Daniel M. Santosa

A Review and Perspective of Recent Bio-Oil Hydrotreating Research

The pathway for catalytic hydrodeoxygenation (HDO) of biomass-derived fast pyrolysis oil represents a compelling route for production of liquid transportation fuels. This is a review of the published research and patent literature in bio-oil HDO over the last 6 years performed with actual bio-oils and identifiable strategy for production of an infrastructure compatible liquid transportation fuel. Research is moving towards continuous, industrially relevant processes generating data to inform techno-economic analysis (TEA) and understand the nature of the fuels produced. Research gaps identified include: (1) focus on process integration; (2) developing appropriate quality metrics for intermediates; (3) evaluating research by TEA; and (4) meeting fuel functional requirements and comparison to ASTM standards for existing fuels.

Impact of thermal pretreatment on the fast pyrolysis conversion of southern pine

Background: Thermal pretreatment of biomass ranges from simple (nondestructive) drying to more severe treatments that cause devolatization, depolymerization and carbonization. These pretreatments have demonstrated promise for transforming raw biomass into feedstock material that has improved milling, handling, storage and conversion properties. In this work, southern pine material was pretreated at 120, 180, 230 and 270°C, and then subjected to pyrolysis tests in a continuous-feed bubbling-fluid bed pyrolysis system. Results: High pretreatment temperatures were associated with lower specific grinding energies, higher grinding rates and lower hydrogen and oxygen contents. Higher pretreatment temperatures were also correlated with increased char production, decreased total acid number and slight decrease in the oxygen content of the pyrolysis liquid fraction. Conclusion: Thermal pretreatment has both beneficial and detrimental impacts on fast pyrolysis conversion of pine material to bio-oil, and the effect of thermal pretreatment on upgrading of pyrolysis bio-oil requires further attention.

A survey of Opportunities for Microbial Conversion of Biomass to Hydrocarbon Compatible Fuels

Biomass is uniquely able to supply renewable and sustainable liquid transportation fuels. In the near term, the Biomass program has a 2012 goal of cost competitive cellulosic ethanol. However, beyond 2012, there will be an increasing need to provide liquid transportation fuels that are more compatible with the existing infrastructure and can supply fuel into all transportation sectors, including aviation and heavy road transport. Microbial organisms are capable of producing a wide variety of fuel and fuel precursors such as higher alcohols, ethers, esters, fatty acids, alkenes and alkanes. This report surveys liquid fuels and fuel precurors that can be produced from microbial processes, but are not yet ready for commercialization using cellulosic feedstocks. Organisms, current research and commercial activities, and economics are addressed. Significant improvements to yields and process intensification are needed to make these routes economic. Specifically, high productivity, titer and efficient conversion are the key factors for success.

Catalytic Hydrothermal Gasification of Lignin-Rich Biorefinery Residues and Algae Final Report

This report describes the results of the work performed by PNNL using feedstock materials provided by the National Renewable Energy Laboratory, KL Energy and Lignol lignocellulosic ethanol pilot plants. Test results with algae feedstocks provided by Genifuel, which provided in-kind cost share to the project, are also included. The work conducted during this project involved developing and demonstrating on the bench-scale process technology at PNNL for catalytic hydrothermal gasification of lignin-rich biorefinery residues and algae. A technoeconomic assessment evaluated the use of the technology for energy recovery in a lignocellulosic ethanol plant.

Driving towards cost-competitive biofuels through catalytic fast pyrolysis by rethinking catalyst selection and reactor configuration

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

Fast Pyrolysis Conversion Tests of Forest Concepts' Crumbles™. Final Report

4.34 per gasoline gallon equivalent (GGE), which represents a cost reduction of

Final Project Report Project 10749-4.2.2.1 2007-2009

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

Field-to-Fuel Performance Testing of Lignocellulosic Feedstocks: An Integrated Study of the Fast Pyrolysis–Hydrotreating Pathway

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.

Pyrolysis of Woody Residue Feedstocks: Upgrading of Bio-oils from Mountain-Pine-Beetle-Killed Trees and Hog Fuel

The report describes the work done by PNNL on assessing Forest Concepts engineered feedstock using the bench-scale continuous fast pyrolysis system to produce liquid bio-oil, char and gas. Specifically, bio-oil from the following process were evaluated for its yield and quality to determine impact of varying feed size parameters. Furthermore, the report also describes the handling process of the biomass and the challenges of operating the system with above average particle size.

Red Mud Catalytic Pyrolysis of Pinyon Juniper and Single-Stage Hydrotreatment of Oils

This is the final report for the DOE Project 10749-4.2.2.1 for the FY2007 - FY2009 period. This report is non-proprietary, and will be submitted to DOE as a final project report. The report covers activities under the DOE Project inside CRADA 269 (Project 53231) as well as project activites outside of that CRADA (Project 56662). This is the final report that is summarized from the non-proprietary quarterlies submitted to DOE over the past 2.5 years, which in turn are summaries from the proprietary technical reporting to UOP.