Progress 08/15/23 to 08/14/24
Outputs
Target Audience:The targeted audiences for this project are: Commercial Aviation Industry: Specifically, stakeholders within the aviation industry focused on reducing greenhouse gas emissions by using renewable, cost-effective bio-jet fuels. Scientific and Academic Communities: Researchers, students, and professionals in chemical engineering, renewable energy, and catalysis, who benefit from new insights and training in advanced fuel technologies. Socioeconomically Disadvantaged Communities: Indirectly targeted by the project's aim to develop cleaner fuel technologies, which support environmental health and can reduce pollution in communities disproportionately impacted by climate change. Research and Development Partners: Partner institutions (e.g., WSU, UNL) and associated scientists engaged in collaborative development, sharing expertise to enhance project outcomes and contribute to renewable fuel research. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?This project has provided an excellent environment for members of both groups to deepen their subject matter expertise, gain professional development opportunities, and engage in training that supports the development of the next generation of scientists. In PI Lin's group, a Ph.D. student strengthened their knowledge of core characterization techniques, including chemisorption, BET, and XRD. This student also learned the publishing process, working on their first manuscript, and plans to present their research at the CHARGE H2 Hydrogen Conference. Additionally, an undergraduate student developed skills in thermodynamics, chemical reaction design, and analysis, with a focus on the safe operation of high-pressure reactions. This student also gained foundational knowledge of characterization techniques. How have the results been disseminated to communities of interest?The results of this project have been shared with relevant communities through a series of invited talks, seminars, conference presentations, and a poster session. Key dissemination activities include: Invited Seminars by PI Lin: "Towards Holistic Approach for Decarbonizing Energy System" was presented at several institutions: Los Alamos National Laboratory (April 11, 2024) Clariant (February 14, 2024) PNNL/WSU Bioproducts Institute, Pacific Northwest National Laboratory (February 6, 2024) Department of Chemical Engineering, Northeastern University (January 17, 2024) SUNCAT, Stanford University (December 11, 2023) Presentations by Co-PI Cahoon: Invited Oral Presentation: "Towards Meeting the Sustainable Aviation Fuel Grand Challenge: Alternative Oilseeds and Vegetative Oil-Rich Biomass Crops" at Corteva Agriscience New Frontiers Conference, Indianapolis, IN (June 20, 2024). Invited Seminar: Presented at the Plant Biotech Academy Seminar Series 2024 at Bayer Crop Science, St. Louis, MO (January 12, 2024). Conference Presentation: "Co-Optimization of Camelina Oil Quality and Conversion Technologies for Sustainable Aviation Fuel" at the 1st International Camelina Conference, Lincoln, NE (July 19, 2024). Conference Poster: A poster titled "Co-Optimization of Camelina Oil Quality and Conversion Technologies for Sustainable Aviation Fuel" was presented by Nazarenus, T.J., Jia, C., Jangam, A., Floyd, J.B., Lin, H., and Cahoon, E.B. at the 1st International Camelina Conference in Lincoln, NE (July 19-20, 2024). Through these seminars, presentations, and poster sessions, the project team engaged academic, industrial, and scientific audiences, furthering awareness and discussion of innovations in sustainable aviation fuel production and related technologies. What do you plan to do during the next reporting period to accomplish the goals?In the next reporting period, the Lin group plans to complete reaction screenings on next-generation blended transgenic camelina oils. Additionally, several fundamental scientific questions have emerged during the manuscript preparation process, particularly concerning the catalyst structure/activity relationship. The Lin group will further investigate these observations, and the resulting oil activity data will be shared with the Cahoon group to facilitate effective collaborative design.
Impacts
What was accomplished under these goals?
In previous reports, PI Lin's group demonstrated the capability of the tandem biphasic catalytic process to produce jet-fuel range alkanes from transgenic oils. Development of Ru-based catalysts has been ongoing, and a publication summarizing recent results is currently in progress. Lin's group highlights the enhanced performance of the 5% Ru/C catalyst when modified with TiO2. In 4 hours at 175°C, the Ru/C-TiO2-N2catalyst achieved an 80.5% yield of heptadecane from oleic acid, or ~95% of the theoretical yield. By comparison, at an equal Ru loading, the Ru/C catalyst produced a 59.3% yield. The TiO2-modified Ru/C catalyst was further investigated under different gas environments--He, H2, and N2. Interestingly, the H2 treated Ru catalyst achieved an 82.7% heptadecane yield (4 hours at 175°C), similar to the N2 treated one, while the He treated catalyst had a 72.7% yield. It is currently hypothesized that H? and N? atmospheres increase the presence of metallic Ru, enhancing activity compared to He atmosphere. Physiochemically, the N? and H? treated samples had similar BET surface areas (527.3 and 526.3 m²/g, respectively), while He treated one had a lower surface area of 461.4 m²/g. It is evident that these atmospheres induce structural changes that correlate with activity results. Lin's group plans to explore these findings further and apply the insights to previously investigated and newly developed oils. In previous reports, consistency issues were noted between feedstocks and their corresponding yields. This issue has been addressed through rigorous troubleshooting. The Gen. I oils--C8, C10, C12, C14, C16, and C18--were used as a baseline for further modification. After reacting with the Ru/C-TiO2-N2 catalyst, all oils yielded jet-fuel range alkanes to varying degrees at 220°C over 4 hours, with yields as follows: C8 (5.8%), C10 (13.9%), C12 (15.1%), C14 (20.2%), C16 (6.6%), and C18 (7.6%). C14 produced the highest yield (20.2%), likely due to higher C14 and C16 fatty acid levels. Compared to the wild-type control, which had a yield of 6.93%, all oils except C8 and C16 exceeded the control, indicating the success of the first-generation transgenic feedstock. Notably, the C8 fatty acid, after decarboxylation, forms a C7 alkane and is thus excluded from jet-fuel range alkane yield calculations. The C16 oil, being significantly more viscous, is hypothesized to have lower performance due to this property. In Gen. II oils (C10/C14, C10/C12/C14, and C10/C14/C16), reactions under identical conditions (220°C, 4 hours) yielded 24.1%, 19.9%, and 21.6% jet fuel for C10/C14, C10/C12/C14, and C10/C14/C16, respectively. While these values are comparable with the C14 oil from Gen. I, the average Gen. I yield was 11.5%, while the Gen. II average was 21.9%. The average jet fuel yield between generations has nearly doubled, with the best-performing oil (C10/C14) producing 3.5 times more jet fuel than the wild-type control. Next, we plan to optimize the reaction conditions for C10/C14 oil to achieve higher jet-fuel range alkane yields. Simultaneously, co-PI Cahoon's group further developed their transgenic oils. During the current reporting period, the 2023 field plot seeds were analyzed for fatty acid composition, oil content, germination rate, and seed weight. The top-performing line in terms of total C8-C16 fatty acid content was the C10+C12+C14+C16 line (54%), with a mixture primarily of C10 (8%), C14 (12%), and C16 (30%) fatty acids. The C8+C10+C12+C14+C16 line accumulated 33% C8-C16 fatty acids, with a primary mix of C10 (8%) and C16 (20%) fatty acids. Total seed oil content for the C8+C10+C12+C14+C16 (32%) and C10+C12+C14+C16 (31%) lines was comparable to the wild-type (32%). Other lines were also similar to wild-type levels, with the C14 line having the highest oil content at 34%. Germination rates were over 93% for all lines except for the C12 (20%) and C16 (63%) lines. Seed weight (mg/100 seeds) for C10 (76 mg) and C8+C10+C12+C14+C16 (74 mg) lines was comparable to the wild-type (83 mg) but lower for the C12 (67 mg), C10+C12+C14+C16 (67 mg), C8 (66 mg), and C14 (66 mg) lines. The C16 line had a higher seed weight (107 mg) than the wild-type (83 mg). Oil from the 2023 field-grown engineered camelina lines was provided to WSU in November 2023 for additional BiTCP conversion research on individual and blended oils. A new C14-accumulating camelina line (C14+CnLPAAT) was bulked in the greenhouse during winter 2023 for field planting in 2024. Field plantings of this line were conducted on 0.1 acres at the UNL Plant Biotechnology Field Facility in Mead, NE, during the 2024 spring growing season. Wild-type camelina and the previously analyzed C14 line were also included in these plots. Seeds from these plots were harvested in July 2024. The greenhouse seeds underwent analyses for fatty acid composition, oil content, germination rate, and seed weight. The new C14 line accumulated more C8-C16 fatty acids (47%) than the original C14 line (29%), with a mixture primarily of C14 (28%) and C16 (19%) fatty acids. However, the total oil content of the C14+CnLPAAT line (27%) was lower than that of the C14 line (33%). The C14+CnLPAAT line's seed weight was higher (114 mg) than the wild-type (99 mg), though germination was quite low (15%). The 2024 field plot seeds are currently undergoing analysis for fatty acid composition, oil content, germination rate, and seed weight.
Publications
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2024
Citation:
Conference Poster
Nazarenus, T.J., Jia, C., Jangam, A., Floyd, J.B., Lin, H., Cahoon, E.B. (2024). Co-Optimization of Camelina Oil Quality and Conversion Technologies for Sustainable Aviation Fuel. 1st International Camelina Conference, July 1920, Lincoln, NE.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2024
Citation:
Lin, H; Invited seminar: Towards Holistic Approach for Decarbonizing Energy System , Los Alamos National Laboratory, April 11, 2024
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2024
Citation:
Lin, H; Invited seminar: Towards Holistic Approach for Decarbonizing Energy System , Clariant, February 14, 2024
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2024
Citation:
Lin, H; Invited seminar: Towards Holistic Approach for Decarbonizing Energy System , PNNL/WSU Bioproducts Institute, Pacific Northwest National Laboratory, February 6, 2024
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2024
Citation:
Lin, H; Invited seminar: Towards Holistic Approach for Decarbonizing Energy System , Department of Chemical Engineering, Northeastern University, January 17, 2024
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2024
Citation:
Cahoon, EB; Invited conference oral presentation: Corteva Agriscience New Frontiers Conference, Indianapolis, IN, Towards Meeting the Sustainable Aviation Fuel Grand Challenge: Alternative Oilseeds and Vegetative Oil-Rich Biomass Crops , June 20, 2024.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2024
Citation:
Cahoon, EB; Invited seminar: Plant Biotech Academy Seminar Series 2024, Bayer Crop Science, St. Louis, MO, Towards Meeting the Sustainable Aviation Fuel Grand Challenge: Alternative Oilseeds and Vegetative Oil-Rich Biomass Crops , January 12, 2024.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2024
Citation:
Cahoon, EB; Conference oral presentation: 1st International Camelina Conference, Lincoln, NE, Co-Optimization of Camelina Oil Quality and Conversion Technologies for Sustainable Aviation Fuel , July 19, 2024.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2023
Citation:
Lin, H; Invited seminar: Towards Holistic Approach for Decarbonizing Energy System , SUNCAT, Stanford University, December 11, 2023
|
Progress 08/15/22 to 08/14/23
Outputs
Target Audience:
Nothing Reported
Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?This project has created a plethora of direct training and professional development opportunities, which have been seized by a variety of individuals. In PI Lin's group, two undergraduate students were able to learn the principles of reaction engineering, utilizing an array of reactors, characterization instruments, and other various equipment. Fundamentals of process safety, reaction engineering, kinetics and thermodynamics were taught by senior graduate students and post-doctoral students and actualized in hands-on training in a safe laboratory environment. General research skills, such as logical experiment design, thorough review of literature, and thoughtful safety consideration, are held as valuable teachings passed from senior leadership to newer students. Of many field-specific teachings, fundamentals of chemisorption, physisorption, reactive chemistry and analytical chemistry (NMR, XRD, XPS, etc.), are emphasized and nurtured by an environment of well-informed peers, and experienced leadership. Soft skills, such as presenting findings, and navigating professional environments through collaborative work, are necessary and coached for the duration of this project. The Lin group would have one undergraduate student join as a graduate student, acquire and train an additional undergraduate student, and mentor two high-school interns through the lens of this project. Co-PI Cahoon hosted Carlos Bucio, a Hispanic American undergrad from University of North Texas at UNL as an REU (Research Experiences for Undergraduates) student during the summer of 2023. The REU student conducted research on crop engineering to enhance oil production for biofuel and bioproduct applications. He assembled and presented a research poster on his research for the UNL Summer Research Symposium. How have the results been disseminated to communities of interest?The research results have been disseminated to stakeholders and the broader community. PI Lin presented our research outcomes at the 2023 Bioeconomy Project Director Meeting hosted by the USDA National Institute for Food and Agriculture in Kansas City, MO. Co-PI Cahoon presented project findings at the 2023 American Oil Chemists Society (AOCS) Annual Meeting & Expo in Denver, CO to an audience of vegetable oil processors, renewable diesel and sustainable aviation fuel producers, and crop biotechnologists. What do you plan to do during the next reporting period to accomplish the goals?The PI Lin's group has successfully improved the previous Ru/C-TiO2 catalyst to possess greater cracking abilities, however, due to a large number of products being "over-cracked" into the gas phase, reaction parameters need to be tuned to maximize the yield of jet-fuel range alkanes. It is our belief that lower temperatures and short times are required to achieve this goal, however, at too low temperatures, the successful hydrogenolysis of the base triglycerides may not occur. By the next report, we aim to address this challenge directly. With respect to economic and environmental system improvement, two variables have been identified for improvement in the general biphasic tandem catalytic process. Firstly, the development of a novel nonprecious metal catalyst continues, with the goal of creating a stable transition metal phosphide, such as nickel phosphide, which is capable of similar activities, comparable to that of the previously developed noble metal catalyst. It is our hypothesis that the rigorous study and tuning of the Lewis and Brønsted acid sites can lead to selective cracking of the products generated by triglyceride hydrogenolysis and subsequent hydrogenation. Secondly, in efforts to make this process more environment and operator-friendly, the search and implementation of a green organic phase solvent is to be executed. With n-hexane being a desired product, and its primary source being crude oil, it would be beneficial to determine a more sustainable solvent prior to mass implementation. In the co-PI Cahoon's group, the 2023 field plot seeds will undergo analyses for fatty acid composition, oil content, germination rate and seed weight. Oil from the 2023 field-grown engineered camelina lines will be provided to WSU for additional research on the BiTCP conversion of individual and blended oils. A new C14 accumulating camelina line will be bulked in the greenhouse in the winter of 2023 for field planting in 2024.
Impacts
What was accomplished under these goals?
In previous reports, the PI Lin's group has developed an efficient biphasic interfacial catalytic process to achieve the goal of a one-pot production method of bio-jet fuel under mild conditions. The Ru/C-TiO2 catalyst was thoroughly investigated, and the role/importance of oxygen vacancies was explored. Ru/C-TiO2 was prepared and treated at 550°C in N2, Ar, and H2, respectively, to produce different concentrations of oxygen vacancies on the catalyst surface. Of these three different treatments, the N2-treated Ru/C-TiO2 (Ru/C-TiO2-N2) demonstrated the highest yield of 76.9 wt.% in the liquid transportation fuel-range hydrocarbons (C7-C22), utilizing the C14 camelina oil at 200°C. This accounts for 96.2% of the maximum theoretical deoxygenation yield of 79.9 wt.%. Using XPS and O2-TPD techniques, it was determined that Ru/C-TiO2-N2 possess not only a relatively high amount of oxygen vacancies but also relatively well-distributed oxygen vacancies, which are hypothesized to readily adsorb the carboxyl group of the fatty acids, facilitating conversion. This catalyst would then be used with the C8, C10, C12, C14 and C16 enriched feedstocks to produce 8.38%, 10.6%, 11.5%, 33.2% and 25.8% of jet-fuel range hydrocarbons (C8-C16), respectively, at reaction conditions of 220° and 28 bars. The C8, C10, C12, C14 and C16 enriched feedstocks, at these conditions, produced respective liquid alkane product yields of 81.8%, 53.6%, 65.8%, 91.1% and 64.8% with the C17 aliphatic alkane (n-heptadecane) accounting for 49.6%, 28.3%, 36.0%, 41.0% and 27.4% of the yield, respectively. Recently, while the total liquid yields demonstrated the success of the Ru/C-TiO2 catalyst to convert fatty acids to liquid phase alkanes, the large amount of n-heptadecane as a product was identified as a potential source for additional jet-fuel range hydrocarbons per reaction. To address this, the synthesis of the aforementioned Ru/C-TiO2 catalyst was reviewed. Due to the synthesis method relying on the modification of a commercial 5% Ru/C catalyst, the loading and distribution of the active phase is inherently limited to that of the commercial catalyst. To address this, a Ru/C-TiO2 catalyst was synthesized utilizing an oxalate deposition precipitation method. In this approach, a 1:1 mass ratio C-TiO2 support was made, and loaded with 5 wt.% of Ru, by coordinating Ru ions in an oxalate lattice prior to adherence to the support surface. While this method can inherently increase the Ru loading, it increases the dispersion, and lowers the particle size, leading to facilitated cracking of the n-heptadecane product. This catalyst was dubbed Ru/C-TiO2-OX and was loaded in a reaction with n-heptadecane to determine its ability to break this molecule down to the jet fuel range. In 3 hours, at 220°C and 30 bar, 99% conversion was obtained, with a liquid phase product yield of 34%, with the remainder in the gas phase. 77 wt.% of the liquid products coincide with the C8-C16 jet-fuel range, with a total jet-fuel range yield of 26.7%. For context, Ru/C-TiO2-N2 at the same reaction conditions, utilizing C14 enriched oil, produced products such that only 31.0 wt. % of its liquid products were in the jet-fuel range. With Ru/C-TiO2-OX demonstrating a greater ability to crack, it was tested in a reaction series that utilized the blended enriched oils of C10/C14, C10/C12/C14 and C10/C14/C16. At reaction conditions of 4 hours, 220°C and 30 bar of H2, these oils had liquid alkane product yields (C7-C22) yields of 52.5%, 51.0% and 48.55% respectively. Jet-fuel range alkane (C8-C16) yield was the highest with the C10/C14 oil, at 27.4%. The C10/C12/C14 and C10/C14/C16 oils produced 20.6% and 24.3% jet-fuel range yield respectively. Notably, the n-heptadecane yields of C10/C14, C10/C12/C14 and C10/C14/C16 oils were 17.8%, 21.3% and 17.5% respectively, which is a significant decrease when compared to the higher levels of C17 in the products of previous reactions. The coPI Cahoon's group continued to design, cultivate, and harvest new lines of camelina. The lines generated in the prior reporting period with transgene combinations to generate oils enriched in C8+C10+C12+C14+C16 fatty acids and C10+C12+C14+C16 fatty acids were taken to homozygosity in the current reporting period. These lines were bulked under greenhouse conditions to obtain enough seeds for field production. Field plantings of these lines were conducted on ~0.7 acres at the UNL Plant Biotechnology Field Facility in Mead, NE in the spring growing season of 2023. The wild-type camelina and previously analyzed lines that produce oils with C8, C10, C12, C14, and C16 fatty acids were also included in these field plots. Seeds from these plots were harvested in August 2023 and were subjected to mechanical pressing in the UNL Industrial Agricultural Products Center to obtain oil and will be shipped to the Lin lab for BiTCP analyses. Fatty acid compositions and oil content were measured for these lines from the greenhouse seed bulking. The top greenhouse performance with regard to total C8-C16 fatty acid content was observed with our new C10+C12+C14+C16 line (58%, C8-C16) and included a mixture of primarily C10 (11%), C14 (15%) and C16 (28%) fatty acids. The C8+C10+C12+C14+C16 line accumulated 41% C8-C16 fatty acid content and included a mixture of primarily C10 (15%) and C16 (19%) fatty acids. The total seed oil content for the C8+C10+C12+C14+C16 and C16 lines (28%) was slightly lower than wild-type and C14 (31%) with all the other lines having less total oil, C8 (26%), C10 (22%), C12 (25%) and C10+C12+C14+C16 (22%). The germination rate in the greenhouse for all lines was >95%, except the C16 line (57%). Seed weight (mg/100 seeds) for C8 (89 mg) and C14 (89 mg) lines were comparable to wild-type plants (95 mg) and slightly lower for the C10 (83 mg), C12 (83 mg), C10+C12+C14+C16 (80 mg) and C8+C10+C12+C14+C16 (82 mg) lines. The C16 line seed weight was higher (113 mg) than wild-type plants (95 mg).
Publications
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2023
Citation:
Cahoon EB, Nazarenus TJ, Lin H (2023) Oilseed Feedstock and Conversion Technology Co-Optimization for Sustainable Aviation Fuel. 2023 American Oil Chemists Society (AOCS) Annual Meeting & Expo, Denver, CO, May 1, 2023
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2023
Citation:
Lin H, Cahoon EB (2023) Efficient Production of Renewable Jet Fuel and Bio-Amines from Genetically Optimized Camelina. USDA National Institute for Food and Agriculture 2023 Bioeconomy Project Director Meeting, Kansas City, MO, July 13, 2023.
|
Progress 08/15/21 to 08/14/22
Outputs
Target Audience:Those who stand to benefit from this project include farmers, consumers in the jet fuel market, and the biofuel industry. The camelina sativa plant has demonstrated a multitude of agricultural advantages, including the ability to grow in multiple climate types and in inhospitable soil. Contemporary farmers of this crop would stand to benefit from the addition of a biofuel-generating industrial purchaser, with the prospect of camelina becoming a new energy crop for those who do not already produce it. The transgenic camelina plant produces a high seed oil content and considerable yield per hectare. This could potentially pad the profit streams of these farms and help sustain agricultural practices domestically and abroad. Consumers of jet fuel, primarily the U.S. government and its armed forces, could possess interest as the 2015 Paris Agreement set the goal of carbon neutrality by 2050, incentivizing the U.S. federal government to find less carbon-intensive methods for the generation of sustainable aviation fuels (SAFs). In the private sector, commercial airlines stand not only the marketing benefit of using SAFs but the prospect that this production method is cheaper, making market costs lower for large consumers. Those who produce biofuel will gain from the creation of another method of production. The diversification of feedstock will provide additional flexibility to these companies, allowing them to operate, despite shortages of other feedstocks. In addition, this system shows the potential to be more efficient than contemporary methods of jet fuel production, increasing the profit margins and production capacities of jet fuel-producing groups. With an increasing demand for low-carbon aviation fuels, this technology will arrive at an employable and profitable time. Washington State University (WSU) and the University of Nebraska - Lincoln (UNL) have benefited through the training and education of undergraduate and graduate-level students who are preparing to enter industrial posts as a high-caliber workforce. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?This project has given the ability for undergraduate and graduate students alike to gain knowledge and skills in areas such as catalysis, bio-fuel synthesis, and general instrumentation. Undergraduate students have been trained in various field-specific skills such as catalytic synthesis, reaction engineering and characterization with advanced analytical techniques, including various chromatographs, spectroscopy and gas adsorption techniques. In addition, many pragmatic skills, including reactor repair and wholistic research tactics how been passed from a senior generation of students to the upcoming class. Both undergraduate and graduate students have personally grown, gaining many opportunities to practice both professional communications and the presentation of technical content before an audience. Co-PI Cahoon hosted an African American student from Nebraska Wesleyan University at UNL as an REU (Research Experiences for Undergraduates) student during the summer of 2022. The REU student conducted research on crop engineering to enhance oil production for biofuel and bioproduct applications. He assembled and presented a research poster on his research for the UNL Summer Research Symposium. How have the results been disseminated to communities of interest?The research results have been disseminated to stakeholders and the broader community. We are committed to sharing our experience with other researchers and the public. PI Lin was invited to present our research outcomes at the 26th Annual Green Chemistry & Engineering Conference, Reston, VA. What do you plan to do during the next reporting period to accomplish the goals?For the next reporting period, PI Lin lab plans to develop a new efficient catalyst by considering our understanding of the key characteristics of a catalyst. Our focus will be on enhancing the catalyst's performance towards the yields of jet-fuel range hydrocarbons under mild conditions. The exploration of a novel nonprecious metal catalyst for this system is underway. We will develop transition metal phosphides, such as nickel phosphide, with both Lewis acid and Bronsted acid sites for converting the genetically modified camelina oils in the biphasic tandem catalytic process (biTCP). Besides the catalyst development, we will also focus on the life cycle assessment of the biTCP to understand the sustainability of the process. Co-PI Cahoon lab will collect oil pressed from seeds of the 2022 field-grown engineered camelina lines and provide them to WSU for additional research on BiTCP conversion of individual and blended oils. The new camelina lines with C8+C10+C12+C14+C16- and C10+C12+C14+C16-enriched oils will be bulked in the greenhouse in the winter of 2022 for field planting in 2023.?
Impacts
What was accomplished under these goals?
The lines generated in the prior reporting period with transgene combinations to generate oils enriched in C10+C14-fatty acids, C10+C12+C14 fatty acids, and C10+C14+C16 fatty acids were taken to homozygosity in the current reporting period. These lines were bulked under greenhouse conditions to obtain sufficient amounts of seeds for field production. Field plantings of these lines were conducted on ~0.5 acres in the UNL Plant Biotechnology Field Facility in Mead, NE, in the spring growing season of 2022. Wild-type camelina and previously analyzed lines that produce oils with C10, C12, C14, and C16 fatty acids were also included in these field plots. Seeds from these plots were harvested in July 2022 and are currently being subjected to mechanical pressing in the UNL Industrial Agricultural Products Center to obtain oil for the Lin lab for biTCP analyses. Fatty acid compositions and oil content were measured for these lines from field plots and our greenhouse seed bulking. The top field performance with regard to total C10-C16 fatty acid content was observed with our new C10/C14 (52%, C10-C16) and C10+C14+C16 (57%, C10-C16) lines. For most of the lines, C10-C16 content was higher under greenhouse versus field conditions. The exceptions were the C14 and C10+C14+C16 lines, which had C10-C16 content of ~5% of total fatty acids higher than seeds from greenhouse-grown plants. In addition, the total seed oil content for most of the lines was comparable or slightly higher in field-grown versus greenhouse-grown plants. One exception was the C10+C14+C16 line (28% oil in the field vs. 31% oil in the greenhouse). The seed germination rate in the field for all lines was >95%, except the C16 line (72%). Seed weight (mg/100 seeds) was comparable for most of the field-grown lines relative to wild-type plants (91-95 mg). The two exceptions were seeds from the C14 line (84 mg) and the C16 line (122 mg). Constructs containing transgene combinations to generate C8+C10+C12+C14+C16- and C10+C12+C14+C16-enriched oils were completed and introduced into camelina. T2 lines with these constructs produced oils highly enriched in C8-C16 fatty acids. The top line from the C10+C12+C14+C16 accumulated C8-C16 fatty acids in the seed oil to amounts of 57% of total fatty acids and included a mixture of primarily C10 (13%), C14 (15%), and C16 (23%) fatty acids. The top C8+C10+C12+C14+C16 line accumulated C8-C16 fatty acids in the seed oil to 46% of the total fatty acids and was enriched in C10 fatty acids (24%). In the previous reports, PI Lin group has developed an efficient biphasic interfacial catalytic process to realize the one-pot production of bio-jet fuel under mild conditions. We have also identified a few key catalyst properties which influence the catalysis of the deoxygenation reaction significantly. In the current period, we have further modified the Ru supported over metal oxide catalyst to achieve uniform oxygen vacancy density. In order to explore the oxygen vacancy's effect on the deoxygenation reaction of fatty acids in the biphasic system, the vacancies concentration was adjusted by the calcination of TiO2 in different gas atmospheres. The as-prepared Ru/C-TiO2 catalysts were calcined at 550 oC in N2, Ar, and H2, respectively, to produce different concentrations of oxygen vacancies on the metal oxide surface. Among the gaseous environments, the catalyst treated in N2 gas gave the highest yield of 76.9 wt.% in the liquid transportation fuel-range hydrocarbons (C7-C22) with C14 camelina oil at 200 oC, accounting for 96.2% of the maximum theoretical deoxygenation yield (79.9 wt.%). After optimizing the reaction parameters, the highest yield of jet-fuel-range hydrocarbons (C8-C16) can reach 43.1 wt.% with an additional 24.2 wt.% yield in diesel-fuel-range hydrocarbons (C17-C22) at 220 oC in 600 psi H2. Furthermore, by considering XPS and O2-TPD results, we have observed that besides the density of oxygen vacancies, the distribution plays a crucial role in promoting the deoxygenation reaction of fatty acids in the biphasic system. The best result for the N2-treated catalyst is due to the uniform distribution of oxygen vacancies on the catalyst's surface. The carboxyl group in the fatty acid molecules can readily be adsorbed on the oxygen vacancies located at the metal oxide surface, indicating that more oxygen vacancies on the surface would be more favorable for the deoxygenation reaction. Besides, the performance of the Ru/C-TiO2-N2 was further explored for the various genetically modified camelina oils with the enrichment of C8, C10, C12, C14, and C16 moieties in the oil. The C8, C10, C12, C14 and C16 oil variants were cable of generating 81.8%, 53.6%, 65.8%, 91.1% and 64.8%, respectively, of liquid alkane products ranging from C7 to C22 aliphatic alkanes. Of that, the C17 aliphatic alkane yield for C8 was 49.6%, C10 was 28.3%, C12 was 36.0%, C14 was 41.0%, and C16 was 27.4%. The total jet fuel-range alkane yield was 8.38%, 10.6%, 11.5%, 33.2%, and 25.8%, respectively. Overall, C14-enriched camelina oil showed the potential as the forerunning oil in the efficient synthesis of jet-fuel range hydrocarbons under the mild experimental condition of 220 °C and H2 pressure of 28 bars. Finally, the content and uniformity of surface oxygen vacancies and the genetic modification of oil variants were proved to realize the efficient production of renewable jet fuel in the biphasic interfacial catalytic process under mild conditions.
Publications
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2022
Citation:
Chuhua Jia, Hongfei Lin, Integration of Metabolic Engineering and Catalytic Upgrading to Produce Sustainable Aviation Fuel from Transgenic Camelina, the 26th Annual Green Chemistry & Engineering Conference, Reston, VA, June 6-8, 2022.
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Progress 08/15/20 to 08/14/21
Outputs
Target Audience:The target audiences include farmers, the aviation fuel industry, and professionals. Since camelina has several beneficial agronomic attributes: a short growing season, tolerance of cold weather, drought, semiarid conditions, and low-fertility or saline soils, it is an ideal crop for farmers who live in different areas and have different types of resources. With the high seed oil content and high yield per hectare, farmers can benefit from the biofuels industry and have a steady add-on income source by growing camelina. We also reach out to the energy company, Phillip 66, which may benefit from this project that provides innovative biorefining technology. The new technology is potentially more cost-effective and more efficient than the traditional hydroprocessed esters and fatty acids (HEFA) technology. It will allow energy companies to add the production capacity on an additional biofuel product line, sustainable aviation fuels with reduced greenhouse gas emissions, by leveraging the existing refinery infrastructure. The commercialization of this new technology will meet the fast-growing market demand for low-carbon aviation fuels. University of Nebraska - Lincoln (UNL) and Washington State University (WSU) will also benefit from this project. The students and postdocs who have been being trained in this project will gain expertise and become a high-quality workforce in related areas. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?The project has provided many opportunities to graduate and undergraduate students at WSU. The undergraduate students gained research experience and deepened their understanding of catalysis. The senior graduate student presented the research outcomes in the Virtual Symposium on Thermal and Catalytic Sciences for Biofuels and Biobased Products. They could communicate with other people in the same field and get feedback from their latest work, improving their presentation and communication skills. The UNL team initiated a Research Experience for Undergraduates program during the summer of 2021 that targeted African American students for 1890 land grant universities. One of the two students hosted at the University of Nebraska-Lincoln from Alabama A&M University participated in research involving the characterization of fatty acid compositions of seed oils from the engineered camelina lines used in our studies. The student not only conducted research but also assembled and presented a research poster on his lipid analyses. How have the results been disseminated to communities of interest?The WSU team presented their research outcomes in the Virtual Symposium on Thermal and Catalytic Sciences for Biofuels and Biobased Products. Also, one peer-reviewed paper was published in the scientific journal, Fuel. Research outcomes of the UNL team were presented at the 2021 American Oil Chemists Society Annual Meeting and Expo on May 6, 2021, by co-PD Cahoon in a talk titled "Synthetic Biology Application for Development of High-value Oil Traits." What do you plan to do during the next reporting period to accomplish the goals?The WSU team plans to develop a new efficient catalyst during the next reporting period based on our understanding of the key catalytic properties and then evaluate the genetically modified camelina oil that contains jet-fuel-type fatty acids in the biphasic interfacial catalytic process. For the byproduct of camelina cake, we plan to use amino acids as a sustainable nitrogen source to produce pyrazines with glycerol (a byproduct from renewable fuel production). Moreover, we plan to utilize the recovered meal from seed pressing to produce nitrogen-doped biochar, which can be used as catalyst support in the production of aviation fuel from camelina oil. This work will broaden the application of the byproduct camelina cake. Oil will also be pressed from seeds of the 2021 field-grown engineered camelina lines and provided to WSU for additional research on BiTCP conversion of individual and blended oils. Our camelina lines with C10+C14-enriched oils will be bulked in the greenhouse in the winter of 2021 for field planting in 2022. Top-performing T1 camelina lines with C10+C14/C12- and C10+C14/C16-enriched oils will be identified and advanced to homozygosity with a possible small field planting in 2022. Transgenic camelina lines transformed with transgene combinations for C10+C14/C16/C12- and C10+C14/C16/C12/C18-enriched oils will be identified and advanced to the T1 stage for evaluation of the fatty acid composition of the resulting seed oils.
Impacts
What was accomplished under these goals?
In the last report, we developed a biphasic interfacial catalytic process to realize the one-pot production of bio-jet fuel under mild conditions. However, the key catalyst properties that control activity and selectivity in the biphasic interfacial catalytic process were still ambiguous. Moreover, the effect of surface and bulk oxygen vacancies distribution on the deoxygenation reaction in the biphasic process was unclear. Currently, we have completed the determination of key catalytic properties in the catalytic deoxygenation reaction of camelina oil in the biphasic interfacial catalytic process and developed a fundamental understanding of the metal oxide effect. Using these insights, we can develop more efficient catalysts in the biphasic interfacial catalytic process. Based on the previous result, we developed efficient metal oxide-supported ruthenium catalysts to increase the deoxygenation reaction rate and unravel the effect of various catalytic properties on the reaction in the biphasic interfacial catalytic process. Here ruthenium catalysts with different wettability were synthesized by tuning the carbon and metal oxide ratios. It was found that wettability played a significant role in the biphasic systems. Our previous study proved that the oil-in-water emulsion system would promote the fatty acids' deoxygenation reaction rate. By adjusting the wettability, the yield of heptadecane (C17H36) reached the highest value of ~39.4% at 150 °C when the optimal ratio of carbon to metal oxide was 3:3. In contrast, either increasing or decreasing the carbon to metal oxide ratio from the optimal value led to the reduced heptadecane yield, which was ascribed to the stronger hydrophilicity or hydrophobicity. The too strong hydrophobicity of the catalyst made the oil-in-water interface less stable. On the other hand, since fatty acid was mainly partitioned into the organic phase even under high temperatures, too strong hydrophilicity may retain the catalyst in the aqueous phase and therefore inhibit the fatty acids molecule from being in contact with the catalyst. Thus, the catalyst with suitable wettability is crucial for biphasic catalysis. Besides, in order to investigate various metal oxides' effect on the deoxygenation reaction, we prepared reducible and non-reducible metal oxide supported catalysts to investigate how the oxygen vacancies would influence the catalytic performance. These catalysts were characterized by XRD, XPS, H2-TPR, O2-TPD, etc. The existence of oxygen vacancies in the reducible metal oxide was found to play an important role in the deoxygenation reaction in the biphasic interfacial catalytic process. The reducible metal oxide that can create oxygen vacancies exhibited better catalytic performance than non-reducible metal oxides. Reducible metal oxide modified Ru/C catalyst gave higher yields of the deoxygenation products (25.9% of C17 and 6.0% of C18) than those modified with non-reducible metal oxide (14.5% of C17 and 2.6% ofC18) at 150 oC. Meanwhile, both the quantity and distribution of oxygen vacancies in the titania can affect the catalytic performance. Higher content of oxygen vacancies on the titania surface is beneficial for the deoxygenation reaction through the adsorption of the carboxyl group in the fatty acid molecules. The fundamental understanding of the catalytic properties would be beneficial for developing next-generation efficient catalysts for the deoxygenation of genetically modified camelina oil that contains jet-fuel-type fatty acids. Field plantings of individual engineered camelina lines with oils enriched in C10, C12, C14, C16, and C18 fatty acids were conducted on ~0.75-acre plots in the UNL Plant Biotechnology Field Facility in Mead, NE in the spring growing seasons of 2020 and 2021. Seeds from these lines were harvested in July 2020 were subjected to mechanical pressing to obtain one to two gallons of vegetable oil from each line. One gallon samples of this oil and meal were provided to the Lin lab for BiTCP and amine bio-conversion. Oils from C10 lines contained 12.5% capric acid (10:0), C12 lines contained 22% lauric acid (12:0), C14 lines contained 24% myristic acid (14:0), C16 lines contained 41% palmitic acid (16:0), and C18 lines contained 71% oleic acid (18:1). The oil content of seeds from C14 and C18 lines was not significantly different from the oil content of non-engineered wild-type seeds and ranged from 32% to 35% of seed weight. The C10, C12, and C16 lines had reduced oil content compared to wild-type seeds. The oil content of seeds from C10 and C12 was 29% of seed weight, and the oil content of seeds from C16 lines was 23% of seed weight. Seeds from 2021 field plots were harvested in July 2021 and await characterization and oil pressing. We also applied synthetic biology methods for modular assembly of transgenes to generate seed oils in engineered camelina that contain mixtures of fatty acid chain lengths to mimic Jet A fuel. We succeeded in generating engineered lines that have mixtures of C10 and C14 fatty acids and have advanced the top-performing lines to homozygosity. Seed oils from these lines produce ≤48% of C8 to C16 fatty acids versus 7.5% of these fatty acids in conventional camelina oil. Transgene combinations to generate C10+C14/C12- and C10+C14/C16-enriched oils were introduced into camelina. T1 lines from these transformations are now under greenhouse cultivation. We have completed the construction of transgene combinations for C10+C14/C16/C12- and C10+C14/C16/C12/C18-enriched oils. These gene constructs are currently being used to transform the camelina.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2021
Citation:
Chuhua Jia, Cheng Zhang, Shaoqu Xie, Wanli Zhang, Ziling Wang, and Hongfei Lin. "One-pot production of jet fuels from fatty acids and vegetable oils in biphasic tandem catalytic process." Fuel, 302, 121060. (2021)
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2020
Citation:
Chuhua Jia, Hongfei Lin. A generic biphasic approach towards the production of renewable fuels via catalytic deoxygenation of fatty acids. The 2020 Symposium on Thermal and Catalytic Sciences for Biofuels and Biobased Product, Virtual Conference, October 6, 2020.
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Progress 08/15/19 to 08/14/20
Outputs
Target Audience:The target audiences include farmers, jet fuel processors, the aviation industry, and universities. Since camelina has several beneficial agronomic attributes: a short growing season, tolerance of cold weather, drought, semiarid conditions, and low-fertility or saline soils, it is an ideal crop for farmers who live in different areas and have different types of resources. With the high seed oil content and high yield of oil per hectare, farmers can benefit from the biofuels industry and will have a steady add-on income source by growing camelina. The energy company will benefit from this project that provides innovative biorefining technology. The new technology is potentially more cost-effective and more efficient than the current technology. It will allow energy companies to add the production capacity on an additional biofuel product line, sustainable aviation fuels with reduced greenhouse gas emissions, by leveraging the existing refinery infrastructure. The commercialization of this new technology will meet the fast-growing market demand for low-carbon aviation fuels. University of Nebraska - Lincoln (UNL) and Washington State University (WSU) will also benefit from this project. The students and postdocs who are trained in this project will gain expertise and become a high-quality workforce in related areas. Changes/Problems:Due to the lab closure at Washington State University (WSU) caused by the Covid-19 pandemic from March 24th to June 30th, 2020, the research activities were disrupted. Though the lab is reopened currently, the department staff team at WSU is still required to telework to comply with the governor's order and institutional policies. The office will be open only one day per week for package pickups. This will influence the purchase of supplies and chemicals significantly, which may impact future project progress. What opportunities for training and professional development has the project provided?The project has provided many opportunities to undergraduates, graduates, and postdocs. Undergraduates students gained research experience and learned a new insight into catalysis. From the project, they had the chance to examine what they learned in their textbook. For graduate students and postdoc, they obtained the opportunities to present their research outcomes in the Green Chemistry & Engineering 2020 Virtual Conference. The research experiences are geared to enhance the learning and scholarship of the participating students and to nurture their self-growth to be more independent and life-long learners and researchers. The postdoc also developed leadership skills through working as a mentor of graduate and undergraduate students. How have the results been disseminated to communities of interest?We are committed to disseminating our results to the communities of interest. The research outcomes we have completed so far were presented in the Green Chemistry & Engineering 2020 Virtual Conference and at the virtual 2020 Annual Meeting of the Korean Society for Plant Biotechnology. Many energy companies attended the conference, some of which may be interested in our technology. We also shared our experience with other researchers. Besides, two peer-reviewed papers were published on the premier scientific journals, one on ACS Sustainable Chemistry & Engineering and another on iScience. What do you plan to do during the next reporting period to accomplish the goals?During the next reporting period, we plan to complete the kinetic studies of the catalytic deoxygenation of camelina oil in the continuous stirred tank reactor and the catalyst longevity evaluation. For the byproduct of camelina cake, we will continue to work on the deoxygenation of amino acids to produce bio-based amines under mild reaction conditions. We expect to realize the deoxygenation reaction with the low-cost catalyst to replace noble metal used in our previous studies. Besides, we plan to utilize lignocellulosic components in camelina cake and convert them into aromatics and value-added products. The oil will also be pressed from seeds of the field-grown engineered camelina lines and provided to WSU for biTCP conversion of individual and blended oils. The recovered meal from seed pressing will also be used in bio-based amine production. We will also complete the assembly of our nine transgene expression vector and initiate camelina transformation experiments
Impacts
What was accomplished under these goals?
The market demand for bio-jet fuels is driven by the need for reducing carbon emission in the commercial aviation industry. Considering that the traditional biofuel production processes are complex and energy-intensive, it is imminent to develop mild, effective, and efficient conversion processes. In this project, our objective is to engineer camelina that produces enriched mid-chain fatty acids and develop a catalytic conversion process to produce bio-jet fuel from engineered camelina feedstock with significantly improved reaction rates. Meanwhile, for sustainable development, the camelina cake, a byproduct after pressing out the oil from engineered camelina, will be converted to amine co-products due to its high content in protein. Amines are widely used in pesticide, pharmaceutical, and chemical industries. The farmers will directly benefit from the biofuels industry and will have a steady add-on income source by growing camelina. The energy company will benefit from this project that provides an innovative, more cost-effective, and more efficient biorefining technology, which reduces the operation and production cost. The commercialization of this new technology will meet the fast-growing market demand for low-carbon aviation fuels. Currently, we have completed the development of a high-efficient catalyst for the conversion of camelina oil to bio-jet fuel in the biphasic tandem catalytic process (biTCP) and the conversion of amino acids (hydrolysis product of protein) to biobased amines for decreasing the reliance on fossil resources. The technology was successfully tested at WSU using high oleic acid camelina oil generated at UNL. We also initiated the production of camelina oil with different fatty acid chain-lengths ranging from C10 to C18 for BiTCP to generate JetA fuel functionality. Individual engineered camelina lines with oils enriched in C10, C12, C14, C16, and C18 fatty acids were initially grown under greenhouse conditions at UNL to bulk seed production. Seeds from these lines were confirmed to retain the target fatty acid compositions and were planted on a ~0.75 acre plot in the UNL Plant Biotechnology Field Facility in Mead, NE. Seeds from these lines were harvested in July 2020 and are now awaiting pressing to obtain oil for BiTCP and meal for amine bio-conversion. We also initiated efforts to generate camelina lines that produce C8-C18 fatty acid-rich oils in single seeds, as an optimized biTCP oil feedstock. To date, we have generated transcriptional units for six of the nine genes needed for synthetic biology-based modular assembly of our expression vector for camelina transformation. We also set up a continuous stirred tank reactor for the evaluation of the catalyst longevity. In the section for the conversion of camelina oil to bio-jet fuel, the biphasic interfacial catalytic process was developed to realize the one-pot production of bio-jet fuel under mild conditions. It was found that the cracking selectivity can be tuned through adjusting the ratios of cyclohexane and water. Next-generation ruthenium on carbon catalysts were synthesized and characterized with BET, XRD, SEM, TEM, NH3-TPD, XPS, etc. Compared with the commercial ruthenium on carbon catalyst, the deoxygenation reaction rate was increased five times. The carbon yield of jet-fuel-range alkanes can reach ~ 35.2 wt% at a relatively low temperature (260 oC). The catalyst also showed good stability after 5 cycles. The application of the efficient biphasic process was further extended to triglycerides and crude vegetable oil for the production of bio-jet fuel. In terms of the conversion of amino acids, the diamine (cadaverine) was produced in a high yield from the second most-produced commercial amino acid (L-lysine). In the selective deoxygenation of lysine, the synergistic effect of the carbon-supported ruthenium catalyst and the phosphoric acid co-catalysts, the role of hydrogen gas, and the activation and suppression of the functional groups of lysine were elucidated in great detail. Under the optimum conditions, a 100% conversion of L-lysine and a ∼94% total yield of amines, with a ~ 51% selectivity to diamines, were attained at 200 °C within two hours. Moreover, both characterization and kinetic studies of the probe reactions were used to understand the reaction mechanism. The knowledge gained in this study may provide fundamental insights into the selective deoxygenation of other N-containing renewable feedstocks. Overall, in this reporting period, we have developed a high-efficient catalyst for the mild, effective, and efficient conversion process of camelina oil to bio-jet fuel. The successful conversion of amino acids to biobased amines is also well-prepared for the utilization of camelina cake in the following work.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2020
Citation:
Shaoqu Xie, Chuhua Jia, Ziling Wang, Scott Sergio Go Ong, Mei-jun Zhu, and Hongfei Lin. "Mechanistic insight to selective deoxygenation of L-lysine to produce biobased amines." ACS Sustainable Chemistry & Engineering, 8 (31), 1180511817. (2020)
- Type:
Journal Articles
Status:
Published
Year Published:
2020
Citation:
Shaoqu Xie, Chuhua Jia, Scott Sergio Go Ong, Ziling Wang, Mei-jun Zhu, Qiaojuan Wang, Yanhui Yang, Hongfei Lin. "A shortcut route to close nitrogen cycle: bio-based amines production via selective deoxygenation of chitin monomers over Ru/C in acidic solutions" iScience, 23 (5), 101096. (2020)
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