonstrated CFP carbon yield and oil oxygen content similar to those of the 2 wt% Pt/TiO₂ catalyst, offering proof-of-concept that the lower-cost catalysts can be effective for CFP and providing a route to reduce the modelled MFSP to $3.86–3.91 GGE⁻¹. This report links foundational science and applied engineering to demonstrate the potential of fixed-bed CFP and highlights the impact of coupled TEA to guide research activities towards cost reductions.

A necessary transformation for a sustainable economy is the transition from fossil-derived plastics to polymers derived from biomass and waste resources. While renewable feedstocks can enhance material performance through unique chemical moieties, probing the vast material design space by experiment alone is not practically feasible. Here, we develop a machine-learning-based tool, PolyID, to reduce the design space of renewable feedstocks to enable efficient discovery of performance-advantaged, biobased polymers. PolyID is a multioutput, graph neural network specifically designed to increase accuracy and to enable quantitative structure-property relationship (QSPR) analysis for polymers. It includes a novel domain-of-validity method that was developed and applied to demonstrate how gaps in training data can be filled to improve accuracy. The model was benchmarked with both a 20% held-out subset of the original training data and 22 experimentally synthesized polymers. A mean absolute error for the glass transition temperatures of 19.8 and 26.4 °C was achieved for the test and experimental data sets, respectively. Predictions were made on polymers composed of monomers from four databases that contain biologically accessible small molecules: MetaCyc, MINEs, KEGG, and BiGG. From 1.4 × 10⁶ accessible biobased polymers, we identified five poly(ethylene terephthalate) (PET) analogues with predicted improvements to thermal and transport performance. Experimental validation for one of the PET analogues demonstrated a glass transition temperature between 85 and 112 °C, which is higher than PET and within the predicted range of the PolyID tool. In addition to accurate predictions, we show how the model's predictions are explainable through analysis of individual bond importance for a biobased nylon. Overall, PolyID can aid the biobased polymer practitioner to navigate the vast number of renewable polymers to discover sustainable materials with enhanced performance.

Thermochemical conversion of lignocellulosic biomass is a promising route to produce fuels and oxygenated chemicals and could enable circular carbon utilization. In most thermochemical conversion processes, however, some chemical co-products are lost in aqueous waste streams that are both dilute and heterogeneous. Cost-competitive isolation of these chemical co-products is challenging due to the high-purity requirements typically necessary for bulk chemical production. Here, we demonstrate the production and isolation of two biomass-derived monomers, phenol and catechol, from a comprehensively characterized aqueous waste stream generated via catalytic fast pyrolysis. Specifically, we separate phenol and catechol to 97 wt% purity using the industrially relevant processes of liquid–liquid extraction, distillation, and recrystallization. Techno-economic analysis predicts that a mixed phenolics stream can be produced from the waste stream at a minimum selling price of $1.06 kg⁻¹. Overall, this work demonstrates an approach to high-purity oxygenated aromatic compounds that is potentially economically feasible and technically achievable which increases the atom efficiency of thermochemical conversion through waste stream valorization.

In an attempt to recreate the microenvironment necessary for directed hematopoietic stem cell differentiation, control over the amount of ions available to the cells is necessary. The release of potassium ion and calcium ion via the control of cross-linking density of a poly(2-hydroxyethyl methacrylate) (pHEMA)-based hydrogel containing 1 mol % 2-methacryloyloxyethyl phosphorylcholine (MPC) and 5 mol % oligo(ethylene glycol) (400) monomethacrylate [OEG(400)MA] was investigated. Tetra(ethylene glycol) diacrylate (TEGDA), the cross-linker, was varied over the range of 1–12 mol %. Hydrogel discs (ϕ = 4.5 mm and h = 2.0 mm) were formed by UV polymerization within silicone isolators to contain 1.0 M CaCl₂ and 0.1 M KCl, respectively. Isothermal release profiles, were measured at 37 °C in 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid sodium salt (HEPES) buffer using either calcium ion or potassium ion selective electrodes (ISE). The resulting release profiles were found to be independent of cross-linking density. Average (n = 3) release profiles were fit to five different release models with the Korsmeyer-Peppas equation, a porous media transport model, exhibiting the greatest correlation (R² > 0.95). The diffusion exponent, n was calculated to be 0.24 ± 0.02 and 0.36 ± 0.04 for calcium ion and potassium ion respectively indicating non-Fickian diffusion. The resulting diffusion coefficients were calculated to be 2.6 × 10⁻⁶ and 11.2 × 10⁻⁶ cm²/s, which compare well to literature values of 2.25 × 10⁻⁶ and 19.2 × 10⁻⁶ cm²/s for calcium ion and potassium ion, respectively.