Basic research on the utilization of animal manures as feedstocks to produce value-added products is being undertaken as a cooperative project between Washington State University and PNNL. The products of interest include medium-volume commodity chemicals such as glycols or diols and protein-based products such as chemicals or feed supplements. The research focuses on two aspects of this approach including the analysis and treatment of the feedstock to produce intermediate chemical precursors and the aqueous phase conversion of these intermediates to chemicals and other value-added products.
The PNNL effort has been aimed at determining the necessary process steps to make manure hydrolysates useful as chemical feedstock. Chemical analysis of the hydrolysates was undertaken to identify and quantify sugar products, as well as, contaminants. Intermediate processing steps such as ultra-filtration and activated carbon treatment were applied to evaluate their utility in making the hydrolysates compatible with catalysts. Details: Value-Added Chemicals from Animal Manures (.pdf, 199Kb)
Modified Carbon Supports for Aqueous Phase Catalysis-Applications for the Conversion of Glucose and Fermentation Products to Value-Added Chemicals
PNNL has extensive experience and a leading technical competency in developing novel aqueous phase catalysis processes to convert sugars and organic acids to industrial chemicals. This research project strengthens this competency by adding the fundamental expertise modifying carbon support materials as part of catalyst synthesis. In FY01 this project focused on the use of thermal and chemical treatments to modify the physical and chemical properties of the carbon support material. Thermal treatments influence the pore size distribution of the carbon and allow tailoring of both micro- and meso-pores, while the chemical treatments influence the surface chemistry of the support material and can lead to the formation of acid surface groups, basic surface groups, or neutral functionality on the carbon surface. The carbon support material plays a critical role in the development of highly active catalyst systems and the support is a critical component of the catalyst system, having a significant impact on metal dispersion, metal stability and diffusion.
Advanced Production Of Liquid Fuels From Syn-Gas Derived From Biomass
The objective of this project is to develop novel microtechnology-based processes for producing biomass-derived transportation fuels. Conventional gas to liquid technology is only economically attractive at a large-scale (for example, >200,000Bbl/D), and is suitable for petroleum-derived feedstock. Biomass-derived feedstock, on the other hand, has the nature of small scale. Therefore, we further wish to demonstrate that the processes based on microchannel reactor technology are potentially cost-competitive at the small scale. Three liquid fuel types are being investigated: Fischer-Tropsch (FT) gasoline (.pdf, 3.5Mb); Single reactor sequential synthesis of methanol (MeOH) and dimethylether (DME); and synthesis of higher alcohols, such as ethanol, propanols or butanols. The specifics of the objective include:
- Development of highly active and selective catalysts suitable for microchannel reactors
- Identification and optimization of process conditions unique to the biomass-derived syn-gas
- Development of a highly intensified and cost-effective microchannel-based reactor for syn-gas to fuel conversion
- Analysis of process economics and market based on biomass derive gas-to-liquid processes using microchannel technology
This project has assembled a collection of filamentous fungi from the three major groups of true fungi: Basidiomycota, Ascomycota and Zygomycota. Almost all of the strains in the collection have been screened for organic acid production using a novel high-throughput-screening technique based on the 96 well format. This new technique greatly accelerated the screening of filamentous fungi for organic acid production and shows that many fungi exude organic acids of interest in bioproduct research. Several fungal strains from the PNNL collection produced organic acids of interest at promising concentrations in the absence of contaminating organic acid co-products. These strains are being assessed as candidates for bioprocesses. The fungal culture collection will be queried again for hemicellulase enzyme activity; this second screening will take advantage of new information about the substrate utilization characteristics of the fungi in the collection resulting from the organic acid screening to refine the query for the hemicellulases. Thus, each query of the collection adds valuable information that can be used to increase the speed of subsequent screenings and the likelihood of their success.
In addition, a survey of the diversity of fungi in composts and soils has been initiated with the aim of discovering novel fungi with novel traits, as well as contributing to the scientific community at large through an estimate of the diversity of this large but understudied kingdom. The diversity of fungi in soils was even greater than expected and many of these fungi are "unculturable" or fastidious. The research to date shows that the percentage of "unculturable" fungi is about 70-90%, confirming the hypothesis that the fungal kingdom represents an untapped wealth of microbial diversity. Details: Fungal Discovery (.pdf, 135Kb)
The goal of this research is to understand the parameters necessary to create novel fermentation processes utilizing filamentous fungi and to ensure that laboratory-developed techniques are relevant to industrial processes. The result of this research will be the integrated capability necessary to rapidly develop novel bioprocessing techniques utilizing fungal organisms to convert biomass into industrial and energy products.
Our hypothesis is that discovery and bioprocess research using microorganisms to convert large amounts of biomass derived carbon into valuable products is most efficiently accomplished by initial screening in milliliter volumes in micro-plates, confirmation in shake flasks and then evaluation in laboratory bioreactors. It is necessary to develop basic protocols for using the "bioreactor instruments" that are available for the further study of fungi identified in the Discovery Process or in the Fungal Genetics project. Fungi are extremely diverse, but the major taxonomic groups have similarities so that research on inoculation, biomass estimation, agitation, pH control, foaming and aeration is useful to establish baseline data for process parameters.
In this research the two general types of bioreactors commonly used for commercial bioprocesses, the airlift fermentor and the aerated stirred tank fermentor, are being employed. Fungal organisms from each of the three major taxonomic groups have been evaluated in the bioreactors. A citric acid producing strain of Aspergillus niger was studied. The design research for a process to evaluate engineered strains of A. niger has been completed. Preliminary research on use of the stirred tank bioreactors has been performed using a Zygomycete (Rhizopus), a Basidiomycete (Phanerochaete) and Ascomycetes/Deuteromycetes (Trichoderma and Aspergillus).
Significant modification or reconfiguration of bioreactor vessels and associated hardware is often required to grow filamentous fungi and considerable effort is often required to define the exact process parameters necessary to achieve the optimal production conditions for these organisms. However, once defined, these processes have significant advantages relative to those using common single-cell organisms. New fungi capable of synthesizing desired products and potentially useful at a manufacturing scale should be evaluated in lab-scale bioreactors that simulate the airlift and/or the stirred tank designs. Commercial implementation of a new fungus and new bioprocesses can proceed rapidly if the research has been performed using equipment and procedures that model typical conditions in the production plant. Details: Bioprocess Development (.pdf, 162Kb)
Novel Catalysts and Pathways for Monomers from Carboxylic Acids
PNNL has a leadership position in applying novel aqueous phase catalysis processes to convert sugars and organic acids to industrial chemicals. To expand our aqueous phase catalysis expertise to functionalized carboxylic acids we have chosen to study reactions with glutamic acid and lysine (fermentation products of glucose). The initial work has been directed toward hydrogenation reactions. Under aqueous phase hydrogenation glutamic acid undergoes a dehydrative cyclization to form (S)-(+)-2-pyrollidinone-5-carboxylic acid which is hydrogenated to (S)-(+)-5-hydroxymethyl-2-pyrollidinone. Further reduction leads to (S)-(+)-5-methyl-2-pyrollidinone and 2-pyrollidinone. Deamination products, including 1,5-pentanediol and -valerlactone have also been identified in these reactions. From this work we have identified specific needs for catalyst and process development to be done in FY02 for the development of novel chiral monomers.
The goal of this project is to develop a new process for production of the chemical, 1,3-propanediol (PDO) from agriculturally-derived biomass (glucose). The key objectives are to develop a new fermentation organism and process for the production of malonic acid and then to convert that acid to PDO via a catalyst. The project involves a CRADA partner, the National Corn Growers Association, who provides process economic assessments and commercialization partner integration. Details: 1,3-Propanediol Production via Fermentation-Derived Malonic Acid (.pdf, 101Kb)
Conversion of Biomass Wastes to Levulinic Acid and Derivatives
The Biofine process is projected to economically convert cellulosic biomass feedstock, a renewable resource formerly considered waste material, into levulinic acid. Once limited to high-value specialty applications, this platform chemical can be converted to a variety of other chemicals such as methyl tetrahydrofuran (MTHF), an oxygenated fuel additive that is becoming increasingly important. A process developed and patented by Pacific Northwest National Laboratory should help make MTHF available to the market. Details: Conversion of Biomass Wastes to Levulinic Acid and Derivatives (.pdf, 13Kb)
Pacific Northwest National Laboratory's work on optimizing polyol production from biomass provides improvements in catalysts and processing. Working with International Polyol Chemicals, Inc. (IPCI), researchers developed stabilized catalysts for the IPCI process that converts sugars to polyols. Polyol products (ethylene glycol, propylene glycol, glycerol, and other diols) can be produced from biomass more energy efficiently than the current production from petroleum. The ability to selectively favor the production of a specific polyol product from a platform chemical (in this case, sorbitol) is important in making this process economical in a given market environment. Details: Sorbitol Hydrogenolysis (.pdf, 104Kb)
Production of Chemicals from Biologically Derived Succinic Acid
A new process converts corn into a cost-efficient, environmentally friendly source of the chemicals used to make polymers, clothing fibers, solvents, paints, inks, food additives, automobile bumpers, and an array of other industrial and consumer products. Known as the BDSA (Biologically Derived Succinic Acid) process, it uses a novel microorganism in fermentation and new catalytic technology in the value-added step. Details: Production of Chemicals from Biologically Derived Succinic Acid (.pdf, 118Kb)
Kinetics of Formation of Monosaccharides for Grain Fiber and Related Constituents
This project involved the development of a kinetics measurement system based on the high-frequency carbon-13 nuclear magnetic resonance (NMR) spectrometry capability that exists at PNNL. The project developed and refined the measurement of acid-catalyzed hydrolysis kinetics. It involved both the development of glass pressurized microreactor systems for chemical reactions in aqueous environments and the refinement of the analytical capability of the NMR for complex carbohydrate mixture analysis. In essence, a new capability subset was developed with a specific use in bio-based products, but which can have broad application outside this field.
Aqueous Phase Catalytic Processing
The ultimate success of all pressurized aqueous catalytic conversion processes depends on the ability to develop robust catalysts and supported catalysts that can withstand aggressive hydrothermal reaction conditions. Using powder synthesis and ceramic forming techniques unique to PNNL, ZrO2 supports were synthesized with the required surface area, porosity, mechanical integrity, and chemical stability necessary for this application. In addition, newly emerging schemes for the formation of mesoporous structures from hybrid surfactant templates based on titania and zirconia were used to synthesize next generation supports. Stability of both noble (Ru, Pd, Pt) and base metals (Ni) were evaluated on carbon support materials. Useful candidate catalyst formulations were tested in model reactions to determine stability of the catalyst activity in the aqueous processing environment. Surface analysis techniques were used to evaluate mechanisms of catalyst degradation, as well as catalytic reduction. Details: Aqueous Phase Catalytic Processing (.pdf, 160Kb)
Catalytic Upgrading of C5 Feedstocks to Ethylene and Propylene Glycols
The objective of this project was to develop capabilities and technologies for the conversion of pentose sugars (C5) to value-added products. Primary products from the conversion of pentose sugars are ethylene and propylene glycols. In this project, we developed processing methods for the production of commodity chemicals from C5 feedstocks. The work focused on catalytic hydrogenation and hydrogenolysis for the production of glycols. Chemical analytical methods were developed in order to adequately evaluate the processing experiments. Preliminary economics of the process were also determined for the process. Details: Catalytic Upgrading of C5 Feedstocks to Ethylene and Propylene Glycols (.pdf, 100Kb)
Development of Hydrolysis Processes
This acid hydrolysis project concentrated on evaluating the effect of process conditions on the products of reaction. Acid hydrolysis is envisioned as a front-end "pre-treatment" step to create an appropriate feedstock for enzymatic processing and/or catalytic processing to produce value added products. The "product" streams from the acid hydrolysis process are 1) hydrolysate as a feedstock to enzymatic processing and/or catalytic processing, and 2) filtercake which could potentially be as an upgraded cattle feedstock, feed to enzymatic processing for further breakdown to mainly C-6 sugars, or disposed of as a waste by-product.
The Wheat Milling Byproducts project involves development of an innovative process for the recovery of a glucose product from mill feed, the low-value byproduct of wheat flour milling; and testing of the subsequent processes for conversion of that glucose product solution into a value-added product by either a catalytic or fermentation process.
In this project we worked with lactose product from Hilmar Cheese Company (Hilmar, CA) to demonstrate on the lab scale the processing of the lactose through hydrolysis and catalytic hydrogenation to glycol products and glycerol. The hydrolysis step was performed in cooperation with Applexion Inc. (Rosemont, IL), who developed the hydrolysis technology. The project was funded by the California Dairy Research Foundation. Details: Production of Chemicals from Whey Permeate Lactose (.pdf, 369Kb)