Progress 05/01/24 to 04/30/25
Outputs
Target Audience:During the current reporting period, our project continued to engage a wide range of target audiences through academic showcases, professional conferences, and industry collaborations, with a strong focus on both dissemination and feedback integration. Firstly, graduate students involved in the project presented our research at three separate university-level graduate research symposia held at Auburn University. Each event attracted approximately 200 attendees, primarily graduate students, faculty, and staff across engineering and scientific disciplines. These presentations served as a platform for early-career researchers to present preliminary findings, receive constructive feedback, and build academic visibility for the biolubricant project. In addition to academic audiences, we sustained strong connections with our industry collaborators. Several virtual and in-person meetings were held throughout the year to share recent progress, brainstorm research directions, and align our objectives with real-world application and commercialization needs. These discussions included representatives from lubricant formulation companies and industry experts who offered insight into product compatibility, regulatory trends, and testing protocols, helping us fine-tune our research approach. We also participated in the annual Tribology Symposium hosted at Auburn University. This event brought together researchers and professionals from sectors such as grease, hydraulic fluids, heavy-duty lubricants, and industrial lubricant formulation. Our project team delivered a targeted presentation followed by technical Q&A sessions, furthering engagement with about 20 industry attendees and establishing new networking channels. Nationally, our team contributed to the American Society of Agricultural and Biological Engineers (ASABE) Annual International Meeting held in Anaheim, California. Our research was presented in the Bioproduct Development session, which drew approximately 50 attendees, including academic researchers, industry professionals, and graduate students focused on sustainability and renewable product development. The presentation sparked discussions around waste valorization, catalytic processing of bio-based feedstocks, and market readiness of biolubricants. In addition to conference presentations, the team submitted a manuscript titled "Comparative analysis of biolubricants produced via transesterification, epoxidation, and a novel Friedel-Crafts acylation-based process" to ACS Sustainable Chemistry & Engineering. The manuscript is currently under peer review and, if accepted, will further expand our outreach to researchers in the fields of green chemistry, catalysis, and sustainable materials. Through these multi-faceted outreach activities, our project continued to effectively engage its core audience (academic researchers, graduate students, industry partners, and bio-based product stakeholders) thereby contributing to both the scientific development and real-world relevance of sustainable biolubricant technologies. Changes/Problems:During this reporting period, several strategic adjustments were made to the project's original approach in response to experimental findings, practical considerations, and emerging opportunities. These changes were implemented to optimize the research process, address technical challenges, and enhance the scientific and commercial impact of the work, while remaining consistent with the overall project goals and objectives. One significant change was the continued refinement and advancement of the low-temperature Friedel-Crafts (FC-LT) synthesis pathway, which emerged as a superior alternative to the originally proposed high-temperature dehydration method. While the original plan focused on thermal dehydration of fatty acids, the high temperature requirement posed limitations in terms of energy efficiency and reaction control. To address this, we transitioned to a catalytic route that involves the formation of fatty acid chlorides and anhydrides using SOCl?. Although this adjustment introduces chlorinated intermediates not included in the original proposal, it has significantly improved reaction efficiency and product quality. The modification also provides a new platform for techno-economic analysis (TEA) and life cycle assessment (LCA), offering the potential to quantify both cost savings and environmental benefits. These modeling components are now being formally incorporated into the research plan. A second notable development was the inclusion of additive compatibility and solvency testing, which was not originally outlined in the proposal. This change was driven by the project's strong experimental outcomes and increasing engagement with industry partners. To evaluate the performance of the synthesized biolubricants under real-world operating conditions, a series of studies will be conducted using commercial additives such as viscosity index improvers and pour point depressants. These tests are critical for assessing formulation compatibility and advancing the technology toward market readiness. Furthermore, based on the promising results obtained at laboratory scale, we are planning to initiate bench-scale process scale-up to evaluate synthesis reproducibility, reaction consistency, and preliminary production metrics. This expansion, though not explicitly listed in the original work plan, is a natural progression of the research and is essential for future commercialization and industry validation. Another adaptation involved narrowing the scope of the chemical model compounds investigated. While the original proposal included a broad set of lignin-derived cyclic compounds (e.g., furan, guaiacol, cyclopentanone), preliminary findings revealed only minor differences in reactivity among them. To streamline our efforts and better align with the project timeline, the team has focused on anisole as a representative aromatic compound, allowing for more in-depth mechanistic exploration and clearer correlation with final product properties. Finally, one personnel-related challenge worth noting is that one of the Ph.D. students originally recruited for this project was unable to join the team until January 2025 due to a prolonged visa delay. This impacted the timeline for TEA and kinetics work. However, since joining, the student has been rapidly progressing and contributing meaningfully to the project. What opportunities for training and professional development has the project provided?During this reporting period, the project provided extensive training and professional development opportunities for three Ph.D. students--two from Biosystems Engineering and one from Mechanical Engineering, who were directly or partially supported by this USDA-NIFA award. One Ph.D. student, who has been with the project since Summer 2023, continued to build on her technical skill set by receiving hands-on training in a range of advanced analytical techniques. This included gel permeation chromatography (GPC), tribological testing using a ball-on-disk tribometer (Bruker UMT-3), and wear profile analysis via stylus profilometry. The student also gained further experience using DSC, TGA, GC, flash point analyzers, and viscometers. She presented her research at the ASABE Annual International Meeting in Anaheim, California in July 2024, and participated in the 2024 Auburn University Tribology Symposium, which provided valuable exposure to industry stakeholders and academic peers in the lubricants field. A second Ph.D. student officially joined the project in January 2025 after a year-long visa delay. Since joining, the student has been trained on key instrumentation including NMR, TGA, GPC, GC, and flash point analyzers, and learned to operate laboratory-scale reactors such as the Parr reactor and a tandem microreactor system. These skills are foundational for upcoming work on reaction kinetics, catalyst optimization, and techno-economic modeling. The student also presented initial results at the 2025 Graduate Research Symposium at Auburn University, helping build confidence and experience in scientific communication. The third student, from the Mechanical Engineering Department, was partially supported by this project and contributed tribology expertise, specifically focusing on wear and friction testing of synthesized biolubricants. This student helped perform Stribeck curve analysis, boundary lubrication assessments, and wear volume measurements. Through this collaboration, both biosystems and mechanical engineering students benefited from interdisciplinary knowledge exchange. How have the results been disseminated to communities of interest?During this reporting period, the research team expanded its dissemination efforts to reach multiple technical and professional communities relevant to the development and application of sustainable biolubricants. The goal was to engage academic peers, industry stakeholders, and the broader research community through targeted presentations and peer-reviewed publication activities. The project was prominently featured at the 2024 Annual Internationam Meeting of the American Scosiety of Agricultural and Biological Engineers (ASABE)in Anaheim, California. The presentation, delivered as part of the Bioproducts Development session, attracted significant interest from both industry and academic attendees, including professionals from the biolubricants, additives, and sustainable materials sectors. The session provided an opportunity to exchange insights on renewable lubricant development and valorization of waste cooking oil, directly aligning with the project's goals and impact. In addition, the team participated in the 2024 Auburn Tribology Symposium, where research findings were shared with professionals and technical experts in the field of friction, wear, and lubrication. The presentation focused on lubricant characterization, tribological testing outcomes, and formulation strategies, and was followed by discussions with industry representatives on performance metrics, application areas, and formulation compatibility. Locally, students presented their research at several events on the Auburn University campus, including the Graduate Rresearch Symposiumand the 3-Minute Thesis (3MT) competition. These forums helped students develop scientific communication skills while raising awareness of the project among a broader academic audience. One student also presented a poster on biolubricant characterization at the Auburn Research Symposium in early 2025, focusing on the performance comparison between traditional and novel synthetic routes. In parallel with these activities, the team completed a manuscript titled "Comparative analysis of biolubricants produced via transesterification, epoxidation, and a novel Friedel-Crafts acylation-based process", which is currently under peer review with ACS Sustainable Chemistry & Engineering. This manuscript consolidates key technical findings from the current reporting period and will serve as an accessible resource for both researchers and industry professionals. Moving forward, additional manuscripts and national conference presentations are planned to further disseminate outcomes related to catalyst optimization, techno-economic analysis, and lifecycle assessment. Overall, dissemination efforts this year were designed to ensure the project's scientific contributions are shared with communities best positioned to apply, expand, and benefit from this research. What do you plan to do during the next reporting period to accomplish the goals?During the next reporting period, our team will continue to advance the objectives of the project through a combination of laboratory experimentation, process optimization, and modeling efforts. The focus will be on deepening our understanding of reaction kinetics, expanding biolubricant testing with performance-enhancing additives, and initiating scale-up trials that reflect real-world formulation conditions. To support Objective 1 (reactivity of WCO model compounds) and Objective 2 (reaction mechanisms and kinetics), we will begin kinetic studies using representative model compounds to better understand the rate behavior and mechanistic pathways of key reactions--particularly the Friedel-Crafts acylation and hydrodeoxygenation steps. These studies will include both isotopically labeled compounds and real WCO derivatives to account for feedstock variability and impurity effects. Additionally, we will examine how residual oxidation products and other impurities influence catalyst performance, including potential poisoning and regeneration dynamics. In line with Objective 3 (bio-lubricant production from real WCO and TEA), a comparative synthesis will be conducted using both waste cooking oil and virgin vegetable oil to assess how feedstock composition impacts product quality and process economics. This study will result in a second manuscript draft, which we aim to submit to a peer-reviewed journal. The student leading this task will also begin preliminary techno-economic analysis (TEA) using updated experimental data. This will help identify key cost drivers and opportunities for economic optimization. Where feasible, preliminary life cycle assessment (LCA) modeling will also be initiated to assess environmental trade-offs between pathways. We will also initiate solvency and additive compatibility testing of the synthesized biolubricants. These studies will explore how different classes of additives (e.g., pour point depressants, viscosity index improvers) interact with the FC-based biolubricant base oil. Batches with varying additive concentrations will be formulated to assess homogeneity, miscibility, and performance under thermal cycling. This is a critical step toward validating the commercial applicability of the product, particularly for use in automotive, hydraulic, or industrial lubrication systems. Lastly, the team will explore scale-up of the FC-based synthesis process at bench-scale to begin assessing the feasibility of consistent batch production. This will include evaluation of reaction reproducibility, separation efficiency, and product consistency.
Impacts
What was accomplished under these goals?
A major accomplishment during this reporting period was the development and official filing of a provisional patent application with the United States Patent and Trademark Office (USPTO) for the newly established low-temperature Friedel-Crafts (FC-LT) biolubricant synthesis pathway. The patent, titled "Low-Temperature Synthesis of Advanced Friedel-Crafts Bio-Lubricants from Vegetable Oils" (Application No. 63/791,875), was submitted on April 21, 2025, with Hossein Jahromi, Sushil Adhikari, and Noor Fatima listed as inventors. This filing represents a significant step toward technology transfer and potential commercialization of the process. Significant progress was made during this reporting period toward all three objectives of the project, including experimental validation of a novel catalytic pathway, detailed characterization of the resulting biolubricants, comparative analysis with traditional methods, and industry engagement for real-world application testing. Objective 1: Investigate the reactivity of WCO model compounds. We conductedexperiments using oleic acid as a model compound to represent waste cooking oil (WCO). These experiments were carried out in a tandem microreactor using different catalysts to examine reactivity and potential aromatization pathways. A novel low-temperature synthesis route was developed to convert hydrolyzed fatty acids into fatty acid chlorides using SOCl?. These intermediates were further reacted to produce fatty acid anhydrides, which then underwent Friedel-Crafts (FC) acylation with anisole in the presence of zinc chloride and choline chloride. These reactions successfully produced biolubricants with the desired molecular architecture--long saturated hydrocarbon chains coupled with cyclic rings and low oxygen content. This work laid the foundation for ongoing studies into feedstock-catalyst interaction and optimal reaction conditions. Objective 2: Reaction mechanism, catalyst poisoning, and kinetics. The newly developed low-temperature Friedel-Crafts pathway was extensively evaluated against traditional transesterification and epoxidation routes, using both linear (methanol) and cyclic (cyclopentanol) alcohols for comparative benchmarking. While cyclic structures could be introduced through transesterification with cyclopentanol, the resulting lubricants exhibited inferior performance compared to those produced via the FC method. These experiments provided insights into reaction selectivity, byproduct formation, and the influence of chemical structure on tribological and thermal performance. Comprehensive characterization--including FTIR, GC, DSC, TGA, viscometry, Noack volatility, flash point, and oxidative stability--was completed to support reaction mechanism understanding and kinetic modeling. Although full kinetic modeling is ongoing, this period laid the groundwork for reaction pathway validation and catalyst screening. Objective 3: Bio-lubricant production from real WCO and techno-economic analysis (TEA). Progress under Objective 3 was impacted by delays in personnel availability. The Ph.D. student originally recruited to lead this task faced visa-related challenges and was only able to officially join the research team in January 2025. Despite the delayed start, the student has quickly gained momentum and contributed meaningfully to advancing this objective. Since onboarding, real waste cooking oil (WCO) was sourced from a local restaurant, pre-characterized, and successfully utilized in the low-temperature Friedel-Crafts synthesis route. The resulting biolubricant samples were analyzed using thermal and tribological characterization techniques, and samples were delivered to our industrial partner, RSC Bio Solutions, for additional evaluation. Notably, oxidative stability testing of both high- and low-temperature FC products yielded promising results, validating the applicability of the synthetic routes to real-world feedstocks. Additionally, work began to align experimental process data with techno-economic analysis (TEA) modeling. The previously developed FC-HT pathway is being used as a benchmark for assessing energy requirements, yields, and cost competitiveness of the FC-LT approach. The student is currently compiling process yield data and side-product characterization to support preliminary TEA modeling in the next reporting period. Tribological testing, including Stribeck curve analysis, was performed using facilities in the Mechanical Engineering Department at Auburn University to evaluate friction and wear across lubrication regimes. The synthesized lubricants showed competitive performance in boundary, mixed, and hydrodynamic regimes, and wear measurements further confirmed the durability of the products. Additionally, a manuscript titled "Comparative analysis of biolubricants produced via transesterification, epoxidation, and a novel Friedel-Crafts acylation-based process" was submitted to ACS Sustainable Chemistry & Engineering and is currently under review.
Publications
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2024
Citation:
A comparative investigation of bio-lubricants synthesized via (trans)esterification, epoxidation, and Friedel-Crafts reaction using cooking oil and oleic acid as feedstocks.
Authors: Noor Fatima, Hossein Jahromi, Sushil Adhikari
ASABE 2024, Anaheim, CA
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Progress 05/01/23 to 04/30/24
Outputs
Target Audience:During the current reporting period, our project successfully engaged with diverse target audiences through a series of impactful presentations. These efforts were aimed at disseminating our research findings and fostering meaningful interactions within both academic and industrial communities. Firstly, our team delivered two University-level poster presentations at Auburn University, catering to graduate students and faculty members across various engineering disciplines. These sessions provided a platform to showcase our research outcomes and exchange insights with approximately 100 attendees, facilitating discussions on emerging trends and advancements within the field of biolubricants. Furthermore, our project extended its reach to industry professionals through a specialized presentation hosted at Auburn University's Tribology Symposium. With representatives from diverse sectors such as grease, hydraulic fluids, heavy-duty lubricants, and lubricant formulation industries, our engagement attracted around 20 experts. This industry-level discourse enabled us to not only share our progress but also to collect valuable industry perspectives and establish collaborative opportunities for future endeavors. Lastly, our team participated in the 2023 American Institute of Chemical Engineers (AIChE) Annual Meeting held in Orlando, FL, where we delivered a conference presentation. This platform, attended by approximately 100 delegates, provided an invaluable opportunity to disseminate our research on a broader scale, fostering dialogue and knowledge exchange among peers in the respective session. Changes/Problems:During the course of our research, minor changes were made to our approach in response to challenges encountered and insights gained. One notable issue with the initially proposed method was the high-temperature requirement for the dehydration step, presenting practical limitations and potentially compromising efficiency. To address this, our team has innovated a low-temperature method for producing acid chlorides and subsequent acid anhydrides, crucial building blocks for the final lubricant formulation. This novel approach introduces the use of chlorinated materials such as SOCl2, necessitating a strategy for chlorine recycling. While this new method enhances process yield, it also introduces the incorporation of additional chemicals not initially outlined in the project narrative. Despite this slight deviation, the team perceives it as an opportunity to engage with new scientific inquiries, particularly in Techno-Economic Analysis (TEA) and Life Cycle Assessment (LCA). This shift prompts the exploration of novel questions surrounding the environmental and economic implications of our revised methodology, aligning with Objective 3 of our project. Furthermore, as we progressed, it became apparent that the comprehensive investigation of all proposed cyclic compounds, including furan, cyclopentanone, and guaiacol, among others, would require substantially more time than initially anticipated. Moreover, preliminary findings suggested that the differences in reactivity among the listed compounds might not yield significantly distinct results. Consequently, during this reporting period, our focus has narrowed to the investigation of anisole as a representative lignin model compound, specifically examining its reactivity with vegetable oil-derived fatty acids. This adjustment enables us to streamline our efforts, ensuring alignment with project timelines while still capturing meaningful insights into the interactions between key chemical constituents of lignocellulosic biomass and vegetable oil. Moving forward, we anticipate further refinement of our chemical selection to encapsulate the diversity of macromolecules present in lignocellulosic biomass, thereby optimizing our research efforts and advancing toward the project objectives. What opportunities for training and professional development has the project provided?Two graduate students (PhD level) have been budgeted to work on this project. While the PI has offered admission to two students (both international students), only one student has been able to obtain a US Visa, while the other student's visa application is still pending. The current PhD student has started working on this project in Summer 2023. During this reporting period, the PhD student was trained on the use of various analytical instruments, including DSC, TGA, pour point, GC, and NMR, as well as handling different reactors and other lab equipment. The student had the opportunity to participate in various research symposiums, such as the Auburn Tribology Symposium, and two graduate research symposiums, which provided her with insights into the industrial and professional aspects of growth. How have the results been disseminated to communities of interest?The dissemination of our research findings has been tailored to engage relevant communities, with a focus on technical audiences, including industry stakeholders within the fields of biolubricants, lubricant formulation, hydraulic fluid manufacturing, and lubricant additives. One significant avenue for dissemination was our participation in the Auburn Tribology Symposium, where our presentation was specifically designed to address the interests and concerns of this targeted audience. Through an oral presentation followed by breakout sessions, we facilitated in-depth discussions and one-to-one meetings to explore potential pathways for advancing the project in light of emerging trends, particularly the transition from fossil-based to renewable lubricants, with a view to improving overall carbon emissions. Furthermore, our research findings were presented at the AIChE 2023 conference, broadening the reach of our work within the chemical engineering community. Additionally, we have secured acceptance to present our findings at the upcoming ASABE annual conference (July 2024), further extending the dissemination efforts within the agricultural and biological engineering community. Last but not least, we are currently in the process of preparing a manuscript for submission to a high-profile journal. Anticipated to be submitted by the end of Summer 2024, this manuscript will serve as a comprehensive resource for researchers and practitioners alike, ensuring the continued impact and relevance of our research within the broader scientific community. What do you plan to do during the next reporting period to accomplish the goals?During the upcoming reporting period, our team has outlined several key objectives to advance towards our project goals. Firstly, we intend to conduct a comprehensive analysis and characterization of waste cooking oil, focusing on identifying contaminants, oxidation products, and pre-processing requirements. This examination will provide essential insights into the composition and suitability of the feedstock for our processes. Furthermore, we plan to investigate the impact of these impurities on catalyst reactivity, specifically examining issues related to poisoning and regeneration across multiple stages, including dehydration, Friedel-Crafts acylation, and hydrotreatment. Understanding the intricate interplay between impurities and catalyst performance is crucial for optimizing process efficiency and product quality. In line with our continuous improvement efforts, we aim to improve our processes by exploring the possibility of integrating the hydrolysis and dehydration steps into a single-pot reaction. This consolidation not only has the potential to enhance process yield but also contributes to the economic viability of our approach by minimizing resource consumption and operational complexity. Additionally, we are committed to developing preliminary Techno-Economic Analysis (TEA) and Life Cycle Assessment (LCA) models, taking into account any slight adjustments made to our experimental plans. By incorporating these considerations early in the project, we can proactively identify potential economic and environmental implications, facilitating informed decision-making throughout the research process. Finally, our team will work on detailed reaction mechanism studies and begin the development of preliminary kinetic models for each reaction involved in our process.
Impacts
What was accomplished under these goals?
Since the initiation of the project, significant progress has been made toward achieving the outlined goals, with notable accomplishments across multiple facets of the proposed catalytic process. The project's objectives were approached methodically, with each step contributing to the overall advancement of our research endeavors. Regarding our first goal, which aimed to produce a diverse mixture of molecules featuring both linear long chain and cyclic structures, we selected two key feedstocks: oleic acid as a representative model compound for waste cooking oil (WCO), and fresh cooking oil (canola oil) for its comparative simplicity. Through careful experimentation, our team successfully synthesized bio-lubricants exhibiting unique chemical structures characterized by a blend of linear chains and naphthenic rings. Various synthetic routes were explored, including traditional methods such as epoxidation and transesterification, serving as baselines for comparison against the newly developed method. By studying the reactions of model compounds and hydrolyzed vegetable oils with anisole, we characterized the resulting products across multiple parameters, including lubricity, chemical composition, and cold flow properties. Furthermore, a novel low-temperature method was developed involving the chlorination of hydrolyzed vegetable oil followed by the Friedel-Crafts reaction. This approach aimed to mitigate the formation of undesirable side products while concurrently enhancing the energy efficiency of the overall system. In alignment with Objective 3, considerable progress was made in collecting experimental data pertinent to Techno-Economic Analysis (TEA) and Life Cycle Assessment (LCA). Critical metrics such as process yields, losses, and side-product generation were systematically recorded, laying the groundwork for comprehensive economic and environmental evaluations in future stages of the project. While substantial achievements have been made in addressing the objectives outlined in the project narrative, it's important to note that certain aspects, particularly those relating to Objective 2 - namely, kinetic studies and investigations into catalyst poisoning - were deferred to subsequent reporting periods due to the nature and scope of the experiments conducted within the first budget year. These elements will be prioritized in the forthcoming phases of our research, ensuring a holistic understanding of the catalytic processes under investigation.
Publications
- Type:
Conference Papers and Presentations
Status:
Accepted
Year Published:
2023
Citation:
Ecofriendly Biolubricant Production from Waste Cooking Oil and Lignocellulosic Biomass-Derived Oxygenates.
Authors: Hossein Jahromi, Sushil Adhikari
AIChE 2023, Orlando, FL
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