Progress 01/01/13 to 12/31/16
Outputs Target Audience:Scientists and companies working in the corn ethanol or corn milling industries interested in improving the environmental and economic impacts. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?We have hired one graduate and two post-doctoral students and have trained them in both the science of the project as well as mentored them on professional development. Professional development has also included having the student present findings at past conferences including: Xiang, Z., Anthony, R., and Runge, T. (2014). Bio-based film and coating with enhanced mechanical properties by cross-linking arabinoxylan with glutaraldehyde. 2014 Wisconsin Energy Institute (WEI) Energy Hub Annual Conference: The Taste ofEnergy, November 12, Madison, WI, USA. Xiang, Z., and Runge, T. (2014). Film and coating with enhanced properties by cross-linking oxidized xylan with soy protein. 248th American Chemical Society National Meeting & Exposition, August 10-14, 2014, San Francisco, CA, USA. Xiang, Z., Anthony, R., Watson, J., and Runge, T. (2014). Alkaline extraction of hemicelluloses from dried distillers' grains and the production of paper coatings. 247th American Chemical Society National Meeting & Exposition, March 16-20, 2014, Dallas, TX, USA. Xiang, Z., and Runge, T. (2013). Production of furfural from dried distillers' grains: an economic point of view. 2013 Wisconsin Energy Institute (WEI) Bioenergy Showcase, October 15-16, Madison, WI, USA. Xiang, Z., and Runge, T. (2013). Co-production of feed and furfural from dried distillers' grains to improve corn ethanol profitability. International Bioenergy & Bioproducts Conference: A Fresh Look at Biomass Utilization, September 18-20, 2013, Green Bay, WI, USA. How have the results been disseminated to communities of interest?We have 8 papers published as peer review articles directly from this research. Anthony, Renil, Mahmoud A. Sharara, Troy M. Runge, and Robert P. Anex. "Life cycle comparison of petroleum-and bio-based paper binder from distillers grains (DG)."Industrial Crops and Products96 (2017): 1-7. Xiang, Zhouyang, Renil Anthony, Wu Lan, and Troy Runge. "Glutaraldehyde Crosslinking of Arabinoxylan Produced from Corn Ethanol Residuals." Cellulose,23 no. 1 (2016): 307-321. Xiang, Zhouyang, and Troy Runge. "Emulsifying properties of succinylated arabinoxylan-protein gum produced from corn ethanol residuals."Food Hydrocolloids52 (2016): 423-430. Anthony, Renil, Zhouyang Xiang, and Troy Runge. Paper Coating Performance of Hemicellulose-rich Natural Polymer from Distiller's Grains, Progress in Organic Coatings 89 (2015): 240-245 Xiang, Zhouyang and Troy Runge. "Emulsifying Properties of Succinylated Arabinoxylan-Protein Gum Produced from Corn Ethanol Residuals" Food Hydrocolloids 52 (2015) 423-430. Xiang, Z., Anthony, R., Tobimatsu, Y., and Runge, T. (2014). Emulsifying properties of an arabinoxylan-protein gum from distillers' grains and the co-production of animal feed. Cellulose, 21, 3623-3635. Xiang, Z., Watson, J., Tobimatsu, Y., and Runge, T. (2014). Film-Forming Polymers from Distillers' Grains: Structural and Material Properties. Industrial Crops and Products, 59, 282-289. Xiang, Z., and Runge, T. (2014). Co-production of feed and furfural from dried distillers' grains to improve corn ethanol profitability. Industrial Crops and Products, 55, 207-216. Additionally, we have provided several updates to our industrial partners Didion Inc (Cambria, WI) who have expressed interested in potential commercialization of the DDG based-products. What do you plan to do during the next reporting period to accomplish the goals?
Nothing Reported
Impacts What was accomplished under these goals?
This study is dedicated to the research of producing additional value-added products from a corn ethanol biorefinery system to improve profitability and sustainability, with an emphasis on finding additional value in the hemicellulosic components of distillers' grains (DG), a corn ethanol byproduct, for potential products or utilizations as furfural, edible films, paper coatings and emulsifying agents. Conditions were optimized to extract the DG's hemicelluloses as monomeric sugars by dilute acid at 140-160 °C, or in their polymeric forms by alakaline solutions at 25-75 °C. The pentoses of the mono sugars from the acidic extraction were further dehydrated at 160-180 °C to produce furfural; whereas the polymeric hemicelluloses from the alkaline extraction were evaluated for their potential utilizations as films, paper coatings and emulsifying agents. A techno-economic model was built which indicated that the corn ethanol plan profitability could be most enhanced by producing polymeric hemicellulose material if these material could replace commercial polyvinyl alcohols in paper making or gum arabic as a rheological modifier. Studies were conducted to demonstrate that both these substitutions could be made with some properties being enhanced and some degraded.To further enhance their utility, the polymeric hemicelluloses from DG were cross-linked by glutaraldehyde in dilute acid solution to improve their film and paper coating mechanical and physical properties, or were acylated by succinic anhydride in dilute alkaline solution to improve their emulsifying properties. The avoidance of using organic solvents during the modifications was a consideration for the economy, environment and product toxicity. The DG residues after acid hydrolysis or alkaline extraction were also evaluated for their animal feed qualities to maximize products produced and thus the economics of the process. The results indicated a loss of some crude protein but an enhanced digestability. 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, and a lifecycle assessment was conducted. Several allocations were investigated, with results indicating generally that non-renewable energy was higher for the DG polymer production than petroleum based polymers, GHG emissions from DG gum production were lower than petroleum based polymers, and eutrophication poetnal were slightly higher thanpetroleum based polymers.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2016
Citation:
Xiang, Zhouyang, and Troy Runge. "Emulsifying properties of succinylated arabinoxylan-protein gum produced from corn ethanol residuals." Food Hydrocolloids 52 (2016): 423-430.
- Type:
Journal Articles
Status:
Published
Year Published:
2016
Citation:
Xiang, Zhouyang, Renil Anthony, Wu Lan, and Troy Runge. Glutaraldehyde Crosslinking of Arabinoxylan Produced from Corn Ethanol Residuals. Cellulose, 23 no. 1 (2016): 307-321.
- Type:
Journal Articles
Status:
Published
Year Published:
2017
Citation:
Anthony, Renil, Mahmoud A. Sharara, Troy M. Runge, and Robert P. Anex. "Life cycle comparison of petroleum-and bio-based paper binder from distillers grains (DG)." Industrial Crops and Products 96 (2017): 1-7.
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Progress 01/01/15 to 12/31/15
Outputs Target Audience:Scientists and companies working in the corn ethanol or corn milling industries interested in improving the environmental and economic impacts. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?One graduate student was trained and finished a PhD on this project. One post-doctroral and one undergraduate student were trained on this project. How have the results been disseminated to communities of interest?We have been succesful with several journal articles in this time period. Additionally, we have presented to several businesses potentially interested in producing the DG gum material or using as a paper coating. What do you plan to do during the next reporting period to accomplish the goals?In the next reporting period, we will finish the experiments we need to complete the lifecycle assessment comparing this natural coating material to oil-produced polymeric binders. Additionally, we need to complete documentation of the research results with several more journal articles.
Impacts What was accomplished under these goals?
This study is dedicated to the research of producing additional value-added products from a corn ethanol biorefinery system to improve profitability and sustainability, with an emphasis on finding additional value in the hemicellulosic components of distillers' grains (DG), a corn ethanol byproduct, for potential products or utilizations as furfural, edible films, paper coatings and emulsifying agents. The DG's hemicelluloses were either extracted as monomeric sugars by dilute acid at 140-160 °C, or in their polymeric forms by alakaline solutions at 25-75 °C. The pentoses of the mono sugars from the acidic extraction were further dehydrated at 160-180 °C to produce furfural; whereas the polymeric hemicelluloses from the alkaline extraction were evaluated for their potential utilizations as films, paper coatings and emulsifying agents. The DG residues after acid hydrolysis or alkaline extraction were also evaluated for their animal feed qualities to maximize products produced and thus the economics of the process. This was further developed with created economic models that were optimized by maximizing the furfural or polymeric hemicelluloses as well as the extraction residue yields and minimizing the energy input. Thus, by analyzing the economic model, the DG valorizing processes were guided towards the direction with maximum profitability and sustainability. To further enhance their utility, the polymeric hemicelluloses from DG were cross-linked by glutaraldehyde in dilute acid solution to improve their film and paper coating mechanical and physical properties, or were acylated by succinic anhydride in dilute alkaline solution to improve their emulsifying properties. The avoidance of using organic solvents during the modifications was a consideration for the economy, environment and product toxicity.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2015
Citation:
Xiang, Zhouyang and Troy Runge. Emulsifying Properties of Succinylated Arabinoxylan-Protein Gum Produced from Corn Ethanol Residuals Food Hydrocolloids 52 (2015) 423-430.
- Type:
Journal Articles
Status:
Published
Year Published:
2015
Citation:
Anthony, Renil, Zhouyang Xiang, and Troy Runge. Paper Coating Performance of Hemicellulose-rich Natural Polymer from Distiller's Grains, Progress in Organic Coatings 89 (2015): 240245.
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Progress 01/01/14 to 12/31/14
Outputs Target Audience: Scientists and companies working in the corn ethanol or corn milling industries interested in improving the environmental and economic impacts. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided? We have 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. Professional development has also included having the student present finding at conferences. How have the results been disseminated to communities of interest? We have presented ourfindings at conferences including: Xiang, Z., Anthony, R., and Runge, T. (2014). Bio-based film and coating with enhanced mechanical properties by cross-linking arabinoxylan with glutaraldehyde. 2014 Wisconsin Energy Institute (WEI) Energy Hub Annual Conference: The Taste ofEnergy, November 12, Madison, WI, USA. Xiang, Z., and Runge, T. (2014). Film and coating with enhanced properties by cross-linking oxidized xylan with soy protein. 248th American Chemical Society National Meeting & Exposition, August 10-14, 2014, San Francisco, CA, USA. Xiang, Z., Anthony, R., Watson, J., and Runge, T. (2014). Alkaline extraction of hemicelluloses from dried distillers’ grains and the production of paper coatings. 247th American Chemical Society National Meeting & Exposition, March 16-20, 2014, Dallas, TX, USA. We have papers published as peer review articles in “Industrial Crops and Products” and “Cellulose”. Xiang, Z., Anthony, R., Tobimatsu, Y., and Runge, T. (2014). Emulsifying properties of an arabinoxylan-protein gum from distillers' grains and the co-production of animal feed. Cellulose, 21, 3623-3635. Xiang, Z., Watson, J., Tobimatsu, Y., and Runge, T. (2014). Film-Forming Polymers from Distillers’ Grains: Structural and Material Properties. Industrial Crops and Products, 59, 282-289. Xiang, Z., and Runge, T. (2014). Co-production of feed and furfural from dried distillers’ grains to improve corn ethanol profitability. Industrial Crops and Products, 55, 207-216. 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? The rheological properties of modified DG gum will be investigated in order to evaluate the possibility of applying DDG gum as emulsification aid or rheological modifier. Additionally, DG gum will be combined with other nano-materials such as nano-cellulose to make high value of composite materials. We will finish our techno-economic analysis and work toward getting our industrial partners interested in commercialization. Lastly we will finish the publication ofour results.
Impacts What was accomplished under these goals?
Previously, we have produced furfural from the pentosan in dried distillers’ grains (DDG) in a conversion rate of 68% (% of pentosan in DDG). We have also extracted natural gum materials rich in arabinoxylan from DDG with a highest yield of 30% (% of DDG), and the gum was made into films and paper coatings showing an ability to improve paper dry and wet tensile strength. For both processes of furfural conversion and gum extraction from DDG, the composition and in vitro true dry matter digestibility (IVTDMD) analyses of the conversion or extraction residues suggested their potential applications as animal feed. The economic analyses have demonstrated both processes could make the corn ethanol industries more profitable. In 2014, we have extended our research. Novel application of the extracted natural gum materials rich in arabinoxylan from DDG has been proposed. The potential use of the gum as an emulsifying agent in a water-oil emulsion system were investigated and compared with gum arabic, a commercial available counterpart. The analyses of particle size, zeta potential and changes in turbidity over time for the gums emulsifying a water-oil system suggested DG gum a potential substitute for gum arabic in food or beverage making industries. Furthermore, in order to improve its material properties, DG gum was esterified by succinic anhydride and cross-linked by glutaraldehyde. For both modifications, DG gum had film strength greatly enhanced (increase 2-3 times) at a low degree of substitution (DS). The modified DG gum was coated on paper to test its ability to be used as paper coating binders. The glutaraldehyde modified gum has demonstrated the abilities to improve paper’s dry and/or wet tensile strength as well as to increase paper hydrophobicity. Unmodified DG gum, pure purchased xylan, commercial available counterpart polyvinyl alcohol (PVA), DG gum esterified by succinic anhydride, and DG gum cross-linked with glutaraldehyde were applied as paper coating binders and each mixed with calcium carbonate to make paper coatings based on a commercially used formulation (10% binder and 90% calcium carbonate in the solid part). The DG gum cross-linked with glutaraldehyde and commercial PVA based paper coatings demonstrated comparable tensile strength and paper surface properties (opacity, brightness, whiteness, contact angle, etc.) suggesting glutaraldehyde modified DG gum’s potential utilization as a commercial paper coating binder. 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. Simulated several scenarios on the process model were built based on experimental DG gum extraction parameters and paper coating test results. Based on the defined Goal and Scope of the LCA and the results of the simulation, material and energy inputs were established with respect to the target yield of DG gum. This information is helping us gather Life Cycle Inventory data from literature and Sima Pro (LCA software).[R1] [R1]Last line from previous paragraph should be replaced by this.
Publications
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2014
Citation:
" Xiang, Z., Anthony, R., and Runge, T. (2014). Bio-based film and coating with enhanced mechanical properties by cross-linking arabinoxylan with glutaraldehyde. 2014 Wisconsin Energy Institute (WEI) Energy Hub Annual Conference: The Taste of Energy, November 12, Madison, WI, USA.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2014
Citation:
" Xiang, Z., and Runge, T. (2014). Film and coating with enhanced properties by cross-linking oxidized xylan with soy protein. 248th American Chemical Society National Meeting & Exposition, August 10-14, 2014, San Francisco, CA, USA.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2014
Citation:
" Xiang, Z., Anthony, R., Watson, J., and Runge, T. (2014). Alkaline extraction of hemicelluloses from dried distillers grains and the production of paper coatings. 247th American Chemical Society National Meeting & Exposition, March 16-20, 2014, Dallas, TX, USA.
- Type:
Journal Articles
Status:
Published
Year Published:
2014
Citation:
Xiang, Z., Anthony, R., Tobimatsu, Y., and Runge, T. (2014). Emulsifying properties of an arabinoxylan-protein gum from distillers' grains and the co-production of animal feed. Cellulose, 21, 3623-3635.
- Type:
Journal Articles
Status:
Published
Year Published:
2014
Citation:
Xiang, Z., Watson, J., Tobimatsu, Y., and Runge, T. (2014). Film-Forming Polymers from Distillers Grains: Structural and Material Properties. Industrial Crops and Products, 59, 282-289.
- Type:
Journal Articles
Status:
Published
Year Published:
2014
Citation:
Xiang, Z., and Runge, T. (2014). Co-production of feed and furfural from dried distillers grains to improve corn ethanol profitability. Industrial Crops and Products, 55, 207-216.
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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).
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