Progress 03/15/24 to 12/14/24
Outputs
Target Audience:The target audience is the scientific community and bioproduct industry. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?The project provided training opportunities for an undergraduate student. How have the results been disseminated to communities of interest?A conference presentation; broader community engagement was through activities in the UToledo College of Engineering such as the UT Experience Day. What do you plan to do during the next reporting period to accomplish the goals?We would like to complete and submit the following two manuscripts, if provided an additional NCE. Gogar R, Viamajala S, Relue P, Varanasi S. 2025. "High yield synthesis of HMF from glucose in the water-organic solvent system." Manuscript under preparation Bharadwaz A, Raheja G, Relue P, Viamajala S. 2025. "Recovery of high-purity glycerol from biodiesel waste? via reactive extraction?." Manuscript under preparation
Impacts
What was accomplished under these goals?
This year we investigated downstream conversion of glycerol to acrolein and acrylic acid. Acrylic acid is one of the most desirable and high demand products obtainable from glycerol and its annual production is ~10 million tons and is expected to continue growth. The traditional process for the synthesis of acrylic acid, developed by BASF, involves oxidation of propylene to acrolein and a subsequent oxidation of acrolein to acrylic acid. As an alternative to this petroleum-based approach to acrylic acid, we investigated a biobased pathway for acrolein (and subsequently acrylic acid) production from glycerol by catalytic dehydration. We investigated both liquid phase and gas phase conversion. Aqueous phase dehydration was explored with a number of acid catalysts at varying concentrations, as well as with the addition of organic additives or co-solvents. The most promising result was obtained in a biphasic system comprised of aqueous glycerol and isododecane with KHSO4 as the acid catalyst. After a 6 h reaction time, the acrolein yield was ~10% and compared favorably with previous results reported in the literature. We also investigated glycerol dehydration by cracking on a hot catalyst bed comprising of 40 wt% acid (H2SO4 or H3PO4)/silica gel catalysts. The acrolein yields using H2SO4, KHSO4 and H3PO4 were 7.7%, 6.4%, and 4.7%, respectively. Finally, we also investigated gas phase dehydration and oxidations reactions of glycerol. Advantages to this approach as compared to homogenous liquid phase catalysis include higher attainable reaction temperatures at lower pressure, simpler separation of reaction products and the ability to couple glycerol dehydration with the known gas phase oxidation of acrolein to afford acrylic acid, which is already employed in the industrial production of acrylic acid from propene. Conversion of glycerol was generally high; however, analysis by GC was difficult due to broad bands and other analyses will need to be pursued.
Publications
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2024
Citation:
Bharadwaz A, Raheja G, Relue P, Viamajala S. Recovery of High-purity glycerol from biodiesel waste via reactive extraction. Poster presentation at the 46th Symposium on Biomaterials, Fuels and Chemicals. Alexandria, VA. (April 28 - May 1, 2024).
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Progress 03/15/23 to 03/14/24
Outputs
Target Audience:The target audience is the scientific community and bioproduct industry. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?This project provided training for graduate students and undergraduate students. How have the results been disseminated to communities of interest?Broadcommunity engagement was through activities in the UToledo College of Engineering such as the UT Experience Day. What do you plan to do during the next reporting period to accomplish the goals?Evaluate the production of polyacrylic acid from purified glycerol obtained after the RE-BE process. Glycerol purified through the RE-BE process will be reacted in a two-phase system to generate acrolein, following a process similar to what we have used previously in generating furans from biomass sugars. The acrolein produced in the reactor would be extracted into toluene and then oxidized to acrylic acid.
Impacts
What was accomplished under these goals?
This year we had the following accomplishments for recovery of diols and triols. Below is a summary of our key results: Diols - We screened the reactive extraction of 1,3 propanediol and 2,3 butanediol due to their importance in several industrial applications. Our results show that we have been able to achieve approximately 36% extraction in the case of 1,3 propanediol at room temperature with a 1-octanol-based organic phase containing 1 M each of the quaternary ammonium salt and boronic acid. Similarly, during our 2,3 butanediol reactive extraction studies with the same organic phase composition at room temperature, the two isomers of the diol - meso and racemic - were reactively extracted to the organic phase at 57% and 43%, respectively, relative to the initial concentration in the feed during a single-stage RE-BE process. We also evaluated extraction using a mixture of the isomers and found that the process has potential use for separating the two isomers due to their differential extraction affinity. Triols - In addition to diols, we assessed the efficacy of using the single-stage RE-BE mechanism on the triol glycerol due to the extensive demand for a cost-effective purification method for glycerol, primarily for biorefinery crude stocks/waste. The prevalent purification methods for obtaining glycerol from a crude glycerol stock are energy intense and therefore expensive. In contrast, using facile extraction conditions, we were able to demonstrate >90% recovery of high purity glycerol in a 3-stage RE-BE process.
Publications
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Progress 03/15/22 to 03/14/23
Outputs
Target Audience:The target audience is the scientific community and bioproduct industry. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?This project provided training opportunities for a graduate studentand an undergraduate student. Students also presented their work at national conferences. How have the results been disseminated to communities of interest?Conference presentations; broader community engagement was through activities in the UToledo College of Engineering such as the UT Experience Day and Introduce a Girl to Engineering Day. What do you plan to do during the next reporting period to accomplish the goals?Next year, we plan to complete studies on recovery of diols and glycerol using SIRE.
Impacts
What was accomplished under these goals?
This year we had the following accomplishments. A novel alternate pathway to separate unreacted sugar and product HMF from the mixed-solvent system was developed by addition of toluene as a ternary solvent. Addition of toluene to the water-DME solution results in the formation of two immiscible phases - (i) a water-acetone phase (heavy) and (ii) a DME-toluene phase (light). HMF preferably partitions into the light organic phase while the unreacted sugars remain in the heavy aqueous phase After single-stage phase splitting, about 85% of initial HMF was recovered in the top-organic phase, which is lean in sugar, spent acid, and water. This enables recovery of HMF without the possibility of its degradation into humins or levulinic acid usually caused by sugar, acid, water, or high temperature. After separation of DME by distillation, HMF could be recovered in toluene and can be used for the synthesis of 2,5-diformylfuran, which can be converted into 2,5-furan dicarboxylic acid - a high value polymer precursor. We have performed initial screening experiments for high-purity recovery of propanediol, butanediol, and glycerol. These polyols are versatile platform chemicals, and when recovered in high purity, can serve as precursors for biobased polymers. Our interest in generating these precursors aligns with the recently-released Federal goal of "demonstrate and deploy cost-effective and sustainable routes to convert bio-based feedstocks into recyclable-by-design polymers that can displace >90% of today's plastics and other commercial polymers at scale". Propanediol and butanediol also have broad applications in cosmetics, antifreeze, solvents, and stabilizers. Similarly, glycerol is a triol that is an equally sought-after commodity in areas such as cosmetics, medicine, industrial applications like hydraulic fluids, and the food industry. The cost-effective recovery of these polyols from fermentation broths or from biodiesel production processes have been a long-standing challenge and our approach provides a novel, economically promising solution.
Publications
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2022
Citation:
Gogar R, Viamajala S, Relue P, Varanasi S. Integrated Pathway for the Efficient Conversion of Lignocellulosic Sugars to HMF. Platform presentation at the 2022 AIChE Annual Meeting, Phoenix, AZ (November 13-18, 2022).
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Progress 03/15/21 to 03/14/22
Outputs
Target Audience:The target audience is the scientific community and bioproduct industry. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?Training opportunities were provided for a graduate student. How have the results been disseminated to communities of interest?Conference presentations to the scientific community; broader community engagement was through activities in the UToledo College of Engineering such as the UT Experience Day. What do you plan to do during the next reporting period to accomplish the goals?Next year, we plan to continue work on the following aspects: Develop methods for separation and recovery of furans from the reaction media. Investigate the use of sire for recovery and purification of industrially relevant polyols such as propane diol, butane diol, and glycerol.
Impacts
What was accomplished under these goals?
This year we had the following accomplishments. We performed experiments in a 2 L meso-scale flow set-up and completed a mass transfer analysis of the SIRE processes to provide process metrics for further scale-up. To study the SIRE process in the meso-scale flow set-up, isomerization and reactive-extraction were first studied as stand-alone processes in a packed bed reactor and hollow fiber membrane contactor, respectively. The transient behavior of the sugar concentration was compared with those from the bench-scale shake-flask experiments. A good agreement of the experimental concentration profile of sugar in the reactive extraction with that predicted from a theoretical model (mass balance/mass transfer) was observed. Finally, the packed bed reactor and HFMC module were integrated and operated together to experimentally implement the simultaneous-isomerization-and-reactive-extraction process. Isomerization studies demonstrated that the packed bed column provides a large interfacial area and local enzyme concentration for isomerization. At a superficial velocity of 20 mm/s, isomerization was not external-diffusion limited. The theoretical model developed for reactive- extraction in recirculation mode agreed with the experimental data. The reactive-extraction experiments in the hollow fiber module revealed that the mass transfer is limited by diffusion across the hydrophobic membrane. We concluded that as the diffusivity of fructose in the aqueous phase was less than that of fructose-complex in the octanol phase, the use of hydrophilic membrane can reduce the resistance to the mass transfer across the membrane. Performed preliminary investigations on extraction of hydroxymethyl furfural in a ternary phase system.
Publications
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2021
Citation:
Gogar R, Viamajala S, Relue P, Varanasi S. High Yield Synthesis of HMF from Glucose in the Water-Organic Solvent System. Platform presentation at the 2021 AIChE Annual Meeting, Boston, MA (November 07-19, 2021).
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2020
Citation:
Gogar R, Schreur J, Viamajala S, Relue P, Varanasi S. Meso-Scale Studies of Simultaneous-Isomerization-Reactive-Extraction of Glucose to Fructose in a Flow Reactor. Platform presentation at the 2021 AIChE Annual Meeting, Boston, MA (November 07-19, 2021).
- Type:
Peer Reviewed Journal Articles
Status:
Published
Year Published:
2021
Citation:
Gogar R, Viamajala S, Relue P, Varanasi S. 2021. Techno-Economic Assessment of Mixed-Furan Production from Diverse Biomass Hydrolysates. ACS Sustainable Chemistry and Engineering 9: 34283438.
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Progress 03/15/20 to 03/14/21
Outputs
Target Audience:The target audience is the scientific community and bioproduct industry. Changes/Problems:During the year, our lab was shut down for nearly 4 months due to COVID lockdown. What opportunities for training and professional development has the project provided?The project provided training opportunities for a graduate student. How have the results been disseminated to communities of interest?Public dissemination of results was limited due to Covid restrictions. A thesis was published. What do you plan to do during the next reporting period to accomplish the goals?Next year, we plan to continue work on the following aspects: Perform experiments for a membrane process for SIRE that would represent a scaled model of a continuous process. Explore methods for separation and recovery of furans from the reaction media.
Impacts
What was accomplished under these goals?
This year we had the following accomplishments. During the year, our lab was shut down for nearly 4 months due to COVID lockdown. Technoeconomic assessments of the SIRE-BE-dehydration process were performed under two scenarios - (i) using ionic liquid (EMIM-HSO4) as the dehydration medium in a biphasic system with tetrahydrofuran, and (ii) using an acidic water-DME reaction medium. Due to the high yields of ketose sugars during SIRE-BE and high HMF yields during dehydration, both process alternatives showed promising price points. At a feed sugar price of $0.30 per kg, the IL process was estimated to produce HMF at a minimum selling price of $1.42/kg after improvements in solvent recovery costs were included. At the same feed sugar price, the water-DME method simulations assessed the minimum furan selling price (MFSP) to be $1.35/kg. Performed initial assessment of a continuous flow, meso-scale SIRE system using a hollow fiber membrane module.
Publications
- Type:
Theses/Dissertations
Status:
Published
Year Published:
2020
Citation:
Gogar R. Economic Production of Furans from Lignocellulosic Sugars. Ph.D. Thesis. The University of Toledo, 2020.
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Progress 03/15/19 to 03/14/20
Outputs
Target Audience:The target audience is the scientific community and bioproduct industry. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?This project provided training opportunities for graduate students and an undergraduate student. Students also presented their work at national conferences. How have the results been disseminated to communities of interest?Conference presentations; broader community engagement was through activities in the UToledo College of Engineering such as the UT Experience Day and Introduce a Girl to Engineering Day. What do you plan to do during the next reporting period to accomplish the goals?Next year, we plan to continue work on the following aspects: Complete technoeconomic analyses for the sugar to furan pathway. Perform experiments for a membrane process for SIRE that would represent a scaled model of a continuous process.
Impacts
What was accomplished under these goals?
This year we had the following accomplishments: Developed reaction media that result in high dehydration yields. Developed monophasic systems of water-organic solvents-acid catalyst that result in high HMF yields when combined with SIRE-BE Multiple co-solvents (tetrahydrofuran, γ-valerolactone, acetonitrile, acetone, and 1,2-dimethoxy ethane (DME)) and multiple acid catalysts (H2SO4, HCl, and methane sulfonic acid) were tested, with and without the addition of NaCl as a furan rate promoter/stabilizer. Results showed that the novel solvent system of water-DME with added HCl (55mM) gave the highest reaction yields. Hydroxymethyl furfural (HMF) yields were nearly 85% at optimal reaction conditions starting with 150 g/L glucose feed that was processed through SIRE-BE and dehydration. Initiated TEA of the integrated SIRE process with a downstream water-DME dehydration step. Completed experimental setup for membrane based SIRE process.
Publications
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2019
Citation:
Gogar R, Viamajala S, Relue P, Varanasi S. Techno-Economic Analysis of Production of Mixed-Furans from Biomass Hydrolysate. Platform presentation at the 2019 AIChE Annual Meeting, Orlando, FL (November 10-14, 2019).
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2019
Citation:
Gogar R, Viamajala S, Relue P, Varanasi S. A Novel Method of Producing 2,5-Diformylfuran at High Yields from Glucose. Platform presentation at the 2019 AIChE Annual Meeting, Orlando, FL (November 10-14, 2019).
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2019
Citation:
Gogar R, Viamajala S, Relue P, Varanasi S. Furan production from biomass hydrolysates: Scale-up and techno-economic study of a novel, high-yield 'SIRE-BE-Dehydration' process. Platform presentation at the 2019 Gordon Research Conference on Biomass to Biobased Chemicals and Materials, Newry, ME (July 14-19, 2019).
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Progress 03/15/18 to 03/14/19
Outputs
Target Audience:The target audience is the scientific community and bioproduct industry. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?This project provided post-doctoral training for Peng Zhang. How have the results been disseminated to communities of interest?Conference presentations and thesis. What do you plan to do during the next reporting period to accomplish the goals?Next year, we plan to continue work on the following aspects: Develop reaction media that results in high sugar dehydration yields for formation of hydroxymethyl furfural (HMF) and furfural Perform experiments for a membrane process for SIRE that would represent a scaled model of a continuous process. Initiate technoeconomic analyses for the sugar to furan pathway.
Impacts
What was accomplished under these goals?
This year we had the following accomplishments: 1. Demonstrated high ketose selectivity with concentrated sugar streams in SIRE Demonstrated >90% selectivity of fructose and xylulose after a 4-stage SIRE process on a 40 g/L feed stream containing glucose and xylose in a 3:1 mass ratio. Demonstrated ~80% fructose selectivity after single stage SIRE on a 160 g/L glucose feed stream. 2. Designed multiple BE strategies that improved purity of the ketose products Developed a two-stage BE method that resulted in high overall purity (~90%) of ketose sugars when concentrated mixed sugar feed stream (220 g/L) was used. The second BE stage resulted in nearly pure ketose sugars (96%). We demonstrated that the conditions of SIRE can be customized to maximize xylulose purity or xylulose yield under equilibrium conditions by changing the N2B:C5 sugar mole ratio. Transient SIRE can be used to exploit the differential isomerization kinetics of glucose and xylose to further increase xylulose purity of the separation. Xylulose yield can be increased by conducting SIRE on the hydrolysate for multiple cycles. Using 5 cycles of transient SIRE, on a sugar stream containing a 1:2 xylose:glucose mass ratio resulted in a 40% xylulose yield with ~90% xylulose purity. This is particularly significant considering that C5 is a minor sugar, initially present in a mole ratio of xyluse:glucose of 0.6, a ratio expected for biomass hydrolysate.
Publications
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2018
Citation:
Gogar R, Viamajala S, Relue P, Varanasi S. Furan Production from Biomass Hydrolysates: Scale-up of a Novel, High-Yield SIRE Process. Platform presentation at the 2018 AIChE Annual Meeting, Pittsburgh, PA (October 28 - November 2, 2018).
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2018
Citation:
Gogar R, Viamajala S, Relue P, Varanasi S. Production of 2,5-Furan Dicarboxylic Acid (FDCA) in Ionic Liquid Media. Platform presentation at the 2018 AIChE Annual Meeting, Pittsburgh, PA (October 28 - November 2, 2018).
- Type:
Theses/Dissertations
Status:
Published
Year Published:
2018
Citation:
Zhang, P. (2018). Optimizing Simultaneous-Isomerization-and-Reactive-Extraction (SIRE) Followed by Back-Extraction (BE) Process for Efficient Fermentation of Ketose Sugars to Products [Doctoral dissertation, University of Toledo]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=toledo1524617555286546
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