PRODUCTION AND APPLICATION OF HIGHLY POROUS ACTIVATED CARBON (HPAC) MATERIALS FROM BIOENERGY CROPS

• Sponsoring Institution: National Institute of Food and Agriculture
• Project Status: TERMINATED
• Funding Source: MCINTIRE-STENNIS
• Reporting Frequency: Annual
• Accession No.: 1007044
• Project No.: WVA00118
• Project Start Date: Jul 30, 2015
• Project End Date: Sep 9, 2019

Project Director
Singh, KA.

Recipient Organization
WEST VIRGINIA UNIVERSITY
886 CHESTNUT RIDGE RD RM 202
MORGANTOWN,WV 26505-2742

Performing Department
Forestry

Non Technical Summary
West Virginia produces 2.41 million dry tons of wood residues per year. In addition, currently there have been significant efforts and investments put in place for growing short rotation woody crops (hybrid poplar and hybrid willow) and herbaceous bioenergy crops (switchgrass, Miscanthus, arundo) on reclaimed mining lands of West Virginia. Approximately, 200 acres of reclaimed mine land and other land has been planted with biomass crops in the state of West Virginia. The Alton site (0.4 ha planted out of 160 ha) has three species, namely; Switchgrass (Kanlow and Bomaster), Miscanthus (Public and Private), and Giant cane planted. At this site, dry matter yield after the fourth growing season averaged 5,200 kg ha-1 for Switchgrass (Kanlow and Bomaster varieties) and 9,000 kg ha-1 for Miscanthus (public and private varieties). In addition, Cave-In-Rock switchgrass was planted on 8 ha at MeadWestvaco (MWV), WV and at The Wilds, OH. After the first growing season, switchgrass production was 752 kg ha-1 at MWV and 1,045 kg ha-1 at The Wilds site. Similarly, woody bioenergy crops yield range from 13.2 to 18.0 tons per ha per year (average= 15.57 tons/ha/year) in the northeastern regions of the United States. While intention of growing these bioenergy crops with significant capital investment was to supply them to a bioethanol plant to be opened in near future, currently, there is no outlet for the harvested bioenergy crops. Therefore, this research is aimed at providing an alternate solution to transform available biomass into bio-char intermediate through in-field pyrolysis and then transforming bio-chars into Highly Porous Activated Carbon (HPAC) materials to be used as a commercial adsorbent or other electrochemical applications.

Animal Health Component

0%

Research Effort Categories

Basic

10%

Applied

70%

Developmental

20%

Classification

Knowledge Area (KA)	Subject of Investigation (SOI)	Field of Science (FOS)	Percent
511	0650	2020	100%

Knowledge Area
511 - New and Improved Non-Food Products and Processes;

Subject Of Investigation
0650 - Wood and wood products;

Field Of Science
2020 - Engineering;

Keywords

activated carbon

thermochemical conversion

bioenergy crops

woody biomass

herbaceous biomass

Goals / Objectives
PurposeThe purpose of this project is to evaluate potential for providing an alternate solution to transform available biomass, grown on reclaimed mine-lands in the state of West Virginia, into bio-char intermediate through pyrolysis and hydrothermal processes and then transforming bio-chars into activated carbons to be used as a commercial adsorbent or other electrochemical applications.ObjectivesCharacterize selected woody and herbaceous bioenergy crops for chemical composition, elemental composition, pore volume, pore size distribution, and moisture desorption behaviorEvaluate the influence of thermal treatment temperature under inert conditions and in hydrothermal conditions on the total pore volume, pore size distribution, and specific surface area of woody and agricultural bioenergy cropsExplore the effects of chemical activation agents as means of biomass pretreatment prior to carbonization or bio-char treatment after pyrolysis on specific surface area, total pore volume and pore size distribution of resulting Highly Porous Activated Carbon (HPAC) materialsCompare Highly Porous Activated Carbon (HPAC) materials produced from selected woody and herbaceous bioenergy crops for adsorption applications

Project Methods
4. Methods4.1. Objective-1: Collection and characterization of woody and herbaceous bioenergy crops4.1.1. Task: Samples of woody (short rotation poplar and willow) and herbaceous biomass (Switchgrass and Miscanthus) will be collected from various marginal land and reclaimed mine lands in West Virginia. Some of the green samples will be characterized for moisture content and moisture desorption behavior. Some biomass samples will be oven-dried at 105 °C and ground to 1 mm sieve using a grinder. The ground samples will be tested for elemental composition, proximate analysis, and chemical composition using fiber analysis (acid detergent fiber, neutral detergent fiber, and lignin) at the Agricultural and Environmental Sciences Lab, Athens, GA. Cellulose, hemicellulose, lignin contents will be calculated from the fiber analysis data.4.2. Objective-2: Effect of thermal and hydrothermal treatment of biomass on pore characteristics4.2.1. Task: Total porosity, pore characteristics (total pore volume and pore size distribution), surface area, and fiber saturation point (FSP) of raw biomass (green), oven-dried biomass (105 °C, nitrogen, 24 h), thermally treated biomass (200 °C, nitrogen, 4 h), and hydrothermally treated (200 °C, 4 h) biomass will be compared. Scanning Electron Microscope images will be taken for green, oven-dried, thermally treated and hydrothermally treated biomass samples. The images of the moist samples will be tricky to take and therefore, either procedure given in Biziks48 will be followed or a standard protocol used during imaging of cells will be used. The latter involves chemically freezing and removal of water and then resin impregnation. The WVU-Shared Facilities team handles this particular task. The pore size distribution, pore volume and fiber saturation point will be measured in a differential scanning calorimeter according to Zauer et al43.4.3. Objective-3: Effects of chemical activation agents as means of biomass pretreatment prior4.3.1. Tasks-1: Preparation of Biomass Samples for CarbonizationSamples (two woody and two herbaceous) of dried-ground biomass will be impregnated with a chemical agents (KOH). The biomass to chemical agent weight ratio will be kept 1:4. Impregnation of the chemical agents will be performed by soaking biomass in the respective chemical agent's solution in distilled water and then oven-drying it at 105 °C. The four KOH-impregnated biomass and four un-impregnated biomass samples will be carbonized using direct pyrolysis (500 °C, nitrogen, 1 h) and using hydrothermal treatment (300 °C, 1 h, nitrogen, zero cold pressure). Resulting bio-chars (pyrolysis chars) and hydrochars (hydrothermal processing chars) will be washed with acetone. The acetone washed samples will be dried in nitrogen at 105 °C for 24 h prior to activation. At the completion of this task, four bio-chars, four hydrochars, four bio-chars from KOH-impregnated biomass, and four hydrochars from KOH-impregnated biomass will be ready for further activation.4.3.2. Task-2: Identifying Activation Temperature for Bio-Chars and HydrocharsWe believe that it is very important to outline how the activation proceeds during post heat treatment of bio-char with and without chemicals. Therefore, we propose to test samples in a TGA-FTIR system. To perform these tests, following samples will be prepared: (a) four bio-chars and four hydrochars; (b) four bio-chars from impregnated KOH; and (c) four hydrochars from impregnated KOH. The bio-chars and hydrochars without prior KOH treatment will be now impregnated with chemical agent weight ratio of 1:4. After impregnation, samples will be dried for 24 h at 105 °C. After preparing the samples, TGA-FTIR analysis will be performed by heating a 10-12 mg sample specimen from room temperature to 900 °C at the rate of 10 °C/min under nitrogen flow rate of 50 cm3/min. While TGA will provide weight-loss taking place at various temperature regimes during activation process, the FTIR data will provide deep insight into types of chemical compounds evolved in the gas phase at various temperatures. Successful completion of this task 2 will enable us to decide the appropriate highest temperature required to complete the activation of various samples, which will be used in the subsequent tasks. It will also provide some understanding on how the activation proceeds in the presence of various chemical agents and under two types of impregnation methods.4.3.3. Task-3: Production of Highly Porous Activated Carbon (HPAC) Materials Once the activation temperature required for the complete activation for the samples from the Task 2 is established, experiments on a relatively larger scale will be performed to quantify the influence of the activation duration (30 and 60 min) and impregnation method on the particle morphology, specific surface area, and pore characteristics of the resulting activated carbon materials. Therefore, 36 (6 specimens × 2 duration × 3 reps) experiments will be conducted to prepare activated carbon materials. The activated carbon materials will be prepared by placing the specimen to be activated in an existing 2" vertical quartz tube in presence of a nitrogen flow. The existing reactor has the capability to process up to a 150 g specimen. In addition, it has a saturator which can be filled with any reagent (for example, water), if needed, to generate the reagent's vapor-rich (for example, steam) nitrogen gas. Detailed mass balance will be performed during the activation experiments. After the activation is complete, the resulting activated carbon samples will be weighed and tested for particle shape and morphology using Scanning Electron Microscopy, specific surface area, pore characteristics [Total pore volume, micropore volume (< 2nm size), mesopore volume (2 to 50 nm size), and macropore volume (50 to 100 nm size)]. Commercially available activated carbon will also be tested for the same properties for comparison. At the successful completion of task 4, we would have compare commercial activated carbons with the biomass crop-derived Highly Porous Activated Carbon (HPAC) Materials.4.4. Objective-4: Testing of Highly Porous Activated Carbon (HPAC) Materials4.4.1. Task: Testing of HPAC for Adsorption of Acetic AcidThe acetic acid will be used for measuring adsorption capacity of the HPAC materials. Acetic acid is a transparent and colorless liquid with a pungent odor. For the adsorption studies, procedure outlined by Dina et al. 51 and 52 will be used. According to the procedure, 0.1 g of activated carbon will be placed in a 250 ml screw-capped flask with 20 ml of acetic acid solution added. The acetic acid solution concentrations will be varied between 0.007 and 0.3948 mol/L. Each mixture will be stirred with a magnetic stirrer at a temperature of 27 (±2) °C until equilibrium is attained. After agitation, each sample will be filtered and the residual concentration will be measured. The adsorbed quantities of acid, will be obtained by subtracting the residual concentration at equilibrium, from the initial concentration. Concentration of the acetic acid will be measured using a FTIR system as outline in a recently submitted manuscript 53.4.5 Data AnalysisThe resulting data will be evaluated to compare pore characteristics of green biomass, dried biomass, thermally treated biomass, and resulting HPAC materials. More specifically, statistical tests will be performed to determine if there are any difference in the HPAC produced from variety of woody and herbaceous bioenergy crops. The HPAC materials will also be evaluated to for their adsorption behavior.

Progress 10/01/18 to 09/30/19

Outputs
Target Audience:Project Director has left West Virginia University without submitting the annual and final report for this project. Changes/Problems:Project Director has left West Virginia University without submitting the annual and final report for this project. What opportunities for training and professional development has the project provided?Project Director has left West Virginia University without submitting the annual and final report for this project. How have the results been disseminated to communities of interest?Project Director has left West Virginia University without submitting the annual and final report for this project. What do you plan to do during the next reporting period to accomplish the goals?Project Director has left West Virginia University without submitting the annual and final report for this project.

Impacts
What was accomplished under these goals? Project Director has left West Virginia University without submitting the annual and final report for this project.

Publications

Progress 07/30/15 to 09/09/19

Outputs
Target Audience:Project Director has left West Virginia University without submitting the annual and final report for this project. Changes/Problems:Project Director has left West Virginia University without submitting the annual and final report for this project. What opportunities for training and professional development has the project provided?Project Director has left West Virginia University without submitting the annual and final report for this project. How have the results been disseminated to communities of interest?Project Director has left West Virginia University without submitting the annual and final report for this project. What do you plan to do during the next reporting period to accomplish the goals?Project Director has left West Virginia University without submitting the annual and final report for this project.

Impacts
What was accomplished under these goals? Project Director has left West Virginia University without submitting the annual and final report for this project.

Publications

Progress 10/01/17 to 09/30/18

Outputs
Target Audience: Nothing Reported Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Nothing Reported How have the results been disseminated to communities of interest?The project led to publication of one doctoral dissertation, submission of 1 journal manuscript, preparation of 2 additional journal manuscripts, which are currently being finalized for submission. In addition, 19 oral and poster presentations were made at various international conferences. In addition, Dr. Kaushlendra Singh has been teaching three courses ("WDSC 444- Bio-based Energy Systems", "WDSC 340 and WDSC 540 (Adv)- Physical Properties of Wood", and "WDSC 100- Forest Resources in U. S. History" both online and inclass. What do you plan to do during the next reporting period to accomplish the goals?Finalize all journal articles and submit for publication

Impacts
What was accomplished under these goals? The purpose of this project is to evaluate potential for providing an alternate solution to transform available biomass, grown on reclaimed mine-lands in the state of West Virginia, into bio-char intermediate through pyrolysis and hydrothermal processes and then transforming bio-chars into activated carbons to be used as a commercial adsorbent or other electrochemical applications. ?Activity 1: Effect of pyrolysis temperature on the thermal stability and physicochemical characteristics of biochars produced from herbaceous biomass (Singh) Biochar's use as soil amendment is considered beneficial for soil quality improvement with an added benefit of carbon sequestration. To ensure the use of biochar for these purposes, there is a need to understand its thermal stability and resistance against abiotic and biotic degradation. This is predicated on the feedstock type and pyrolysis conditions used in producing the biochar. The objective of this study was to characterize the thermal stability and physicochemical properties of biochars produced from two herbaceous biomass feedstocks at pyrolysis temperatures of 500, 700 and 900 °C. The thermal stability of the biochars was estimated by thermally degrading them in air at 950 °C. Physicochemical properties of the biochars were also quantified. The thermal stability of the biochars were found to increase with the pyrolysis temperature. The pH values increased with the pyrolysis temperature from slightly alkaline to highly alkaline. The electrical conductivities of the biochars were between 1.21 and 4.07 mS/cm. The BET surface area of the Kanlow Switchgrass biochars increased from 0.91 to 519.49 m2/g with an increase in pyrolysis temperature from 500 to 900 ºC. Similarly, the BET surface area of Public Miscanthus biochars increased from 0.25 to 783.74 m2/g with increase in pyrolysis temperature from 500 to 900 ºC. The result of the Raman analysis showed that the pyrolysis temperature did not significantly caused a conversion of disordered sp2 carbon to ordered sp2 carbon crystallites. The XPS analysis showed a reduction in the atomic percentage of the oxygen functional groups as the pyrolysis temperature increased, making the biochars more hydrophobic. Activity 2: Effect of Activating Agent Type and Impregnation Route on Properties of Activated Carbon Synthesized from Herbaceous Biomass (Singh) The objective of this study is to investigate the effect of activating agent type and impregnation route (1. Biomass + activation agent -> activated carbon and 2. Biomass-> Biochar + activation agent -> activated carbon) on the properties of activated carbons produced from herbaceous biomass. The precursors were Kanlow Switchgrass and Public Miscanthus biomass and their biochars produced at pyrolysis temperature of 500 ºC. The precursors were impregnated with either phosphoric acid or potassium hydroxide. The impregnated precursors were activated at a temperature 900 ºC for 30 mins in inert condition. The pore characteristics, surface functionalities, and microstructure of the activated carbons were characterized. the activated carbons were used in adsorbing two pharmaceutical active compounds; acetaminophen and caffeine. The biomass-derived activated carbons had the highest BET surface areas ranging between 999 and 1597 m2/g. The adsorption isotherms of the KOH/biomass-derived and KOH/biochar-derived activated carbons showed that they are microporous in nature. The surface morphology of the biochar-derived carbons showed pores with varying sizes and that the activated carbons retained the original cell wall structure of the parent materials. The surface morphology of KOH/biomass-derived activated carbons showed that the cell wall structures of the parent materials were not retained. The Raman analysis showed that the KOH/biomass-derived and KOH/biochar-derived activated carbons had more disordered sp2 carbon atoms in comparison to the H3PO4 samples. The XPS analysis showed that the KOH/biomass-derived activated carbons have C1s in the hydroxyl groups and also have higher percentage of O1s in the hydroxyl and carbonyl groups. The biomass-derived activated carbons had the highest adsorption capacities of 93.73 - 167.17 mg/g and 85.41 - 152.89 mg/g for both caffeine and acetaminophen respectively. Activity 3: Template-Free Synathesis of Hihgly Ordered Carbon from Knalow Switchgrass Biomass/Biochar and Activated Carbons for Supercapacitor Applications. (Singh and Sabolsky) The most widely used electrode materials for the electrochemical double layer supercapacitor (EDLC) applications are activated carbon materials, due to their high specific surface area, low cost and ease of processing. The electrode material and its surface/pore characteristics, such as pore size distribution, pore volume and surface area have an important role on the energy and power densities, and thus, overall performance of the supercapacitors. Therefore, template based synthesis approaches commonly are applied to synthesize highly ordered carbon materials with high specific surface area and controlled pore characteristics. However, it is known these methods require a final processing step for the removal of template materials, which increases the processing time and overall cost. Hence, it is important to address the template free synthesis techniques. A performance improvement can be achieved by enhancing the activated carbon materials via chemical activation and/or metal oxide addition (pseudocapacitive mechanism). These processes result in an increase in specific surface area and surface functional groups, which lead an enhancement in the capacitive performance of the supercapacitors as a result of the pseudocapacitance effect and electronic conductivity. These methods are known to be effective, since the electrochemical performance also is influenced by the microstructure and surface chemistry of the electrode materials. Therefore, the effect of modifying the surface chemistry and microstructure of biomass derived activated carbons was investigated. The main aim was to synthesize biomass derived (Kanlow switchgrass) and modified activated carbon samples, to fabricate the supercapacitors and to test their electrochemical performance. The chemical activation and metal oxide (MnO2, NiO) addition methods were utilized to improve the pore structure, surface chemistry and electrochemical performance. XPS, SEM, TGA and N2 physisorption techniques were used to investigate influence of the experimental parameters on the surface chemistry, morphology, specific surface area and pore characteristics. For the supercapacitor fabrication, 85 wt% of the synthesized activated carbons were mixed with 5 wt% carbon black and 10 wt% polyvinylidene fluoride, and casted into their final form. Stainless steel, potassium hydroxide and Nafion were used as current collector, liquid electrolyte and separator, respectively, to assemble the supercapacitors. Their electrochemical performance was characterized by self discharge (50 cycles) and constant current charge/discharge (1000 cycles) tests conducted at 0.1 A/g. They displayed the required electrochemical stability and reversibility with up to 142 F/g specific capacitance, which depended on the specific surface area, pore characteristics, microstructure and surface chemistry

Publications

• Type: Journal Articles Status: Under Review Year Published: 2019 Citation: Oginni, O. and K. Singh. ?. Soil Amendment and Carbon Sequestration Potential of Biochars Produced from Three Herbaceous Biomass Feedstock Crops. Agriculture Ecosystem and Environment. Being Revised
• Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: 1. Oginni, O. J., Singh, K., Mcdonald, L. M., Yumak, t., Sabolsky, E. M., Sivanandan, L. (2018). ADSORPTION AND PHYSICAL CHARACTERISITCS OF ACTIVATED CARBONS PREPARED VIA TWO IMPREGNATION ROUTES FROM HERBACEOUS BIOMASS (pp. 33). 2018 S-1041 Science and Engineering for a Biobased Industry and Economy Poster Abstracts Symposium Presentation Abstracts.
• Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: 2. Oginni, O. J., Singh, K., Mcdonald, L. M. (2018). Adsorption of pharmaceutical active compounds using activated carbons synthesized from herbaceous biomass (vol. 255). ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY.
• Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Oginni, O. J., Singh, K., Mcdonald, L. M., Oporto, G. S., Sabolsky, E. M., Sivanandan, L. (2018). Effect of Pyrolysis Temperature on the Thermal Stability and Agronomic Characteristics of Biochars Produced from Herbaceous Biomass. (pp. 25). 2018 Proceedings of Northeast Agricultural and Biological Engineering Conference.

Progress 10/01/16 to 09/30/17

Outputs
Target Audience: Nothing Reported Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Nothing Reported How have the results been disseminated to communities of interest?The project led to preparation of 2 journal manuscripts, which are currently being finalized for submission. In addition, Dr. Kaushlendra Singh has been teaching three courses ("WDSC 444- Bio-based Energy Systems", "WDSC 340 and WDSC 540 (Adv)- Physical Properties of Wood", and "WDSC 100- Forest Resources in U. S. History" both online and inclass. What do you plan to do during the next reporting period to accomplish the goals?For the next reporting period, the manuscripts are being finalized and remaing adsorption experiments are being completed.

Impacts
What was accomplished under these goals? The purpose of this project is to evaluate potential for providing an alternate solution to transform available biomass, grown on reclaimed mine-lands in the state of West Virginia, into bio-char intermediate through pyrolysis and hydrothermal processes and then transforming bio-chars into activated carbons to be used as a commercial adsorbent or other electrochemical applications. Activity 1: Effect of pyrolysis temperature on the recalcitrance and agronomic characteristics of biochars produced from herbaceous biomass and forest residues (Singh) Biochar application into the soil is considered beneficial for soil quality improvement with an added benefit of carbon sequestration. In order to ensure the use of biochar for these purposes, there is a need to understand its stability and recalcitrance against abiotic and biotic degradation. This is majorly predicated on the aromaticity, compositional properties, feedstock type and pyrolysis conditions used in producing the biochar. The objective of this study was to characterize the recalcitrance and agronomic properties of biochars produced from herbaceous biomass and forest residues at three different pyrolysis temperatures. The biochars were produced at pyrolysis temperature of 500, 700 and 900 °C. The produced biochars were thermally degraded in air at a temperature of 950 °C in order to estimate their thermal recalcitrance. Compositional and agronomic properties of the biochars were also quantified. The thermal recalcitrance of the biochars were found to increase with the pyrolysis temperature. The pH values increased with the pyrolysis temperature from slightly alkaline to highly alkaline. Activity 2: Effect of Impregnation Route on Activated Carbon Properties from Herbaceous Biomass (Singh) The objective of this study is to investigate the adsorption characteristics of activated carbons (AC) synthesized from herbaceous biomass following two different impregnation routes. The precursors for the activated carbon synthesis were Kanlow Switchgrass (KSBM) and Public Miscanthus (PMBM) biomass and their biochars (KSBC and PMBC respectively). The precursors were impregnated with phosphoric acid and thereafter activated at a temperature of 900 °C in inert condition. Also, the activated carbons were used in adsorbing two pharmaceutical active compounds; acetaminophen and caffeine. Activated carbons synthesized from the Kanlow Switchgrass biochar (KSBC) had a higher surface area (2459.64 m2/g) compared to its biomass counterpart, KSBM (1024.04 m2/g). Public Miscanthus biomass derived activated carbon (PMBM) however had a higher surface area (999.06 m2/g) compared to its biochar derived (PMBC) activated carbon (161.97 m2/g). The adsorption experimental data were fitted into Langmuir and Freundlich isotherm models. The Langmuir isotherm was found to provide the best fit for the adsorption of the adsorbates with the KSBM derived AC having a maximum monolayer adsorption capacity of 102.04 mg/g and 129.9 mg/g for caffeine and acetaminophen respectively. The maximum monolayer adsorption capacities recorded for the KSBC derived AC were 20.16 mg/g and 49.02 mg/g for caffeine and acetaminophen respectively. The maximum monolayer adsorption capacities recorded for the PMBM derived AC were 101.01 mg/g and 156.25 mg/g for caffeine and acetaminophen respectively. Activity 3: Surface Enhancement of Biomass-derived Activated Carbons for Supercapacitor Applications: The aim of this study was to compare the biomass-derived and modified activated carbon with commercial activated carbon in supercapacitor applications. For this purpose, different activated carbon samples were synthesized from various types of biomasses. Physical/chemical activation methods were applied in order to improve the porous structure and surface chemistry. In addition, the activated carbons were combined with different metal oxides by different techniques in order to investigate the effect of synthesis route on the surface chemistry, microstructure and electrochemical performance of metal-oxide/activated carbon composite electrodes. The metal oxide loading led to a slight decrease in surface area but no significant effect on the porous structure of composite materials. The linear and symmetrical shape of the constant current charge-discharge curves proves that MnO2/AC and NiO/AC based electrodes possess the required electrochemical reversibility and charge/ discharge capabilities. A significant decrease in the ESR drop was obtained by metal oxide loading. The calculated specific capacitance increased by 160% and 56% for NiO/AC (precipitation method) and MnO2/AC (hydrothermal method), respectively when compared to pristine commercial activated carbon based electrodes.

Publications

• Type: Conference Papers and Presentations Status: Published Year Published: 2017 Citation: 1. Singh, K., E. Sabolsky, L. Sivanandan, E. Ciftyurek, O. J. Oginni, and T. Yumak. 2017. Activated Carbon Applications for Electrode Material and Adsorbent. 40th International Activated Carbon Conference, PACS Testing and Consulting, Pittsburgh, PA. (September 14, 2017).
• Type: Conference Papers and Presentations Status: Published Year Published: 2017 Citation: 1. Ciftyurek, E., K. Singh, L. Sivanandan, and E. Sabolsky. 2017. Supercapacitor Electrodes Fabricated from Highly Activated Microporous Carbons Extracted from Commercial Fruit Wastes. American Society of Agricultural and Biological Engineers, Spokane, WA. (July 18, 2017).
• Type: Conference Papers and Presentations Status: Other Year Published: 2017 Citation: 1. Singh, K., O. J. Oginni. 2017. Adsorption Studies of Activated Carbon Synthesized from Herbaceous Biomass. Northeastern Agricultural and Biological Engineers Conference (NABEC), Groton, CT, USA. (July 31, 2017).
• Type: Conference Papers and Presentations Status: Other Year Published: 2017 Citation: 1. S. Rahimi, K. Singh, D. DeVallance. 2017. Influence of Steam or Hydrothermal Treatment on Physical and Mechanical Properties and Drying Behavior Yellow-poplar. American Society of Agricultural and Biological Engineers, Spokane, WA. (July 19, 2017).

Progress 10/01/15 to 09/30/16

Outputs
Target Audience: Nothing Reported Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?The project facilitated participation in the American Society of Agricultural and Biological Engineers Annual International Meeting during July 17-20, 2016 and in the International Conference on Emerging Technologies in Agricultural Engineering, Indian Institute of Technology, Kharagpur India, December 27-30, 2016. 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?The project is ontime and it would follow next task on evaluating adsorption capabilities of activated carbons.

Impacts
What was accomplished under these goals? The purpose of this project is to evaluate potential for providing an alternate solution to transform available biomass, grown on reclaimed mine-lands in the state of West Virginia, into bio-char intermediate through pyrolysis and hydrothermal processes and then transforming bio-chars into activated carbons to be used as a commercial adsorbent or other electrochemical applications. Activity 1: Pyrolysis of Herbaceous Biomass Crops Pyrolysis and characterization of pyrolysis products of two biomass crops (Miscanthus and Switchgrass) grown on reclaimed coal-mining land in Appalachian region were carried out. The oven-dried samples were pyrolyzed in a fixed-bed batch reactor under an inert condition and at a temperature of 500 0C to produce biochar and bio-oil. The product yields, energy and carbon conversion yields, elemental composition, volatile, ash and energy contents of the pyrolysis products were carried out and reported. Statistical analysis of the pyrolysis data showed that there was no significant difference in the biochar yield (about 30.00% yield) obtained from the two varieties of switchgrass and miscanthus. The bio-oil yields were in the range of 45.00 to 51.00% with the miscanthus (private variety) having the highest bio-oil yield of 50.61%. The carbon content of the biomass, biochar and bio-oil were found to be 46.80 - 48.02%, 77.72 - 80.23% and 54.68 - 59.68%, respectively. Average heating values were found to be 19.49 MJ/kg, 29.01 MJ/kg and 24.98 MJ/kg for the biomass, biochar and bio-oil, respectively. CO and CO2 were found to be the major components of the non-condensable gas and the high concentration of CO2 as a non-combustible gas makes the non-condensable gas samples unfit as a fluidizing medium. Activity 2: Activated Carbons from Herbaceous Biomass Crops of West Virginia Activated carbon production from herbaceous biomass crops harvested from a reclaimed mining land in West Virginia was carried out in this study. Impregnation of biomass and biochar samples of switchgrass and miscanthus with phosphoric acid was performed and the impregnated samples were heat-treated at 900 0C using a thermogravimetric analyzer. The resulting carbonized samples were characterized for their surface morphology, textural properties, adsorption capacity, and pore size distribution. In addition, the produced activated carbon is under study for adsorption of pharmaceutical and personal care products residuals in waste water. Additionally, the activated carbon (AC) materials were tested for electrochemical properties. Activity 3: Electrochemical Performance of Activated Carbons (ACs): ACs acquired by the pyrolysis and followup activated of switchgrass and miscanthus were used and tested as Electrode Double Layer Capacitors (EDLC). Two different herbaceous biomass derived AC materials were used in this work to form the high surface areas carbons. The micro-structure of carbon electrode materials were characterized via scanning electron microscopy (SEM) with an attached energy dispersive x-ray spectroscopy (EDS) apparatus. The chemical state of the carbon was characterized using X-ray photoelectron spectroscopy (XPS). XPS was used for quantification and chemical state analysis of the elements on the surface of the carbon electrodes. Distinctive attention was paid to the quantification of functional groups on the surface. The Brunauer-Emmett-Teller (BET) surface area, in addition to the gas adsorption/desorption isotherms of the carbon materials, were analyzed using nitrogen (N2) adsorption in a Micromeritics ASAP 2020. Electrochemical characterization was completed by testing the carbon material in a two-electrode assembly on the basis of CR-2032 casing architecture. The constant current charge/discharge (CCD) profile for the supercapacitors with AC electrodes showed repeatable cyclic behavior generally associated with high surface area ACs. The AC material had surface area of 2469 m2/g, which was comparable to some of the most advanced graphene-based material (specific surface area of 1810 m2/g and 3523 m2/g). The AC material had 72% mesoporosity, which is significantly suitable for EDLC applications. Specific capacitance values of 85.54 and 85.39 F/g for discharge current values of 2 and 3 mA, respectively, which is comparable to some of the best ACs available (40-100 F/g).

Publications

• Type: Journal Articles Status: Published Year Published: 2016 Citation: Oginni, O., K. Singh, J. Zondlo. 2016. Pyrolysis of Energy Crops Grown on Reclaimed Mining Land in West Virginia. Journal of Applied and Analytical Pyrolysis. http://dx.doi.org/10.1016/j.jaap.2016.11.013
• Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Ciftyurek, E., O. Ozmen, K. Singh, K. Sabolsky, and E. M. Sabolsky. 2016. Clean and Sustainable Energy Conversion and Storage. Displayed at Showcasing Advancements in CCUS Technology, Coal Utilization Research Council and the US DOE, Washington D.C. September 29, 2016.
• Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Oginni, O. and K. Singh. 2016. Assessment of Soil Amendment and Carbon Sequestration Potential of Miscanthus and Switchgrass Biochars. Presented at Forest Products Society International Convention. June 27  29, 2016, Portland, OR.
• Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Oginni, O. and K. Singh. 2016. Activated Carbons from Herbaceous Bioenergy Crops for Adsorption of Pharmaceutically Active Compounds. Presented at Forest Products Society International Convention. June 27  29, 2016, Portland, OR.
• Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Oginni, O. and K. Singh. 2016. Assessment of Soil Amendment and Carbon Sequestration Potential of Miscanthus and Switchgrass Biochars. Presented at American Society of Agricultural and Biological Engineers Annual International Meeting. July 17  20, 2016, Orlando FL.
• Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Oginni, O. and K. Singh. 2016. Activated Carbons from Herbaceous Bioenergy Crops for Adsorption of Pharmaceutically Active Compounds. ASABE Paper No. 2433897. ASABE Annual International Meeting, Orlando, FL, July 17 to 20, 2016.
• Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Akharume, F., K. Singh, W. and L. Sivanandan. 2016. Drying Characteristic of Wood and Wood Polymers Using TGA 701 (Proximate Analyzer). Presented at American Society of Agricultural and Biological Engineers annual international meeting, July 17- 21, 2016. Orlando FL.
• Type: Conference Papers and Presentations Status: Other Year Published: 2016 Citation: Ciftyurek, E., O. Oginni, K. Singh, and E. Sabolsky. 2016. Applications of Bio-Chars Produced from Herbaceous Biomass. Poster presented at the International Conference on Emerging Technologies in Agricultural Engineering, Indian Institute of Technology, Kharagpur India, December 27-30, 2016.

Progress 07/30/15 to 09/30/15

Outputs
Target Audience: Nothing Reported Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Nothing Reported 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?The next task is to perform biomass characterization.

Impacts
What was accomplished under these goals? IMPACT - The project task for the year 2015 (August 2015 to December 2015) was to perform extensive literature review and prepare samples. The project is on schedule and it has supported one doctoral graduate students, Mr. Oluwatosin Oginni. Mr. Tosin has presented his preliminary literature review and research findings during a multistate project meeting. ACCOMPLISHMENTS - Biomass samples have been collected and extensive literature review is being done.

Publications

• Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Oginni, O. and K. Singh. 2015. Activated Carbons from Herbaceous Bioenergy Crops. S-1041 Multistate Project Meeting, Wooster, OH August 10, 2015.