Progress 08/16/19 to 08/15/24
Outputs
Target Audience:The target audiences of this project include researchers, graduate stundents, undergradaute students, and professionals. Changes/Problems:Due to COVID in the earlier years, Florida Tech and Idaho National Lab were unable to perform a few tasks, which were completed in the extended year under one year no-cost extension. What opportunities for training and professional development has the project provided?This project exposed graduate students: Nepu Saha, Md. Tahmid Islam, Al Ibtida Sultana, and Vahab Ghalandari to mild hydrothermal preprocessing, biofuel characterization, combustion, and technoeconomic assessment. Dr. Nepu Saha defended his PhD on 2022 and now workign at the Idaho National Laboratry. Dr. Md. Tahmid Islam has defended his PhD in Fall 2022 and has now joined Joint Bioenergy Institute (JBEI) as a postdoc. Dr. Al Ibtida Sultana defende her PhD dissertation on Spring 2023 and is currently working at Intel Corpotation. Dr. Vahab Ghalandari graduated in Summer 2023 and now workign at the Cemex Cement Industry. All PhD students have presented their research in multiple conferences including the Florida Section of American Society of Agricultural and Biological Engineers (FASABE), American Institute of Chemical Engineers (AIChE), ASABE, and Florida Academy of Sciences. How have the results been disseminated to communities of interest?Results have been shared among the research team, including PD and co-PDs, graduate students, and staff. A total of 22 peer-reviewed journal papers have been published from this project. Dr. Nepu Saha and Dr. Tahmid Islam's PhD dissertations are reported the major findings of the project. Besides, a total of 29 conference presentations were delivered at ASABE, FASABE, AIChE, and other renowned conferences. Finally, a total of 5 invited presentations were delivered to NIFA, Department of Energy, and NASA. What do you plan to do during the next reporting period to accomplish the goals?
Nothing Reported
Impacts
What was accomplished under these goals?
Air Classification of corn stover: INL generated, retained, and distributed more corn stover samples as well as begin a campaign to investigate the co densification of corn stover with hydrothermally carbonized corn stover. The samples were generated in a manner like what was previously reported. Briefly, a splitter divides the sample into 8 analytical subsamples. Some of the material was carried on to be air classified (AC) and divided into two main fractions: heavier particles (not entrained in the air separator), typically with lower inorganic/ash content and lighter particles/tissues (entrained in the air separator) that typically have a higher inorganics/ash concentration. The samples were then ground in a hammermill fit with a one inch retention screen. Some of this corn staver was taken to test densification properties prior to the pilot scale run. Pellet formation stress/strain curves were captured for pellets ranging from approximately 900 to 1100 kg/m^3 density, and at 60, 90, and 120°C. The strength of these pellets are hypothesized to be link to this density, or how tightly bound the biomass is. Laying the pellets (~1"x1/4") on their side, an electromechanical loadframe was used to measure the maximum force when radially crushing the pellet. Combustion characteristics of corn stover: This study investigated the combustion properties of corn stover-derived hydrochars using cone calorimeter. Hydrochars were prepared by hydrothermal carbonization (HTC) at 200, 230, and 260 °C for 30 min. Six different heat fluxes (5-50 kW/m2) were applied to hydrochars to determine critical heat flux (CHF), ignition temperature, thermal response, peak heat release rate (pHRR), thermal hazard risk, and combustion efficiency. Results show that increasing the HTC temperature decreased the CHF and ignition temperature but increased the thermal resistivity. Increasing the heat flux decreased the thermal resistivity and ignition time of all the hydrochars. Thermal hazard analysis indicated that the hydrochars posed lower thermal risk than raw corn stover. Finally, combustion kinetics were proposed using two parallel first order reactions for volatile matters and fixed carbon. The reaction rate of volatile matter was significantly higher than the reaction rate of fixed carbon. HTC increased the fixed carbon activation energies to as high as 24.0 MJ/mol. Overall, HTC forms hydrochars which are less flammable, more stable, and a lower thermally risk material for piloted ignition than raw corn stover. Pelletization of corn stover with hydrochar.In this project, the research team investigated the durability and shear strength of blended pellets made of high ash fraction (HAF) derived hydrochar and low ash fraction (LAF) corn stover. The hydrochar utilized in this campaign was synthesized from HAF under specific conditions set at 200 °C with a residence time of 30 minutes. The screening crush test encompassed the incorporation of hydrochar in varying percentages--specifically 0%, 5%, 10%, 15%, 20%, and 50%--with the remainder constituted by raw LAF. Using an Instron single pellet press mill, approximately 8-10 pellets were produced for each specified hydrochar inclusion ratio. These pellets were then subjected to compressive strength analysis using the Instron Load Frame. The observed data indicated a direct relationship between the hydrochar content and the force required to crush the pellet, with a noted 25% increase in the crush force as the hydrochar content escalated from 15% to 20%, and a further 30% increase when the hydrochar content was augmented from 20% to 50%. As the improvement of the shear strength was not that significant for the addition of extra 30% (from 20% to 50%) hydrochar compared to the improvement happened due to the addition of extra 5% (from 15% to 20%), the research team selected a 20% hydrochar inclusion for scaled-up production utilizing a flat die pellet mill designed for kilogram-scale processing. Pellets were made at three distinct temperature ranges: 30-60 °C, 60-80 °C, and above 80 °C. The mechanical durability and compressive strength of the resultant pellets were meticulously assessed and benchmarked against those of non-blended, raw LAF pellets. It was observed that the durability of the blended pellets ranged between 84-93%, while the durability for the raw LAF pellets was recorded between 66-87%. The throughput for the blended pellets was measured at 7.4 kg/h on a dry basis, in contrast to 3.9 kg/h for the raw LAF pellets. Additionally, the team quantified the energy consumption associated with the pelletization process. It was determined that the energy consumption required to produce raw LAF pellets was 1.3 times greater than that for the blended pellets. The findings from this analytical campaign suggest that the integration of hydrochar not only enhances the structural integrity of the pellets but also results in increased production throughput and a reduction in energy consumption during pellet formation. Process design and optimization. Air classification (AC) is a cost-effective technology that separates theenergy-dense light ash fraction (LAF) from the inorganic-rich high ash fraction (HAF) of corn stover. HAF could be upgradedinto energy-dense solid fuel by hydrothermal carbonization (HTC). However, HTC is a high-temperature, high-pressureprocess, which requires additional energy to operate. In this study, three different scenarios (i.e., AC only, HTC only, andintegrated AC-HTC) were investigated for the energy recovery of corn stover. AC was performed on corn stover at an 8 Hzfan speed, which yielded 84.4 wt. % LAF, 12.8 wt. % HAF, and 2.8 wt. % below screen particles. About 27 wt. % ash wasreduced from LAF by the AC process. Furthermore, HTC was performed on raw corn stover and the HAF of corn stover at200, 230, and 260 °C for 30 min. To evaluate energy recovery, solid products were characterized in terms of mass yield, ashyield, ultimate analysis, proximate analyses, and higher heating value (HHV). The results showed that the energy density wasincreased with the increase in HTC temperature, meanwhile the mass yield and ash yield were decreased with the increase inHTC temperature. Proximate analysis showed that fixed carbon increased 18 wt. % for original char and 27 wt. % for HAFchar at 260 °C, compared to their respective feedstocks. Finally, the hydrochar resulting from HAF was mixed with LAF andpelletized at 180 bar and 90 °C to densify the energy content. An energy balance of the integrated AC-HTC process wasperformed, and the results shows that integrated AC with HTC performed at 230 °C resulted in an additional 800 MJ/ton ofenergy recovery compared to the AC-only scenario. Technoeconomic assessment and sensitivity analysis. The objective of this study is to investigate the economic feasibility of hydrothermal carbonization (HTC) process of waste corn stover. Two different cases of HTC of waste corn stover were considered for a 544,320 kg/d as-received corn stover plant. Case-I assumed a batch HTC process, while case-II assumed a continuous HTC process. Results show that both cases were economically feasible, however, case-I reached the break-even point at 3-y while case-II reached at 4-y. Additionally, case-I showed greater return on investment (5.02) than case-II (3.98) at the end of 20-y project life, including 26.6 % lower total capital investment. About 73 % of fixed capital cost came from investment in the reactor alone for case-I, while 63 % came from the reactor for case-II. The break-even selling price of the product was found to be $ 86.1/kg. A sensitivity analysis showed that the break-even selling price of the product was the most sensitive to the variation of the cost of corn stover and the least sensitive to the variation of tipping income.
Publications
|
Progress 08/16/22 to 08/15/23
Outputs
Target Audience:
Nothing Reported
Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?This project exposed graduate students: Nepu Saha, Md. Tahmid Islam, Al Ibtida Sultana, and Vahab Ghalandari to mild hydrothermal preprocessing, biofuel characterization, combustion, and technoeconomic assessment. Md. Tahmid Islam has defended his PhD in Fall 2022 and has now joined Joint Bioenergy Institute (JBEI) as a postdoc. Vahab Ghalandari also graduated in Summer 2023. All PhD students have presented their research in multiple conferences including the Florida Section of American Society of Agricultural and Biological Engineers (FASABE), American Institute of Chemical Engineers (AIChE), ASABE, and Florida Academy of Sciences. How have the results been disseminated to communities of interest?We published the following peer-reviewed journal article: Islam, M.T., Saha, N., Klinger, J., Reza, T., Technoeconomic Assessment Comparison of Batch and Continuous Hydrothermal Carbonization of Waste Corn Stover into Advanced Biorefinery Feedstock, Biofuels, Bioproducts, and Biorefinery, 2023, in press. https://doi.org/10.1002/bbb.2533 Sultana, AI, Cheatham, R., Reza, T., Unveiling Role of Biopolymers in Altering Surface Porosity to Enhance CO2 Capture Capacity of Biomass-Derived Activated Hydrochars, Biomass Conversion and Biorefinery, in-press. https://doi.org/10.1007/s13399-023-04414-3 Islam, M.T., Reza, T., Evaluation of Fuel and Combustion Properties of Hydrochar Derived from Co-Hydrothermal Carbonization of Biomass and Plastic, Biomass Bioenergy, 2023, 172, 106750 Sultana, AI, Cheatham, R., Reza, T., Deep Eutectic Solvent Pretreatment Alters Surface Morphology and Functionality of Activated Hydrochar Resulting in Enhanced Carbon Dioxide Capture, Journal of CO2 Utilization, 2023, 68, 102350 (Invited) Islam, Md Tahmid; Al Ibtida Sultana, Cadianne Chambers, Swarna Saha, Nepu Saha, Kawnish Kirtania, Reza, M. Toufiq, Recent Progress on Emerging Applications of Hydrochar, Energies, 2022, 15 (24), 9340. Sultana, AI, Chambers, C., Ahmed, M.N., Pathirathna, P., and Reza, T., Multifunctional Loblolly Pine- Derived Superactivated Hydrochar: Effect of Hydrothermal Carbonization on Hydrogen and Electron Storage with Carbon Dioxide and Dye Removal, Nanomaterials, 2022, 12, 3575. Islam, Md Tahmid; Klinger, Jordan L.; Reza, M. Toufiq, Evaluating Combustion Characteristics and Combustion Kinetics of Corn Stover-derived Hydrochars by Cone Calorimeter, Chemical Engineering Journal, 2023, 452, 139419. Conference Presentations Md Tahmid Islam*, Jordan Klinger and Toufiq Reza, 64a - Evaluation of Combustion Properties of Corn Stover-Derived Solid and Liquid Biofuels by Cone Calorimeter, 2022 AIChE Annual Meeting, Phoenix, AZ, November 13-18, 2022. Al Ibtida Sultana*, and Toufiq Reza, 144e - Investigation of Hydrothermal Carbonization and Chemical Activation Process Conditions on Hydrogen Storage in Loblolly Pine-Derived Superactivated Hydrochars, 2022 AIChE Annual Meeting, Phoenix, AZ, November 13-18, 2022. Md Tahmid Islam*, Nepu Saha, Jordan Klinger and Toufiq Reza, 195d - Advanced Biorefinery Feedstocks from Waste Biomass: Technoeconomic Assessment of Integrated Air Classification-Hydrothermal Carbonization-Pelletization Processes, 2022 AIChE Annual Meeting, Phoenix, AZ, November 13-18, 2022. Md Tahmid Islam*, Laura Guidugli, Jordan Klinger and Toufiq Reza, 414c - Removing Selective Structural Inorganics from Corn Stover By Type III Deep Eutectic Solvent, 2022 AIChE Annual Meeting, Phoenix, AZ, November 13-18, 2022. Al Ibtida Sultana*, and Toufiq Reza, 592f - Effect of Fundamental Biopolymers in the Development of Surface Porosity and CO2 capture Capacity of Superactivated Hydrochars, 2022 AIChE Annual Meeting, Phoenix, AZ, November 13-18, 2022. Other Presentations (invited) Toufiq Reza*, Hydrothermal Carbonization: A Thermochemical Pathway to Convert Biomass to Biofuels and Materials, KSC Town Hall Seminar Series, NASA Kennedy Space Center, August 29, 2023. Toufiq Reza*, Development and Optimization of Mild Hydrothermal Preprocessing for High Ash Biomass into Pelletized Biorefinery Feedstocks, Panel A1414, 2023 Bioeconomy Project Director Meeting, USDA-NIFA, July 14, 2023 What do you plan to do during the next reporting period to accomplish the goals?Process liquid as binder: MHP-derived process liquid contains significant binding materials but is discarded as a waste. However, we are studying the effect of clean biomass conditioning with different ratio of process liquid on the pelletization properties of the clean biomass. This will reveal the opportunity to utilize MHP-derived liquid waste as a binding material and potentially reduce the wastewater treatment cost. Pelletization: In the upcoming reporting period, the primary focus will be on densification of the upgraded hydrochar blended with the LAF mixture. A flat die mill at INL facility will be utilized to process up to 10 kg of the blended feedstock, with a ratio of 1:10 (hydrochar:LAF). To explore the mill parameter space, a single ¼" pellet die will be employed to establish a relationship between pellet durability (measured by maximum axial crushing strength using an electromechanical load frame) and unit density. This investigation aims to correlate the performance of the pellet mill with the resulting formation forces and operating conditions. A crucial consideration is achieving an appropriate balance between the materials' consolidation behavior and the applied force during pellet formation. A longer die path results in higher compaction force (via wall friction), leading to increased pellet durability and density. However, this may be accompanied by higher energy consumption and reduced throughput. The optimization of the pelletization process will be approximated. Energy consumption will be closely monitored, comparing cases with and without the addition of hydrochar. This assessment will enable the team to make informed decisions on the energy efficiency and overall performance of the densification process, leading to further improvements and potential scale-up.
Impacts
What was accomplished under these goals?
Binding properties of hydrochar: This FY, the LAF corn stover was pelleted using a single pellet press at different temperatures. Subsequently, the strength tests of these pellets were conducted. The stress-strain curves of pellet formation were captured and correlated with the resulting pellet density. The valuable information obtained from these tests was then utilized to guide the pelletization process in a flat die mill pellet press. At the flat die mill, kilogram-scale pellets were prepared from the LAF corn stover at three different temperature ranges: 30-60 °C, 60-80 °C, and >80 °C. The durability and crushing strength of these pellets were thoroughly examined. Durability was measured following the ASABE Standards S269.4, while the crushing strength was assessed by placing a pellet (~1"x1/4") on its side within an electromechanical load frame to measure the maximum force exerted when radially crushing the pellet. For all the pellets generated in the flat die mill at various temperatures, the crush force was related to the density and the pellet length. This relationship (coefficient of correlation of ~0.8), along with the very strong correlation (coefficient of correlation > 0.96) between pellet durability according to the ASABE standard and the density, shows a proof of concept for the thesis for this task. In the next fiscal year, the focus will shift towards investigating the durability of mixed pellets, consisting of a LAF and hydrochar. Co-MHP of biomass-plastic blend: Co-hydrothermal carbonization (Co-HTC) thermochemically transforms multiple solid feedstocks into energy-dense hydrochar. Herein, this study investigated the corn stover-polyurethane mixture at various feedstock ratios (5-15% polyurethane and balance corn stover) on fuel and combustion properties of the hydrochar prepared at various Co-HTC conditions. Results indicate that Co-HTC shows less mass yield than control HTC with corn stover only, however, it shows significant improvement in energy densification (7.8-34.5 %) and fuel ratio (0.22-0.64). The thermogravimetric analysis shows that Co-HTC-derived hydrochars are more thermally stable and persistent than raw corn stover. The combustion properties evaluated by cone calorimeter indicates that the Co-HTC-derived hydrochar shows maximum 1.3 times the peak heat release rate of raw corn stover. The Co-HTC-derived hydrochars along with raw corn stover and control hydrochar persist in smoldering phase (slow combustion) of combustion while raw polyurethane persists in flaming phase (fast combustion). Moreover, Co-HTC-derived hydrochars show relatively lower combustion efficiencies (49.2-75.2 %) than raw corn stover (77.2-89.9 %) or control hydrochar (75.2-77.9 %). In addition, increasing polyurethane composition in the corn stover-polyurethane mixture could reduce the combustion efficiency. Technoeconomic analysis of MHP process: The objective of this study is to investigate the economic feasibility of hydrothermal carbonization (HTC) process of waste corn stover. Two different cases of HTC of waste corn stover were considered for a 544,320 kg/d as-received corn stover plant. Case-I assumed a batch HTC process, while case-II assumed a continuous HTC process. Results show that both cases were economically feasible, however, case-I reached the break-even point at 3-y while case-II reached at 4-y. Additionally, case-I showed greater return on investment (5.02) than case-II (3.98) at the end of 20-y project life, including 26.6 % lower total capital investment. About 73 % of fixed capital cost came from investment in the reactor alone for case-I, while 63 % came from the reactor for case-II. The break-even selling price of the product was found to be $ 86.1/kg. A sensitivity analysis showed that the break-even selling price of the product was the most sensitive to the variation of the cost of corn stover and the least sensitive to the variation of tipping income.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2023
Citation:
Islam, M.T., Saha, N., Klinger, J., Reza, T., Technoeconomic Assessment Comparison of Batch and Continuous Hydrothermal Carbonization of Waste Corn Stover into Advanced Biorefinery Feedstock, Biofuels, Bioproducts, and Biorefinery, 2023, in press. https://doi.org/10.1002/bbb.2533
- Type:
Journal Articles
Status:
Published
Year Published:
2023
Citation:
Sultana, AI, Cheatham, R., Reza, T., Unveiling Role of Biopolymers in Altering Surface Porosity to Enhance CO2 Capture Capacity of Biomass-Derived Activated Hydrochars, Biomass Conversion and Biorefinery, in-press. https://doi.org/10.1007/s13399-023-04414-3
- Type:
Journal Articles
Status:
Published
Year Published:
2023
Citation:
Islam, M.T., Reza, T., Evaluation of Fuel and Combustion Properties of Hydrochar Derived from Co-Hydrothermal Carbonization of Biomass and Plastic, Biomass Bioenergy, 2023, 172, 106750
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2022
Citation:
Md Tahmid Islam*, Nepu Saha, Jordan Klinger and Toufiq Reza, 195d - Advanced Biorefinery Feedstocks from Waste Biomass: Technoeconomic Assessment of Integrated Air Classification-Hydrothermal Carbonization-Pelletization Processes, 2022 AIChE Annual Meeting, Phoenix, AZ, November 13-18, 2022.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2022
Citation:
Md Tahmid Islam*, Laura Guidugli, Jordan Klinger and Toufiq Reza, 414c - Removing Selective Structural Inorganics from Corn Stover By Type III Deep Eutectic Solvent, 2022 AIChE Annual Meeting, Phoenix, AZ, November 13-18, 2022.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2022
Citation:
Al Ibtida Sultana*, and Toufiq Reza, 592f - Effect of Fundamental Biopolymers in the Development of Surface Porosity and CO2 capture Capacity of Superactivated Hydrochars, 2022 AIChE Annual Meeting, Phoenix, AZ, November 13-18, 2022.
- Type:
Journal Articles
Status:
Published
Year Published:
2023
Citation:
Sultana, AI, Cheatham, R., Reza, T., Deep Eutectic Solvent Pretreatment Alters Surface Morphology and Functionality of Activated Hydrochar Resulting in Enhanced Carbon Dioxide Capture, Journal of CO�2 Utilization, 2023, 68, 102350
- Type:
Journal Articles
Status:
Published
Year Published:
2022
Citation:
Sultana, AI, Chambers, C., Ahmed, M.N., Pathirathna, P., and Reza, T., Multifunctional Loblolly Pine- Derived Superactivated Hydrochar: Effect of Hydrothermal Carbonization on Hydrogen and Electron Storage with Carbon Dioxide and Dye Removal, Nanomaterials, 2022, 12, 3575.
- Type:
Journal Articles
Status:
Published
Year Published:
2022
Citation:
Islam, Md Tahmid; Klinger, Jordan L.; Reza, M. Toufiq, Evaluating Combustion Characteristics and Combustion Kinetics of Corn Stover-derived Hydrochars by Cone Calorimeter, Chemical Engineering Journal, 2023, 452, 139419.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2022
Citation:
Md Tahmid Islam*, Jordan Klinger and Toufiq Reza, 64a - Evaluation of Combustion Properties of Corn Stover-Derived Solid and Liquid Biofuels by Cone Calorimeter, 2022 AIChE Annual Meeting, Phoenix, AZ, November 13-18, 2022.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2022
Citation:
Al Ibtida Sultana*, and Toufiq Reza, 144e - Investigation of Hydrothermal Carbonization and Chemical Activation Process Conditions on Hydrogen Storage in Loblolly Pine-Derived Superactivated Hydrochars, 2022 AIChE Annual Meeting, Phoenix, AZ, November 13-18, 2022.
- Type:
Other
Status:
Other
Year Published:
2023
Citation:
Toufiq Reza*, Hydrothermal Carbonization: A Thermochemical Pathway to Convert Biomass to Biofuels and Materials, KSC Town Hall Seminar Series, NASA Kennedy Space Center, August 29, 2023.
- Type:
Other
Status:
Other
Year Published:
2022
Citation:
Toufiq Reza*, Development and Optimization of Mild Hydrothermal Preprocessing for High Ash Biomass into Pelletized Biorefinery Feedstocks, Panel A1414, 2023 Bioeconomy Project Director Meeting, USDA-NIFA, July 14, 2023
- Type:
Theses/Dissertations
Status:
Published
Year Published:
2023
Citation:
Islam, M.T. Hydrothermal Preprocessing of Waste Corn Stover into Advanced Biorefinery Feedstock, PHD Dissertation, Florida Institute of Technology
|
Progress 08/16/21 to 08/15/22
Outputs
Target Audience:
Nothing Reported
Changes/Problems:Due to covid, our reserach progress was slower in the past Fall and part of Spring semesters. What opportunities for training and professional development has the project provided?This project exposed graduate students: Nepu Saha, Md. Tahmid Islam, and Vahab Ghalandari to mild hydrothermal preprocessing, biofuel characterization, combustion, and technoeconomic assessment. Nepu Saha has defended his PhD last year and has now joined INL as research scientist. All three PhD students have presented their research in multiple conferences including the Florida Section of American Society of Agricultural and Biological Engineers (FASABE), American Institute of Chemical Engineers (AIChE), ASABE, and Florida Academy of Sciences. How have the results been disseminated to communities of interest?We have pulished seven journal articles andthirteen conference presentations. Beside these, we also have several invited presentations where we have presented our resreach. Toufiq Reza, Upcycling Waste Plastics into Valuable Fuels and Chemicals, Lifelong Learning Society, Florida Institute of Technology, July 14, 2022 Toufiq Reza, Upcycling Wastes into Valuable Products: Solvothermal Conversion of Waste Plastics, American Chemical Society Student Chapter, University of Dhaka, February 27, 2022 Toufiq Reza, SolvX: Solvothermal Conversion of Plastic Wastes, University of Nevada, Reno, February 04, 2022 Toufiq Reza, Challenges and Opportunities to Produce Power and Energy from Municipal Solid Wastes, IEEE Melbourne, Power and Energy Section, November 17, 2021 Toufiq Reza, Hydrothermal Carbonization of Waste Biomass to Fuel and Materials, ReHyCaRe Seminar Series, Bangladesh Agricultural University, December 22, 2021. Toufiq Reza, Converting Waste to Energy & Materials, Florida Tech Alumni Lunch and Learn Series, August 19, 2021 What do you plan to do during the next reporting period to accomplish the goals? One pot synthesis: Our objective is to remove inorganics from the biomass structure as well as increase nitrogen functionality by one pot MHP process of loblolly pine and deep eutectic solvent. We are analyzing the fate of ash by SEM-EDX and analyzing the fuel and combustion characteristics of the hydrochar using thermogravimetric analyzer. We are also extending our study by incorporating the activation of the hydrochar and observing carbon capture efficiency. Process liquid as binder: MHP-derived process liquid contains significant binding materials but is discarded as a waste. However, we are studying the effect of clean biomass conditioning with different ratio of process liquid on the pelletization properties of the clean biomass. This will reveal the opportunity to utilize MHP-derived liquid waste as a binding material and potentially reduce the wastewater treatment cost. Pelletization: Continuing from the prior work, the INL team used air classification to generate a high-ash and a low-ash fraction (HAF and LAF) of corn stover for use in pellet production. This year, the INL team received a portion of the HAF that has been through FIT's hydrothermal carbonization process (hydrochars). Hydrochars enhance the heating value and assist in pellet formation. In the next reporting period, the team will focus on densification where INL will use a flat die mill to process up to 10 kg of blended upgraded hydrochars and the LAF (provisionally using a 1:10 ratio). To investigate the mill parameter space the team will use a single ¼" pellet die to relate the pellet durability (maximum axial crushing strength with an electromechanical loadframe) to unit density. This will translate performance in the pellet mill to formation forces and operating conditions. The most critical factor to balance is the materials consolidation behavior with the applied force during pellet formation. The longer the die path, the larger the compaction force (via wall friction) and the higher the pellet durability and density. This typically comes at the cost of higher operation energy and lower throughput. Optimization of the pellet process can be approximated at this small scale to inform the large run where energy consumption will be monitored for cases with and without added hydrochars.
Impacts
What was accomplished under these goals?
Air Classification of biomass: In this fiscal year INL generated, retained, and distributed more corn stover samples as well as begin a campaign to investigate the co densification of corn stover with hydrothermally carbonized corn stover. The samples were generated in a manner like what was previously reported. Briefly, a splitter divides the sample into 8 analytical subsamples. Some of the material was carried on to be air classified (AC) and divided into two main fractions: heavier particles (not entrained in the air separator), typically with lower inorganic/ash content and lighter particles/tissues (entrained in the air separator) that typically have a higher inorganics/ash concentration. The samples were then ground in a hammermill fit with a one inch retention screen. Some of this corn staver was taken to test densification properties prior to the pilot scale run. Pellet formation stress/strain curves were captured for pellets ranging from approximately 900 to 1100 kg/m^3 density, and at 60, 90, and 120°C. The strength of these pellets are hypothesized to be link to this density, or how tightly bound the biomass is. Laying the pellets (~1"x1/4") on their side, an electromechanical loadframe was used to measure the maximum force when radially crushing the pellet. This pellet production/durability screening was started this FY, and will continue into the next. Binding properties of hydrochar: Inadequate weather resistance and hydrophilic nature of biomass pellets are two major concerns for transportation, storage, and conversion. This study investigates how hydrophobicity of air classified corn stover pellets can be increased by blending corn stover with hydrochar. Hydrochar was prepared by hydrothermal carbonization (HTC) of waste corn stover at 260 °C for 30 min of residence time. Pellets were prepared from various blends of corn stover and hydrochar ranging from 0-50 wt. % hydrochar, and hydrophobic nature of the blend pellets were characterized by equilibrium moisture content (EMC) and contact angle measurement. The results show that hydrochar can significantly improve the hydrophobicity by reducing EMC by 25-40 % at relative humidity >50 % and resulting in a higher contact angle (from 53° to 83°) indicating lower wettability. Further investigation of the surface morphology of the blend pellets after moisture uptake showed that blend pellet disintegration can be attenuated significantly with the increase of hydrochar composition. Moreover, the mass and energy densities of the pellets were increased by 4-22 % and 17-73 %, respectively, with the addition of hydrochar. Combustion characteristics of corn stover: This study investigated the combustion properties of corn stover-derived hydrochars using cone calorimeter. Hydrochars were prepared by hydrothermal carbonization (HTC) at 200, 230, and 260 °C for 30 min. Six different heat fluxes (5-50 kW/m2) were applied to hydrochars to determine critical heat flux (CHF), ignition temperature, thermal response, peak heat release rate (pHRR), thermal hazard risk, and combustion efficiency. Results show that increasing the HTC temperature decreased the CHF and ignition temperature but increased the thermal resistivity. Increasing the heat flux decreased the thermal resistivity and ignition time of all the hydrochars. Thermal hazard analysis indicated that the hydrochars posed lower thermal risk than raw corn stover. Finally, combustion kinetics were proposed using two parallel first order reactions for volatile matters and fixed carbon. The reaction rate of volatile matter was significantly higher than the reaction rate of fixed carbon. HTC increased the fixed carbon activation energies to as high as 24.0 MJ/mol. Overall, HTC forms hydrochars which are less flammable, more stable, and a lower thermally risk material for piloted ignition than raw corn stover. Co-MHP of biomass-plastic blend: Co-hydrothermal carbonization (Co-HTC) thermochemically transforms multiple solid feedstocks into energy-dense hydrochar. Herein, this study investigated the corn stover-polyurethane mixture at various feedstock ratios (5-15% polyurethane and balance corn stover) on fuel and combustion properties of the hydrochar prepared at various Co-HTC conditions. Results indicate that Co-HTC shows less mass yield than control HTC with corn stover only, however, it shows significant improvement in energy densification (7.8-34.5 %) and fuel ratio (0.22-0.64). The thermogravimetric analysis shows that Co-HTC-derived hydrochars are more thermally stable and persistent than raw corn stover. The combustion properties evaluated by cone calorimeter indicates that the Co-HTC-derived hydrochar shows maximum 1.3 times the peak heat release rate of raw corn stover. The Co-HTC-derived hydrochars along with raw corn stover and control hydrochar persist in smoldering phase (slow combustion) of combustion while raw polyurethane persists in flaming phase (fast combustion). Moreover, Co-HTC-derived hydrochars show relatively lower combustion efficiencies (49.2-75.2 %) than raw corn stover (77.2-89.9 %) or control hydrochar (75.2-77.9 %). In addition, increasing polyurethane composition in the corn stover-polyurethane mixture could reduce the combustion efficiency. Technoeconomic analysis of MHP process: Corn stover is one of the most abundant agronomic resources in the U.S., however, those are either incinerated or unprocessed in the field to avoid high logistical cost, economic forfeiture, and environmental complications. Air classification has been proposed to separate clean corn stover from waste corn stover. Waste corn stover can be hydrothermally carbonized (HTC) into solid binder called hydrochar. Clean corn stover from air classification can be pelletized with hydrochar in a high moisture pelleting process (HMPP). The final product of the integrated process, pelletized corn stover, is a conversion-ready biorefinery feedstock. Different scenarios were considered for technoeconomic analysis to convert 544 tonne/day original corn stover into HMPP pellets. While, optimized air classification and HMPP process parameters are obtained from our prior studies, HTC process was optimized using two cases. Case I assumed a batch HTC process and case II assumed a continuous HTC process in the integration system. Results show that both cases are economically feasible, where case I showed 5y break-even years earlier than case II (7y). Additionally, case II showed greater capital and manufacturing investment compared to case I. The case I showed Return on Investment (ROI) of 3.3 while case II showed 1.9. A sensitivity analysis was also performed which revealed that the effect of solid content in air classified waste corn stover or reactor's feed, feedstock pumping cost, and total equipment cost were the influential parameters on breakeven selling price of the hydrochar.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2021
Citation:
Al Ibtida Sultana, Nepu Saha, Toufiq Reza, Upcycling simulated food wastes into superactivated hydrochar for remarkable hydrogen storage, Journal of Analytical and Applied Pyrolysis, 2021, 159, 105322. https://doi.org/10.1016/j.jaap.2021.105322
- Type:
Conference Papers and Presentations
Status:
Other
Year Published:
2022
Citation:
Al Ibtida Sultana, and Toufiq Reza*, Effect of biopolymers in the development of surface porosity and gas storage capacity of superactivated hydrochars, 2022 ASABE Annual Meeting, July 19, 2022, Houston, TX
- Type:
Conference Papers and Presentations
Status:
Other
Year Published:
2022
Citation:
Md Tahmid Islam, and Toufiq Reza*, Evaluation of Combustion Properties of Hydrochars by Cone Calorimeter, 2022 ASABE Annual Meeting, July 19, 2022, Houston, TX
- Type:
Journal Articles
Status:
Published
Year Published:
2022
Citation:
(Editorial) Toufiq Reza, Hydrothermal conversion, Energies 2022, 15(15), 5491.
- Type:
Journal Articles
Status:
Published
Year Published:
2022
Citation:
Sultana, AI, Reza, T., Investigation of hydrothermal carbonization and chemical activation process conditions on hydrogen storage in loblolly pine-derived superactivated hydrochars, International Journal of Hydrogen Energy, 2022, 47(62), 26422-26434
- Type:
Journal Articles
Status:
Accepted
Year Published:
2022
Citation:
Islam, Md Tahmid; Cadianne Chambers, Klinger, Jordan L.; Reza, M. Toufiq, Blending Hydrochar Improves Hydrophobic Properties of Corn Stover Pellets, Biomass Conversion and Biorefinery. 2022, In press. https://doi.org/10.1007/s13399-022-02521-1
- Type:
Journal Articles
Status:
Accepted
Year Published:
2022
Citation:
Sultana, AI, Reza, T., Techonomic Assessment of Superactivated Hydrochar Production by KOH Impregnation Compared to Direct Chemical Activation, Biomass Conversion and Biorefinery. 2022, In-press, https://doi.org/10.1007/s13399-022-02364-w
- Type:
Journal Articles
Status:
Published
Year Published:
2022
Citation:
Md Tahmid Islam, Cadianne Chambers, Toufiq Reza, Effects of Process Liquid Recirculation on Material Properties of Hydrochar and Corresponding Adsorption of Cationic Dye, Journal of Analytical and Applied Pyrolysis, 2022, 161, 105418.
- Type:
Journal Articles
Status:
Published
Year Published:
2021
Citation:
(Invited Publication) Islam, Md Tahmid; Sultana, Al Ibtida; Saha, Nepu; Klinger, Jordan L.; Reza, M. Toufiq, Deep Eutectic Solvent Pretreatment Enhances Fuel Properties of Hydrochar, I&EC Research. Invited Manuscript for the 2021 Class of Influential Researchers. 2021, 60 (43), 15479-15491
- Type:
Conference Papers and Presentations
Status:
Other
Year Published:
2022
Citation:
Md Tahmid Islam*, and Toufiq Reza, Combustion Analysis of Hydrochar of Corn Stover in Cone Calorimeter, 2022 FASABE Annual Meeting, May 20, 2022, Clearwater, FL
- Type:
Conference Papers and Presentations
Status:
Other
Year Published:
2022
Citation:
Al Ibtida Sultana*, and Toufiq Reza, Enhanced Carbon Dioxide Capture in Loblolly Pine Derived Superactivated Hydrochar by Altered Surface Morphology and Functionality, 2022 FASABE Annual Meeting, May 20, 2022, Clearwater, FL
- Type:
Conference Papers and Presentations
Status:
Other
Year Published:
2022
Citation:
Md Tahmid Islam*, and Toufiq Reza, Evaluation of Combustion Characteristics of Hydrochar by Cone Calorimeter, 2022 Florida Academy of Science, March 11, 2022 (virtual)
- Type:
Conference Papers and Presentations
Status:
Other
Year Published:
2022
Citation:
Al Ibtida Sultana*, and Toufiq Reza, Enhanced CO2 capture using porous superactivated hydrochars derived from deep eutectic solvent pretreated loblolly-pine, 2022 Florida Academy of Science, March 11, 2022 (virtual)
- Type:
Conference Papers and Presentations
Status:
Other
Year Published:
2021
Citation:
Md Tahmid Islam*, Nepu Saha, Jordan Klinger and Toufiq Reza, 395b - Co-Hydrothermal Carbonization (Co-HTC) of Biomass-Plastic Blend: Enhancement of Fuel Quality, 2021 AIChE Annual Meeting, Boston, MA, November 7-11, 2021
- Type:
Conference Papers and Presentations
Status:
Other
Year Published:
2021
Citation:
Al Ibtida Sultana*, and Toufiq Reza, 406e - Carbon Dioxide Capture on Superactivated Hydrochars Derived from Loblolly Pine and Functionalized By Deep Eutectic Solvents, 2021 AIChE Annual Meeting, Boston, MA, November 7-11, 2021
- Type:
Conference Papers and Presentations
Status:
Other
Year Published:
2021
Citation:
Md Tahmid*, Jordan Klinger and Toufiq Reza, 519f - Deashing of Biomass By Deep Eutectic Solvent to Enhance Biomass Conversion Process, 2021 AIChE Annual Meeting, Boston, MA, November 7-11, 2021
- Type:
Conference Papers and Presentations
Status:
Other
Year Published:
2021
Citation:
(Poster) Md Tahmid Islam*, Cadianne Chambers, Nepu Saha, Jordan Klinger and Toufiq Reza, 170f - Effect of Recycling HTC Process Liquid on Hydrochar Morphology and Its Corresponding Performance on Dye Adsorption, 2021 AIChE Annual Meeting, Boston, MA, November 7-11, 2021
- Type:
Conference Papers and Presentations
Status:
Other
Year Published:
2021
Citation:
Al Ibtida Sultana*, and Toufiq Reza, 592d - Effect of Recycling Potassium Hydroxide on Surface Morphology Superactivated Hydrochar Derived from Loblolly Pine, 2021 AIChE Annual Meeting, Boston, MA, November 7-11, 2021
- Type:
Conference Papers and Presentations
Status:
Other
Year Published:
2021
Citation:
Al Ibtida Sultana*, and Toufiq Reza, 709d - Upcycling Food Waste for Hydrogen Storage: Technoeconomic Assessment, 2021 AIChE Annual Meeting, Virtual, November 16-19, 2021
- Type:
Conference Papers and Presentations
Status:
Other
Year Published:
2022
Citation:
(Poster) Md Tahmid Islam*, Gordon Nelson, Toufiq Reza, Combustion Kinetics of Hydrothermally Carbonized Lignocellulosic Biomass by Cone Calorimeter, 2022 ACS Fire and Polymers, Napa Valley, CA, May 05, 2022
|
Progress 08/16/20 to 08/15/21
Outputs
Target Audience:
Nothing Reported
Changes/Problems:Due to COVID-19, our lab was not accessible for a few months. We have utilized that time on data curation, analysis, and presentation slides. What opportunities for training and professional development has the project provided?This project has provided opportunities for the PI and graduate students to attend AIChE, FAS, FASABE, and ASABE conferences and presentresults. Presentation list has been provided on the product page. How have the results been disseminated to communities of interest?We have published multiple articles on hydrothermal carbonization, pretretment, air classification, and process engineering. Besides, we have presented at the national American Soceity of Agricutural and Biological Soceinty (ASABE) and AmericanInstitute of Chemical Engineers (AIChE) in this year. Please see the product page for the jounral article and presentation details. What do you plan to do during the next reporting period to accomplish the goals? Semi-batch Reaactor Operation:We have purchased a 1.5 gallon Parr reactor, which will be used to prepare large quantity MHP samples. We will prepare 1 kg of hydrochar of each MHP process condition and ship the char to INL for pelletization using pilot pellet mill (ECO-10). We will also use the reactor as semi-batch process by adding biomass continuously during MHP operation. Equilibrium Moisture Content:We have preparedhydrochar and LAF mixed pellets at various ratio. We have started equilibrium moisture content of pellets with the goal to evaluate how hydrochar enhances hydrophobicity of LAF pellets. We have also sent a batch of mixed pellets to INL, where pulse nuclear magnetic resonance (NMR) has beenappliedto determine the free and bound moisture of the pellets Deashing of HAF biomass:HAF contains structural and free inorganics. We are studying various pretreatment process including deep eutectic solvents to reduce structural inorganic of biomass. This is a spin off idea from the project, which as origianlly not included in the proosal. Preliminary Technoeconomic Assessment: In the last year, we have evaluated integrated AC-HTC-pelletizationprocess. In the upcoing year, we will evaluate preliminary technoeconomic assessment of the integrated AC-HTC-pelletization process.
Impacts
What was accomplished under these goals?
Air classification: In this fiscal year, INL has supplied two 5-gallon buckets of each of the following samples (a) Original (ORG) Cornstover (CS), (b) Light Ash Fraction (LAF) CS, (c)High Ash Fraction (HAF) CS, (d)ORG Loblolly Pine (LP), (e) LAF LP, and (f)HAF LP. The original samples have been gone through various mechanical stages to make the final sample set (listed above). The detailed processes are discussed here:A super sack of the deconstructed CS bale (6" size) was received for this project. The super sack was divided using a custom rotary splitter that consists of a conveyor and eight bins mounted on a rotating table. In this unit, a feed hopper accommodates approximately 120 L of sample and a live-bottom style belt feeder slowly dispenses the samples to 8 sample bins below. The 45 L bins rotate over 100 times during each splitting operation and make at least one full rotation for each belt flight to ensure the samples are representative of the original bulk solid. Both the belt feeder and the rotary table are equipped with speed control devices (variable frequency drive and/or DC potentiometer) to adjust the processing parameters according to the sample feed behavior to ensure analytical splitting. A total of 4 batches of split were conducted to finish the whole super sack. These split samples were referred as ORG CS. Three of the batches were stored at INL for future use. Rest of the batch was used for further mechanical separation. Six bins out of eight in that batch were air classified (AC) using 2× Air Cleaner equipped with an Iso-flo dewatering infeed shaker (Key Technologies, Walla Walla, WA, USA). AC separates the samples into two main fractions as the material is passed over a screen-covered fan: Heavies (referred as LAF) and Lights (referred as HAF). AC was performed on CS feedstocks using a 2× Air Cleaner equipped with an Iso-flo dewatering infeed shaker (Key Technologies, Walla Walla, WA, USA). The HAF is blown upward and removed while the LAF (air classified material) remains. During the air classification of ORG CS, the infeed shaker and blower frequencies were set up at 60 Hz and 8 Hz, respectively. The air classified samples (HAF and LAF) including the remaining ORF were further size reduced through a Schutte Buffalo Hammermill (Buffalo, NY). A 1" screen was used while the motor frequency was set at 60 Hz. Each size reduced sample was store in 5-gallon bucket and shipped to FIT. Pretreatment of high ash fraction of corn stover:Hydrothermal carbonization (HTC) or mild hydrothermal preprocessing (MHP) is a novel thermochemical conversion that converts wet biomass into energy dense solid fuel. Residual moisture under subcritical conditions reacts with lignin-cellulose-hemicellulose matrix with the major reactions being identified as dehydration and decarboxylation. Among other reaction parameters (e.g., temperature, time, pressure), biomass morphology often plays a key role to HTC. The hypothesis of this study was enhancing porous structure of biomass without significantly affecting biopolymer composition would augment hydrothermal carbonization (HTC). To prove the hypothesis, two type-III deep eutectic solvents (DES) namely choline chloride:urea (ChCl:Urea, 1:2 mole/mole) and methyltriphenylphosphonium bromide:ethylene glycol (MTPB:EG, 1:4 mole/mole) were studied to pretreat loblolly pine at room temperature and ambient pressure for 1 hour. DES pretreatment shows swelling of the biomass, increasing the surface fiber-to-fiber gap length by 52 % and 185 % for ChCl:Urea and MPTB:EG pretreatments, respectively. The total pore volume remained intact (2.6×10-3 cm3/g), although new small pores were evolved, and existing pores were abated with DES pretreatment. Hydrochars prepared from DES pretreated loblolly pine showed a high O/C and H/C ratio resulting in significant increase of energy content (up to 42 %) and decrease of mass yield (up to 50 wt. %), indicating an enhancement of HTC severity due to the alteration of surface morphology by DES. A preliminary process economics revealed that integrated DES pretreatment-HTC would increase fixed capital investment but decrease the cost of operation and manufacturing than standalone HTC process. Integrated AC-MHP-Pelletization process:Air classification (AC) is a cost-effective technology that separates the energy-dense light ash fraction (LAF) from the inorganic-rich high ash fraction (HAF) of corn stover. HAF could be upgraded into energy-dense solid fuel by hydrothermal carbonization (HTC). However, HTC is a high-temperature, high-pressure process, which requires additional energy to operate. In this study, three different scenarios (i.e., AC only, HTC only, and integrated AC-HTC) were investigated for the energy recovery of corn stover. AC was performed on corn stover at an 8 Hz fan speed, which yielded 84.4 wt. % LAF, 12.8 wt. % HAF, and 2.8 wt. % below screen particles. About 27 wt. % ash was reduced from LAF by the AC process. Furthermore, HTC was performed on raw corn stover and the HAF of corn stover at 200, 230, and 260 °C for 30 min. To evaluate energy recovery, solid products were characterized in terms of mass yield, ash yield, ultimate analysis, proximate analyses, and higher heating value (HHV). The results showed that the energy density was increased with the increase in HTC temperature, meanwhile the mass yield and ash yield were decreased with the increase in HTC temperature. Proximate analysis showed that fixed carbon increased 18 wt. % for original char and 27 wt. % for HAF char at 260 °C, compared to their respective feedstocks. Finally, the hydrochar resulting from HAF was mixed with LAF and pelletized at 180 bar and 90 °C to densify the energy content. An energy balance of the integrated AC-HTC process was performed, and the results shows that integrated AC with HTC performed at 230 °C resulted in an additional 800 MJ/ton of energy recovery compared to the AC-only scenario. MHP process liquid recirculation:Hydrochar has been gaining tremendous interest as adsorbent materials, however, change in material properties due to process liquid recirculation has not been studied yet, although commercial hydrothermal carbonization (HTC) is likely to recycle HTC process liquid in order to preheat the feedstock as well as minimize the wastewater accumulation. Therefore, this study focused on the process liquid recirculation up to 9 times and evaluated how surface functionalities as well as Rhodamine B adsorption capacities change with the number of recycle. HTC of corn stover was performed at a fixed temperature (230 °C) and a fixed residence time (30 mins) with 50 wt. % process liquid recirculation. Results indicate that the mass yield for control was 60.6 ± 0.9 wt. % which was increased to 66.9±0.0 wt. % with HTC process liquid recirculation. Meanwhile, ash was concentrating with HTC process liquid recirculation (from 10.3 ± 1.1 % to 13.9±0.3 %). The Brunauer, Emmett, and Teller (BET) surface area and total pore volume for control were 6.7±0.1 m2/g and 9.8×10-3 cm3/g, respectively, which were increased to 7.4 ± 0.0 m2/g (recycle-1) - 10.8 ± 0.1 m2/g (recycle-9) and 12.4×10-3 cm3/g (recycle-1) -17.3×10-3 cm3/g (recycle-9). However, Boehm titration revealed that the recycle-3 retained higher oxygen-containing surface functional group density (231.2±3.9 µmol/g) than control (161.9±2.5 µmol/g) and recycle-9 (132.2±1.5 µmol/g). These morphological characteristics also reflect on the Rhodamine B adsorption capacities, where maximum equilibrium adsorption capacity was found for recycle-3 (30.7 mg/g) followed by recycle-9 (23.6 mg/g) and control (21.4 mg/g) and the adsorption isotherms were following combined Langmuir-Freundlich isotherm.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2021
Citation:
Md. Rifat Hasan, Nepu Saha, Thomas Quaid, Toufiq Reza, Formation of Carbon Quantum Dots via Hydrothermal Carbonization: Investigate the Effect of Precursors, Energies, 14 (4), 986.
- Type:
Journal Articles
Status:
Published
Year Published:
2020
Citation:
Nepu Saha, Kyle McGaughy, M. Toufiq Reza, Elucidating hydrochar morphology and oxygen functionality change with hydrothermal treatment temperature ranging from subcritical to supercritical conditions, Journal of Analytical and Applied Pyrolysis, 2020, 152, 104965.
- Type:
Journal Articles
Status:
Published
Year Published:
2020
Citation:
Nepu Saha, Maurizio Volpe, Roberto Volpe, Luca Fiori, Antionio Messineo, M. Toufiq Reza, Cationic dye adsorption on hydrochars of winery and citrus juice industries residues: performance, mechanism, and thermodynamics, Energies, 2020, 13 (18), 4686.
- Type:
Journal Articles
Status:
Published
Year Published:
2020
Citation:
Nepu Saha, Kyle McGaughy, Michael Held, Toufiq Reza, Hydrothermal degradation of ?-estradiol and oxytetracycline at selective reaction severities, Springer Nature Applied Science, 2020, 2 (9), 1-9
- Type:
Theses/Dissertations
Status:
Published
Year Published:
2021
Citation:
Nepu Saha, Behavior of selective oxygen functional groups upon hydrothermal carbonization and pyrolysis of biomass and their roles on selective applications. PhD Dissertation, 2021, Florida Institute of Technology
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2021
Citation:
Al Ibtida Sultana, Nepu Saha, and M. Toufiq Reza, Capturing Carbon Dioxide on Deep Eutectic Solvent Functionalized-Superactivated Hydrochars Synthesized from Loblolly Pine, ASABE Virtual Annual Meeting, July 12-16, 2021
- Type:
Conference Papers and Presentations
Status:
Other
Year Published:
2021
Citation:
Md Tahmid Islam, Nepu Saha, Jordan Klinger, M. Toufiq Reza, Enhancing Hydrophobicity of Biomass Pellets by Addition of Hydrochars, ASABE Virtual Annual Meeting, July 12-16, 2021
- Type:
Journal Articles
Status:
Accepted
Year Published:
2021
Citation:
Islam, Md Tahmid; Sultana, Al Ibtida; Saha, Nepu; Klinger, Jordan L.; Reza, M. Toufiq, Deep Eutectic Solvent Pretreatment Enhances Fuel Properties of Hydrochar, I&EC Research. Invited Manuscript for the 2021 Class of Influential Researchers. In-press. DOI: 10.1021/acs.iecr.1c03068&ref=pdf
- Type:
Journal Articles
Status:
Published
Year Published:
2021
Citation:
Al Ibtida Sultana, Nepu Saha, Toufiq Reza, Upcycling simulated food wastes into superactivated hydrochar for remarkable hydrogen storage, Journal of Analytical and Applied Pyrolysis, 2021, 159, 105322. https://doi.org/10.1016/j.jaap.2021.105322
- Type:
Journal Articles
Status:
Published
Year Published:
2021
Citation:
Md. Tahmid Islam, Nepu Saha, Sergio Hernandez, Jordan Klinger, Toufiq Reza, Integration of Air Classification and Hydrothermal Carbonization to Enhance Energy Recovery of Corn Stover, Energies, 2021, 14 (5), 1397.
- Type:
Conference Papers and Presentations
Status:
Other
Year Published:
2021
Citation:
Md Tahmid Islam, Nepu Saha, M. Toufiq Reza, Effect of Selected Type III Deep Eutectic Solvent Pretreatment on Hydrothermal Carbonization of Loblolly Pine, ASABE Virtual Annual Meeting, July 12-16, 2021
- Type:
Conference Papers and Presentations
Status:
Other
Year Published:
2021
Citation:
Md Tahmid Islam, Toufiq Reza, ENG-04: Effect of Recycled Liquid Waste on Hydrothermal Characterization Process, 2021 Florida Academy of Sciences
- Type:
Conference Papers and Presentations
Status:
Other
Year Published:
2020
Citation:
Md Tahmid Islam, Sergio Hernandez, Jordan Klinger, and M. Toufiq Reza, Hydrophobic Behavior of Hydrothermally Carbonized Biomass, 2020 AIChE Annual Meeting, November 2020, San Francisco, CA
- Type:
Conference Papers and Presentations
Status:
Other
Year Published:
2020
Citation:
Md Tahmid Islam, Sergio Hernandez, Jordan Klinger, and M. Toufiq Reza, Significance of Oxygen Functional Groups on Pelletization of Hydrochar, 2020 AIChE Annual Meeting, November 2020, San Francisco, CA
- Type:
Conference Papers and Presentations
Status:
Other
Year Published:
2020
Citation:
Nepu Saha, Kyle McGaughy, Toufiq Reza, Effect of Hydrothermal Treatment Temperature on Surface Morphology and Oxygen Functionality of Hydrochar Produced from Cellulose, 2020 AIChE Annual Meeting, November 2020, San Francisco, CA
- Type:
Other
Status:
Other
Year Published:
2021
Citation:
Toufiq Reza, Converting Waste to Energy & Materials, Florida Tech Alumni Lunch and Learn Series, August 19, 2021
- Type:
Conference Papers and Presentations
Status:
Other
Year Published:
2020
Citation:
Toufiq Reza, Keynote: Hydrothermal Carbonization: Opportunities and Challenges, 6th International Conference on Chemical Engineering, December 20-22, 2020
- Type:
Other
Status:
Other
Year Published:
2020
Citation:
Toufiq Reza, Hydrothermal Carbonization of Waste Biomass for Energy and Energy Storage Materials, Distinguished Alumni Lecture Series: Emerging Research and Innovation, Bangladesh University of Engineering and Technology, October 31, 2020
|
Progress 08/16/19 to 08/15/20
Outputs
Target Audience:
Nothing Reported
Changes/Problems:Due to COVID-19, our lab was not accessible for two months. We have utilized that time on data curation, analysis, and presentation slides. What opportunities for training and professional development has the project provided?This project has provided opportunities for PI and graduate students to attend AIChE and ASABE conferences and present results. Presentation list has been provided on the product page. How have the results been disseminated to communities of interest?We have presented an invited presentation at the Department of Energy Workshop in Arlington, VA M. Toufiq Reza, Hydrothermal Carbonization: A Thermochemical Pathway to Convert Wastes to Conversion ready Feedstocks. BETO Workshop: Advancing the Bioeconomy: From Waste to Conversion Ready Feedstocks, Arlington, VA, February 19, 2020 Besides, we have presented at the national American Soceity of Agricutural and Biological Soceinty (ASABE) and American Institute of Chemical Engineers (AIChE) in this year. Please see the product page for the presentation details. What do you plan to do during the next reporting period to accomplish the goals? Initial crack analysis of the raw and hydrochar pellets have been done usingthe scanning electron microscope (SEM). More pellets will be prepared and will be sent to Idaho National Laboratory (INL) to verify the reproducibility of the results. MICUM test will be performed to analyze the durability of the pellets. This study will help to analyze the effect of HTC on pelletization. The total acidic and basic functional groups of the hydrochar samples (raw, HTC 200, HTC 230, HTC 260, HTC 290, HTC 320) at three different pelletization pressures (25bar, 50bar, 100bar) and fixed temperature (90ºC) will be found to analyze the functional group effect on the pelletization. The new idea is to perform air classification (AC) of CS- HTC of HAF-pelletize LAF with hydrochar from HTC and discuss how integrated process yields higher energy densification (with better fuel property in terms of ash) that any individual process (AC, HTC, or pelletization) could not achieve. The equilibrium moisture content (EMC) will be determined for 7 different pellets (CS LAF(light ash fraction), CS HAF HTC 260, LAF and HAF HTC 260 mixture: 90%:10%, 80%:20%, 70%:30%, 60%:40%, 50%:50%) in several different relative humidites. The temperature will be maintained at 30ºC and the relative humidity will be varied from 11% to 83%. To analyze the effect of process liquid (PL) recycling in inorganics accumulation in the MHP reactor, ten HTCs at 230ºC and 260ºC were performed in which the PL from the immediate previous HTC was used as 50% and deionized water (DI water) was used as 50% in each HTC. The process liquid was collected from each HTC and the total organic carbon (TOC) was found only once. Duplicate will be done to verify the results. The nitrogen, sulfate and phosphorus content will be found. All the process liquid was acidic in nature. The MY and % of PL obtained in each HTC did not change very much for both HTC 230 and HTC 260. Same procedure will be followed for HTC 200.
Impacts
What was accomplished under these goals?
The main goal of the first year was to perform air classification (AC) at Idaho National Lab and distinguish the appropriate particle size from heterogeneous feedstock (corn stover and loblolly pine (high ash fraction, HAF)), perform hydrothermal carbonization of the corresponding particle and characterize the solid hydrochars. First, AC was performed for both pine residues and corn stover.Air classification (AC) separates the samples into two fractions as the material passes through a screen covered air stream. The particles separate based on the respective drag properties the depend on tissue densities, particle sizes and morphologies, etc. Depending on the conditions of the classifier, a portion of the material is entrained in the air stream and is elutriated to a separate collection bin. The two streams are referred to as 'lights' for material that is suspended and carried away and 'heavies' for the material fractions are are to dense and simply fall into a collection bin at the end of the feeder. Air classification was performed on CS feedstocks using a 2x Air Cleaner equipped with an Iso-flo dewatering infeed shaker (Key Technologies, Walla Walla, WA). The forest residues were screened through a range of Processing Parameters (PPs, air speed) and Material Attributes (moisture content, tissue type) to determine an operational space with respect to the desired separation of anatomical tissue types. Both light and heavy fractions were collected and shipped after classification for hydrothermalprocessing at Florida Tech. Florida Techperformed sieve shaking of ACcorn stover HAF (CS HAF). It is found that the retained weight (%) increased with the particle size, showing highest retained weight (55 %) for 0.59-2.00 mm but a sudden decrease to 14 % for 2.00 mm and above. The highest retained weight and corresponding lower ash were the main facts to narrow down the choices to 0.59-2.00 mm particle size in order to proceed for hydrothermal carbonization (HTC) and densification of energy study. The 0.59-2.00 mmparticle size HAF CS was hydrothermally carbonized at 200,230, and 260ºC for 30 mins in 300 mL batch Parr reactor. The experiments were triplicated to maintain the reproducibility of the experiments. Is was found that the mass yield(MY) decreased with the increase of HTC temperature. The MY started with 59.2 ± 2.8 % at HTC 200, while it decreased to 36.7 ± 9.9 % at HTC 260. The ash yield (AY) showed slight change in their values for hydrochars at 200, 230 and 260ºC, although a significant decrease (~39 %) was found from raw HAF CS to HTC 200. The energy content was found maximum (~22 MJ/kg) for HTC 260, which was almost 5.4 MJ/kg higher than raw HAF CS (~17 MJ/kg).It was also observed that as the incrase of HTC temperature, the energy densification ratio (EDR) increasesby an increment of 10 % for each HTC that led to a maximum 30 % increment for HTC 260 from the raw HAF CS. Table below presents the results from HTC of HAF CS. HTC condition MY Ash (%) AY (%) HHV (MJ/kg) EY (%) EDR Raw 100.0±0.0 10.3±1.1 10.3±1.1 16.8±0.1 100.0±0.0 1.0±0.0 HTC 200 59.2±2.8 10.6±0.6 6.3±0.6 18.6±0.2 65.5±2.8 1.1±0.0 HTC 230 54.3±9.0 10.6±0.2 5.7±0.8 19.9±0.1 64.2±10.6 1.2±0.0 HTC 260 36.7±9.9 14.3±0.4 5.3±1.5 22.2±0.2 48.4±12.8 1.3±0.0 Van Soest fiber analysis showed that the extractives in HTC 200 was lowered but gradually increased with the increase of HTC temperature. For the case of hemicellulose, all the hydrochars were well below <6 %, while the raw CS HAF contained 22.6 %. The cellulose for HTC 200 and HTC 230 were above the raw HAF CS, while HTC 260 showed significantly low amount. Finally, the remaining (analogus to lignin and ash) in all the hydrochars were well above the raw CS and it reached to 36.3%. Table below shows the van Soest fiber analysis of the hydrochar. Table below presents the van Soest analysis results. HTC condition Extractives (%) Hemicellulose (%) Cellulose (%) Remaining (%) RAW 33.9±0.4 22.6±0.9 29.9±1.8 13.6±1.9 HTC 200 25.6±0.5 2.9±0.8 49.4±1.6 22.1±1.5 HTC 230 37.8±2.5 4.0±1.7 34.7±1.6 23.5±0.4 HTC 260 54.7±1.4 2.5±0.3 6.5±1.1 36.3±1.0 We made pellets of hydrochar produced at different HTC conditions using single press pellet press and measured mass and energy density of the pellets.The mass density (MD)of HTC 200 showed an increase from the raw CS. The MD increased with the elevated HTC temperature and reached maximum at 230 ?C and then slightly decreased at 260 ?C. We have also found thatthe energy density (ED) had a remarkable increase from raw CS to HTC 200 although the other hydrochars showed same increment about 2 GJ/m3 compared to the immediate earlier hydrochar. The ED for HTC 260 was about 53 % higher than the raw CS and 23 % higher than HTC 200. Figure below shows biomass and hydrochar pellets as well as mix pellets.
Publications
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2020
Citation:
Md. Tahmid Islam, Nepu Saha, Sergio Harnandez, Jordan Klinger, Toufiq Reza, Hydrothermal carbonization of high ash fraction corn stover from air classification, 2020 ASABE Virtual Annual Meeting, July 2020, Omaha, NE
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2020
Citation:
Al-Ibtida Sultana, Nepu Saha, Toufiq Reza, Superactivated hydrochar for hydrogen storage, 2020 ASABE Virtual Annual Meeting, July 2020, Omaha, NE
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2019
Citation:
Md. Tahmid Islam, Jordan Klinger, Sergio Hernandez, M. Toufiq Reza, Fate of Inorganics during Hydrothermal Carbonization of High Ash Fraction of Air Classified Biomass, 2019 AIChE Annual Meeting, November 2019, Orlando, FL.
- Type:
Journal Articles
Status:
Published
Year Published:
2019
Citation:
Nepu Saha, M. Toufiq Reza, Effect of pyrolysis on basic functional groups of hydrochars, Biomass Conversion and Biorefinery, 2019, 1, 1-8
- Type:
Journal Articles
Status:
Published
Year Published:
2020
Citation:
Akbar Saba, Nepu Saha, Keenan-Conrad Williams, Charles Coronella, M. Toufiq Reza, Binder-free torrefied biomass pellets: significance of torrefaction temperature and pelletization parameters by multivariate analysis. Biomass Conversion and Biorefinery. In-press. (2020). https://doi.org/10.1007/s13399-020-00737-7
- Type:
Other
Status:
Published
Year Published:
2020
Citation:
M. Toufiq Reza, Hydrothermal Carbonization: A Thermochemical Pathway to Convert Wastes to Conversion ready Feedstocks. BETO Workshop: Advancing the Bioeconomy: From Waste to Conversion Ready Feedstocks, Arlington, VA, February 19, 2020
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