Christopher J. Scarlata

Compositional Analysis of Lignocellulosic Feedstocks. 1. Review and Description of Methods

As interest in lignocellulosic biomass feedstocks for conversion into transportation fuels grows, the summative compositional analysis of biomass, or plant-derived material, becomes ever more important. The sulfuric acid hydrolysis of biomass has been used to measure lignin and structural carbohydrate content for more than 100 years. Researchers have applied these methods to measure the lignin and structural carbohydrate contents of woody materials, estimate the nutritional value of animal feed, analyze the dietary fiber content of human food, compare potential biofuels feedstocks, and measure the efficiency of biomass-to-biofuels processes. The purpose of this paper is to review the history and lineage of biomass compositional analysis methods based on a sulfuric acid hydrolysis. These methods have become the de facto procedure for biomass compositional analysis. The paper traces changes to the biomass compositional analysis methods through time to the biomass methods currently used at the National Renewable Energy Laboratory (NREL). The current suite of laboratory analytical procedures (LAPs) offered by NREL is described, including an overview of the procedures and methodologies and some common pitfalls. Suggestions are made for continuing improvement to the suite of analyses.

Compositional Analysis of Lignocellulosic Feedstocks. 2. Method Uncertainties

The most common procedures for characterizing the chemical components of lignocellulosic feedstocks use a two-stage sulfuric acid hydrolysis to fractionate biomass for gravimetric and instrumental analyses. The uncertainty (i.e., dispersion of values from repeated measurement) in the primary data is of general interest to those with technical or financial interests in biomass conversion technology. The composition of a homogenized corn stover feedstock (154 replicate samples in 13 batches, by 7 analysts in 2 laboratories) was measured along with a National Institute of Standards and Technology (NIST) reference sugar cane bagasse, as a control, using this laboratorys suite of laboratory analytical procedures (LAPs). The uncertainty was evaluated by the statistical analysis of these data and is reported as the standard deviation of each component measurement. Censored and uncensored versions of these data sets are reported, as evidence was found for intermittent instrumental and equipment problems. The censored data are believed to represent the “best case” results of these analyses, whereas the uncensored data show how small method changes can strongly affect the uncertainties of these empirical methods. Relative standard deviations (RSD) of 1−3% are reported for glucan, xylan, lignin, extractives, and total component closure with the other minor components showing 4−10% RSD. The standard deviations seen with the corn stover and NIST bagasse materials were similar, which suggests that the uncertainties reported here are due more to the analytical method used than to the specific feedstock type being analyzed.

Compositional Analysis of Water-Soluble Materials in Switchgrass

Any valuation of a potential feedstock for bioprocessing is inherently dependent upon detailed knowledge of its chemical composition. Accepted analytical procedures for compositional analysis of biomass water-soluble extracts currently enable near-quantitative mass closure on a dry weight basis. Techniques developed in conjunction with a previous analytical assessment of corn stover have been applied to assess the composition of water-soluble materials in four representative switchgrass samples. To date, analytical characterization of water-soluble material in switchgrass has resulted in >78% mass closures for all four switchgrass samples, three of which have a mass closure of >85%. Over 30 previously unknown constituents in aqueous extracts of switchgrass were identified and quantified using a variety of chromatographic techniques. Carbohydrates (primarily sucrose, glucose, and fructose) were found to be the predominant water-soluble components of switchgrass, accounting for 18-27% of the dry weight of extractives. Total glycans (monomeric and oligomeric sugars) contributed 25-32% to the dry weight of extractives. Additional constituents contributing to the mass balance for extractives included various alditols (2-3%), organic acids (10-13%), inorganic ions (11-13%), and a distribution of oligomers presumed to represent a diverse mixture of lignin-carbohydrate complexes (30-35%). Switchgrass results are compared with previous analyses of corn stover extracts and presented in the context of their potential impact on biomass processing, feedstock storage, and future analyses of feedstock composition.

Chemicals from Biomass: A Market Assessment of Bioproducts with Near-Term Potential

Production of chemicals from biomass offers a promising opportunity to reduce U.S. dependence on imported oil, as well as to improve the overall economics and sustainability of an integrated biorefinery. Given the increasing momentum toward the deployment and scale-up of bioproducts, this report strives to: (1) summarize near-term potential opportunities for growth in biomass-derived products; (2) identify the production leaders who are actively scaling up these chemical production routes; (3) review the consumers and market champions who are supporting these efforts; (4) understand the key drivers and challenges to move biomass-derived chemicals to market; and (5) evaluate the impact that scale-up of chemical strategies will have on accelerating the production of biofuels.

Development and validation of a fast high pressure liquid chromatography method for the analysis of lignocellulosic biomass hydrolysis and fermentation products.

A simple, precise, and accurate 10-min high pressure liquid chromatography (HPLC) method was developed and validated for the analysis of organic acids, alcohols, and furans from processing biomass into renewable fuels. The method uses an H(+) form cation-exchange resin stationary phase that has a five-fold shorter analysis time versus that in the traditional method. The new method was used for the analysis of acetic acid, ethanol, 5-hydroxymethyl furfural, and furfural. Results were compared with a legacy method that has historically has been used to analyze the same compounds but with a 55 min run time. Linearity was acceptable on the new method with r(2)>0.999 for all compounds using refractive index detection. Limits of detection were between 0.003 and 0.03 g/L and limits of quantification were between 0.1 and 0.01 g/L. The relative standard deviations for precision were less than 0.4% and recoveries ranged from 92% to 114% for all compounds.

Perspectives on Process Analysis for Advanced Biofuel Production

Abstract Numerous approaches to converting lignocellulosic biomass to fuels have been described in the literature. These include technologies to produce ethanol, butanol, biodiesel, lipid-based fuel, aerobic bioprocesses for hydrocarbons, Fischer–Tropsch diesel, upgraded pyrolysis oil, and other methods. The sheer number of conversion technologies and products creates a challenge for policy makers, research organizations, and investors to make sound decisions for how to allocate resources. Fortunately, there are tools available to aid decision-makers when contemplating the tradeoffs that biomass conversion technologies offer, including feasibility studies, social and life-cycle cost-benefit analysis, financial analysis, and techno-economic analysis. This chapter focuses on the engineering aspects of such analyses and how process analysis can reveal the pros and cons of different biomass-to-hydrocarbon fuel technologies.