Location: Renewable Product Technology Research
2023 Annual Report
Objectives
The goal of this project is to create new chemical, biochemical, and chemocatalytic processes for economically producing value-added products from biomass, particularly from plant lipids and lignocellulose. Project team members will collaborate within the project, with other ARS researchers, and external partners to reach the following objectives:
Objective 1. Enable biochemical/chemical processes to convert commodity crops, crop oils, and byproducts into value-added commercial bioproducts.
Objective 2. Develop innovative lipid and biopolymer-based encapsulation systems for delivering, preserving, or promoting the activity of bioactive ingredients.
Objective 3. Resolve difficult catalytic processes to produce consumer products and industrial chemicals from crop residue, lignocellulosics, and biorefinery byproducts.
Approach
This research will enhance the economic viability and competitiveness of U.S. agriculture commodities by expanding domestic and global market opportunities associated with the growing bioeconomy through the development of environmentally friendly, value-added food and non-food biobased technologies and products. Plant lipids such as vegetable oil and lecithin are already available in high purity, while lignocellulose is abundant yet chemically complex. To properly exploit these valuable resources, new chemical, biochemical, and chemocatalytic processes must be developed that selectively generate higher value products. The challenge, therefore, centers on finding the most effective chemical, biochemical, and/or chemocatalytic conversion methods, optimizing process reaction conditions for effecting the desired biomass transformations, isolation and purification of the targeted bioproducts, and demonstrating that the bioproducts have equivalent or superior properties to commercially available products.
We have developed several distinctive and innovative approaches to reaching our goal. Our approach involves finding and modifying (in some cases) those catalysts and processes that perform the desired biomass transformation. Biochemical/biocatalytic and chemocatalytic methods will be developed to produce select chemicals from vegetable oils and lignocellulosics. Isolated enzymes will be used to convert lipids and lipid byproducts to consumer-targeted products. Designed multi-layered phospholipids and polysaccharide-based nanoparticles will be used to enhance and deliver bioactive ingredients in food and cosmetics. The sourcing of starting materials from agricultural feedstocks and byproducts in each of these endeavors to find solutions to the barriers that exist in the creation of a biobased economy.
Progress Report
In support of Objective 1, methods for production of feruloyl soy glycerides were improved. Feruloyl soy glycerides are produced commercially for personal care ingredients using ARS technology to modify soybean oil with a natural plant component, called ferulic acid, that has ultraviolet blocking and antioxidant properties. One problem with the commercial process is that only 55–65% of the ferulic acid is incorporated onto the soybean oil molecule, leaving 35–45% of it unreacted. Methods were developed to separate nearly 100% of the unreacted ferulic acid from the final product allowing it to be used in subsequent production runs. This improved production process could save up to 25% in feedstock cost in the commercial production of feruloyl soy glycerides.
In addition, two natural compounds, 1-feruloyl-sn-glycerol (FG) and 1,3-diferuloyl-sn-glycerol (F2G), found in many plants were discovered as byproducts in the commercial production of feruloyl soy glycerides. The discovery of FG and F2G as side products in this process was noteworthy since these compounds have been shown to provide photoprotective and antioxidative protection to pollen and waxy leaves and have the potential to be useful ultraviolet absorbing and antioxidant ingredients in numerous applications. One of the problems with using these types of compounds was the lack of rapid approaches to produce and study these novel products. Methods were developed to optimize the production and purification of these natural compounds, which then provided sufficient product for laboratory characterization. The fluorescence and light absorbing properties of FG and F2G were shown to be an efficient method to distinguish between the two related chemical structures. This technique has potential uses in the cosmeceutical and personal care industries, thereby helping expand the use of these agri-based materials into unconventional markets beyond food, feed and fuel.
In support of Objective 2, progress was made in demonstrating the ability to encapsulate oil-like material within polysaccharide nanoparticles made using ARS technology. Nanoparticles are used throughout the personal skin care, cosmetic, pharmaceutical, and food industries as carriers of desired compounds. There is growing customer demand that these nanoparticles be made from natural ingredients. We have demonstrated that these polysaccharide nanoparticles can encapsulate oil-based feruloyl soy glycerides allowing them to be mixed with water-based solutions. Work is ongoing to further describe the ultraviolet-blocking and antioxidant properties of the encapsulated FSG.
In support of Objective 3, progress was made in the development of new uses for bioethanol to further expand market potential beyond its use as a transportation fuel. Methods were developed to convert ethanol to products used for manufacturing of disinfectants and pharmaceuticals. This was accomplished by using electrical energy and novel agriculturally based catalysts to facilitate the electrochemical conversion reaction and production of desired compounds. This process is potentially advantageous over current methods because the electrical energy to drive the reaction can be derived from renewable resources. Additionally, this technology was utilized to convert a compound derived from corn cobs to a 100% biobased product, which could replace styrene in a variety of applications. Styrene is a petroleum-based chemical that is used extensively in the manufacturing of plastics and rubbers.
New drop-in replacements for petroleum derived chemicals were also produced from biobased butanol. Butanol can be produced fermentatively from agricultural feedstocks, such as corn or biomass. Methods were developed to convert butanol into chemicals that can be used in plastics and personal care products. Work is ongoing to further increase the yield of the desired product.
Accomplishments
1. Efficient production of acetaldehyde from bioethanol for a variety of useful products. Acetaldehyde has many uses in the production of resins, disinfectants, pharmaceuticals, dyes, and solvents, and is typically obtained from petroleum sources. The global market for acetaldehyde was valued at $1.6 billion in 2022 and is expected to expand at a 3.3% annual rate to a market value of $2 billion by 2029. It can be made by the chemical conversion of bioethanol, but reaction efficiencies are typically insufficient for large-scale production. ARS researchers in Peoria, Illinois, developed an improved method that utilizes electrical energy to facilitate the production of acetaldehyde from ethanol. This electrochemical process is an attractive approach because it can rely on renewable energy and provides new markets for ethanol produced from corn. This work will be of benefit to growers and companies in the green chemicals industry.
2. Biobased replacement for petroleum derived 2-ethylhexanol. The chemical, 2-ethylhexanol, which is currently produced from petroleum, has global market size of approximately $6 billion and is widely used in the manufacturing of plastics and personal care products. ARS researchers in Peoria, Illinois, developed an improved method to convert biobutanol, an alcohol produced by fermentation of agricultural feedstocks such as corn or biomass, into the industrially important compound, 2-ethylhexanol. This new technology has the potential to produce 2-ethylhexanol at lower costs compared to other biobutanol conversion methods due to higher productivities and easier product recovery. Synthesizing chemicals from agricultural resources to replace those typically derived from petroleum opens new market opportunities to producers and will help support the growing bioeconomy.
3. Nanoparticle encapsulation system for personal care ingredients from soybean oil. Nanoparticle materials are frequently used as delivery agents of desired compounds, particularly those with limited solubility in water. There is increasing consumer demands that these delivery systems be made of biodegradable materials such as lipids and sugars. The biodegradable nanoparticle market size was valued at $687.5 million in 2021 and is projected to grow to $1.89 billion by 2029. ARS researchers in Peoria, Illinois, have developed a method to utilize polysaccharide nanoparticles made using ARS technology to encapsulate feruloyl soy glycerides (FSG) for applications that require suspending this oil-based product in water solutions. FSG has ultraviolet absorbing and antioxidant properties useful in personal care products. This research will create new, expanded market opportunities for agriculturally based polysaccharides for uses in the pharmaceutical, personal care and agricultural markets.
Review Publications
Kenar, J.A., Compton, D.L., Peterson, S.C., Felker, F.C. 2022. Characterization and properties of starch-dicarboxylic acid inclusion complexes prepared by excess steam jet cooking. Carbohydrate Polymers. 296. Article 119955. https://doi.org/10.1016/j.carbpol.2022.119955.
Vaughn, S.F., Liu, S.X., Berhow, M.A., Moser, J.K., Peterson, S.C., Selling, G.W., Hay, W.T., Jackson, M.A., Skory, C.D. 2023. Production of an odor-reducing, low-dust, clumping cat litter from soybean hulls and soybean hull biochar. Bioresource Technology Reports. 21. Article 101317. https://doi.org/10.1016/j.biteb.2022.101317.
Eller, F.J., Vaughn, S.F., Price, N.P., Kenar, J.A., Jackson, M.A., Berhow, M.A., Brownstein, K.J., Selling, G.W. 2023. Extraction, purification and characterization of an arabinogalactan from frost (riverbank) grape (Vitis riparia michx.) stems. BioResources. 18(3): 4610-4635. https://doi.org/10.15376/biores.18.3.4610-4635.
Selling, G.W., Hay, W.T., Evans, K.O., Peterson, S.C., Utt, K.D. 2023. Improved hydroxypropyl methylcellulose films through incorporation of amylose-N-1-hexadecylammonuium chloride inclusion complexes. Industrial Crops and Products. 194. Article 116352. https://doi.org/10.1016/j.indcrop.2023.116352.
