Source: OKLAHOMA STATE UNIVERSITY submitted to NRP
DEVELOPMENT OF BIOLOGICAL GAS CONVERSION TECHNOLOGY FOR RENEWABLE FUELS AND CHEMICALS
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
COMPLETE
Funding Source
HATCH
Reporting Frequency
Annual
Accession No.
1006481
Grant No.
(N/A)
Cumulative Award Amt.
(N/A)
Proposal No.
(N/A)
Multistate No.
(N/A)
Project Start Date
Jun 15, 2015
Project End Date
Sep 30, 2019
Grant Year
(N/A)
Program Code
[(N/A)]- (N/A)
Recipient Organization
OKLAHOMA STATE UNIVERSITY
(N/A)
STILLWATER,OK 74078
Performing Department
Biosystems & Ag Engineering
Non Technical Summary
The current growth in the biofuel industry is largely motivated by enhancing energy security, environmental protection and meeting the Renewable Fuels Standard (RFS2) mandate of 16 billion GPY renewable cellulosic biofuels by 2022. A crucial step in developing a sustainable biobased economy is establishing viable integrated biorefineries capable of converting biomass feedstocks and waste materials into biofuels, biopower and biobased chemicals. Thermochemical, biochemical and hybrid conversion technologies are in early stages of development. These technologies can be employed in different parts of the U.S. and abroad, based on the type of feedstock used and availability of other resources to sustain the biorefinery. Oklahoma is well-positioned to take a leading role in the biobased economy and help meet part of the demand for biofuels from cellulosic biomass.Gasification-syngas fermentation is a hybrid conversion process that involves the partial oxidation of biomass, coal and municipal solid wastes to syngas, primarily containing carbon monoxide, carbon dioxide and hydrogen, followed by the fermentation of syngas to alcohols and other co-products using various microorganisms. To develop a feasible syngas fermentation process, technical challenges associated with high cost of fermentation medium, mass transfer limitations and low productivity should be addressed. The primary goal of this project is to investigate the production of alcohols (ethanol, butanol and hexanol) and value added products (acetic, butyric and hexanoic acids) from lignocellulosic biomass through the gasification-fermentation route with focus on strategies to enhance alcohol productivity and gas utilization such as reducing gas-liquid mass transfer limitations. Process development and reactor design and control will be assessed for syngas utilization efficiency and alcohol productivity during the fermentation process. In addition, potential alternative products will be explored and mathematical models describing the kinetics of the fermentation process will also be developed. Data collected from this project are expected to be valuable in designing large scale bioreactors for viable commercial alcohol production using the gasification-syngas fermentation process.
Animal Health Component
50%
Research Effort Categories
Basic
20%
Applied
50%
Developmental
30%
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
5111629202030%
5114010202050%
5114020202020%
Knowledge Area
511 - New and Improved Non-Food Products and Processes;

Subject Of Investigation
1629 - Perennial grasses, other; 4010 - Bacteria; 4020 - Fungi;

Field Of Science
2020 - Engineering;
Goals / Objectives
The overall goal of this project is to enhance, optimize, and assess syngas utilization in three reactors to identify reactor designs that increase the alcohol (for example ethanol or butanol) productivity and syngas utilization during continuous fermentation. Mathematical models will be developed to describe the kinetics of syngas fermentation and predict the effectiveness of the various reactor designs.Objective 1: Evaluate a trickle-bed reactor (TBR) performance for syngas fermentation. The effect of gas and liquid flow rates, as well as the size of packing materials, will be investigated. A counter-current and co-current flow of liquid and gas configurations will be examined.Objective 2: Examine the ability of a hollow fiber membrane reactor (HFR) for syngas fermentation. The effect of gas and liquid flow rates will be explored. Optimum operating conditions (examples include liquid and gas flow rate, pH etc.) will be determined.Objective 3: Investigate syngas fermentation and methods to enhance the gas-liquid mass transfer rates in a continuous stirred tank reactor (CSTR). Optimum operating conditions such as liquid and gas flow rate, agitation rate and pH will be determined.Objective 4: Develop mathematical models for alcohol production from CO, CO2 and H2 that describe the relationships between gas utilization rate, microorganism growth rate and product formation rate during syngas fermentation in the TBR, HFR and CSTR reactors. The models will incorporate the effect of initial gas composition, pressure and mass transfer coefficients on the fermentation process. These models will be useful in process development, reactor design and scale-up.
Project Methods
Several commonalities exist between objectives 1, 2 and 3 regarding reactor conditions and sampling techniques. The inlet gas composition will be the same to aid in the comparison of previous studies. Gas mixtures containing CO:H2:CO2 [40:30:30] similar to gas produced from gasification of coal and CO:H2:CO2:N2 [20:5:15:60] similar to the gas made from gasifying switchgrass will be used. The reactors will be operated at 37 ºC. The liquid media will be the same composition and the reactors will be inoculated with a similar level of inoculum containing the selected microorganism. The inoculum will be prepared following two passaging and the cells will be in the exponential growth stage just prior to inoculation. The pH for growth will be established at 5.5 and once the cell concentration reaches the desired concentration, the pH will be controlled at 4.7.Liquid samples will be withdrawn periodically to measure cell and product concentrations. Ethanol, butanol, hexanol, acetic, butyric and hexanoic acids concentrations will be measured using a Gas Chromatograph (GC) with a flame ionization detector as previously described (Liu et al., 2014a). The cell concentration will be determined by measuring the optical density (OD) using a spectrophotometer at 660 nm. Gas samples will be taken periodically to measure the CO, CO2, H2, and N2 concentrations in order to calculate syngas conversion efficiency and product yields. The gas analysis will be performed using a GC with a thermal conductivity detector as previously described (Liu et al., 2014a).Objective 1. A 1 L TBR reactor will be used with the addition of a recirculation loop and pH controller to aid in comparison between the reactors. Berl saddles will be used as packing material. Berl saddles provide high surface area and low gas flow resistance, which make them a good candidate to establish a biofilm in the TBR. A counter-current and co-current flow of liquid and gas will be examined. A pH probe, sampling port, and small reservoir (approximately 250 ml) will be placed in the recirculation loop to control the pH and obtain liquid samples. The effect of liquid flow rate on mass transfer, syngas conversion efficiency and product formation will be determined. Liquid and gas samples will be withdrawn from the reactor periodically and analyzed. Cell growth rates, alcohol and organic acid production rates, CO, H2 and CO2 consumption rates and maximum mass transfer rates will be calculated from the above measurements. All studies will be performed in triplicate.The overall mass transfer coefficient (kLa) values for TBR with the selected packing material will be measured at the specified liquid flow rate using previously reported methods (Orgill et al., 2013). Mass transfer theory can then be used to estimate the overall kLa values for CO, CO2, and H2 based on the kLa for O2 according to the boundary layer theory (Sherwood et al., 1975).Objective 2. Experiments will be conducted in a 1-L hollow fiber membrane reactor. Product formation during syngas fermentation will be assessed at various liquid flow rates and agitation speeds. Liquid and gas samples will be taken periodically and analyzed as previously mentioned. Alcohol and organic acid production rates, CO, H2 and CO2 consumption rates, and maximum mass transfer rates will be calculated. All studies will be performed in triplicate.Objective 3. Experiments will be conducted in a 2-L stirred tank bioreactor. Cell and product formation during syngas fermentation will be assessed at various liquid flow rates and agitation speeds. Liquid and gas samples will be taken periodically and analyzed as previously mentioned. Cell growth rates, alcohol and organic acid production rates, CO, H2 and CO2 consumption rates, and maximum mass transfer rates will be calculated. All studies will be performed in triplicate.Comparison of ReactorsFor objectives 1, 2 and 3, the CSTR reactor liquid volume will be 2 liters. However, the TBR will have a volume of 1 liter (total void volume prior to addition of liquid and packing material) due to height limitations of the autoclave that will be used to sterilize the TBR. The HFR will also have a volume of 1-L. The gas flow rate per unit liquid volume (vvm) in each reactor configuration will be the same for ease of comparison between the three reactors. The overall kLa, alcohol and organic acid production rates and consumption rates of CO, H2 and CO2 will be compared.Objective 4. The formulation of a fermentation model involves determination of an expression for the growth rate. In many cases this involves the use of the Monod model with additional terms to take into account substrate and product inhibition. Kinetic models for substrate consumption and product formation rates are then formulated using yields coefficients. In ethanol fermentation, product formation kinetics is growth associated (Atiyeh, 2003; Bailey and Ollis, 1986). The simplest types of product formation kinetics arise when there are simple connections between product formation and substrate utilization or cell growth. Kinetic expressions for alcohol formation and organic acid production will be developed. The effect of syngas composition, pressure and mass transfer coefficients on the fermentation process will be included in the models for the three reactor designs.

Progress 06/15/15 to 09/30/19

Outputs
Target Audience:The target audiences include biofuel and biobased product producers, government officials involved in bioenergy policy, farmers interested in biomass production, researchers, and undergraduate and graduate students interested in bioenergy. Other target audiences include chemical, petrochemical, agricultural, biotechnology and environmental industries interested in the conversion of waste streams, coal or natural gas to carbon monoxide, carbon dioxide and hydrogen followed by biological conversion to useful products. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?One Ph.D. and one MS student were trained on syngas fermentation, acetone-butanol-ethanol (ABE) fermentation, bioreactor setup and operation, and medium formulation. A Post-Doc Research Associate was trained on bioconversion of gases and sugars into fuels and chemicals. How have the results been disseminated to communities of interest?Several journal articles were published and a couple in review in refereed journals. One book chapter was published. Two US Patents were issued and one US and International Patent Application Publication were published. Several conference presentations were delivered at local, regional, national and international meetings. What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? Process Development of Syngas Fermentation Syngas fermentations were examined using different strains in defined media and media containing yeast extract and biochar made from switchgrass (SGBC), forage sorghum (FSBC), redcedar (RCBC) and poultry litter (PLBC). Results showed that reactor geometry and operating conditions affect the mass transfer, gas utilization and biofuel productivity. Compared to expensive yeast extract medium, PLBC and SGBC enhanced ethanol and butanol production by Clostridium carboxidivorans. These findings are critical for formulating low cost media for efficient biofuels production from syngas, which were published in several peer-reviewed journals. My team has also developed tools to facilitate design and control of large-scale bioreactors with increased alcohol selectivity and productivity. We developed control algorithms and other methods to sustain culture activity, gas uptake, and improve selectivity for alcohol production from syngas. These methods were reported in U.S. Patents and patent application publications. My team also characterized new syngas fermenting clostridia strains (strains A, B and C) for potential use for ethanol and butanol production from syngas. C. carboxidivorans P7A was the best overall solvent producer including higher alcohols compared to strains A, B and C. Strains B and C produced more ethanol compared to P7A and strain A. Strain B was the best acid producer. These results are expected to open new opportunities for further development of these strains for commercial alcohol production from syngas. Process scale up was performed using Aspen Plus gasification-syngas fermentation model for production of a 37 million gallons per year ethanol from switchgrass, which was reported in a peer-reviewed journal. We also estimated the economic potential for making ethanol from agricultural and forest residuals using gasification-syngas fermentation technology. The feedstocks considered in the model include wood chips, wheat straw, corn stover, oilseed rape (OSR) meal and 50/50 mixture of wheat straw/swine manure. The preliminary economic feasibility and amounts of ethanol produced at coop- (1-2 million gallons per year, MGY) and regional-scale (50 MGY) facilities were estimated. Results showed that the feedstock cost played a considerable role in determining the minimum ethanol selling price (MESP). The MESP with the co-op scale facility was almost twice ($5.61-$9.49/gal) that from the 50 MGY facility ($2.28-$5.13/gal). The scale-up effects construction cost and MESP. Regional scale ethanol facility can be sustainable by blending with gasoline at comparable prices. This study also identified important challenges including the need for more research and development of a pilot scale gasification-syngas fermentation facility to accurately evaluate the economic and feasibility of small scale units. This research is important because the demonstration of an economically viable small scale conversion facility provides potential income to farmers from the use of sustainable agricultural and forest residuals. Process development and economic feasibility results were published in peer-reviewed journals. Development of Biochemical Conversion Technologies My team exams cell metabolism, enzyme activities, development of new microbial systems and process development to make fuels and chemicals via the biochemical conversion platform. Butanol is a drop-in fuel that can be converted to jet fuels. Butanol can be produced by the traditional acetone-butanol-ethanol (ABE) fermentation from molasses, starch and recently from lignocellulosic biomass. Butanol yield from lignocellulosic biomass is low because significant amount of the biomass is converted by Clostridium species to un-captured carbon dioxide and hydrogen. It is critical to increase the conversion efficiency to make butanol production viable. Our efforts were focused on determining the conditions that favour butanol production, and optimizing reactor conditions to maximize butanol yield. The research team generated lignocellulose-derived microbial inhibitory compounds (LDMIC)-tolerant Clostridium beijerinckii strains that grew in the presence of LDMICs. We also completed a life cycle of analysis for various jet fuel production pathways, including a novel conversion technology of cellulosic biomass to butanol that was subsequently converted to jet fuel. We are also investigating the synergistic role of fungi and bacteria in delignification of switchgrass and the feasibility of butanol production. My team also reduced the cost of the ABE fermentation medium by over 80% and enhanced solvent production by 80% with the use of biochar compared to standard ABE fermentation medium. We expect that the use of biochar could be an economical strategy for large scale ABE production. Results from this project were submitted for publication in peer-reviewed journals. Impact My research efforts impact conversion efficiency, cost of production, reactor design and process development of integrated fermentation technologies for implementation in sustainable biorefineries and reducing CO2 emissions. Our developed tools represent a break-through characterization of the production mechanisms that underline the commercially deployed fermentation process, and can be implemented in industrial control systems for process operation. These tools can be used on an industrial scale to maintain high conversion of syngas components to alcohols requiring moderately skilled operators thereby reducing the capital and operating costs. Some outcomes of this research include advancing the science and technology and educating youth, undergraduate and graduate students, and the public about the benefits of alternative energy and renewable fuels and chemicals production using various fermentation technologies.

Publications

  • Type: Journal Articles Status: Published Year Published: 2020 Citation: Sun, X., H. K. Atiyeh, M. Li and Y. Chen. 2020. Biochar Facilitated Bioprocessing and Biorefinery for Productions of Biofuel and Chemicals: A Review. Bioresource Technology. 295: 122252.
  • Type: Journal Articles Status: Published Year Published: 2019 Citation: Ro, K. S., M. A. Dietenberger, J. A. Libra, R. Proeschel, H. K. Atiyeh, K. Sahoo and W. J. Park. 2019. Production of Ethanol from Livestock, Agricultural, and Forest Residuals: An Economic Feasibility Study, Environments. 6(8), 97; doi.org/10.3390/environments6080097.
  • Type: Journal Articles Status: Published Year Published: 2019 Citation: Liu, K., J. R. Phillips, X. Sun, S. Mohammad, R. L. Huhnke and H. K. Atiyeh. 2019. Investigation and Modeling of Gas-Liquid Mass Transfer in a Sparged and Non-Sparged Continuous Stirred Tank Reactor with Potential Application in Syngas Fermentation, Fermentation. 5(3), 75; doi.org/10.3390/fermentation5030075.
  • Type: Journal Articles Status: Published Year Published: 2019 Citation: Sun, X., H. K. Atiyeh, R. L. Huhnke and R. S. Tanner. 2019. Syngas Fermentation Process Development for Production of Biofuels and Chemicals: A review. Bioresource Technology Reports. 7: 100279, https://doi.org/10.1016/j.biteb.2019.100279.
  • Type: Journal Articles Status: Published Year Published: 2019 Citation: Sun, X., H. K. Atiyeh, H. Zhang, R. S. Tanner and R. L. Huhnke. 2019. Enhanced Ethanol Production from Syngas by Clostridium ragsdalei in Continuous stirred Tank Reactor Using Medium with Poultry Litter Biochar. Applied Energy. 236: 12691279.
  • Type: Journal Articles Status: Published Year Published: 2019 Citation: Orgill, J.J., M.C. Abboud, H. K. Atiyeh, Devarapalli, M., X. Sun and R. S. Lewis. 2019. Measurement and Predictions of Mass Transfer Coefficients for Syngas Constituents in a Hollow Fiber Reactor, Bioresource Technology. 276: 17.
  • Type: Book Chapters Status: Published Year Published: 2019 Citation: Yasin, M., M. Cha, I. S. Chang, H. K. Atiyeh, P. Munasinghe and S. K. Khanal. "Syngas Fermentation into Biofuels and Biochemicals", in "Biofuels: Alternative Feedstocks and Conversion Processes for the Production of Biofuels" (2nd Edition), A. Pandey, C. Larroche, E. Gnansounou, S. K. Khanal, C.-G. Dussap, S. Ricke, Eds, Academic Press, USA. 2019.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Sun, X., H. K. Atiyeh, Y. Adesanya, H. Zhang, C. Okonkwo and T. Ezeji Enhanced Acetone-Butanol-Ethanol Production by Clostridium beijerinckii Using Biochar, ASABE 2019 Annual International Meeting, Boston, Massachusetts, July 7-10, 2019 (10 pages), Paper number: ASABE -1900256. St. Joseph, Mich.: ASABE.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Pamula, A., D. J. Lampert and H. K. Atiyeh, Well-to-Wake Analysis of Switchgrass to Butanol Via Co-Fermentation of Sugar and Gas with Subsequent Conversion to Jet Fuel, 2019 AIChE Annual Meeting, Orlando, FL, November 10  15, 2019. Oral.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Pamula, A., D. J. Lampert and H. K. Atiyeh, Well-to-Wake Analysis of Switchgrass to Butanol Via Co-Fermentation of Sugar and Gas with Subsequent Conversion to Jet Fuel, 2019 AIChE Annual Meeting, Orlando, FL, November 10  15, 2019. Poster.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Sun, X., H. K. Atiyeh, R. L. Huhnke and R. S. Tanner Characterization of New Syngas-Fermenting Acetogens for Biofuel Production, 2019 AIChE Annual Meeting, Orlando, FL, November 10  15, 2019. Oral.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Sun, X., H. K. Atiyeh, Y. A. Adesanya, H. Zhang, C. Okonkwo and T. Ezeji " Supplementation of Growth Medium with Biochar enhances Production of Acetone-Butanol-Ethanol from Switchgrass by Clostridium beijerinckii, 2019 AIChE Annual Meeting, Orlando, FL, November 10  15, 2019. Oral.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Sun, X., H. K. Atiyeh, R. L. Huhnke and R. S. Tanner Comparison of New Syngas-Fermenting Acetogens for Ability to Produce of Alcohols and Fatty Acids, S-1075- Science and Engineering for a Biobased Industry and Economy, National Renewable Energy Laboratory, Golden, CO , July 29-30, 2019. Poster.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Sun, X., H. K. Atiyeh, Y. A. Adesanya, H. Zhang, C. Okonkwo and T. Ezeji "Enhanced Acetone-Butanol-Ethanol Production by Clostridium beijerinckii Using Biochar, 2019 ASABE Annual International Meeting, Boston, Massachusetts, July 7-10, 2019. Oral.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Adesanya, Y.A., H. K. Atiyeh, X. Sun, C. Okonkwo, V. Ujor and T. Ezeji "Butanol Production from Non-Detoxified Switchgrass Hydrolysate Using New Inhibitor Tolerant Strains of Clostridium beijerinckii, 2019 ASABE Annual International Meeting, Boston, Massachusetts, July 7-10, 2019. Oral.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Sun, X., H. K. Atiyeh, R. L. Huhnke and R. S. Tanner "Alcohol Production by New Syngas Fermenting Microorganisms, 2019 ASABE Annual International Meeting, Boston, Massachusetts, July 7-10, 2019. Oral.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Marsh, W., Murdoch, R., Loffler, F., Mark, K., Atiyeh, H., Fathepure, B. Applying a Halophilic Mixed-Culture to Remediate Hydrocarbon Contaminated Produced Water. Microbiology and Molecular Genetics Symposium, Oklahoma State University, Stillwater, OK. April 12, 2019. Poster.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Sun, X., Y. Adesanya, T. C. Ezeji and H. K. Atiyeh, Butanol production from switchgrass with genetically modified microorganisms, CEAT Research Week, Stillwater, OK, USA, February 28, 2019. Poster.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Adesanya, Y., X. Sun, T. C. Ezeji and H. K. Atiyeh, Effect of Biomass Pretreatment on Butanol Production from Switchgrass, FAPC-OK Research Symposium, Stillwater, OK, USA, February 26, 2019. Poster.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Pamula, A., D. J. Lampert and H. K. Atiyeh, Assessment of the Environmental Impacts of Switchgrass to Jet Fuel, FAPC-OK Research Symposium, Stillwater, OK, USA, February 26, 2019. Poster.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Adesanya, Y., X. Sun, T. C. Ezeji and H. K. Atiyeh, Effect of Biomass Pretreatment on Butanol Production from Switchgrass, ASABE Oklahoma Section Annual Meeting-three minute presentations, Stillwater, OK, USA, February 22, 2019. Oral.


Progress 10/01/17 to 09/30/18

Outputs
Target Audience:The target audiences include biofuel and biobased product producers, government officials involved in bioenergy policy, farmers interested in biomass production, researchers, and undergraduate and graduate students interested in bioenergy. Other target audiences include chemical, petrochemical, agricultural, biotechnology and environmental industries interested in conversion of waste streams, coal or natural gas to carbon monoxide, carbon dioxide and hydrogen followed by biological conversion to useful products. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?Two Ph.D. students were trained on syngas fermentation, bioreactor setup and operation, and medium formulation. A second Ph.D. student was trained in the development of carbon monoxide detection and monitoring system. One Master student is trained on butanol fermentation from lignocellulosic biomass. A Post-Doc Research Associate is being trained on bioconversion of gases and sugars into fuels and chemicals. How have the results been disseminated to communities of interest?Several journal articles were published and a couple in review in refereed journals. One book chapter is in review. Two US Patents were issued and three US and International Patent Application Publications were published. Several conference presentations were delivered at local, regional, national and international meetings. What do you plan to do during the next reporting period to accomplish the goals?Continue working to achieve project goals

Impacts
What was accomplished under these goals? Enhanced ethanol and butanol production from syngas by incorporating biochar in the fermentation medium Syngas fermentation is an emerging technology to produce fuels and chemicals from gasified biomass, coal, petcoke and solid wastes. This technology can also be used to make fuels and chemicals from gas streams that contain carbon monoxide, carbon dioxide and hydrogen. Challenges for commercialization of syngas fermentation technology include mass transfer limitations and low alcohol productivity associated with low cell mass concentration in the bioreactor and inhibition effects of high carbon monoxide concentrations on key enzymes such as hydrogenase. Our goal is to develop a sustainable and feasible hybrid gasification-syngas fermentation process for alcohol production enriches understanding of the effects of mass transfer on alcohol productivity in syngas bioreactors. Syngas fermentations were examined using different strains in defined media and media containing yeast extract and biochar from switchgrass (SGBC), forage sorghum (FSBC), redcedar (RCBC) and poultry litter (PLBC). Biochar contains minerals and metals that can serve as nutrients for acetogens to produce ethanol via syngas fermentation. Results showed that reactor geometry and operating conditions affect the mass transfer, gas utilization, and biofuel productivity. Compared to expensive yeast extract medium, RCBC and PLBC improved ethanol production by C. ragsdalei, while PLBC and SGBC enhanced ethanol and butanol production by C. carboxidivorans. These findings are critical in designing reactors and formulating media for efficient biofuels production from syngas, which was published in several peer-reviewed journals. Direct monitoring of dissolved carbon monoxide and hydrogen concentrations in the fermentation medium is a key to improve productivity and process stability. A real-time monitoring system for the dissolved carbon monoxide and hydrogen concentrations is being developed, which includes a built in-house dissolved carbon monoxide sensor and an off-the-shelf dissolved hydrogen sensor. The carbon monoxide sensor was tested with gas samples containing carbon monoxide concentration range generally found in bioreactors at typical operating pressures and achieved a sensitivity of over 10 mV/ppm CO. Further work is focused on improving the sensors' performance and its integration with the bioreactor control for efficient syngas fermentation. Process Development of Syngas Fermentation My team has developed various tools to facilitate design and control of large-scale bioreactors with increased alcohol productivity and selectivity and gas utilization to make the hybrid conversion process for the production of biofuels economically viable. We developed a novel method to sustain culture activity, gas uptake, and improve selectivity for ethanol production during syngas fermentation. We discovered that the addition of activated carbon in the fermentation medium sustained the acetogen's activity, prolonged the fermentation process, and resulted in a high concentration of ethanol produced. In 2018, my team obtained a U.S. Patent No. US 10,053,711 B2) entitled "Method Improving Producer Gas Fermentation". The patented method resulted in the production of twenty-six times the ethanol concentration compared to the conventional method. The enhanced ethanol production and fermentation stability were attributed to the effect of carbon in altering the mass transfer and presumably in retaining the nutrients to sustain fermentation activity. My team also developed a patented novel pH control method for ethanol production from syngas (U.S. Patent No. US 10,017,789 B2) in 2018. The gas flow was automatically adjusted by a proportional-integral-derivative process controller to control the pH in the fermentation broth. The development of automatic control of syngas feed rate which maintained constant pH increased stability, ethanol selectivity and concentration, and doubled the production of ethanol assures commercial potential in the biofuel industry. We also developed a control algorithm to maximize the conversion of syngas to ethanol and productivity based on mass transfer, kinetics, and thermodynamic parameters of the fermentation process. The algorithm provides an effective new tool for process design and control of fermentation, described in U.S. Patent Application Publication No. US 2017/0356012 A1. Findings of our Aspen Plus gasification-syngas fermentation model, which predicted an annual production of 37 million gallons of ethanol from 1200 tons per day switchgrass, were published in 2017. Another tool my team has developed is a mid-infrared carbon monoxide (CO) sensor for measurement of dissolved CO during syngas fermentation. We designed a real-time CO sensor and real-time CO/H2 monitoring system. Monitoring of CO and H2 levels in the bioreactor is expected to facilitate efficient gas conversion to liquid fuels and chemicals. This work also provides valuable guidance towardthe operation of large-scale bioreactors with increased alcohol productivity and syngas utilization. Development of Biochemical Conversion Technologies Challenges in the biochemical conversion route include the high cost of pretreatment and enzymes and inefficient co-fermentation of five carbon and six carbon sugars. My team aims to tackle these challenges through examining cell metabolism, enzyme activities, development of new microbial systems and process development to make fuels and chemicals. Butanol has been produced by the traditional acetone-butanol-ethanol (ABE) fermentation using molasses and hydrolyzed starches. About 50% of the sugar in the ABE process is lost to the production of coproducts other than ABE. It is critical to increase the conversion efficiency to make butanol production viable. Efforts were focused on determining the conditions that favor butanol production and optimizing reactor conditions to maximize butanol yield. We are also investigating the synergistic role of fungi and bacteria in delignification of switchgrass and the feasibility of butanol production. Impact My research efforts impact conversion efficiency, cost of production, reactor design and process development of integrated syngas fermentation technologies for implementation in sustainable biorefineries and reducing CO2 emissions. The developed tools represent a break-through characterization of the production mechanisms that underline the commercially deployed fermentation process and can be implemented in industrial control systems for process operation. These tools can be used on an industrial scale to maintain high conversion of syngas components to alcohols requiring moderately skilled operators thereby reduces capital and operating costs. Opportunities abound to apply this hybrid conversion technology throughout the country to meet increasing energy needs and reduce CO2 emissions. Upon its full development, this hybrid technology can provide 35% more ethanol from the same amount of biomass as compared to the biochemical conversion technology. If biofuel producers adopt this hybrid technology to produce 25% of the mandated 16 billion GPY renewable transportation fuels, such as ethanol (i.e., 4 billion GPY), my research suggests a projected annual savings of over $650 million due to the use of 13.1 million tons less biomass with the hybrid technology.

Publications

  • Type: Theses/Dissertations Status: Other Year Published: 2018 Citation: Xiao Sun, Ph.D. Biosystems Engineering, Oklahoma State University, 2014  2018. Dissertation: Enhanced Alcohol Production During Syngas Fermentation Using Biochar. Completed July 2018
  • Type: Journal Articles Status: Published Year Published: 2018 Citation: Sun, X., H. K. Atiyeh, A. Kumar, H. Zhang and R. S. Tanner. 2018. Biochar Enhanced Ethanol and Butanol Production by Clostridium carboxidivorans from Syngas. Bioresource Technology. 265: 128138.
  • Type: Journal Articles Status: Published Year Published: 2018 Citation: Pardo-Planas, H. K. Atiyeh, O., R. A. Prade, M. Muller, and M. R. Wilkins. 2018 Continuous Aryl Alcohol Oxidase Production Under Growth-Limited Conditions Using a Trickle Bed Reactor. Bioresource Technology. 255: 149155.
  • Type: Journal Articles Status: Published Year Published: 2018 Citation: Sun, X., H. K. Atiyeh, A. Kumar and H. Zhang. 2018. Enhanced ethanol production by Clostridium ragsdalei from syngas by incorporating biochar in the fermentation medium. Bioresource Technology. 247:291-301.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Sun, X., H. K. Atiyeh, A. Kumar, H. Zhang and R. S. Tanner. Biochar Enhanced Alcohol Production from Syngas by Clostridium carboxidivorans, 2018 AIChE Annual Meeting, Pittsburgh, PA, October 28  November 2, 2018. Oral.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Atiyeh, H. K., P. Munasinghe, K. Liu, R. S. Tanner and T. Ezeji "Co-Fermentation of Sugars and Gases for Enhanced Alcohols Production", 2018 ASABE Annual International Meeting, Detroit, Michigan, July 29-August 1, 2018. Oral.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Sun, X., H. K. Atiyeh, R. S. Tanner, A. Kumar and H. Zhang "Enhanced Ethanol and Butanol Production from Synthesis Gas Using Biochar", 2018 ASABE Annual International Meeting, Detroit, Michigan, July 29-August 1, 2018. Oral.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Dang, J., H. K. Atiyeh and N. Wang "Development of a Mid-Infrared Sensor for Measurement of Dissolved Carbon Monoxide during Syngas Fermentation", 2018 ASABE Annual International Meeting, Detroit, Michigan, July 29-August 1, 2018. Oral.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Sun, X., H. K. Atiyeh, H. Zhang and R. S. Tanner Enhanced Ethanol Production from Syngas Using Medium with Poultry Litter Biochar, S-1041- Science and Engineering for a Biobased Industry and Economy, Annual Meeting and Symposium, USDA FS Forest Products Laboratory, Madison, WI, July 9-10, 2018. Poster.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Dang, J., H. K. Atiyeh and N. Wang Development of a Dissolved Carbon Monoxide Sensor for Syngas Fermentation Bioreactors, S-1041- Science and Engineering for a Biobased Industry and Economy, Annual Meeting and Symposium, USDA FS Forest Products Laboratory, Madison, WI, July 9-10, 2018. Poster.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Sun, X., J. R. Phillips, R. L. Huhnke and H. K. Atiyeh Continuous Biological Conversion of Syngas to Ethanol Using a Novel pH Controller, USDA-NIFA-Consortium for Advanced Bioeconomy Leadership Education (CABLE), Stillwater, Oklahoma, April 4, 2018. Poster.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Sun, X., H. K. Atiyeh, A. Kumar and H. Zhang Enhanced Bioethanol Production via Syngas Fermentation in Media with Biochar, USDA-NIFA-Consortium for Advanced Bioeconomy Leadership Education (CABLE), Stillwater, Oklahoma, April 4, 2018. Poster.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2017 Citation: Dang, J., N. Wang and H. K. Atiyeh, Development CO Sensor for Syngas Fermentation for Production of Fuels and Chemicals, 2017 AIChE Annual International Meeting, Minneapolis, MN, October 29 - November 3, 2017. Oral.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2017 Citation: Atiyeh, H. K., P. Munasinghe, K. Liu, R. S. Tanner and T. Ezeji, Enhanced Alcohols, Ketones and Organic Acids Production via Co-Fermentation of Sugars and Gases, 2017 AIChE Annual International Meeting, Minneapolis, MN, October 29 - November 3, 2017. Oral.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2017 Citation: Sun, X. and H. K. Atiyeh, Enhanced Bioethanol Production from Syngas Using Medium with Biochar, 2017 ASEE Midwest Section Conference, Stillwater, Oklahoma, September 24-26, 2017.


Progress 10/01/16 to 09/30/17

Outputs
Target Audience:The target audiences include biofuel and biobased product producers, government officials involved in bioenergy policy, farmers interested in biomass production, researchers, and undergraduate and graduate students interested in bioenergy. Other target audiences include chemical, petrochemical, agricultural, biotechnology and environmental industries interested in conversion of waste streams, coal or natural gas to carbon monoxide, carbon dioxide and hydrogen followed by biological conversion to useful products. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?One PhD student was trained on syngas fermentation, bioreactor setup and operation and medium formulation. A second PhD student was trained on development of carbon monoxide detection and monitoring system. How have the results been disseminated to communities of interest?Several journal articles were published in refereed journals. One book chapter was published. One invention disclosure was filed and nine conference and invited presentations were delivered at national and international meetings. What do you plan to do during the next reporting period to accomplish the goals?Continue working to achieve project goals

Impacts
What was accomplished under these goals? Development CO Sensor for Syngas Fermentation for Production of Fuels and Chemicals Syngas fermentation is an emerging technology to produce fuels and chemicals from gasified biomass, coal, petcoke and solid wastes. This technology can also be used to make fuels and chemicals from gas streams that contain carbon monoxide, carbon dioxide and hydrogen. Challenges for commercialization of syngas fermentation technology include mass transfer limitations and low alcohol productivity associated with low cell mass concentration in the bioreactor and inhibition effects of high carbon monoxide concentrations on key enzymes such as hydrogenase. Direct monitoring of dissolved carbon monoxide and hydrogen concentrations in the fermentation medium is a key to improve productivity and process stability. A real-time monitoring system for the dissolved carbon monoxide and hydrogen concentrations is being developed, which includes a built in-house dissolved carbon monoxide sensor and an off-the-shelf dissolved hydrogen sensor. The carbon monoxide sensor was tested with gas samples containing carbon monoxide concentration range generally found in bioreactors at typical operating pressures and achieved a sensitivity of over 10 mV/ppm CO. Further work is focused on improving the sensors' performance and its integration with the bioreactor control for efficient syngas fermentation. Enhanced ethanol production from syngas by incorporating biochar in the fermentation medium Biochar contains minerals and metals that can serve as nutrients for acetogens to produce ethanol via syngas fermentation. Four fermentation media containing biochar from switchgrass (SGBC), forage sorghum (FSBC), red cedar (RCBC) and poultry litter (PLBC) were compared with standard yeast extract (YE) medium for syngas fermentation using Clostridium ragsdalei. Results showed that media containing RCBC and PLBC improved ethanol production by 16% and 59%, respectively, compared to YE medium. C. ragsdalei consumed 69% more hydrogen and 40% more carbon monoxide in PLBC medium compared to YE medium. However, no enhancement of ethanol production was observed in SGBC and FSBC media. The highest release of minerals such as sodium, potassium and phosphorous was from PLBC, which was considered to contribute in enhancement of ethanol production. Continuous Ethanol Production from Syngas in a Trickle-Bed Reactor A trickle-bed reactor (TBR) can improve gas-liquid mass transfer because a very thin liquid film is in contact with the gas phase. Continuous syngas fermentation was performed in a one liter TBR for ethanol production by Clostridium ragsdalei. Results showed that carbon monoxide and hydrogen conversion efficiencies reached over 90% when the gas flow rate was maintained below 2.8 standard cubic centimeters per minute (sccm) at a dilution rate of 0.009 h−1. A molar ratio of ethanol to acetic acid of 4:1 was obtained in co-current continuous mode. Operating the TBR in a co-current mode avoided flooding issues that occurred during the counter current mode and allowed production of over twofold more ethanol than in the counter current mode. A Microbial Conversion Process of Gaseous Substrates to Various Products Chemoautotrophic microbes produce a wide range of chemicals via the Wood-Ljungdahl pathway such as acetic acid, butyric acid, hexanoic acid, ethanol, butanol and hexanol. Production of acetic acid supplies energy for synthesis of cell mass, including lipids, proteins and other complex cell components from carbon monoxide, hydrogen and carbon dioxide. The low solubility of carbon monoxide and hydrogen requires that these gases to be continually replenished in the fermentation broth to sustain production. The attainment of high mass transfer represented in the volumetric mass transfer coefficient is critical for feasible syngas fermentation processes. However, the rate of mass transfer should be balanced with the rate of reaction to avoid accumulation of carbon monoxide that inhibits key enzymes in syngas fermentation. The gasification-syngas fermentation process has the potential to achieve high ethanol yields compared to typical enzymatic hydrolysis fermentation. This is due to utilization of all components of the biomass, including lignin during gasification to produce the syngas that is converted into ethanol. Current Techno-economic analysis studies are based on technical data and assumptions for first generation biorefineries. Further technology advancements will provide stable, controlled and efficient biofuel conversion processes, which are expected to make future biorefineries feasible. In addition, the use of dedicated biomass energy crops, waste biomass and municipal and industrial wastes as feedstock for energy and chemical synthesis promotes reuse and recycling. This can establish a true cycle of renewable, carbon-neutral, energy and chemical production. Advanced Gasification-Syngas Fermentation Model An advanced gasification-syngas fermentation model was developed to examine various operational scenarios for the hybrid conversion process. The effects of critical syngas fermentation parameters such as specific gas uptake rate, ethanol concentration and substrate gas conversion efficiency on reactor volume and energy requirements were investigated. The Aspen Plus model enabled simulation of commercial production of ethanol from gasification of 1200 tons of switchgrass per day. The results showed that about 37 million gallons of anhydrous ethanol can be produced per year from 1200 tons per day switchgrass. The process yielded about 98 gallons ethanol per dry ton of biomass, which is higher than the 70 gallons ethanol per dry ton of biomass typically achieved by the biochemical platform. This work can be a basis of a detailed techno-economic analysis of the proposed technology to help in designing efficient commercial gasification-syngas fermentation biorefineries.

Publications

  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Sun, X., H. K. Atiyeh, A. Kumar and H. Zhang. 2018. Enhanced ethanol production by Clostridium ragsdalei from syngas by incorporating biochar in the fermentation medium. Bioresource Technology. 247:291-301.
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Pardo-Planas, O., H. K. Atiyeh, J. R. Phillips, C. P. Aichele and S. Mohammad. 2017. Process Simulation of Ethanol Production from Biomass Gasification and Syngas Fermentation. Bioresource Technology. 245:925-932.
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Pardo-Planas, O., R. A. Prade, M. Muller, H. K. Atiyeh and M. R. Wilkins. 2017. Prevention of melanin formation during aryl alcohol oxidase production under growth-limited conditions using an Aspergillus nidulans cell factory. Bioresource Technology. 243:874-882.
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Phillips, J. R., R. L. Huhnke and H. K. Atiyeh. 2017. Syngas Fermentation: A Microbial Conversion Process of Gaseous Substrates to Various Products. Fermentation. 3:28; doi:10.3390/fermentation3020028.
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Devarapalli, M., R. S. Lewis and H. K. Atiyeh. 2017. Continuous Ethanol Production from Synthesis Gas by Clostridium ragsdalei in a Trickle Bed Reactor. Fermentation. 3(2), 23; doi:10.3390/fermentation3020023.
  • Type: Books Status: Published Year Published: 2016 Citation: Wilkins, M. R., H. K. Atiyeh and S. K. Khanal, Syngas Fermentation, in Bioenergy: Principles and Applications, Y. Li and S. K. Khanal, Eds, John Wiley and Sons, New York, NY, USA. 2016.
  • Type: Other Status: Other Year Published: 2016 Citation: Atiyeh, H. K.. Development of Novel Biocatalytic Conversion Process for Production of Alcohols, Ketones and Organic acids. Submitted to Oklahoma State University-Technology Development Center. disclosure number 2016-008.
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2017 Citation: Sun, X. and H. K. Atiyeh, Enhanced Bioethanol Production from Syngas Using Medium with Biochar, 2017 ASEE Midwest Section Conference, Stillwater, Oklahoma, September 24-26, 2017. Poster.
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2017 Citation: Dang, J., N. Wang and H. K. Atiyeh, Development of a Mid-Infrared Carbon Monoxide Sensor, 2017 ASEE Midwest Section Conference, Stillwater, Oklahoma, September 24-26, 2017. Poster.
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2017 Citation: Sun, X. and H. K. Atiyeh, Enhanced Ethanol Production from Syngas with Various Medium Formulations, 2017 ASABE Annual International Meeting, Spokane, Washington, July 16-19, 2017. Oral.
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2017 Citation: Atiyeh, H. K., J.R. Phillips, R.L. Huhnke and R.S. Lewis Enhanced Syngas Fermentation for Ethanol Production Using Activated Carbon, 2017 ASABE Annual International Meeting, Spokane, Washington, July 16-19, 2017. Oral.
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2017 Citation: Wilkins, M., O. Pardo-Planas, R. Prade and H. K. Atiyeh, Reduction of melanin formation during aryl alcohol oxidase production by an Aspergillus nidulans cell orverproducing mutant, 2017 ASABE Annual International Meeting, Spokane, Washington, July 16-19, 2017. Oral.
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2017 Citation: Atiyeh, H. K., Development of the Hybrid Conversion Technology for Sustainable Production of Fuels and Chemicals, 2017 Oklahoma Engineering Conference. Moore Norman Technology Center, OKC, June 15-16, 2017. Oral.
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2017 Citation: Sun, X. and H. K. Atiyeh, Continuous Production of Ethanol with Limited Accumulation of Acetate via Syngas Fermentation, 2017 Annual Meeting Oklahoma Section ASABE, Stillwater, OK, February 24, 2017. Poster.
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2016 Citation: Atiyeh, H. K., J.R. Phillips, R. L. Huhnke and R. S. Lewis, Enhanced Ethanol Production via Activated Carbon Addition During Syngas Fermentation, AIChEs 2016 Annual Meeting, San Francisco, CA, November 13-18, 2016. Oral.


Progress 10/01/15 to 09/30/16

Outputs
Target Audience:The target audiences include biofuel and biobased product producers, government officials involved in bioenergy policy, farmers interested in biomass production researchers, and undergraduate and graduate students interested in bioenergy. Other target audiences include chemical, petrochemical, agricultural, biotechnology and environmental industries interested in conversion of waste gas streams containing carbon dioxide, carbon monoxide and/or hydrogen into useful products. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?One PhD student was trained on syngas fermentation, bioreactor setup and operation and medium design. A second PhD student was trained on development of carbon monoxide detection and monitoring system. How have the results been disseminated to communities of interest?Several journal articles were published in refereed journals. Three patent applications and one provisional patent application were filed. One invention disclosure was filed and five conference and invited presentations were delivered at national and international meetings. What do you plan to do during the next reporting period to accomplish the goals?Continue working to achieve project goals

Impacts
What was accomplished under these goals? Biological Ethanol Production from Syngas Using Novel Control Method Syngas containing carbon monoxide, carbon dioxide and hydrogen is produced by gasification of biomass, coal, petcoke and waste materials. Production of fuels and Chemicals from syngas at industrial levels requires high conversion efficiency and product specificity. The bacterium Clostridium ragsdalei converts syngas to organic acids and alcohols. A new method to control syngas fermentation was developed in this project. The method uses an industrial control system to regulate syngas supply to maintain a constant fermentation pH by formation of weak acetate buffer and reduces nearly all produced acetic acid to ethanol. Continuous fermentations were operated for over 2000 hours in a 3-liter bioreactor. Over 90% of the carbon monoxide and hydrogen uptake by the bacterium were converted into ethanol. Ethanol production up to 25 g/L was achieved. In addition, a ratio of ethanol to acetic acid of greater than 100 moles per mole was demonstrated. The novel control technique also allowed stabilized syngas fermentation with sustained high conversion efficiency and selectivity to ethanol, which can be applied in commercial syngas fermentation. Enhanced Ethanol Production During Syngas Fermentation Using Activated Carbon Production of ethanol relies on efficient transfer of syngas components to the bacterium cells at rates that match the bacterium's kinetic capability to process the syngas. Cells are inhibited when too much carbon monoxide accumulates in the liquid broth. This causes reduction in utilization of other syngas components such as hydrogen and carbon dioxide. Batch syngas fermentations in a 3-Liter bioreactor with and without activated carbon were compared. Fine powdered activated carbon particles were added to the broth to alter the gas mass transfer and provide additional surface for Clostridium ragsdalei growth. The addition of activated carbon sustained activity of the biocatalyst increasing total carbon monoxide and hydrogen uptake six fold compared to no carbon. Fermentations with activated carbon produced 19 g/L ethanol with less than 1 g/L total acetic acid. However, only about 1 g/L ethanol and 5 g/L acetic acid were produced without activated carbon. The maximum carbon monoxide and hydrogen conversion efficiencies with activated carbon were 88% and 86%, respectively. The operation of syngas fermentation with activated carbon resulted in higher stability, selectivity and energy conservation than any previously reported results, indicating potential for commercial biofuels production and other biological gas conversion processes.

Publications

  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Ramachandriya, KD, DK Kundiyana, AM Sharma, A Kumar, HK Atiyeh, RL Huhnke, MR Wilkins. 2016. Critical factors affecting the integration of biomass gasification and syngas fermentation technology. AIMS Bioengineering. 3, 188-210
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: M�ller, M, R. A. Prade, F. Segato, H. K. Atiyeh and M.R. Wilkins. 2015. Continuous Xylanase Production with Aspergillus Nidulans Under Pyridoxine Limitation Using a Trickle Bed Reactor. Bioresource Technology. 188, 219-225.
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2016 Citation: Atiyeh, H. K., Development of the Hybrid Conversion Technology for Sustainable Production of Fuels and Chemicals, Masdar Institute of Science and Technology, Abu Dhabi, UAE, June 2, 2016.
  • Type: Other Status: Other Year Published: 2015 Citation: Atiyeh, H. K. and N. Wang. Development of gas sensor for efficient biological gas conversion to fuels and chemicals. Submitted to Oklahoma State University-Technology Development Center on 09/10/15. disclosure number 2016.08.
  • Type: Other Status: Other Year Published: 2015 Citation: Atiyeh, H. K., J. R. Phillips and R. L. Huhnke. Fermentation Control for Optimization of Syngas Utilization. US Provisional Patent Application, Filed: 11/13/2015.
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2016 Citation: Phillips, J.R., H. K. Atiyeh and R. L. Huhnke, Enhanced Biological Ethanol Production from Syngas Using Novel Control Method, 2016 ASABE Annual International Meeting, Orlando, Florida, July 17-20, 2016. Oral.
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2015 Citation: Phillips, J. R., H. K. Atiyeh and R. L. Huhnke, Novel Feedback Control Method for Enhanced Ethanol Production via Syngas Fermentation, AIChEs 2015 Annual Meeting, Salt Lake City, UT, November 8-13, 2015, Oral.
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2015 Citation: Phillips, J. R., H. K. Atiyeh, R. S. Tanner, J. R. Torres, J. Saxena, M. R. Wilkins, and R. L. Huhnke. Fermentation Techniques and Medium Development for Butanol and Hexanol Production from Syngas by Clostridium carboxidivorans, AIChEs 2015 Annual Meeting, Salt Lake City, UT, November 8-13, 2015, Oral.
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2015 Citation: Phillips, J. R., H. K. Atiyeh and R. L. Huhnke, Driving Potentials for Mass Transfer, Reaction Kinetics and Thermodynamics Define Syngas Fermentation to Produce Ethanol, AIChEs 2015 Annual Meeting, Salt Lake City, UT, November 8-13, 2015, Poster.


Progress 06/15/15 to 09/30/15

Outputs
Target Audience:The target audiences include biofuel and biobased product producers, government officials involved in bioenergy policy, farmers interested in biomass production, researchers, and undergraduate and graduate students interested in production of biofuels and biobased products. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?Two Post Doctorate Research Associates and one PhD student were trained on syngas fermentation, bioreactor setup and operation and medium design. The students and Post-Doc Fellows had the opportunity to present their work at national and international conferences. How have the results been disseminated to communities of interest?Several journal articles were published in refereed journal. One book chapter was publishedand over 5 conference presentations were also delivered at national and international meetings. What do you plan to do during the next reporting period to accomplish the goals?Continue working to achieve project goals

Impacts
What was accomplished under these goals? Syngas fermentation for butanol and hexanol production Butanol and hexanol have higher energy density than ethanol and are more compatible with fuel infrastructure. The objective of this prject was to develop a minimal synthetic medium and culture technique for production of higher alcohols from syngas. The results showed that butanol (over 1.0 g/L), hexanol (up to 1.0 g/L) and ethanol (over 3.0 g/L) were produced in bottle fermentations by strain P7. In addition, minimal medium and controlled supply of CO and H2 should be used in characterizing candidate butanol and hexanol producing strains to select for commercial potential. ABE (acetone-butanol-ethanol) fermentation using redcedar and switchgrass ABE fermentations using redcedar and switchgrass were performed. Redcedar is an invasive softwood species causing problems in the Central Plains of the United States. Butanol production from eastern redcedar is more difficult than ethanol production due to more sensitivity of bacteria to the content of redcedar hydrolyzate. The goal of the study was to develop a conversion process for redcedar to butanol. The results showed that the type of buffer used is critical for efficient ABE fermentation. Acetate buffer was selected for enzymatic hydrolysis and ABE fermentation because citrate buffer inhibited ABE fermentation. Hydroxymethylfurfural, furfural, cinnamaldehyde, vanillic acid and syringaldehyde were among the inhibitors detected in the redcedar prehydrolyzate and hydrolyzate. Detoxification of redcedar hydrolyzate was required to remove inhibitors and enhance growth and butanol production. Butanol (13 g/L) and total ABE (19 g/L) were produced from detoxified redcedar hydrolyzate, which were comparable to glucose medium. The second project was focused on process development of butanol from switchgrass and quantification of inhibitors and detoxification of hydrolyzate. Hydrothermolysis-pretreated switchgrass at solid loading of 14% was hydrolyzed using Accellerase 1500. Clostridium acetobutylicum ATCC 824 fermented the hydrolyzate to ABE. Fermentations of non-detoxified and detoxified switchgrass hydrolyzates were compared. The results showed that pH adjustment and calcium carbonate addition to switchgrass hydrolyzate improved ABE production without detoxification. However, butanol production (6 g/L) was still very low due to presence of furanic and phenolic inhibitors in the hydrolyzate. Activated carbon detoxification removed detected inhibitors except cinnamaldehyde. In addition, detoxification of switchgrass hydrolyzate increased butanol titer from 1 to 11 g/L with a total of 17 g/L total ABE concentration. These results show the potential of butanol production from biomass feedstocks such as redcedar and switchgrass.

Publications

  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Devarapalli, M. and H. K. Atiyeh. 2015. A Review of Conversion Processes for Bioethanol Production with a Focus on Syngas Fermentation. Biofuel Research Journal. 7, 268-280.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Phillips, J. R., H. K. Atiyeh, R. S. Tanner, J. R. Torres, J. Saxena, M. R. Wilkins, and R. L. Huhnke. 2015. Butanol and Hexanol Production in Clostridium carboxidivorans Syngas Fermentation: Medium Development and Culture Techniques. Bioresource Technology. 190, 114-121.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Liu, K., H. K. Atiyeh, O.P. Planas, T. Ezeji, V. Ujor, J. Overton, K. Berning, M. R. Wilkins, and R. S. Tanner. 2015. Butanol Production from Hydrothermolysis-Pretreated Switchgrass: Quantification of Inhibitors and Detoxification of Hydrolyzate, Bioresource Technology. 189, 292-301.
  • Type: Book Chapters Status: Published Year Published: 2015 Citation: Wilkins, M. R., H. K. Atiyeh and S. K. Khanal, Syngas Fermentation, in Bioenergy: Principles and Applications, Y. Li and S. K. Khanal, Eds, ohn Wiley and Sons, New York, NY, USA. 2015.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: 6- Liu, K., H. K. Atiyeh*, O.P. Planas, K. D. Ramachandriya, M. R. Wilkins, T. Ezeji, V. Ujor and R. S. Tanner. 2015. Process Development for Butanol Production from Eastern Redcedar, Bioresource Technology. 176, 88-97.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Phillips, J. R., H. K. Atiyeh and R. L. Huhnke, Novel Feedback Control Method for Enhanced Ethanol Production via Syngas Fermentation, AIChEs 2015 Annual Meeting, Salt Lake City, UT, November 8-13, 2015, Oral.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Phillips, J. R., H. K. Atiyeh, R. S. Tanner, J. R. Torres, J. Saxena, M. R. Wilkins, and R. L. Huhnke. Fermentation Techniques and Medium Development for Butanol and Hexanol Production from Syngas by Clostridium carboxidivorans, AIChEs 2015 Annual Meeting, Salt Lake City, UT, November 8-13, 2015, Oral.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Phillips, J. R., H. K. Atiyeh and R. L. Huhnke, Driving Potentials for Mass Transfer, Reaction Kinetics and Thermodynamics Define Syngas Fermentation to Produce Ethanol, AIChEs 2015 Annual Meeting, Salt Lake City, UT, November 8-13, 2015, Poster.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Liu, K., H. K. Atiyeh, O. P. Planas, T. Ezeji, V. Ujor, J. Overton, K. Berning, M. Wilkins and R. S. Tanner, Production of Butanol from Switchgrass with and without Detoxification, 2015 ASABE Annual International Meeting, New Orleans, LA, Jul 26-29, 2015. Oral.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Phillips, J.R., H. K. Atiyeh and R. L. Huhnke, Enhanced Mass Transfer in Gas Fermentation Reactors, 2015 ASABE Annual International Meeting, New Orleans, LA, Jul 26-29, 2015. Oral.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Atiyeh, H. K., J. R. Phillips and R. L. Huhnke, Process Control for Enhanced Ethanol Production Using Syngas Fermentation, Bioenergy 2015: Opportunities in a Changing Energy Landscape, Walter E. Washington Convention Center, Washington, D.C., USA, June 23-24, 2015. Poster.