CARBON MONOLITH CATALYSTS FROM WOOD FOR BIOBASED PLATFORM CHEMICALS

• Sponsoring Institution: National Institute of Food and Agriculture
• Project Status: COMPLETE
• Funding Source: AFRI COMPETITIVE GRANT
• Reporting Frequency: Annual
• Accession No.: 1011654
• Grant No.: 2017-67021-26136
• Cumulative Award Amt.: $472,965.00
• Proposal No.: 2016-08060
• Project Start Date: Mar 1, 2017
• Project End Date: Aug 31, 2023
• Grant Year: 2017
• Program Code: [A1531]- Biorefining and Biomanufacturing

Recipient Organization
UNIVERSITY OF GEORGIA
200 D.W. BROOKS DR
ATHENS,GA 30602-5016

Performing Department
COLLEGE OF ENGINEERING

Non Technical Summary
Program Area Priority: Bioprocessing and BioengineeringGoal: Our goal is to develop new markets, products, and processes using activated carbon monolith catalysts produced from wood and to generate value added products from platform chemicals derived from agricultural and forest resources. Rationale: Activated carbon monolithic catalysts (ACMC) have many advantages over traditional catalysts and reactor design methods targeted for bio-based platform chemical production, yet are not currently used industrially and rarely studied. ACMC would enable continuous processing, lower operating costs, and allow rapid scale-up of hydrogenation and esterification reactions in fine, specialty, and bio-based chemicals production.Objectives: 1) Develop a continuous hydrogenation process using carbon monolith catalysts derived from wood to produce cyclopentanone from furfural for liquid crystals, fragrances, and pharmaceuticals, 2) Develop a bi-functional carbon monolith catalyst capable of continuously producing bicyclopentane (aviation fuel) from cyclopentanone, 3) Develop a method to attach enzymes to the carbon monolith catalyst and demonstrate a biocatalytic reaction using the newly developed material.Impact: This research will improve the efficiency of bio-based chemicals from biomass, engineer a new product from forest resources, and enhance the sustainability of chemical and materials production from biomass.

Animal Health Component

50%

Research Effort Categories

Basic

50%

Applied

50%

Developmental

(N/A)

Classification

Knowledge Area (KA)	Subject of Investigation (SOI)	Field of Science (FOS)	Percent
402	0650	2000	100%

Knowledge Area
402 - Engineering Systems and Equipment;

Subject Of Investigation
0650 - Wood and wood products;

Field Of Science
2000 - Chemistry;

Keywords

biocatalysis

bioproducts

carbon monoliths

catalysts

enzymes

platform chemicals

value added

Goals / Objectives
Goal: Our goal is to develop new markets, products, and processes using activated carbon monolith catalysts produced from wood and to generate value added products from platform chemicals derived from agricultural and forest resources. Our specific research objectives are the following.1.Develop a continuous hydrogenation process using carbon monolith catalysts derived from wood to produce cyclopentanone from furfural.2.Develop a bi-functional, carbon monolith catalyst capable of continuously producing bicyclopentane fuel from cyclopentanone, as an aviation fuel alternative.3.Develop a method to attach enzymes to the carbon monolith catalyst and demonstrate a biocatalytic reaction using the newly developed material.

Project Methods
Our first step will be to target cyclopentanone (CPON) and bicyclopentane (BCPentane) production using the metal/activated carbon monolith (ACMC, see Fig. 1) by hydrogenating furfural. Given the recent report using the bi-metal combination of Pd and Cu on carbon to selectively produce CPON we will work with our industrial partner, Applied Catalysts, to produce this Pd-Cu/ACMC. Our main focus will be engineering the design of ACMC's for CPON synthesis, but as a minor part of the project we will also like pursue synthesis of BCPentane from CPON. BCPentane is a potential aviation fuel replacement due to its very high energy density. BCPentane formation from CPON requires condensation and hydrogenation and thus a different catalyst formulation. For BCPentane we will develop a Pd/Base-ACMC for this required dual functionality. Simultaneously another graduate student will work on lipase attachment to the ACMC and demonstrating biocatalysis. Given the limitations of enzyme adsorption and entrapment (loss of enzyme due to leaching), we will focus on covalent attachment of lipase to the activated carbon surface (L-ACMC). Our focus for L-ACMC will be on biocatalytic esterification and formation of flavor esters used in the pharmaceutical, food, fragrance, and cosmetic industries (estimated $22B market). Specifically, we will target ethyl valerate synthesis from ethanol and valeric acid using a Candida antartica and C. rugose lipase.Fig. 1: Monolith structures prepared from activated carbon.

Progress 03/01/17 to 08/31/23

Outputs
Target Audience:Target audiences included researchers and industries in 1) biochemicals from renewable carbon sources, 2) catalysis, 3) production of furfural and its applications, 4) materials and products from wood based activated carbons. As petroleum resources dwindle and as greenhouse gas reductions are mandated, there will be a critical need to synthesize chemicals and materials for societal needs - e.g., pharmaceuticals, carbon materials, engineered polymers, and catalysts from renewable carbon sources generated by farmers and foresters. One aspect of this need has been termed the "bio-based" economy, where as much as possible, products are sourced/synthesized from renewables. Moreover, more consumers are switching to products that are bio-based, thus driving new markets, indicated by the number of niche products produced from biomass sources - e.g., bio-ethanol in Tide and glycerol acetalized with ethyl levulinate as a new bio-based solvent. Extreme fluctuations in oil prices and availability have precipitated academic and industrial research and development (R&D) on the production of fuels and energy from renewable carbon sources. Agricultural systems (e.g., corn, sugar cane, switchgrass) and sustainable forestry (e.g., Southern Pine) have played a major role in supplying these carbon neutral feedstocks for biofuels and energy production. Results from these efforts suggest that sugar from lignocellulosics and their subsequent conversion to biofuels is nearing commercialization.Biofuels production (ethanol for blending and to gasoline via zeolites) has plateaued due to the recent precipitous drop in oil prices. Moreover, increasing advancement in solar, wind, and battery technology, increasing fuel efficiency, and the possibility of a long term oversupply of oil, suggest there may be limited future need for biofuels and energy generation from lignocellulosics and starch crops.One may also argue that since economical technology and commercial pathways exist for biofuels production from starch and lignocellosics, except for jet and diesel fuel, at $3-4/gal gasoline, additional research in this area is not urgently needed. Thus, there has been much research and commercialization efforts for biofuel production, yet limited focus on the synthesis of chemicals and materials from agricultural or forest resources.Only recently has research focused on a chemicals based biorefinery.This research was initiated by the identification of platform chemicals that could be produced from biomass.Looking at selected pathways for synthesis of value-added products from these platform chemicals one can see that all steps require catalytic material.This is most apparent in the conversion of furfural to a range of value-added products. Many of the platform chemicals can be produced using a metabolically engineered microorganism (e.g., glucose to succinic acid)or acid hydrolysis of biomass (e.g., xylose to furfural),yet ultimate conversion to the final products of interest requires heterogeneous catalysts. One of the most important reactions requiring catalysis is hydrogenation/hydrogenolysis. Examples include succinic acid to g-butyrolactone and furfural to cyclopentanone.Except for the development of solid acid carbon catalysts (performing dehydration, hydrolysis, and esterification reactions),there has been limited research on the development of catalytic materials from agricultural and forest resources for these critical reactions. It is true that fine and specialty chemical manufacturers primarily use activated carbon supported catalysts,but there has been limited development of these catalysts for continuous processing and targeting the reaction environment in bio-based platforms (e.g., aqueous, acidic conditions). Furfural (FUR) is one of the few biomass platform chemicals currently produced on a large scale at ~400 kt/yr (relative to other bio-based platforms).In these processes, lignocellulosics containing high levels of hemicellulose (e.g., corn cobs, sugar cane bagasse, cottonseed hulls) undergo acid hydrolysis, typically using H2SO4. Hemicellulose is hydrolyzed to xylose, which is then dehydrated to furfural and steam stripped to generate an ~20 wt.% furfural stream (acetone and acetic acid are also present as co-products). An analysis by Shell Global indicates that current costs of furfural production prohibit biofuel production from this platform chemical.Current plants are too small to supply the volume of furfural needed, energy inputs need to be reduced, and yields must be increased (50 to ≥ 80%). Until significant improvements are made in furfural production, the synthesis of specialty chemicals from furfural may be a better option. Many of the products proposed to be synthesized from furfural have been resins (furfuryl alcohol), biofuels (ethyl furfuryl ether, methyl furan, MTHF), blending agents for fuels (ethyl levulinate), or solvents (furan).However, other higher value products can be synthesized from furfural that have smaller volume markets. Furfural can be hydrogenated to form cyclopentanone, cyclopentanol, or 5-hydroxy-2-pentanone, which are platform chemicals for the synthesis of liquid crystals, fungicides, pharmaceuticals, rubber chemicals, and fragrances.The competitive petroleum-based route to cyclopentanone is from adipic acid (1,6-butanedicarboxylic acid).Adipic acid is cyclized to cyclopentanone (CP) at 250°C using barium metal or hydrogenated to a diol then cyclized to CP at 475°C using a metal oxide catalyst.Adipic acid is derived from benzene, cyclohexane, or phenol via oxidation with nitric acid using metal salts and used primarily for nylon-6,6 production.The process generates large volumes of hazardous waste and NOx.The reported price for adipic acid is $1,600/ton (2012)compared to $1,000-1,400 for furfural (2014-2016).Given the similarity in price between the feedstocks it seems reasonable to suggest that bio-based CP and CPO could be competitive with the petroleum based process, if a continuous catalytic process can be developed for FUR to CP and CPO. Our goal in this project wasto develop new markets, products, and processes using activated carbon monolith catalysts produced from wood and to generate value added products from platform chemicals derived from agricultural and forest resources. Target audiences are catalytic reaction engineering, biochemicals production, biofuels/biochemicals industry, and the wood products industry. Our specific research objectives are the following. Develop a continuous hydrogenation process using activated carbon monolith catalysts derived from wood to produce cyclopentanone from furfural. Develop a bi-functional (base/metal), carbon monolith catalyst capable of continuously producing bicyclopentane fuel from cyclopentanone, as an aviation fuel alternative. Our original objective was to develop a method to attach enzymes to the carbon monolith catalyst and demonstrate a biocatalytic reaction (catalytic esterification) using the newly developed material. However, after further analysis it was decided to graft strong acid or base sites to the carbon monoliths, instead of enzymes. Our target reactions, esterification and condensation, would be performed at much higher rates using acid or base catalysis instead of enzymes. And would be more stable at the industrial conditions anticipated for the reactions. Note: We have changed this objective to focus on attaching acid sites on the carbon and carbon monolith instead of enzymes. Note: In addition to adding acid sites instead of enzyme attachment, our research group also focused on addition of basic sites to activated carbon and the activated carbon monoliths. Changes/Problems:In Objective 3: Develop a method to attach enzymes to the carbon monolith catalyst and demonstrate a biocatalytic reaction using the newly developed material. We changed this objective to focus on attaching acid sites on the carbon and carbon monolith instead of enzymes. The acid sites will perform the same function as the lipase enzymes (i.e., esterification) yet is more robust (tolerant of solvents, can operate at higher temperatures), is applicable to a wider range of reactants, and should generate higher reaction rates compared to the enzyme. In addition to adding acid sites instead of enzyme attachment our research group also focused on addition of basic sites to activated carbon and the activated carbon monoliths. This adds more functionality to the activated carbon materials - both for catalysis and adsorption applications. Problems: During the summer of 2018 we had to move our entire lab across campus. This has resulted in some instrument damage (mostly PC's not working) and a slow down in our research output. It has taken time and some cost to set-up the lab and bring the reactors and instruments on-line. COVID-19 prohibited lab work for about 3 months and one graduate lost a parent to the virus - of course this was devistating for her and our small research group. For the last 2 years of the project, an instrument critical to our work that characterizes the catalysts we synthesize failed and needed to be replaced. The instrument measures surface area, pore size distribution, acid site density, base site density, H2 chemisorption, metal oxide reduction temperature peaks, and metal particle dispersion on catalysts. The company does not support the instrument anymore and it is not repairable. In some cases, our industrial partner provided surface area data, but they do not have the instrumentation to perform the other measurements. This significantly reduced the value of our research output. Funding is currently not available to replace this instrument (~85,000) and to the best of my knowledge there is not another instrument similar to this on UGA's campus. What opportunities for training and professional development has the project provided? An undergraduate student (Nida Janulaitis, BS Biochemical Engineering at UGA) was funded to contribute to this project and was accepted at the University of Washington to pursue a PhD in Chemical Engineering - she worked on, and was on the first 3 publications from objectives 1 and 2. One PhD student graduated (Maryam Pirmoradi) - Maryam worked on development of bi-metal and bi-functional carbon monolith catalysts for furfural hydrogenation and developed a kinetic model for furfural hydrogenation using the Pd-TiO2/ACM catalyst. Maryam has beenhired as a Catalytic Reaction Engineering specialst as Soulgen in Houston, TX. One PhD student (Sarada Sripada) is focusing on synthesis of acid and base functional carbon catalysts with a focus on studying esterification and condensation reactions. She has developed data for her thesis proposal, a publication, a patent disclosure, several presentations at AICHE conferences, and completion is anticipated in Fall 2023. More publications are anticipated - one on continous catalytic esterification using the sACM, one on catalytic esterification of fermentation derived pyruvic acid, and one on continuous catalytic condensation of cyclopentanone using the ht ACM. Sarada will defend her PhD thesis Fall 2023 and has been offered a Post-Doc at the Great Lakes Energy Center, University of Wisconsin, Madison. She will start the post-doc in January 2024. One Masters student was graduated with a MS Thesis and focused on the synthesis of base functional carbon catalysts for condensation of ketones (acetone, cyclopentanone, and cross reactions between acetone and cyclopentanone) and possible production of aviation fuels. This student is now working on a PhD with another professor at UGA. How have the results been disseminated to communities of interest?Results have been disseminated by publication in peer reviewed journals and by presentations at AICHE and IBE conferences What do you plan to do during the next reporting period to accomplish the goals?This awarded USDA project forms the basis of the following future work (if funding is found), Continuous catalytic esterification of fermentative pyruvic acid - extends work on esterification Coupling of fermentation with chemical catalyst for biofuels and biochemicals Continuous base catalysis using htACM for aviation fuel production Carbon capture using the functionalized ACM form for direct air capture, biogas to renewable natural gas, and post/pre CO2 capture Catalytic conversion of CO2 to value added chemicals using ACM derived catalysts Develop methods to attach enzymes to activated carbon and focus on high value chiral catalysis methods and products (especially focusing on continuous processing)

Impacts
What was accomplished under these goals? A series of monolithic catalysts with channels have been synthesized from wood activated carbon (ACM). Monoliths have much lower pressure drop (thus saving energy) and much higher gas/liquid mass transfer rates and thus much higher space time yields (amount of product per unit volume of reactor per time) compared to granular or particulate catalysts. They can also enhance liquid mass transfer rate and overall reaction rates. The ACM catalyst product can be scaled for continuous processing enhancing industrial applications. A series of ACM catalysts were synthesized, each having industrial applications - Pd/ACM, Pd/Fe/ACM, Pd/Cu/ACM, Pd-TiO2/ACM, SO3-ACM, MgAlOOH-ACM (hydrogenation/dehydration/ring opening/acid/base catalysis applications) Continuous catalytic hydrogenation of furfural was estabilished and demonstrated using an activated carbon monolith (ACM) catalyst A single metal (Pd) on activated carbon monolith (ACM) made from wood (Pd/ACM) was synthesized in cooperation with Applied Catalysts and demonstrated to have much higher space time yields (STY) for hydrogenation of furfural compared to traditional granular catalysts. Furfuryl alcohol and 2-methyl furan were the primary products and reached STY's of 50-70 g/L/h. Reference: Continuous Hydrogenation of Aqueous Furfural Using a Metal-Supported Activated Carbon Monolith, ACS omega 5 (14), 7836-7849, 2020 A bi-metal on ACM (Pd/Cu and Pd/Fe) catalyst was made from wood activated carbon monolith and demonstrated to have higher STY's for products of furfural hydrogentation than single metal ACM. The Pd/Fe on ACM catalyst was more stable than Pd/ACM and shifted the furfural hydrogenation pathway to furfuryl alcohol (FA) and tetrahydrofurfuryl alcohol (THFA). STY's for FA and THFA reached 150 and about 275 g/L/h, respectively (the bi-metal Pd/Fe reduced over hydrogenation of furfural intermediates). The Pd/Fe on ACM had STY's and activity (in terms of turnover frequency or TOF) similar to commercial catalysts reported in the patent literature. Reference: Bi-Metal-Supported Activated Carbon Monolith Catalysts for Selective Hydrogenation of Furfural, Industrial & Engineering Chemistry Research 59 (40), 17748-17761, 2020 A bi-functional (metal/acid) ACM was synthesized that altered the furfural hydrogenation pathway to fufuryl alcohol ring opening products. In this work a Pd/TiO2 on ACM catalyst was synthesized. The Ti functional group was shown to act as a Lewis acid and in cooperation with Pd altered the furfural hydrogenation pathway to form primairly 5-hydroxy-2-pentanone or 5H2P (a valuable platform chemical). STY's of 5H2P approached 150 g/L/h. Reference: Continuous hydroxyketone production from furfural using Pd-TiO2 supported on activated carbon, Catalysis Science & Technology 10 (20), 7002-7015, 2020. Using the bi-functional Pd/TiO2 ACM catalyst, a kinetic model for furfural hydrogenation was developed. The kinetic model could be used to design reactors for hydrogenation of furfural using this catalyst. Reference: A kinetic model of multi-step furfural hydrogenation over a Pd-TiO2 supported activated carbon catalyst, Chemical Engineering Journal 414, 128693, 2021 Strong acid on sGAC and sACM catalysts have been developed to replace petroleum-based acid resins used in acid catalysis (s, indicates a sulfonation process and sulfonated carbon with strong acid groups on the surface). These catalysts can replace liquid-based acid catalysts that are environmentally unfriendly. A more sustainable method of producing the sulfonated GAC and ACM was developed. The process uses much lower amounts of sulfuric acid (much lower E values, where E is an environmental factor = kg of waste/kg of product) and lower energy inputs (much shorter time and temperatures) using a novel plasma process. The sGAC and sACM catalysts have been demonstrated for catalytic esterification of fermentatively derived carboxylic acids and we have recently demonstrated these catalysts can be used in continuous esterification mode. References: S Sripada, JR Kastner. Catalytic Esterification Using Solid Acid Carbon Catalysts Synthesized by Sustainable Hydrothermal and Plasma Sulfonation Techniques. Industrial Engineering Chemistry Research, Ind. Eng. Chem. Res., 61, 11, 3928-3940, 2022. (https://doi.org/10.1021/acs.iecr.2c00086) and Reference: S Sripada, JR Kastner. Sustainable Sulfonated Carbon Catalysts for Continuous Esterification and Production of Biochemicals (686d-Presentation). In Reaction Engineering in Pharmaceuticals and Fine Chemicals Session, 2022. AIChE Annual Meeting, Phoenix AZ, November 18, 2022 A base site functionalized GAC (granular activated carbon) and ACM has been developed for both catalysis and adsorption applications. Hydrotalcite (MgAl double layered hydroxides) have been impregnated and activated on htGAC and the htACM (ht is hydrotalcite). The htGAC was demonstrated to perform catalytic condensation and cross condensation of acetone and cyclopentanone forming dimers and trimers that can be converted to aviation fuel. Reference: Seyedehsan Vasefi. Development of a Sustainable Solid Base Hydrotalcite Catalyst Supported by Granular Activated Carbon. MS Thesis. MS Biochemical Engineering. Major Advisor Jim Kastner, Graduated Summer 2021. The htACM has been characterized by XRD analysis and SEM/EDS and shown to have uniformly formed hydrotalcite on the surface throughout the activated carbon monolith. The htACM can form the basis for a novel base catalyst (e.g., doped metal or alkali metal htACM), especially for continuous catalytic condensation of ketones to aviation fuel and conversion of carbon dioxide, and as carbon capture media for separation of CO2 from process streams (e.g., removal of CO2 from biogas to generate renewable natural gas or RNG). This is ongoing work with the current PhD student - S. Sripada

Publications

• Type: Journal Articles Status: Published Year Published: 2017 Citation: Justin Weber, Aaron Thompson, Jared Wilmoth, Robert J Gulotty, James R Kastner. Coupling Red-Mud Ketonization of a Model Bio-oil Mixture with Aqueous Phase Hydrogenation Using Activated Carbon Monoliths. Energy & Fuels 31 (9), 9529-9541, 2017, DOI: 10.1021/acs.energyfuels.7b01500
• Type: Conference Papers and Presentations Status: Published Year Published: 2017 Citation: Maryam Pirmoradi, James R. Kastner, Robert Gulotty. Continuous Hydrogenation of Furfural to Cyclopentanone Using Activated Carbon Monolith Catalysts. 533b: Chemical and Catalytic Conversions and Processes for Renewable Feedstocks, AICHE Symposium, Nov. 1st, 2017. Minneapolis, MN.
• Type: Journal Articles Status: Published Year Published: 2019 Citation: J Weber, A Thompson, J Wilmoth, VS Batra, N Janulaitis (UGA Undergraduate), JR Kastner. Effect of metal oxide redox state in red mud catalysts on ketonization of fast pyrolysis oil derived oxygenates. Applied Catalysis B: Environmental (Impact Factor 19.5) 241, 430-441, 2019.
• Type: Journal Articles Status: Published Year Published: 2020 Citation: M Pirmoradi, N Janulaitis (UGA Undergraduate), RJ Gulotty Jr, JR Kastner. Continuous Hydrogenation of Aqueous Furfural Using a Metal-Supported Activated Carbon Monolith. ACS Omega 5 (14), 7836-7849, 2020
• Type: Journal Articles Status: Published Year Published: 2020 Citation: M Pirmoradi, N Janulaitis (UGA Undergraduate), RJ Gulotty Jr, JR Kastner. Bi-Metal-Supported Activated Carbon Monolith Catalysts for Selective Hydrogenation of Furfural. Industrial & Engineering Chemistry Research 59 (40), 17748-17761, 2020.
• Type: Journal Articles Status: Published Year Published: 2020 Citation: M Pirmoradi, RJ Gulotty, JR Kastner. Continuous hydroxyketone production from furfural using PdTiO2 supported on activated carbon, Catalysis Science & Technology 10 (20), 7002-7015, 2020.
• Type: Theses/Dissertations Status: Published Year Published: 2020 Citation: Maryam Pirmoradi. PhD BioChemical Engineering. Advisor. Activated Carbon Monolith Catalysts: A Bridge from Green Chemicals to Value-added Products. Major Advisor Jim Kastner, PhD Thesis, Graduated Spring 2020.
• Type: Theses/Dissertations Status: Published Year Published: 2021 Citation: Seyedehsan Vasefi. Development of a Sustainable Solid Base Hydrotalcite Catalyst Supported by Granular Activated Carbon. MS Thesis. MS Biochemical Engineering. Major Advisor Jim Kastner, MS Thesis, Graduated Summer 2021.
• Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: Sarada Sripada, Jim Kastner. Sustainable Solid Acid Carbon Catalysts from Renewable Biomass for Fine and Specialty Chemical Synthesis. AICHE Conference. Virtual Poster. Nov., 2020
• Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: Sarada Sripada, James R. Kastner. Development of Sustainable Solid Acid Carbon Catalysts for Applications in the Production of Commodity Chemicals. Institute of Biological Engineering. 2021 Annual Meeting (Virtual Presentation). April 10th, 2021.
• Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: Sarada Sripada, Jim Kastner. Sustainable Solid Acid Carbon Catalysts for Production of Biochemicals. AICHE Annual Conference. Boston, MA, In Person Poster. Nov. 7-11, 2021.
• Type: Journal Articles Status: Published Year Published: 2022 Citation: S Sripada, JR Kastner. Catalytic Esterification Using Solid Acid Carbon Catalysts Synthesized by Sustainable Hydrothermal and Plasma Sulfonation Techniques. Industrial Engineering Chemistry Research, Ind. Eng. Chem. Res., 61, 11, 3928-3940, 2022. (https://doi.org/10.1021/acs.iecr.2c00086)
• Type: Conference Papers and Presentations Status: Published Year Published: 2022 Citation: S Sripada, JR Kastner. Sustainable Sulfonated Carbon Catalysts for Continuous Esterification and Production of Biochemicals (686d-Presentation). In Reaction Engineering in Pharmaceuticals and Fine Chemicals Session, 2022. AIChE Annual Meeting, Phoenix AZ, November 18, 2022
• Type: Other Status: Accepted Year Published: 2020 Citation: Award to Sarada Sripada, Jim Kastner. Sustainable Solid Acid Carbon Catalysts from Renewable Biomass for Fine and Specialty Chemical Synthesis. 2020. Air & Waste Management Association, Georgia Chapter Graduate Student Scholarship. $1,000.
• Type: Other Status: Accepted Year Published: 2020 Citation: Award to Sarada Sripada, Jim Kastner. Sustainable Solid Acid Carbon Catalysts from Renewable Biomass for Fine and Specialty Chemical Synthesis. 2020. SENIC Catalyst grant, National Nanotechnology Coordinated Infrastructure (NNCI), National Science Foundation (Grant ECCS-1542174). $1,000.
• Type: Other Status: Accepted Year Published: 2019 Citation: Award to Sarada Sripada, Jim Kastner. Sustainable Solid Acid Carbon Catalysts from Renewable Biomass for Fine and Specialty Chemical Synthesis. 2019 Innovative and Interdisciplinary Research Grant, UGA Graduate School. $1,000.
• Type: Journal Articles Status: Published Year Published: 2021 Citation: M Pirmoradi, JR Kastner. A Kinetic Model of Multi-Step Furfural Hydrogenation Over a Pd-TiO2 Supported Activated Carbon Catalyst. Chemical Engineering Journal, 414, 128693, 2021 (Impact Factor 10.652).
• Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: Ehsan Vasefi, James R. Kastner. Development of Solid Base Activated Carbon Catalysts for Ketone Condensation and Aviation Fuel Synthesis, University of Georgia, School of Chemical, Materials, and Biomedical Engineering, IBE 2020, Institute of Biological Science 2020 Annual Conference, Athens GA, March 19-21
• Type: Journal Articles Status: Published Year Published: 2023 Citation: Sarada Sripada, James R. Kastner. Continuous Catalytic Esterification Using a Solid Acid Activated Carbon Monolith: Comparison of Granular and Monolith forms with a Commercial Catalyst, Chemical Engineering Journal, 476 (2023) 146586 https://doi.org/10.1016/j.cej.2023.146586
• Type: Theses/Dissertations Status: Under Review Year Published: 2023 Citation: Sarada Sripada, Development of Sustainable Solid Acid and Base Carbon Catalysts for the Synthesis of Value Added Chemicals and Aviation Fuels. PhD Dissertation, University of Georgia, School of CHemical, Materials, and Biomedical Engineering, Direction - James R Kastner, Anticipated Fall 2023
• Type: Journal Articles Status: Other Year Published: 2024 Citation: Sarada Sripada, James R. Kastner. Kinetics of 2-Hydroxyisobutyric Acid Using Solid Acid Carbon Catalysts, Chemical Engineering Journal or equivalent, In Preparation, To be Submitted, 2024
• Type: Journal Articles Status: Other Year Published: 2024 Citation: Sarada Sripada, James R. Kastner. Catalytic Esterification of Pyruvic Acid Using Solid Acid Carbon Catalysts, Green Chemistry or Equivalent, In Preparation, To be Submitted, 2024
• Type: Journal Articles Status: Other Year Published: 2024 Citation: Development of Solid Base Carbon Monolith Catalysts for Continuous Condensation of Ketones, Catalysis Communications or Equivalent, In Preparation, To be Submitted, 2024

Progress 03/01/22 to 02/28/23

Outputs
Target Audience: Academic Audience - A manuscript was published this period Industry/Academic Audience - A presentation was made at the AIChE Annual Meeting Changes/Problems:Changes/Problems Problems: During the summer of 2018 we had to move our entire lab across campus. This has resulted in some instrument damage (mostly PC's not working) and a slow down in our research output. It has taken time and some cost to set-up the lab and bring the reactors and instruments on-line. Recently, an instrument critical to our work that characterizes the catalysts we prepare has failed and needs to be replaced. The company does not support the instrument anymore and is not repairable. This has significantly reduced the value of our research output. Funding is currently not available to replace this instrument (~85,000). Major goals of the project Objective 3: Develop a method to attach enzymes to the carbon monolith catalyst and demonstrate a biocatalytic reaction using the newly developed material. Note: We have changed this objective to focus on attaching acid sites on the carbon and carbon monolith instead of enzymes. The acid sites will perform the same function as the lipase enzymes (i.e., esterification) yet is more robust (tolerant of solvents, can operate at higher temperatures), applicable to a wider range of reactants, and should generate higher reaction rates compared to the enzyme. Note: In addition to adding acid sites instead of enzyme attachment our research group also focused on addition of basic sites to activated carbon and the activated carbon monoliths. This adds more functionality to the activated carbon materials - both for catalysis and adsorption applications. What opportunities for training and professional development has the project provided? One PhD student (Sarada Sripada) is focusing on synthesis of acid (and acid/metal) functional carbon catalysts with a focus on studying esterification reactions. She has developed data for her thesis proposal, a recent publication and patent disclosure, and completion is anticipated in 2023. One Masters student graduated with a MS Thesis focused on the synthesis of base functional carbon catalysts for condensation of ketones (acetone, cyclopentanone, and cross reactions between acetone and cyclopentanone) and possible production of aviation fuels How have the results been disseminated to communities of interest?Results have been published and presentated at a conference: S Sripada, JR Kastner. Catalytic Esterification Using Solid Acid Carbon Catalysts Synthesized by Sustainable Hydrothermal and Plasma Sulfonation Techniques. Industrial Engineering Chemistry Research, Ind. Eng. Chem. Res., 61, 11, 3928-3940, 2022. (https://doi.org/10.1021/acs.iecr.2c00086) S Sripada, JR Kastner. Sustainable Sulfonated Carbon Catalysts for Continuous Esterification and Production of Biochemicals (686d-Presentation). In Reaction Engineering in Pharmaceuticals and Fine Chemicals Session, 2022. AIChE Annual Meeting, Phoenix AZ, November 18, 2022 What do you plan to do during the next reporting period to accomplish the goals?Objective 4 - Solid Acid Carbon Catalyst for Esterification 1.Prepare solid acid catalysts from ACM and determine continuous flow esterification activity 2.Determine catalyst longevity, mechanism of deactivation if it occurs, and test a method of catalyst regeneration 3.Characterize the spent ACM catalysts 4.Extend catalytic esterification studies to pyruvic acid from fermentation systems, and synthesize ethyl pyruvate in a continuous manner 5.Publish a manuscript on these research objectives Objective 3 - Base Functionalized Carbon Catalysts for Condensation Reactions Prepare solid base catalyst from ACM Test the basic/ACM for condensation activity of acetone and cyclopentanone in continuous flow Publish a manuscript on these research objective

Impacts
What was accomplished under these goals? Objective 3: Develop a method to attach enzymes to the carbon monolith catalyst and demonstrate a biocatalytic reaction using the newly developed material. Note: We have changed this objective to focus on attaching acid sites on the carbon and carbon monolith instead of enzymes. The acid sites will perform the same function as the lipase enzymes (i.e., esterification) yet is more robust (tolerant of solvents, can operate at higher temperatures), applicable to a wider range of reactants, and should generate higher reaction rates compared to the enzyme. Note: In addition to adding acid sites instead of enzyme attachment our research group also focused on addition of basic sites to activated carbon and the activated carbon monoliths. This adds more functionality to the activated carbon materials - both for catalysis and adsorption applications. What was accomplished under these goals? Specific Research Objectives: Develop Carbon Monolith Catalysts (ACMC) from Wood Based Activated Carbons Demonstrate a single metal Pd/ACM from wood as a platform catalyst (ACMC) for production of chemicals from furfural Develop a bi-metal ACMC catalyst for industrial applications Develop a base/metal bi-functional carbon catalyst Future work will focus on condensation reactions (e.g., cyclopentanone to bicylic alkanes) Develop a strong acid/metal bi-functional carbon catalyst Future work will demonstrate esterification reactions using the strong acid carbon catalyst Long term plans are to screen transformation of other platform chemicals (long term goals) 5-HMF (5-hydroxymethyl furfural) to other chemicals, muconic acid to adipic, 4-hydroxybenzoic acid to TPA Integrate with fermentation derived feedstocks with catalysis- FermCat Results Specific objectives 3 and 4: Work is ongoing for these objectives A PhD student (Sarada Sripada) is working on this objective (#4). She has obtained preliminary data for her thesis proposal, a patent disclosure, a conference presentation, and a recent publication 2020-108: Functionalized Carbon Catalysts and Adsorbent Materials by Plasma and Novel Hydrothermal Methods (JR Kastner, Sarada Sripada), Invention Disclosure Strong acid on sGAC and sACM catalysts have been developed to replace petroleum based acid resins used in acid catalysis (s indicates a sulfonation process). These catalysts can replace liquid based acid catalysts. A more sustainable method of producing the sulfonated GAC and ACM was developed. The process uses much lower amounts of sulfuric acid (much lower E values, where E is an environmental factor = kg of waste/kg of product) and lower energy inputs (much shorter time and temperatures) using a novel plasma process. The sGAC and sACM catalysts have been demonstrated for catalytic esterification of fermentatively derived carboxylic acids and we have recently demonstrated these catalysts can be used in continuous esterification mode. References: S Sripada, JR Kastner. Catalytic Esterification Using Solid Acid Carbon Catalysts Synthesized by Sustainable Hydrothermal and Plasma Sulfonation Techniques. Industrial Engineering Chemistry Research, Ind. Eng. Chem. Res., 61, 11, 3928-3940, 2022. (https://doi.org/10.1021/acs.iecr.2c00086) and Reference: S Sripada, JR Kastner. Sustainable Sulfonated Carbon Catalysts for Continuous Esterification and Production of Biochemicals (686d-Presentation). In Reaction Engineering in Pharmaceuticals and Fine Chemicals Session, 2022. AIChE Annual Meeting, Phoenix AZ, November 18, 2022 S Sripada, JR Kastner. Catalytic Esterification Using Solid Acid Carbon Catalysts Synthesized by Sustainable Hydrothermal and Plasma Sulfonation Techniques. Industrial Engineering Chemistry Research, Ind. Eng. Chem. Res., 61, 11, 3928-3940, 2022. (https://doi.org/10.1021/acs.iecr.2c00086) S Sripada, JR Kastner. Sustainable Sulfonated Carbon Catalysts for Continuous Esterification and Production of Biochemicals (686d-Presentation). In Reaction Engineering in Pharmaceuticals and Fine Chemicals Session, 2022. AIChE Annual Meeting, Phoenix AZ, November 18, 2022 A MS student has finished a MS Thesis on objective 3. We have synthesized hydrotalcite (a base) on activated carbon and carbon monoliths, and shown activity for condensation of cyclopentanone to a bicyclic alkane, but much more work is required to demonstrate an advantage over traditional solid base catalysts. Seyedehsan Vasefi. Development of a Sustainable Solid Base Hydrotalcite Catalyst Supported by Granular Activated Carbon. MS Thesis. MS Biochemical Engineering. Major Advisor. Graduated Summer 2021. To be published 06/04/2023.

Publications

• Type: Journal Articles Status: Published Year Published: 2022 Citation: S Sripada, JR Kastner. Catalytic Esterification Using Solid Acid Carbon Catalysts Synthesized by Sustainable Hydrothermal and Plasma Sulfonation Techniques. Industrial Engineering Chemistry Research, Ind. Eng. Chem. Res., 61, 11, 3928-3940, 2022. (https://doi.org/10.1021/acs.iecr.2c00086)
• Type: Conference Papers and Presentations Status: Published Year Published: 2022 Citation: S Sripada, JR Kastner. Sustainable Sulfonated Carbon Catalysts for Continuous Esterification and Production of Biochemicals (686d-Presentation). In Reaction Engineering in Pharmaceuticals and Fine Chemicals Session, 2022. AIChE Annual Meeting, Phoenix AZ, November 18, 2022

Progress 03/01/21 to 02/28/22

Outputs
Target Audience:Professionals and academics in the area of bioprocessing and reactor engineering, focused on conversion of renewable carbon sources to value added chemicals Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Maryam Pirmoradi Defended her PhD. PhD in BioChemical Engineering. Advisor-Jim Kastner. Activated Carbon Monolith Catalysts: A Bridge from Green Chemicals to Value-added Products. Major Advisor. Graduated Spring 2020. Maryam is currently a Research Engineer at Solugen in Houston, TX (https://solugen.com/ ) A PhD student (Sarada Sripada) is working on this objective (#4). She has obtained preliminary data for her thesis proposal, a patent disclosure, a conference presentation, and a possible publication in the near future A MS student has finished a MS Thesis on objective 3. We have synthesized hydrotalcite (a base) on activated carbon and shown activity for condensation of cyclopentanone to a bicyclic alkane, but much more work is required to demonstrate an advantage over traditional solid base catalysts. Seyedehsan Vasefi. Development of a Sustainable Solid Base Hydrotalcite Catalyst Supported by Granular Activated Carbon. MS Thesis. MS Biochemical Engineering. Major Advisor. Graduated Summer 2021. How have the results been disseminated to communities of interest?Recent Project Outputs M Pirmoradi, N Janulaitis (UGA Undergraduate), RJ Gulotty Jr, JR Kastner. Continuous Hydrogenation of Aqueous Furfural Using a Metal-Supported Activated Carbon Monolith. ACS Omega 5 (14), 7836-7849, 2020 M Pirmoradi, N Janulaitis (UGA Undergraduate), RJ Gulotty Jr, JR Kastner. Bi-Metal-Supported Activated Carbon Monolith Catalysts for Selective Hydrogenation of Furfural. Industrial & Engineering Chemistry Research 59 (40), 17748-17761, 2020. M Pirmoradi, RJ Gulotty, JR Kastner. Continuous hydroxyketone production from furfural using Pd-TiO2 supported on activated carbon, Catalysis Science & Technology 10 (20), 7002-7015, 2020. M Pirmoradi, JR Kastner. A Kinetic Model of Multi-Step Furfural Hydrogenation Over a Pd-TiO2 Supported Activated Carbon Catalyst. Chemical Engineering Journal, 414, 128693, 2021 (Impact Factor 10.652). J Weber, A Thompson, J Wilmoth, VS Batra, N Janulaitis (UGA Undergraduate), JR Kastner. Effect of metal oxide redox state in red mud catalysts on ketonization of fast pyrolysis oil derived oxygenates. Applied Catalysis B: Environmental (Impact Factor 19.5) 241, 430-441, 2019. Maryam Pirmoradi. PhD BioChemical Engineering. Advisor. Activated Carbon Monolith Catalysts: A Bridge from Green Chemicals to Value-added Products. Major Advisor Jim Kastner, Graduated Spring 2020. Seyedehsan Vasefi. Development of a Sustainable Solid Base Hydrotalcite Catalyst Supported by Granular Activated Carbon. MS Thesis. MS Biochemical Engineering. Major Advisor Jim Kastner, Graduated Summer 2021. Patent Disclosure-Bi-metal Supported Activated Carbon Monolith Catalysts for Selective Hydrogenation of Chemical Reactants (UGA # - D2020-0051) Patent Disclosure-Functionalized Carbon Catalysts and Adsorbent Materials by Plasma and Novel Hydrothermal Methods (UGA # - D2020-0052) What do you plan to do during the next reporting period to accomplish the goals?Objective 4 - Solid Acid Carbon Catalyst for Esterification 1.Prepare solid acid catalysts from ACM and determine esterification activity 2.Characterize the ACM catalysts 3.Apply for a patent disclosure 4.Publish a manuscript on this research objective Objective 3 - Base Functionalized Carbon Catalysts for Condensation Reactions Prepare solid base catalyst from ACM Test the basic/ACM for condensation activity of acetone and cyclopentanone

Impacts
What was accomplished under these goals? Specific Research Objectives: Develop Carbon Monolith Catalysts (ACMC) from Wood Based Activated Carbons Demonstrate a single metal Pd/ACM from wood as a platform catalyst (ACMC) for production of chemicals from furfural Develop a bi-metal ACMC catalyst for industrial applications Develop a base/metal bi-functional carbon catalyst Future work will focus on condensation reactions (e.g., cyclopentanone to bicylic alkanes) Develop a strong acid/metal bi-functional carbon catalyst Future work will demonstrate esterification reactions using the strong acid carbon catalyst Long term plans are to screen transformation of other platform chemicals (long term goals) 5-HMF (5-hydroxymethyl furfural) to other chemicals, muconic acid to adipic, 4-hydroxybenzoic acid to TPA Integrate with fermentation derived feedstocks with catalysis- FermCat Results Objective 1: A manuscript has been published on this objective M Pirmoradi, N Janulaitis (UGA Undergraduate), RJ Gulotty Jr, JR Kastner. Continuous Hydrogenation of Aqueous Furfural Using a Metal-Supported Activated Carbon Monolith. ACS Omega (Impact Factor 3.52) 5 (14), 7836-7849, 2020 Objective 2: Three manuscripts have been published on this objective. A patent application was filed but after consultation with Applied Catalysts it was decided that their original patent covered this intellectual property (but had not been demonstrated) M Pirmoradi, N Janulaitis (UGA Undergraduate), RJ Gulotty Jr, JR Kastner. Bi-Metal-Supported Activated Carbon Monolith Catalysts for Selective Hydrogenation of Furfural. Industrial & Engineering Chemistry Research (Impact Factor 3.72) 59 (40), 17748-17761, 2020. M Pirmoradi, RJ Gulotty, JR Kastner. Continuous hydroxyketone production from furfural using Pd-TiO2 supported on activated carbon, Catalysis Science & Technology (Impact Factor 6.11) 10 (20), 7002-7015, 2020. M Pirmoradi, JR Kastner. A Kinetic Model of Multi-Step Furfural Hydrogenation Over a Pd-TiO2 Supported Activated Carbon Catalyst. Chemical Engineering Journal, 414, 128693, 2021 (Impact Factor 10.652). Maryam Pirmoradi Defended her PhD. PhD in BioChemical Engineering. Advisor-Jim Kastner. Activated Carbon Monolith Catalysts: A Bridge from Green Chemicals to Value-added Products. Major Advisor. Graduated Spring 2020. Maryam is currently a Research Engineer at Solugen in Houston, TX (https://solugen.com/ ) Objective 3 and 4: Work is ongoing for these objectives A PhD student (Sarada Sripada) is working on this objective (#4). She has obtained preliminary data for her thesis proposal, a patent disclosure, a conference presentation, and a possible publication in the near future 2020-108: Functionalized Carbon Catalysts and Adsorbent Materials by Plasma and Novel Hydrothermal Methods (JR Kastner, Sarada Sripada) Sarada Sripada, Jim Kastner. Sustainable Solid Acid Carbon Catalysts from Renewable Biomass for Fine and Specialty Chemical Synthesis. AICHE Conference. Virtual Poster. Nov., 2020. Sarada Sripada, James R. Kastner. Development of Sustainable Solid Acid Carbon Catalysts for Applications in the Production of Commodity Chemicals. Institute of Biological Engineering. 2021 Annual Meeting (Virtual Presentation). April 10th, 2021. Sarada Sripada, Jim Kastner. Sustainable Solid Acid Carbon Catalysts for Production of Biochemicals. AICHE Annual Conference. Boston, MA, In Person Poster. Nov. 7-11, 2021. Sarada Sripada, Jim Kastner. Sustainable Solid Acid Carbon Catalysts from Renewable Biomass for Fine and Specialty Chemical Synthesis. 2020. Air & Waste Management Association, Georgia Chapter Graduate Student Scholarship. $1,000. Sarada Sripada, Jim Kastner. Sustainable Solid Acid Carbon Catalysts from Renewable Biomass for Fine and Specialty Chemical Synthesis. 2020. SENIC Catalyst grant, National Nanotechnology Coordinated Infrastructure (NNCI), National Science Foundation (Grant ECCS-1542174). $1,000. Sarada Sripada, Jim Kastner. Sustainable Solid Acid Carbon Catalysts from Renewable Biomass for Fine and Specialty Chemical Synthesis. 2019 Innovative and Interdisciplinary Research Grant, UGA Graduate School. $1,000. S Sripada, JR Kastner. Catalytic Esterification Using Solid Acid Carbon Catalysts Synthesized by Sustainable Hydrothermal and Plasma Sulfonation Techniques. Industrial Engineering Chemistry Research, In Review, Jan. 2022. A MS student has finished a MS Thesis on objective 3. We have synthesized hydrotalcite (a base) on activated carbon and shown activity for condensation of cyclopentanone to a bicyclic alkane, but much more work is required to demonstrate an advantage over traditional solid base catalysts. Seyedehsan Vasefi. Development of a Sustainable Solid Base Hydrotalcite Catalyst Supported by Granular Activated Carbon. MS Thesis. MS Biochemical Engineering. Major Advisor. Graduated Summer 2021.

Publications

• Type: Journal Articles Status: Accepted Year Published: 2021 Citation: M Pirmoradi, JR Kastner. A Kinetic Model of Multi-Step Furfural Hydrogenation Over a Pd-TiO2 Supported Activated Carbon Catalyst. Chemical Engineering Journal, 414, 128693, 2021 (Impact Factor 10.652).
• Type: Journal Articles Status: Under Review Year Published: 2021 Citation: o S Sripada, JR Kastner. Catalytic Esterification Using Solid Acid Carbon Catalysts Synthesized by Sustainable Hydrothermal and Plasma Sulfonation Techniques. Industrial Engineering Chemistry Research, In Review, Jan. 2022.

Progress 03/01/20 to 02/28/21

Outputs
Target Audience:Target Audience: Academic and industry groups Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? A PhD in Biochemical has been granted to one student funded by this grant One PhD and MS student are working on this project The PhD student currently working on this project has written and received grants from UGA's Graduate School ($1,000) and Southeastern Nanotechnology Infrastructure Corridor ($1,000) to support this work How have the results been disseminated to communities of interest? Our results have been published in peer reviewed journals ACS Omega, Industrial and Engineering Chemistry Research, Catalysis Science and Technology Presentations scheduled at AICHE and IBE conferences were cancelled What do you plan to do during the next reporting period to accomplish the goals? Ask for a 1-year no-cost extension Further our work on making solid acid catalysts from wood based activated carbon Further our work on making solid base catalysts from wood based activated carbon Pursue making solid acid and base catalyst from biochar - we have been contacted by industry that makes biochar with interest in this research area, they are interested in developing new markets for the biochar

Impacts
What was accomplished under these goals? A bi-metal (Pd/Fe, Pd/Cu) on activated carbon monolith catalyst was developed and tested for furfural hydrogenation A bi-functional (metal/acid: Pd-Ti) on activated carbon catalyst was developed and tested for furfural hydrogenation The metal/acid on ACM catalyst produced high levels of 5-hydroxy-2-pentanone (a value added chemical) from furfural Continuous production of value added chemicals from furfural using these catalysts has been demonstrated Acid functionalization of wood based GAC creating a solid acid catalyst has been demonstrated The solid acid carbon catalyst has been demonstrated to be active for esterification The development of solid base carbon catalysts has been started

Publications

• Type: Journal Articles Status: Accepted Year Published: 2020 Citation: M Pirmoradi, N Janulaitis, RJ Gulotty Jr, JR Kastner. Continuous Hydrogenation of Aqueous Furfural Using a Metal-Supported Activated Carbon Monolith. ACS Omega 5 (14), 7836-7849, 2020 M Pirmoradi, N Janulaitis, RJ Gulotty Jr, JR Kastner. Bi-Metal-Supported Activated Carbon Monolith Catalysts for Selective Hydrogenation of Furfural. Industrial & Engineering Chemistry Research 59 (40), 17748-17761, 2020 M Pirmoradi, RJ Gulotty, JR Kastner. Continuous hydroxyketone production from furfural using PdTiO 2 supported on activated carbon. Catalysis Science & Technology 10 (20), 7002-7015, 2020

Progress 03/01/19 to 02/29/20

Outputs
Target Audience:Target Audience: Research results this year have been presented to our industry sponser and academic faculty Efforts: Undergraduate training, preparation of manuscripts, and preparation of patent disclosure Changes/Problems:Changes/Problems Problems: During the summer of 2018 we had to move our entire lab across campus. This has resulted in some instrument damage (mostly PC's not working) and a slow down in our research output. It has taken time and some cost to set-up the lab and bring the reactors and instruments on-line. Recently, an instrument critical to our work that characterizes the catalysts we prepare has failed and is in need of repair. The company does not support the instrument anymore and thus it may not be repairable. This could significantly reduce the value of our research output. Funding is currently not available to replace this instrument (~85,000). Changes Major goals of the project Develop a method to attach enzymes to the carbon monolith catalyst and demonstrate a biocatalytic reaction using the newly developed material. Note: We have changed this objective to focus on attaching acid sites on the carbon and carbon monolith instead of enzymes. The acid sites will perform the same function as the lipase enzymes (i.e., esterification) yet is more robust (tolerant of solvents, can operate at higher temperatures), applicable to a wider range of reactants, and should generate higher reaction rates compared to the enzyme. What opportunities for training and professional development has the project provided? I anticipate the first PhD student (Maryam Pirmoradi) working on the furfural hydrogenation will defend her thesis in Spring 2020 and graduate One PhD student (Sarada Sripada) is focusing on synthesis of acid (and acid/metal) functional carbon catalysts with a focus on studying esterification reactions. She has developed data for her thesis proposal, a possible publication and patent disclosure The Masters student continues to work on the synthesis of base functional carbon catalysts with a focus on condensation of ketones (acetone, cyclopentanone, and cross reactions between acetone and cyclopentanone) for production of aviation fuels An undergraduate student (Nida Janulaitis) funded to contribute on this project was accepted at the University of Washington to pursue a PhD in Chemical Engineering - she will be on the first 3 publications from objectives 1 and 2. How have the results been disseminated to communities of interest?Recent Project Outputs Manuscript:-"Continuous Hydrogenation of Aqueous Furfural Using A Metal Supported Activated Carbon Monolith" in Review Manuscript: "Bi-metal Supported Activated Carbon Monolith Catalysts for Selective Hydrogenation of Furfural" which will be submitted after a patent disclosure is considered What do you plan to do during the next reporting period to accomplish the goals?Objective 1 and 2 - Continuous Furfural Hydrogenation using ACMC Complete patent disclosure on bi-metal ACMC with Applied Catalysts Publish the first two papers on this objective Prepare publication on bi-functional metal/lewis acid ACMC Prepare publication on kinetic and reactor design model for ACMC PhD student successfully defends thesis in Spring 2020 Objective 4 - Solid Acid Carbon Catalyst for Esterification 1.Prepare solid acid catalysts from ACM and determine esterification activity 2.Characterize the ACM catalysts 3.Apply for a patent disclosure 4.Publish a manuscript on this research objective Objective 3 - Base Functionalized Carbon Catalysts for Condensation Reactions Prepare solid base catalyst from ACM Test the basic/ACM for condensation activity of acetone and cyclopentanone

Impacts
What was accomplished under these goals? Results Objective 1 (Demonstrate a single metal Pd/ACM from wood as a platform catalyst): A manuscript is in review for publication Manuscript:-"Continuous Hydrogenation of Aqueous Furfural Using A Metal Supported Activated Carbon Monolith" Space time yields (g of product/L of catalyst/h) or STY's were significantly higher for the Pd on wood based activated carbon monolith (Pd/ACMC) The major products formed from furfural were tetrahydrofurfuryl alcohol (THFA), furfuryl alcohol (FA), and 2-methyl tetrahydrofuran (2MF). STY's were generally 2-3 times higher using the ACMC Objective 2 (Develop a bi-metal ACM catalyst for industrial applications): A manuscript has been prepared and a patent application with Applied Catalysts is being considered Manuscript: "Bi-metal Supported Activated Carbon Monolith Catalysts for Selective Hydrogenation of Furfural" which will be submitted after a patent disclosure is considered The bi-metal (Pd/Fe) significantly altered selectivity towards FA and THFA and offers the ability to tune selectivity in aqueous phase hydrogenations of biobased substrates. To the best of our knowledge no one has done this before in a carbon monolith from wood, thus the interest in a patent Objective 3 and 4 (develop a base/metal bi-functional carbon catalyst,develop a strong acid/metal bi-functional carbon catalyst): Work is ongoing for these objectives A PhD student has been recruited and is working on objectives 4. She has obtained preliminary data for her thesis proposal, a patent disclosure, a conference presentation, and a possible publication in the near future A MS student is working on objective 3 and progress has been slow. We have synthesized hydrotalcite on activated carbon and shown activity for condensation of cyclopentanone to a bicyclic alkane, but much more work is required to demonstrate an advantage over traditional solid base catalysts.

Publications

• Type: Journal Articles Status: Under Review Year Published: 2019 Citation: Continuous Hydrogenation of Aqueous Furfural Using A Metal Supported Activated Carbon Monolith Maryam Pirmoradi1, Nida Janulaitis1, Robert J. GulottyJr.2, James R. Kastner1* 1Biochemical Engineering, College of Engineering Driftmier Engineering Center, The University of Georgia, 597 D.W. Brooks Drive, Athens, Georgia 30602, United States e-mails: [e-mail] [e-mail] [e-mail] 2Applied Catalysts/Applied Ceramics Inc., 2 Technology Place Laurens, SC 29360, Ph: 864-682-2597 x2916 [e-mail]

Progress 03/01/18 to 02/28/19

Outputs
Target Audience:Target Audience: Graduate and undergraduate students Efforts: A course in Advanced Kinetics and Reactor Design (BCHE 8150) was taught this semester. The two new graduate students recently hired on this project were in this course. Research group meetings conducting literature analysis related to this project were conducted once a week (about 1- 1.5 hours). All group members including the undergraduate working in the group attended and were involved in the literature analysis related to our reserach project. Changes/Problems:Changes/Problems Problems: During the summer of 2018 we had to move our entire lab across campus. This has resulted in some instrument damage (mostly PC's not working) and a slow down in our research output. It has taken time and some cost to set-up the lab and bring the reactors and instruments on-line. Major goals of the project Develop a method to attach enzymes to the carbon monolith catalyst and demonstrate a biocatalytic reaction using the newly developed material. Note: We have changed this objective to focus on attaching acid sites on the carbon and carbon monolith instead of enzymes. The acid sites will perform the same function as the lipase enzymes (i.e., esterification) yet is more robust (tolerant of solvents, can operate at higher temperatures), applicable to a wider range of reactants, and should generate higher reaction rates compared to the enzyme. What opportunities for training and professional development has the project provided? Another PhD student has been recruited. She will focus on synthesis of acid (and acid/metal) functional carbon catalysts with a focus on studying esterification reactions. A Masters student has been recruited and has started work on synthesis of base functional carbon catalysts with a focus on condensation of ketones (acetone, cyclopentanone, and cross reactions between acetone and cyclopentanone) for production of aviation fuels An undergraduate in Biochemical Engineering has been working in the lab for 8 months contributing to these projects. More ACMC cores have been prepared by Applied Catalysts Pd/ACMC, Pd/Fe ACMC and Pd/Cu ACMC Our group at UGA has synthesized Pd/Cu, Pd/Fe, and Pd/Ti on crushed ACMC as a base catalyst for testing ACMC was provided by Applied Catalyst Packed Bed Reactor (PBR) and ACMC runs are ongoing Furfural hydrogenation using the bi-metal catalysts Temperature, Pressure, and Residence Time Effects With the newly purchased HPLC pump we test higher flow rates How have the results been disseminated to communities of interest? Nothing Reported What do you plan to do during the next reporting period to accomplish the goals?Continuous Furfural Hydrogenation We need to complete characterization of the used Pd/Powder, Pd/GAC, and Pd/ACMC catalysts. These data will support a publication demonstrating the advantage of the carbon monolith catalysts over traditional forms (granules or powder) for furfural hydrogenation. We need to complete characterization of the used bi-metal on carbon catalysts. These data will support a publication demonstrating the advantage of the bi-metal carbon catalysts over mono-metal forms for furfural hydrogenation. Given the advantage of the bi-metal catalysts for formation of key value-added chemicals from furfural, we will measure the kinetics of hydrogenation and develop a rate law for process scale-up using one of these catalysts. We will select the best bi-metal catalyst which appears to be Pd-Fe for THFA production and Pd-Ti for cyclopentanone. Solid Acid Carbon Catalyst for Esterification 1.A recently recruited graduate student will work on synthesizing carbon catalysts from GAC (granular activated carbon) and carbon monoliths - all wood-based carbons 2.Using these catalysts, we will measure the esterification kinetics of small molecular weight carboxylic acids that can be used to produce platform chemicals - e.g., lactic acid to ethyl lactate, 3-hydroxypropionic acid to ethyl 3-hydroxypropionate, hydroxyisobutyric acid to ethyl hydroxyisobutyrate. Base Functionalized Carbon Catalysts for Condensation Reactions A Masters student has been recruited for this project We plan to add base sites to carbon catalysts from GAC (granular activated carbon) and carbon monoliths - all wood-based carbons. Currently we have used hydrotalcite as the base catalyst to impregnate on/in the carbon These catalysts will then be used to condense cyclopentanone, acetone, and mixtures of the two to aviation fuels. We believe the carbon catalysts have an advantage due to their higher surface area and thus higher density of base sites

Impacts
What was accomplished under these goals? Research Objectives: Conversion of Furfural to Platform Chemicals Using Wood Based Carbon Monoliths We have demonstrated activated carbon monolith (ACM) from wood as a platform catalyst (ACMC) We have synthesized furfuryl alcohol, tetrahydrofurfuryl alcohol, and cyclopentanone from furfural using ACMC in a continuous process Pd, Pd/Cu, Pd/Fe, and Pd/Ti (bimetals) carbon catalysts have been synthesized We are correlating structure with function We will develop transport and kinetic models for scale-up Future work will determine the effect of time on stream studies and a deactivation model Future work will focus on synthesis of bicyclopentane (aviation fuel) from cyclopentanone We have developed a base/metal bi-functional carbon catalyst We are working on the development of a strong acid/metal bi-functional carbon catalyst Future work will demonstrate esterification reactions using the strong acid carbon catalyst Long term plans are to screen transformation of other platform chemicals (long term goals) 5-HMF (5-hydroxymethyl furfural) to other chemicals, muconic acid to adipic, 4-hydroxybenzoic acid to TPA Integrate with fermentation derived feedstocks with catalysis- FermCat Methods Continuous Flow Tubular (with Carbon Monolith Inside) or Packed Bed Reactor System Used Reactant: Furfural-5%, and Furfural - 5% with 1% acetic in water Catalysts -ACMC (activated carbon monolith): Pd, Pd-Cu, Pd-Fe, Pd-Ti -Powder and GAC (granular activated carbon) -Pd/Hydrotalcite (metal/base) Temperature: 100-180°C Pressure: atm-300 psig (or higher in future) Qgas/Qliquid= 12-200 (ACMC) Liquid Residence Time: 5-40 min GC/FID with standards and MS confirmation Correlate catalyst structure with function Measure dispersion, acid/base site density, acid site type, pore size, metal type, coke formation on the catalysts Conclusions - Pd/Carbon Powder vs. Pd/GAC vs. Pd/ACM - Furfural Hydrogenation Results Space time yields (g of product/L of catalyst/h) or STY's were significantly higher for the Pd on wood based activated carbon monolith (Pd/ACMC). We believe this is due to higher mass transfer rates and surface area to volume ratio of the ACMC These results were confirmed at higher liquid flow rates using a new recently purchased pump The major products formed from furfural were tetrahydrofurfuryl alcohol (THFA), furfuryl alcohol (FA), and 2-methyl tetrahydrofuran (2MF) STY's were generally 2-3 times higher using the ACMC We confirmed very high THFA (tetrahydrofurfuryl alcohol) yields, STY's, and selectivity for ACMC vs. GAC (granular activated carbon) and the carbon powder catalysts 100 g/L/h THFA at LHSV of 5-8 1/h (180°C, 300 psig) THFA results are significant Continuous production THFA at high STY's Green solvent used in automobile industry and for pesticide synthesis Market: 85,000 tonnes/y, 4.9% projected annual growth Very few reports on continuous THFA production from furfural Results may have industrial applications Cyclopentanone yields and STY's are low for all catalysts (mono-metals), with the Pd/Carbon Powder catalyst giving higher values than the Pd/GAC and Pd/ACMC catalysts Characterization of the used catalysts have been initiated The surface area of Pd/Powder and Pd/GAC decreased significantly compared to the Pd/ACMC (by 50-90%) A decline in Pd dispersion was significantly larger for the Pd/Powder and Pd/GAC catalysts compared to the Pd/ACMC Micro pore area of the Pd/Powder and Pd/GAC decreased significantly compared to the Pd/ACMC

Publications

• Type: Other Status: Published Year Published: 2018 Citation: US 10,139,306 B1

Progress 03/01/17 to 02/28/18

Outputs
Target Audience:- Industry and researchers via publication - Industry and researchers via presentation at AICHE meeting, 2017 Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? PhD student recruited ACMC cores prepared by Applied Catalysts Pd/GAC and Pd/ACMC, Pd/Fe ACMC and Pd/Cu ACMC Same GAC used in ACMC development provided by Applied Catalyst Packed Bed Reactor (PBR) and ACMC runs ongoing Furfural hydrogenation to cyclopentanone experiments ongoing Temperature, Pressure, and Residence Time Effects Actively looking for another student to conduct cyclopentanone to bicyclic alkane research Pd/Hydrotalcite (metal/base) on carbon and carbon monolith Will work on cyclopentanone condensation/hydrogenation to bicyclic alkane How have the results been disseminated to communities of interest?Recent Project Outputs Justin Weber, Aaron Thompson, Jared Wilmoth, Robert J Gulotty, James R Kastner. Coupling Red-Mud Ketonization of a Model Bio-oil Mixture with Aqueous Phase Hydrogenation Using Activated Carbon Monoliths. Energy & Fuels. Just Accepted Manuscript, DOI: 10.1021/acs.energyfuels.7b01500, Publication Date (Web): August 9, 2017, Energy & Fuels 31 (9), 9529-9541, 2017 Maryam Pirmoradi, James R. Kastner, Robert Gulotty. Continuous Hydrogenation of Furfural to Cyclopentanone Using Activated Carbon Monolith Catalysts. 533b: Chemical and Catalytic Conversions and Processes for Renewable Feedstocks, AICHE Symposium, Nov. 1st, 2017. Minneapolis, MN. What do you plan to do during the next reporting period to accomplish the goals?Conclusions/Results: Furfural Hydrogenation Using Pd/C powder, Pd/GAC, and Pd/ACM in a Continuous Process Cyclopentanone yields lower than literature reports (all batch processes) 5% Pd/C powder has larger yields and STY's compared to 1% Pd/GAC May have been due to mass transfer limitation in granular activated carbon (GAC) Significantly higher Pd dispersion in ACM vs GAC and Powder Remains to be determinedif dispersion (or Pd particle size) influences cyclopentanone yield May need to promote acid catalyzed step - Piancatelli Rearrangement to cyclopentanone Possible need for metal-acid functionality on GAC and ACMC Working on creating these metal-acid on carbon catalysts May need to promote water adsorption on activated carbon surface May need to reduce hydrogenation activity May need to add a second metal such as Fe or Cu to reduce hydrogenation activity Still working on Pd/ACMC hydrogenation HPLC pump repair required (lower liquid flow rates) - this has been done. New HPLC for higher liquid flow rates has been ordered and installed, used for higher flow rate experiments Pd and Bi-metal ACMC prepared and delivered by Applied Catalysts TPD, TPR, Pulse Titration, Chemisorb Instrument repaired Future Work: Working on metal/acid and metal/base ACMC catalyst to test for enhanced furfural to cyclopentanone yields and bi-cyclic alkanes from cyclopentanone Future Plans for Continuous Catalytic Processing: Goal - Increase cyclopentanone yields Goal - Understand role of acid sites, other surface functional groups on carbon, and water in the formation of cyclopentanone Continued testing of Pd/ACMC at higher pressures, atmospheric pressure, and low temperatures Continued testing of Pd/ACMC at higher flow rates using new HPLC pump Development of metal/Lewis acid on ACMC catalyst to improve cyclopentanone yields Testing of bi-metal onACMC to determine if cyclopentanone yields can be improved Detailed characterization of catalysts - pore size, acid site type and density, surface functional group analysis, surface metal particle size Data anticipated by end of Spring/Summer 2018 Effect of higher flow rates using ACMC Effect of bi-metal on furfural hydrogenation Effect of metal/acid sites on furfural hydrogenation using ACMC

Impacts
What was accomplished under these goals? Wood Based Monolith Catalyst (ACM or ACMC) for Hydrogenation of Ketones (Acetone, 2-Butanone, Cyclopentanone) Ketones (acetone, butanones, cyclic ketones) generated from catalytic ketonization of Southern Pine fast pyrolysis oils (aqueous fraction) were hydrogenated using wood based activated carbon monolith catalyst (ACMC) Pd/ACMC had significantly higher hydrogenation Space Time Yields (STY's) with lower metal loading for linear ketone hydrogenation Higher Pd metal dispersion (67% vs. 17-27% for Pd on Powder and GAC) Higher H2 mass transfer rates Significantly higher space time yields (STY, g/L of cat/h) ACMC not significantly impacted by acetic acid and acetone Ketone group hydrogenation slow compared to double bond Results Indicate potential as catalyst platform for hydrogenation and possibly other reactions Especially applicable for biobased feedstocks in aqueous phase Publication on this work was accomplished Research Objectives: Conversion of Furfural to Platform Chemicals Using Wood Based Carbon Monoliths Demonstrate ACM from wood as a platform catalyst (ACMC) Synthesize cyclopentanone from furfural using ACMC Pd and Pd/Cu (bimetal) ACMC compared with granular catalyst Correlate structure with function Develop transport and kinetic model for scale-up Time on stream studies and deactivation model Synthesize bicyclopentane (aviation fuel) from cyclopentanone Develop acid or base/metal bi-functional ACMC Attach an enzyme (lipase) to ACMC for biocatalysis function Demonstrate esterification reaction using ethyl valerate as a flavor/fragrance mode Screen transformation of other platform chemicals (long term goals) 5-HMF (5-hydroxymethyl furfural) to other chemicals, muconic acid to adipic, 4-hydroxybenzoic acid to TPA Integrate with fermentation derived feedstocks with catalysis- FermCat Methods Continuous Flow Tubular (with Carbon Monolith Inside) or Packed Bed Reactor System Used Reactant: Furfural - 5% with 1% acetic in water Catalysts -ACMC (activated carbon monolith): Pd, Pd-Cu, Pd-Fe -Powder and GAC (granular activated carbon) -Pd/Hydrotalcite (metal/base) Temperature: 100-180°C Pressure: atm-300 psig (or higher in future) Qgas/Qliquid= 12-200 (ACMC) Liquid Residence Time: 5-40 min GC/FID with standards and MS confirmation Correlate catalyst structure with function Dispersion, acid/base site density, acid site type, pore size, metal type, coke formation Conclusions - Pd/GAC Carbon - Furfural Hydrogenation Results Furfuryl alcohol is an intermediate Indicated by reduction in FA (furfuryl alcohol) yield and increasing THFA (tetrahydrofurfuryl alcohol), 2-MF (2-methyl furan), and 2-MTHF (2-methyl tetrahydrofuran) yields with decreasing liquid hourly space velocity, LHSV (or longer liquid residence times) LHSV is the catalyst bulk density x liquid flow rate/catalyst mass used, units are 1/time Highest Cyclopentanone yields using 5% Pd/ activated carbon powder 6% Yield with a Space Time Yield of 12 g/L/h (at a LHSV of 6.1 1/h, 300 psig, 180°C) 48% 2-MF (2-methyl furan) and 31 g/L/h (LHSV 1.5 1/h, 300 psig, 180°C) Lower furfural conversion using granular activated carbon (GAC) suggests mass transfer limitation, compared to Pd on powdered activated carbon Conclusions - Pd on Carbon Monolith vs. Granular Activated Carbon Cyclopentanone yields are lower than literature reports (all batch processes vs. our continuous process) 5% Pd/C powder has higher cyclopentanone (CYCP) yields and STY's compared to 1% Pd/GAC and ACMC May have been due to mass transfer limitation in GAC Pd particle size may affect pathway and CYCP yields Need to investigate difference between catalysts to better understand cyclopentanone formation Significantly higher Pd dispersion in ACMC vs GAC and Powder Remains to be determined if dispersion (or Pd particle size) influences cyclopentanone yield May need to promote acid step - Piancatelli Rearrangement Possible need for metal-acid functionality on GAC and ACMC to promote this rearrangement May need to reduce hydrogenation activity to promote cyclopentanone formation Add a another metal such as Fe or Cu to reduce hydrogenation activity Pd/ACMC Furfural Hydrogenation Significantly higher THFA (tetrahydrofurfuryl alcohol) Yields and Selectivity for ACMC vs. GAC (granular activated carbon) Most significant results at low temperatures and pressures 100 g/L/h THFA at LHSV of 4.5 1/h (180°C, 300 psig) THFA results are significant Continuous production THFA at high STY's Green solvent used in automobile industry and for pesticide synthesis Market: 85,000 tonnes/y, 4.9% projected annual growth Very few reports on continuous THFA production from furfural Results may have industrial applications Need to determine ACMC kinetics at higher LHSV's Can we maintain high yield and selectivity and increase STY? Need to determine ACMC longevity Acetic Acid Effect(only tested on Pd/GAC) Acetic acid does not significantly reduce furfural conversions and STY's Acetic acid significantly increased THFA and 2MF (2-methyl furan) yields and selectivity ~ 2X higher for 2MF in presence of acetic acid ~ 3X higher for THFA in presence of acetic acid High conversion of acetic acid observed (95% at 180°C, 300 psig) We need to determine where it goes? Do we form ethanol? Results suggest metal on activated carbon catalysts can be used to convert crude furfural streams, reducing energy inputs for distillation (crude furfural has acetic acid and acetone present) Need to explore this concept using ACMC Pd/ACMC Furfural Hydrogenation: Temperature and Pressure Effects 82% THFA yield observed at 120°C (300 psig) using ACMC vs. < 10% for GAC Yield decreased with increasing temperature 92% THFA yield observed at 180°C and atmospheric pressure vs. < 10% for GAC Yield decreased with increasing pressure

Publications

• Type: Journal Articles Status: Accepted Year Published: 2017 Citation: Justin Weber, Aaron Thompson, Jared Wilmoth, Robert J Gulotty, James R Kastner. Coupling Red-Mud Ketonization of a Model Bio-oil Mixture with Aqueous Phase Hydrogenation Using Activated Carbon Monoliths. Energy & Fuels. Just Accepted Manuscript, DOI: 10.1021/acs.energyfuels.7b01500, Publication Date (Web): August 9, 2017, Energy Fuels 2017, 31, 9529-9541
• Type: Conference Papers and Presentations Status: Published Year Published: 2017 Citation: Maryam Pirmoradi, James R. Kastner, Robert Gulotty. Continuous Hydrogenation of Furfural to Cyclopentanone Using Activated Carbon Monolith Catalysts. 533b: Chemical and Catalytic Conversions and Processes for Renewable Feedstocks, AICHE Symposium, Nov. 1st, 2017. Minneapolis, MN.