Source: UNIV OF WISCONSIN submitted to
DRIED DISTILLER GRAIN BASED POLYMER DISPERSIONS FOR PAPER COATINGS
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
NEW
Funding Source
Reporting Frequency
Annual
Accession No.
0231720
Grant No.
2013-38202-20400
Project No.
WIS01690
Proposal No.
2012-04010
Multistate No.
(N/A)
Program Code
MM.2
Project Start Date
Jan 1, 2013
Project End Date
Dec 31, 2015
Grant Year
2013
Project Director
RUNGE, T.
Recipient Organization
UNIV OF WISCONSIN
21 N PARK ST STE 6401
MADISON,WI 53715-1218
Performing Department
Biological Systems Engineering
Non Technical Summary
Corn ethanol facilities face ongoing financial challenges in the future, with rising input prices for grain and energy and reduced subsidies for the ethanol product. To maintain the vitality of these operations, research into additional revenue streams from by-products is needed. This research will investigate producing a renewable chemical stream from the distillers' dried grains with solubles (DDGS) stream, a by-products of the ethanol production process that are currently used for animal feed. Beyond the protein and oils, these materials are also rich in hemicellulose (xylose and arabinose) which have lower feed value, which could be extracted with minimal damage to the remaining DDGS feed product. Unlike starch or cellulose, hetergeneous hemicelluloses are currently underutilized in most biomass processing operations, which is a trend that is expected to continue with cellulosic biofuel processing operations. The chemical structure of corn grain hemicellulose suggests its use as a paper coating or sizing polymer. The hydroxyl rich polymer is hydrophilic enough to have a low contact angle phases, allowing good wettability of inks, whereas the ferulic acid content assists in plasticizing the polymer to create a pliable film. Unfortunately, due to the viscosity difficulties in handling aqueous solutions of hemicellulose, petroleum based systems that can be easily turned into high solids emulsions or dispersions are more common. This research will seek to remedy this by developing a process to produce stable dispersions out of extracted hemicelluloses and their derivatives for paper coatings. Additionally, the environmental impact of these coatings to traditional polyvinyl alcohol coatings will be analyzed using a lifecycle analysis. Specifically the research will: (1) develop high-solids, low viscosity dispersions of the extracted hemicellulose polymer and (2) compare the environmental impact of utilizing this renewable biomaterial as compared to traditional petroleum based materials. After this development, we will work with industrial partners to commercialize materials for use in paper coatings.
Animal Health Component
25%
Research Effort Categories
Basic
(N/A)
Applied
25%
Developmental
75%
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
51115102000100%
Knowledge Area
511 - New and Improved Non-Food Products and Processes;

Subject Of Investigation
1510 - Corn;

Field Of Science
2000 - Chemistry;
Goals / Objectives
The proposed research will close the technical gaps to allow extracted hemicellulose to be used as a paper coating and quantify the sustainability impact as compared to petroleum based coatings. Specifically the research will: (1) develop high-solids, low viscosity dispersions of the extracted hemicellulose polymer and (2)Compare the environmental impact of utilizing this renewable biomaterial as compared to traditional petroleum based materials. To accomplish this, the project has five specific objectives including: (1)Creation and characterization of extracted hemicellulose from a variety of wood and pulp samples varying extraction conditions; (2) Modification of the extracted hemicellulose barrier properties through chemical derivatization; (3)Development of high-solids, low-viscosity dispersions of the extracted and derivatized materials; (4)Evaluation of the hemicellulose dispersion products as a paper coating utilizing cast film and paper coating experiments; (5) Determination of the paper coating chemical's environmental impact through lifecycle assessment.
Project Methods
Several DDGS samples representing typical conditions will be collected at the beginning of the research, dried and cold stored to prevent deterioration. The samples and subsequent extracted samples will be measured for protein according to AOAC method 990.03; fat by AOAC method 920.39, ash by AOAC method 942.05, and saccharides by ion chromatography with a pulsed amperometric detector after acid hydrolysis. A range of alkaline extraction conditions will be used to extract hemicelluloses and the resulting extracted material will be characterized to identify the best candidates for paper coatings. The extracted materials will be purified using ethanol as the precipitating agent. Next, the leading process conditions for the extraction and purification will be scaled up to allow ample material for the subsequent dispersion and coating work. The dispersion experiments will consist of using a thermo/mechanical process to create a hemicellulose based polymer dispersions using natural fatty acids as dispersion aids. The dispersions will be characterized for their polymer properties and used to create paper and wood composites which will be assessed for their physical properties. The paper coatings will be produced, applied, tested, and recycled at small-batch scales that will provide life cycle inventory data for coating-unique stages of the paper coating life cycle. These life cycle results will then be used to compare against the environmental impacts of traditional polyvinyl alcohol binder and the hemicellulose-based polymer dispersion products.

Progress 01/01/13 to 12/31/13

Outputs
Target Audience: We have reached the technical audience through our articles and conferenc presentations. Additionally, we have provided several updates to our industrial partners Didion Inc (Cambria, WI) and Appleton (Appleton WI) who are interested in potential commercialization of the products. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Wehave hired one graduate and one post-doctoral student and have trained them in both the science of the project as well as mentored them on professional development. Additionally, we have an undergraduate student supported through the Great Lakes Bioenergy Research Center’s Research Experience for Undergraduates work with the graduate students during the summer. This not only allowed for additionally research to be accomplished, but also provided additional development for the students. Professional development has also included having the student present finding at conferences including: 2013 Wisconsin Energy Institute (WEI) Bioenergy Showcase, October 15-16, Madison, WI, USA. 2013 International Bioenergy & Bioproducts Conference, September 18-20, 2013, Green Bay, WI, USA. How have the results been disseminated to communities of interest? The furfural result was published as a peer reviewed articles in Industrial Crops and Products 55 (2014) 207-216, and was presented in 2013 International Bioenergy & Bioproducts Conference, in Green Bay, WI, USA and the International Bioenergy & Bioproducts Conference, September 18-20, 2013, Green Bay, WI, USA. Additionally we have provided several updates to our industrial partners Didion Inc (Cambria, WI) and Appleton (Appleton WI) who are interested in potential commercialization of the products. What do you plan to do during the next reporting period to accomplish the goals? We primarily need to improve both processes yields and input requirements further in order to improve the economic viability. This will be done through additional factorial experiments on reaction conditions as well as investigating the use novel lower cost methods of purification of the products. Additionally, the DDG gum will be chemically modified in order to provide better mechanical strength, hygroscopicity and flexibility for films and coatings. The rheological properties of DDG gum will also be investigated in order to evaluate the possibility of applying DDG gum as emulsification aid or rheological modifier. Once a DDG gum modification has been selected for scale-up, we will also perform dispersions experiments using hemicellulose and various plasticizers to obtain stable dispersions, which will then be characterized for particle size, viscosity and thermodynamic stability. These gums will be used to coat paper and compare to traditional PVA coatings measuring opacity, tensile strength, water resistance, and other printing tests. Finally once a process has been optimized we will complete an ASPEN model of the system to create a mass and energy balance which will be used to complete a Life Cycle Assessment of the system and identify and target the process(es) responsible for major environmental impacts.

Impacts
What was accomplished under these goals? Furfural was produced from dried distillers’ grains (DDG) by a two-stage process including a dilute acid extraction of pentose followed by a reactive distillation dehydration (BRD) process. The maximum furfural conversion rate reached 68% (% of pentosan in DDG). In parallel, analyses of composition and in vitro true dry matter digestibility (IVTDMD) of DDG-residue after dilute acid extraction suggested potential animal feed values. An economic analysis estimated that making furfural from DDG and selling the DDG-residue as animal feed would make an extra 0.2 million US$/year revenue for a corn ethanol plant with capacity of 50000 kg DDG per day showing potential profitability improvement. A process for extraction natural gum materials was developed by alkaline solution under different temperature, time and alkaline concentration. The highest yield were at approximately 30% (% of DDG) which was at approximately 70% of the theoretical yields possible based on the initial composition of the DDG. The gums were rich in polysaccharides and protein with weight average molecular weights (Mw) of 400,000 to 500,000. The gum was made into films and paper coatings showing a unique hygroscopic property and an ability to improve paper dry and wet tensile strength. Models predicting the gum and alkali residue yields and compositions were generated and included into the economic analysis. The results showed that in order to make the DG gum process profitable to corn ethanol industry, DG gum price has to be at least$2.5/kg. A process model for the entire system starting from dry grind milling corn-ethanol plant to processing of animal feed and hemicellulose paper coatings was built in ASPEN Plus for simulating the energy and mass balances across the system. The data obtained from the model will provide inputs for performing Life Cycle Assessment of products generated. Paper coating experiments were conducted using Polyvinyl Alcohol (PVA) of different molecular weights and purchased xylan. Different coating weights were applied using various sizes of metering rods. Water absorption tests (Tappi T441) and Tensile tests (Tappi T494) were performed on coated papers with various coating weights.

Publications

  • Type: Journal Articles Status: Accepted Year Published: 2014 Citation: Xiang, Zhouyang; Runge, Troy; Co-production of Feed and Furfural from Dried Distillers' Grains to Improve Corn Ethanol Profitability. Industrial Crops and Products.
  • Type: Journal Articles Status: Submitted Year Published: 2013 Citation: 4. Xiang, Zhouyang; Watson, Jamison; Tobimatsu, Yuki; Runge, Troy; Isolation of a Hemicellulose-rich Natural Polymer from Dried Distillers Grains and Co-production of Feed and Paper Coating" (Submitted to Journal of Agricultural and Food Chemistry)
  • Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Runge, Troy; Xiang, Zhouyang; Furfural from DDG. International Bioenergy and Bioproducts Conference, Green Bay, WI (Sept. 19, 2013).