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PNNL-13501 - Pacific Northwest National Laboratory

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Study Control Number: PN99070/1398<br />

Fiber Hydrolysis Capability Development (a)<br />

James A. Franz, Todd A. Werpy, Douglas C. Elliott<br />

Vast U.S. resources of low-cost sugars from agricultural-derived products and byproducts are readily available for<br />

conversion to chemicals, fuels, and neutraceuticals. In particlar, the fiber byproducts of corn processing that are currently<br />

used as livestock feed are a major potential source of sugars, and the fiber-derived oils are also potential sources of<br />

important nutraceutical substances, such as cholesterol-reducing sitosterols and tocopherols. Efficient extraction of<br />

sugars and neutraceuticals from grain fiber will have significant economic impact to U.S. agriculture and will make<br />

available substantial amounts of new feedstock for fuels and chemical production. Developing new approaches to<br />

selective sugar and neutraceuticals extraction from fiber requires use of modern approaches in structural chemistry and<br />

kinetics. This project applies modern kinetic and spectroscopic methods to develop new sugar and oil separation methods<br />

that will enable use of a substantial fraction of corn fiber produced by U.S. agriculture and will result in improved<br />

economics for biomass-derived chemicals and fuels.<br />

Project Description<br />

New processing capabilities will be supported by the<br />

development of hydrolysis process information for use in<br />

the production of value-added products from agriculturalderived<br />

feedstocks. The processing capability will be<br />

based upon laboratory testing, including chemical<br />

mechanisms and chemical analytical procedure<br />

development, that was conducted as part of this project.<br />

The project used liquid and solid-state nuclear magnetic<br />

resonance spectroscopy and chromatographic methods to<br />

determine hydrolysis kinetics of cellulose, hemicellulose,<br />

oligermic sugars, and starch with specific feedstock<br />

targets of corn fiber and wheat shorts. Further, a method<br />

was developed for detecting components in oil fractions<br />

of grain fiber hydrolysate products. Procedures for the<br />

measurement of tocopherols and related lipid-like<br />

components were developed and applied to assess<br />

conditions for separation of fiber components.<br />

Introduction<br />

This project examined kinetics of sugar production from<br />

corn fiber and related materials. Potential economic<br />

benefits to be derived from a detailed understanding of<br />

fiber hydrolysis kinetics included<br />

• reduced sugar cost (by as much as 75%) by enabling<br />

use of abundant, low-cost biomass feedstocks<br />

• tailored feedstock streams for each application based<br />

on 5- and 6-carbon sugars<br />

• reduced overall cost of fermentation and catalysis<br />

products.<br />

The identified benefits for DOE include a strong<br />

understanding of hydrolysis and an expanded capability in<br />

processing biomass-derived feedstocks.<br />

Approach<br />

We previously characterized oligomeric and<br />

monosaccharide sugars derived from corn fiber. In that<br />

project, sugar production from batch autoclave hydrolysis<br />

experiments at a variety of temperatures and acidities was<br />

examined. Because of limitations in heating rates and<br />

contact times with the batch (as opposed to flow reactor)<br />

equipment available, results were basically limited to long<br />

exposure times that resulted in substantial conversion to<br />

unwanted sugar dehydration products. Nevertheless, the<br />

study identified major sugar decomposition products and<br />

identified upper limits of conditions for fiber processing.<br />

In order to provide realistic processing data, an improved<br />

kinetic procedure was needed to develop accurate time<br />

profiles for sugar production. Initial scouting studies<br />

were carried out on model disaccharide compounds and<br />

complete kinetic hydrolysis curves were derived for the<br />

model compounds. Several different acids and conditions<br />

were tested to evaluate the kinetics.<br />

(a) Project started in FY 1999 as a task under the project entitled, “Sustainable Production of Value Added Chemicals and Products/Fiber<br />

Hydrolysis.”<br />

Separations and Conversions 421

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