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Integrated Biorefinery Optimization through Biomass Fractionation, Gasification and Advanced Catalytic

Conversion Processes

A Final Report Submitted to

The Southeastern Sun Grant Center

Submitted by

Dr. Mario R. Eden1, Dr. Christopher B. Roberts1, Dr. Sushil Adhikari2, Dr. Steven E. Taylor2

1Department of Chemical Engineering 2Department of Biosystems Engineering

Auburn University Auburn, AL 36849

02/01/2010 – 01/31/2013

June 12, 2013

This project was funded by a grant from the Southeastern Sun Grant Center with funds provided by the United States Department of Transportation, Research and Innovative

Technology Administration.

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ABSTRACT The overall goal of this SunGrant project was to advance the fundamental understanding of the underlying chemistries and physical phenomena encountered in the production of hydrocarbon fuels, hydrogen and consumer chemicals from lignocellulosic biomass resources. To realize this vision, we established a fundamental research program focused on sustainable fuels, chemicals and production of value-added products through integrated biorefining. A multidisciplinary team of researchers from chemical engineering and biosystems engineering was assembled to lead this program. The team has been collaborating for several years and has established significant synergies in their research efforts particularly in catalyst development/characterization, fuels production and process systems engineering. This project leveraged ongoing research by taking advantage of a unique set of testbeds in the Center for Bioenergy and Bioproducts at Auburn University consisting of biomass fractionation and several conversion technologies, most notably a number of gasification platforms that were used to produce synthesis gas from biomass feedstocks. This SunGrant project consisted of five interrelated research topics: Biomass fractionation, biomass gasification, supercritical phase Fischer-Tropsch Synthesis, catalyst characterization, as well as process and product design, integration and optimization. As the project progressed our work focused on primarily on biomass gasification, supercritical Fischer-Tropsch Synthesis (SCF-FTS) as well as various aspects of process and product design.

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TABLE OF CONTENTS Abstract……………………………………………………………………………………………………………..…1 Executive Summary……………………………………………………………………………………………….…4 Basic Information…………………………………………………………………………………………………….5 Final (Actual) Budget………………………………………………………………………………………………...6 Discussion Information………………………………………………………………………………………………7

1. Project Summary………………………………………………………………………………………7 2. How will the Results of this Research be Used………………………………………………….....7 3. Outcomes/Products (Current and Anticipated)……………………………………………………..7 4. For Each Objective, Discuss Accomplishments and Successes…………………………………7 5. Discuss Project Outcomes and Impact…………………………………………………………….22 6. Publications…………………………………………………………………………………………...23 7. Licenses/Inventions………………………………………………………………………………….27 8. Students Funded on Project………………………………………………………………………...27 9. Collaborators and/or Partners………………………………………………………………………28 10. Educational Programs Conducted………………………………………………………………….28 11. Internal and External Grants and Contracts Related to this Project……………………………28

Acknowledgement………………………………………………………………………………………………….30

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LIST OF TABLES AND FIGURES Table 1: Comparison of Fuel Production…………………………………………………………………………14 Table 2: Feedstock Information (All Compositions given in Weight%)……………………………………….16 Table 3: Air/Fuel Ratio for Maximum H2 and CO Production………………………………………………….16 Table 4: Component Flows vs. O2 Concentration in Air Feed – Montana Coal……………………………..18 Table 5: Component Flows vs. O2 Concentration in Air Feed – Illinois Coal………………………………..18 Table 6: Component Flows vs. O2 Concentration in Air Feed – Southern Pine Wood……………………..19 Table 7: Component Flows vs. O2 Concentration in Air Feed – Switchgrass………………………………..19 Figure 1: CO Conversion Comparison…………………………………………………………………….………9 Figure 2: Product Distribution Comparison………………………………………………………………………..9 Figure 3: FTS + Integrated Upgrading Reactor Scheme……………………………………………………….10 Figure 4: Preliminary Example of Product Distribution after Integrated Product Upgrading……………….10 Figure 5: Time on Stream CO and H2 Conversion (Steady State)……………………………………………11 Figure 6: Time on Stream CO2 and CH4 Conversion (Steady State)…………………………………………11 Figure 7: Liquid Product Selectivity……………………………………………………………………………….12 Figure 8: Liquid Functionality Selectivity…………………………………………………………………………12 Figure 9: ASPEN Plus Model of Generic Packed Bed Gas-Phase FTS Process…………………………...13 Figure 10: ASPEN Plus Model of Supercritical Phase FTS Process…………………………......................13 Figure 11: Comparison of Energy Consumption (Gas-Phase FTS = 1)……………………………………...13 Figure 12: Gasifier Model Schematic…………………………………………………………………………….14 Figure 13: Syngas Component Flows vs. A/F Ratio for IL Coal……………………………………………….15 Figure 14: Mole Percent Oxygen in Air vs. Hydrogen Flowrate in Syngas for Montana Coal……………...17 Figure 15: Mole Percent Oxygen in Air vs. Carbon Monoxide Flowrate in Syngas for Montana Coal.…...17 Figure 16: Effect of Slurry-Feed Conditions on Gasifier Product……………………………………………...20 Figure 17: Effect of Air/Fuel Ration on Gasifier Products for Slurry Feeds…………………………………..21 Figure 18: Simplex Diagrams of One Response for Four Components………………………………………22 Figure 19: Single Property Clustering Diagram for All 3 Proporties and All Components………………….22

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EXECUTIVE SUMMARY This SunGrant project consisted of five interrelated research topics: Biomass fractionation, biomass gasification, supercritical phase Fischer-Tropsch Synthesis, catalyst characterization, as well as process and product design, integration and optimization. As the project progressed our work focused on primarily on biomass gasification, supercritical Fischer-Tropsch Synthesis (SCF-FTS) as well as various aspects of process and product design. The biomass gasification studies were focused on understanding the effects of biomass characteristics on syngas composition and tar concentration in a downdraft gasifier. In addition, the effects of thermal treatment (torrefaction) on the physicochemical properties of three different biomass types were studied. We have illustrated that by modifying the FTS process to operate under dense phase conditions (including supercritical fluid recycle, supercritical fluid phase FTS or SCF-FTS) and optimizing the operating conditions, a significant enhancement of middle distillate products and simultaneous reduction of undesirable methane production can be achieved along with significantly prolonging catalyst lifetime. We were able to utilize undesired light products to enhance heat and mass transfer within the media and perform SCF-FTS in a simple fixed bed reactor system. Additionally, we worked on integrating various product upgrading stages including, oligomerization and cracking/isomerization following the SCF-FTS bed to further increase the fuel range product yield. We have developed generic process simulation models of biomass gasification along with both gas-phase and supercritical phase Fischer-Tropsch Synthesis processes. The models were developed using a combination of information available in the open literature and data collected as part of this project. We have illustrated that the SCF-FTS process results in significantly increased production of fuel range products and that while there is an accompanying increase in operating cost (due to the higher pressure), the SCF-FTS process still shows favorable performance compared to the gas-phase process.

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BASIC INFORMATION Date: June 12, 2013 Project Title: Integrated Biorefinery Optimization through Biomass Fractionation, Gasification and

Advanced Catalytic Conversion Processes PI: Dr. Mario R. Eden, Department Chair and McMillan Professor Department of Chemical Engineering

Auburn University Auburn, AL

CO-PIs: Dr. Christopher B. Roberts Dean of Samuel Ginn College of Engineering Auburn University Auburn, AL Dr. Sushil Adhikari Assistant Professor Department of Biosystems Engineering Auburn University Auburn, AL Dr. Steven E. Taylor Department Head and Professor Department of Biosystems Engineering Auburn University Auburn, AL Start Date: February 1, 2010 End Date: January 31, 2013 (after no-cost extension)

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FINAL (ACTUAL) BUDGET

BUDGET ITEM SUN GRANT COST SHARE A. Total Salaries & Wages $149,034.98 $4,231.88 B. Fringe Benefits $9,029.56 $1,464.10 C. Supplies $20,324.63 - D. Equipment - - E. Travel $30,864.28 - F. Publications - - G. Other (Subcontractors, Consultants) - -

Total DIRECT COSTS (Sum of A-G) $209,253.45 $5,695.98 Total INDIRECT (i.e. F&A) COSTS

(IDC Usually = Total Direct Costs*.25) $41,850.93 $1,139.20

H. Graduate Student Tuition - - I. Permanent Equipment ($5,000 or More) - - J. Other Costs Not Requiring Indirect - $55,665.00

Total DOLLARS SPENT (Total Direct + Total Indirect + H + I + J) $251,104.38 $62,500.18

Cost share: • Academic year salary for Drs. Eden, Roberts, Adhikari and Taylor: $4,231.88 • Fringe benefits (charged at prevailing rate each year): $1,464.10 • Indirect cost (charged at prevailing rate each year): $1,139.20 • Waived indirect cost: $55,665.00 • Total cost share: $62,500.18

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DISCUSSION INFORMATION 1. Project Summary: This SunGrant project consisted of five interrelated research topics: Biomass fractionation, biomass gasification, supercritical phase Fischer-Tropsch Synthesis, catalyst characterization, as well as process and product design, integration and optimization. As the project progressed our work focused on primarily on biomass gasification, supercritical Fischer-Tropsch Synthesis (SCF-FTS) as well as various aspects of process and product design. The biomass gasification studies were focused on understanding the effects of biomass characteristics on syngas composition and tar concentration in a downdraft gasifier. In addition, the effects of thermal treatment (torrefaction) on the physicochemical properties of three different biomass types were studied. We have illustrated that by modifying the FTS process to operate under dense phase conditions (including supercritical fluid recycle, supercritical fluid phase FTS or SCF-FTS) and optimizing the operating conditions, a significant enhancement of middle distillate products and simultaneous reduction of undesirable methane production can be achieved along with significantly prolonging catalyst lifetime. We were able to utilize undesired light products to enhance heat and mass transfer within the media and perform SCF-FTS in a simple fixed bed reactor system. Additionally, we worked on integrating various product upgrading stages including, oligomerization and cracking/isomerization following the SCF-FTS bed to further increase the fuel range product yield. We have developed generic process simulation models of biomass gasification along with both gas-phase and supercritical phase Fischer-Tropsch Synthesis processes. The models were developed using a combination of information available in the open literature and data collected as part of this project. We have illustrated that the SCF-FTS process results in significantly increased production of fuel range products and that while there is an accompanying increase in operating cost (due to the higher pressure), the SCF-FTS process still shows favorable performance compared to the gas-phase process. 2. How will the Results of this Research be Used: The research conducted in this project has elucidated some important aspects of the conversion of woody biomass to fuels and chemicals. In particular, we have studied the relationships between biomass composition, gasification conditions and the resulting syngas. This information will be very useful in establishing baseline operational parameters for the large pilot-scale gasifier when it comes online soon. We have also demonstrated that the supercritical phase Fischer-Tropsch Synthesis process performs better than the traditional gas-phase process in terms of yield of fuel range products and catalyst activity/maintenance. These results provide the foundation for further study/optimization of this promising gas-to-liquids technology. 3. Outcomes/Products (Current and Anticipated): This project has resulted in a total of 16 refereed publications (published or in press). In addition, the PIs and their students have given 35 presentations during this project. A complete list of the citations is provided below. Similarly, the initial work performed in this project provided the basis for a number of successful proposal submissions to further investigate the production of fuels and chemicals from biomass resources. 4. For Each Objective, Discuss Accomplishments and Successes: This SunGrant project consists of five interrelated research topics: Biomass Fractionation, Biomass Gasification, Supercritical Phase Fischer-Tropsch Synthesis, Catalyst Characterization, as well as Process and Product Design, Integration and Optimization. Each of these research topics have specific tasks that were outlined in the project description and are presented below: A. Biomass Fractionation:

I. Feedstock Identification and Acquisition II. Initial Fractionation Studies

The results from the fractionation work are rather limited, due to significant problems with the equipment. We were able to make some progress on this task, but it was limited to the acquisition of representative feedstock materials (loblolly pine and switchgrass). Unfortunately, the initial fractionation studies identified several problems with the PureVision PDU that we are still working to resolve.

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B. Biomass Gasification:

I. Optimize Gasification for Woody Biomass II. Sustained Optimized Production (Unfractionated Feedstock)

All the biomass gasification studies were conducted in a downdraft gasifier using woody biomass, agricultural waste (peanut hulls and poultry manure), and bioenergy crop (switchgrass). Ultimate and proximate analyses were carried out to characterize the biomass feedstocks used for gasification. The synthesis gas obtained from different feedstocks at different operating conditions were analyzed using an on-site gas analyzer. Temperature distribution inside the gasifier for different feedstocks and operating conditions were also examined, and a minimum temperature difference inside the gasifier was found in the Auburn downdraft gasifier. Gasification of peanut hull pellets showed the highest heating value (6.1 MJ/m3) of synthesis gas, whereas poultry litter gasification gave the lowest heating value (4.8 MJ/m3). We also studied the effect of mass flow rate and moisture content on the quality of synthesis gas. In another study, composition of carbon monoxide (CO), carbon dioxide (CO2) and hydrogen (H2) in synthesis gas from the biomass gasification process was calculated using equilibrium modeling. Methane concentration predicted by the equilibrium model was almost negligible (<0.15 vol. %) at temperatures above 800oC. Approximately 100 biomass samples were used to calculate synthesis gas composition under adiabatic conditions, and the generalized equations were obtained by multiple regression analysis to predict synthesis gas composition using elemental analysis of biomass. Equilibrium results were compared with the experimental data. Effect of temperature and moisture content on synthesis gas composition was also determined. Although perfect chemical equilibrium conditions cannot be achieved in an actual gasification process, the derived formula generally predicts the syngas composition to a reasonable degree of accuracy. Biomass pellets to be used for gasification studies were characterized and preliminary gasification tests were conducted. In addition, organosolv lignin obtained from hardwood and softwood was characterized using an elemental analyzer. Biomass pellets and woodchips used in the gasification studies have been characterized using proximate and ultimate analyses, and we have completed all the gasification tests using our downdraft gasifier. Nine experiments were run for each biomass type and there were 18 total runs. Three different biomass flow rates were used for each biomass type with three replications for each set of conditions. Primary gases such as hydrogen, carbon monoxide, carbon dioxide, and methane were analyzed using a portable gas analyzer. Tar compounds were collected using a European tar protocol with some modifications. Tar compounds will be analyzed using a GC/MS and altogether 30 major compounds were quantified. We conducted gasification experiments using woodchips and pellets at three different biomass flow rates. One-way ANOVA was used for an experimental design. Altogether 18 experiments were run, nine for each biomass type. Carbon, energy and exergy analyses were conducted for a downdraft gasifier along with the tar analysis. More than thirty compounds in tar were quantified. Among the different compounds in tar, tertiary condensed products such as toluene, o/p-xylene, naphthalene, phenol, styrene, and indene were observed in significant amounts. Tar concentration in the syngas was found to be in the range of 340 to 680 mg/Nm3

. These concentrations were found to be much higher when compared to a similar gasifier using woodchips. The initial experiments performed on the downdraft gasifier continue to be analyzed along with the tar produced. A new laboratory scale gasification reactor is being completed to bridge the gap to the large pilotscale facility which is nearing completion. C. Supercritical Phase Fischer-Tropsch Synthesis:

I. Design Nanoscale Catalyst Architechtures for SCF-FTS II. Optimize Conditions for Biomass Derived Syngas Conversion III. Incorporate Product Upgrading Catalysts in SCF-FTS Reactor

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This project focuses on determining of appropriate catalysts and operating conditions for supercritical fluid phase Fischer-Tropsch Synthesis (SCF-FTS) to tighten product distribution towards middle distillate liquid fuels. So far, our work has demonstrated that SCF-FTS can promote chain growth in the middle distillate range using both Co and Fe catalysts. This work has demonstrated that the supercritical environment affords certain heat and mass transfer benefits, and enhanced solubility of the products providing improved catalyst activity and lifetime. We have employed both conventional catalyst synthesis techniques (e.g. incipient wetness and wet impregnation) as well as seed-mediated nanoparticle growth methods to create a series of supported and unsupported Co and Fe based FT catalysts. FTS experiments were performed in a high-pressure continuous reactor system to determine the relative activities and selectivities of each synthesized catalyst. While initial plans involved the implementation of Co as one of the catalyst choices, it was determined that the Fe based catalysts should be better suited for these biomass-derived syngas applications due to its greater water-gas shift activity allowing the use of the lean syngas typically obtained from biomass gasification. As such, more emphasis was the placed on studying Fe based catalysts. We have synthesized and investigated iron catalysts that were promoted with potassium and copper (standard promoters) and zinc (a less conventional promoter). In particular, it was determined that the best catalyst for FTS performance under supercritical fluid operating conditions involved a molar ratio of 1 Fe : 0.1 Zn : 0.02 K : 0.01 Cu. In this case, supercritical-FTS operation yielded reduced methane selectivity, CO2 selectivity, C3 olefinicity and high yields of diesel-length oxygenates compared to gas phase-FTS. This work has shown increased middle distillate hydrocarbon production by implementing the supercritical hexane reaction medium. For example, the FTS reaction was successfully performed under supercritical conditions by using 1 gram of Fe catalyst at a temperature of 240C and an overall pressure of 77 bar (with a 20 bar partial pressure of syngas) with a syngas flowrate of 50 SCCM and a hexane to syngas ratio of 3.5:1. It is noted that a H2:CO molar ratio of 1.7:1 was used reflecting the lean syngas composition typical for biomass gasification. Figure 1 illustrates that significantly increased CO conversion was commonly obtained under supercritical phase conditions compared to gas-phase operation. The propagation probability under these conditions yielded an alpha value of 0.90 indicating a strong selectivity towards heavy products as illustrated in Figure 2.

Figure 1: CO Conversion Comparison

Figure 2: Product Distribution Comparison

We have also designed and constructed a high pressure 3-bed reactor system that allows for standard FTS in the first bed with subsequent catalytic oligomerization and hydrocracking/hydroisomerization in the second and third bed, respectively. This configuration will allow us to conduct sequential FTS, oligomerization and cracking/isomerization reactions for single-pass production of fuel range products by narrowing the FTS distribution towards gasoline and diesel fractions. The light olefinic products can be oligomerized into the fuel range, while heavy wax products can then be subsequently cracked and isomerized into fuel range hydrocarbons with a greater degree of branching and aromaticity. In our preliminary studies we have employed the previously discussed Fe based catalyst in the first FT bed with

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an amorphous silica alumina (ASA) used as the catalyst in the second oligomerization bed and a Pd on ASA catalyst for the hydrocracking/hydroisomerization (HC/HI) reactions (see Figure 3). Figure 4 provides a preliminary comparison of the FTS product distribution before and after implementation the integrated product upgrading stages. It is noted that work to optimize the operating conditions in the subsequent two stages are currently underway. In addition, detailed liquid product analysis is ongoing.

Figure 3: FTS + integrated upgrading reactor scheme

Figure 4: Preliminary example of product distribution after integrated product upgrading

Experiments were successfully performed that integrate sequential product upgrading stages (oligomerization plus hydrocracking/isomerization) into Fischer-Tropsch Synthesis under both gas-phase and supercritical phase operation. Preliminary product analysis has illustrated a significant shift in product distribution and product type towards fuel range products in both media. Moreover, the supercritical phase operation significantly reduced methane and carbon dioxide production thereby resulting a higher carbon utilization in the fuel range products. We have evaluated the performance of the triple-bed reactor system to verify our previous experimental results by examining the effects of syngas flowrate on gas phase Fischer-Tropsch Synthesis (FTS) with downstream oligomerization, hydrocracking, and isomerization (GP-FTOC). In this gas phase FTOC experiment, 1 g of Fe-based FT catalyst (which we have reported on previously, Fe/Zn/Cu/K molar ratio: 100/10/1/2), was loaded into the first FT bed, while 1 g of amorphous silica alumina (ASA) solid acid catalyst was loaded in the second oligomerization bed, and 1 g of 1wt% Pd on ASA catalyst was loaded in the third hydrocracking/isomerization bed (This catalyst has also been reported on previously). The catalysts were activated in situ at 270 ºC for the Fe-based FT catalyst, 400 ºC for the ASA and 400 ºC for the Pd/ASA for 10 h in a 50 SCCM H2 gas stream. The reactor temperatures were kept at 240 ºC in the first FT bed, 200 ºC in the second oligomerization bed, and 330 ºC in the third hydrocracking/isomerization bed, while the pressure was maintained at 35 bar. The syngas flow rate was initially maintained at 50 SCCM with a H2/CO ratio of 1.75. To start up the reaction, hexanes were injected at a rate of 1ml/min during the heating of each of the reaction beds in this 3 bed reaction system. From our previous experimental results, it was found that under gas phase operation the catalysts’ initial activities were not as high as they were under supercritical phase operation, and in addition, the catalysts deactivated rapidly in the gas phase. There is a significant probability that the catalyst pore volume and surface area were damaged because of the sudden high heat released during the initial period of that particular reaction study. When the bed temperature approaches or has reached the desired reaction temperature, the highly exothermic nature of the reactions can result in a massive release huge amount of heat in a relative short time, which may have

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caused catalyst agglomeration due to sintering and the reduction in active catalyst sites due to coking. Therefore, it was thought that by injecting hexanes during the heating of the catalyst beds to the desired temperature, excess heat and any impurities (which may block active sites) can be efficiently removed due to the greater heat capacity and solvent strength of the hexane solvent media. Once the desired reaction was achieved at steady state, the flow of hexanes was ceased to initiate the gas phase operation. The solvent (in this case, hexane) was collected and recovered in the cold trap before collection of liquid product was initiated from the reaction system. Under these conditions, the carbon monoxide (CO) conversion dropped slowly as a function of time (when compared at the same residence time), as shown in Figure 5. Changes in the syngas flow rate were made during the experiment in order to examine the effect of residence time. Initially the syngas flow rate was 50 SCCM, it was then changed to 100 SCCM (theoretically half the residence time of that of 50 SCCM), and it was then changed back to 50 SCCM and then to 25 SCCM (theoretically a doubled residence time) and then back again to 50 SCCM. The conversion at 50 SCCM syngas flowrate was measured is regarded it as a base line for comparison. Studies were performed a different syngas flowrates, and periodically the syngas flow rate was returned to the value of 50 SCCM so that we could monitor the catalyst activity and ensure that we do not have a biased comparison. Compared to H2 conversion, CO conversion was more sensitive to residence time (relative to syngas flow rate). When we doubled the syngas flow rate to 100 SCCM, the CO conversion was reduced by approximately half, and when the syngas flow rate was reduced to 25 SCCM, the CO conversion was increased to nearly double that obtained at 50 SCCM. However, by evaluating the CO conversion at 50 SCCM at different times on stream (TOS), we found that the CO conversion was slow decreasing indicating that the catalyst was deactivating. This also helps to explain why the CO conversion at 25 SCCM was not exactly twice that when the syngas flow rate was 50 SCCM. A potential reason as to why the H2 conversion was not as sensitive to syngas flowrate is possibly that the hydrogenation /hydrocracking in the third bed was more affected by the concentration of accumulated and fresh products (long chain hydrocarbons), instead of syngas flow rate. However, syngas flow rate will have a significant influence on the performance of the third bed, hence the higher hydrogen conversion. Methane and carbon dioxide selectivity were not as sensitive to changes in syngas flowrate as CO conversion (Figure 6), but they did vary with the changes made in syngas flow rate values. The continuous increase the both of these selectivities with TOS is primarily attribute to catalyst deactivation and local overheating in the gas phase.

Figure 5. Time on stream CO and H2 conversion (steady state)

Figure 6. Time on stream CO2 and CH4 selectivity (steady state)

We evaluated the performance of the triple-bed reactor system by utilizing gas phase Fischer-Tropsch Synthesis (FTS) with downstream oligomerization (GP-FTO). This was done in order to be able to make a direct comparison with previous results obtained using this system under supercritical fluid conditions, as reported in earlier reports. In this gas phase FTO experiment, 1 g of an Fe-based FT catalyst (which was previously reported, Fe/Zn/Cu/K molar ratio: 100/10/1/2), was loaded into the first FT bed. 1 g of amorphous silica alumina (ASA) solid acid catalyst was loaded in the second bed as the oligomerization catalyst. The catalysts

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were activated in situ at 270 ºC for the Fe-based FT catalyst, 400 ºC for the ASA for 10h in a 50 SCCM H2 gas stream. The reactor temperatures were kept at 240 ºC in the first FT bed, and 240 ºC in the second oligomerization bed, while the pressure was maintained at 17 bar. The syngas flow rate was initially maintained at 50 SCCM with a H2/CO ratio of 1.75. Gas phase product and reactant streams were analyzed by on-line GC-TCD. Liquid products, which were collected in cold trap manually, were analyzed by GC-FID and GC-MS. The CO conversion in this two bed reactor arrangement was around 40%, which was comparable to previous gas phase FTS operation (using the same FTS iron catalyst and reaction conditions with a CO conversion of 38%), the CO2 selectivity was basically stable around 28% with a CH4 selectivity of 5%. Figure 7 shows the liquid product selectivity as a function of carbon number on a total collected liquid hydrocarbon product basis. In our previous GP-FT experiment, the liquid C10- C20 selectivity was 68%. However, in this GP-FTO experiment, the C10 - C20 range hydrocarbon selectivity was significantly increased to 90% on a total liquid product basis. The olefin selectivity was remarkably reduced from 53% in the GP-FT to 10% in this GP-FTO operation due to light olefin oligomerization. The branched paraffin selectivity was enhanced from 15% (GP-FT) to 20% and n-paraffin selectivity was 68%. All of these results indicate that the use of this ASA catalyst in the catalytic oligomerization bed downstream of the iron-based FTS bed is viable for conversion of short chain olefins into the middle distillate range hydrocarbons.

Figure 7. Liquid product selectivity

Figure 8. Liquid functionality selectivity

D. Catalyst Characterization:

I. Utilize Advanced Analytical Techniques for Catalyst Characterization The characterization of the catalysts studied in the FTS work above was an ongoing process throughout the project. As the studies were performed, the catalysts were continuously characterized pre- and post reaction. E. Process and Product Design, Integration and Optimization:

I. Development of Process Simulation Models II. Process Integration and Optimization of Fuels Production Systems III. Development of Optimal Fuel Mixture Design Techniques

This work focuses on process simulation, integration and optimization of fuels production technologies developed in this project to ensure efficient use of energy and materials resources. We have developed a generic process simulation model of a gas-phase Fischer-Tropsch Synthesis process. A screenshot from the ASPEN Plus flowsheet is given in Figure 9 below. The model contains several processing steps that can be adjusted to match the specific processing conditions as data becomes available: • Synthesis gas production through reforming

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• Gas clean-up • Fischer-Tropsch reaction • Separation and recycle of unreacted synthesis gas • Fractionation of fuel range products from heavy waxes • Cracking of heavies and fractionation of fuel range products The model has been developed using data available in the open literature and its performance is being validated. In addition, a preliminary model of the supercritical Fischer-Tropsch Synthesis (SCF-FTS) process being studied in Dr. Roberts’ laboratory has been developed. The first model was developed using data from Dr. Roberts’ lab, and as such a hexane solvent stream was initially included in the feed to the Fischer-Tropsch reactor. Once the model was developed, the lights stream from the first fractionation column was compared to the feed to the FTS reactor in order to validate the possibility for recycle. The composition of the lights stream was sufficiently close to the reactor inlet to justify recycle, thus the hexane solvent stream could be safely removed as shown in Figure 10 below.

Figure 9: ASPEN Plus Model of Generic Packed Bed Gas-Phase FTS Process

Figure 10: ASPEN Plus Model of Supercritical Phase FTS Process

A thermal pinch analysis was performed on both the gas-phase model and the supercritical phase models to evaluate the differences in energy consumption. Since the fuel range product yields are higher in the SCF-FTS model for a fixed syngas feed, the comparison can be a little misleading. In Figure 11 below, the results are illustrated with the gas-phase process values normalized to one. The analysis shows that SCF-FTS uses about 10% more energy to process a given syngas feed, however as shown in Table 1 below, the SCF-FTS process produces about 20% more fuel range products as well.

Figure 11: Comparison of Energy Consumption (Gas-Phase FTS = 1).

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Table 1: Comparison of Fuel Production

Due to delays in the construction of the pilotscale fluidized bed gasifier, we initiated work on modeling the gasification of both coal and biomass resources. Given the complexity of coal and biomass resources, it is very difficult to characterize these materials using conventional chemical descriptors. A methodology is being formulated that allows modeling the coal/biomass feed using three sets of parameters: Proximate Analysis: Moisture, Volatile Matter, Fixed Carbon, Ash and HHV Ultimate Analysis: Elementary composition of C, H, N, O, S, Ash Sulfur Analysis: Distribution of elementary sulfur as Pyritic, Organic and Sulfate The use of such characterization data will provide a flexible foundation for studying gasification processes. By specifying the products of the gasification, e.g. CH4, H2, CO, CO2, NH4, H2S, H2O and unreacted N2 and O2, the reactor can be modeled through minimization of the total Gibbs free energy of the system. A screenshot of the gasification model is shown below:

Figure 12: Gasifier model schematic The first reactor (DECOMP) serves to convert/decompose the carbonaceous feedstock, i.e. coal and/or biomass into its constituent parts, i.e. H2, O2, N2, H2O, S, C, and ASH. This is not a true stand alone reactor, but an integral part of the gasification reactor representing a substantial part of the pyrolysis reactions. The decomposition reactor represents the translation of non-conventional solids into pure chemical species and ash. This reactor is specified using a yield distribution obtained from the ultimate analysis data. The second reactor (GASIFIER) converts the decomposed coal and/or biomass into synthesis gas by reacting it with air, oxygen and/or steam (in the screenshot above only the oxygen feed is shown). The stream connecting the two reactors does not exist in reality, but serves to transfer the constituent elements of the decomposed feedstock to the gasification section. It is necessary to link the two reactor blocks by a heat stream in order to take the energy requirements of the decomposition step into account.

Syngas (kmol/hr)

Gasoline (kg/hr)

JP5 (kg/hr) Total Fuel

(kg/hr)D1 D2 Total D1 D2 Total

Gas-Phase FTS 1524 882 526 1348 1271 417 1688 3036

SCF-FTS

Same Syngas Feed 1524 508 1318 1826 1091 756 1848 3674

Same Fuel Product(based on gasoline)

1122 374 974 1348 806 558 1364 2712

Same Fuel Product(based on total

product)1259 420 1090 1510 903 623 1526 3036

Syngas (kmol/hr)

Gasoline (kg/hr)

JP5 (kg/hr) Total Fuel

(kg/hr)D1 D2 Total D1 D2 Total

Gas-Phase FTS 1524 882 526 1348 1271 417 1688 3036

SCF-FTS

Same Syngas Feed 1524 508 1318 1826 1091 756 1848 3674

Same Fuel Product(based on gasoline)

1122 374 974 1348 806 558 1364 2712

Same Fuel Product(based on total

product)1259 420 1090 1510 903 623 1526 3036

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Initial gasification modeling efforts have focused on generating data to relate product gas composition to both air/fuel ratio and gasifier pressure for four different feedstocks: Illinois bituminous coal, Montana sub-bituminous coal, southern pine wood, and switchgrass. The details of each feedstock are given in Table 2 below.

Figure 13: Syngas component flows vs. A/F ratio for IL coal The current model allows for the following products in the synthesis gas: H2, CO, CO2, CH4, NH3, H2S, SOX, and NOX, but minor products are not shown in the included figures. The plot below shows the major component flows when varying the air to fuel ratio while feeding 1000 kg/h of Illinois coal to a gasifier operating at 5 atm. (Note: Air was modeled as 78% mole nitrogen, 21% mole oxygen, and 1% mole argon.) In analyzing the composition of the synthesis gas from the Illinois coal feed, two observations can be made that also extrapolate to the other three studied feedstocks: 1) Hydrogen and carbon monoxide flows reach their respective maxima at a common air to fuel ratio. 2) Methane formation decreases as the air to fuel ratio increases.

Air/Fuel Ratio vs. Syngas Substreams (1000 kg/h Illinois Bituminous Coal Feed)@ Gasifier Pressure = 5 atm

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Table 2: Feedstock information (all composition is given in weight%) Montana Sub-Bituminous Coal Proximate Analysis As Received Dry Basis Ultimate Analysis As Received Dry Basis % Moisture 10.50 % Moisture 10.50 % Ash 11.20 12.51 % Carbon (C) 59.82 66.84 % Volatiles 34.70 38.77 % Hydrogen (H) 4.38 4.89 % Fixed Carbon 43.60 48.72 % Nitrogen (N) 1.33 1.49 100.00 100.00 % Sulfur (S) 1.10 1.22 % Ash 11.20 12.51 % Sulfur (S) 1.10 1.22 % Oxygen (O) 11.67 13.04 100.00 100.00 HHV (BTU/lb) 8600 Illinois Bituminous Coal Proximate Analysis As Received Dry Basis Ultimate Analysis As Received Dry Basis % Moisture 13.00 % Moisture 13.00 % Ash 10.70 12.30 % Carbon (C) 59.82 68.76 % Volatiles 37.00 42.53 % Hydrogen (H) 4.12 4.74 % Fixed Carbon 39.30 45.17 % Nitrogen (N) 1.07 1.23 100.00 100.00 % Sulfur (S) 3.74 4.30 % Ash 10.70 12.30 % Sulfur (S) 3.74 4.3 % Oxygen (O) 7.55 8.68 100.00 100.00 HHV (BTU/lb) 11000 Southern Pine Wood Proximate Analysis As Received Dry Basis Ultimate Analysis As Received Dry Basis % Moisture 8.20 % Moisture 8.20 % Ash 0.30 0.33 % Carbon (C) 42.47 46.26 % Volatiles 72.39 78.86 % Hydrogen (H) 5.16 5.62 % Fixed Carbon 19.10 20.81 % Nitrogen (N) 0.12 0.13 100.00 100.00 % Sulfur (S) 0.00 0.00 % Ash 0.30 0.33 % Sulfur (S) 0.00 0.00 % Oxygen (O) 43.75 47.66 100.00 100.00 HHV (BTU/lb) 8100 Switchgrass Proximate Analysis As Received Dry Basis Ultimate Analysis As Received Dry Basis % Moisture 8.18 % Moisture 8.18 % Ash 2.72 2.96 % Carbon (C) 40.86 44.50 % Volatiles 77.18 84.06 % Hydrogen (H) 5.17 5.63 % Fixed Carbon 11.92 12.98 % Nitrogen (N) 1.10 1.20 100.00 100.00 % Sulfur (S) 0.00 0.00 % Ash 2.72 2.96 % Sulfur (S) 0.00 0.00 % Oxygen (O) 41.97 45.71 100.00 100.00 HHV (BTU/lb) 8250 By generating the same data for Montana coal, pine wood, and switchgrass, the optimum air to fuel ratio for maximizing the production of H2 and CO can be found. The following table summarizes the air to fuel ratio that generates the maximum flows of both H2 and CO for each of the four feeds. Table 3: Air/Fuel Ratio for maximum H2 and CO production

Feed Air/Fuel Ratio Illinois Bituminous Coal 3.7

Montana Sub-bituminous Coal 4.85 Southern Pine Wood 1.2

Switchgrass 0.9

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After establishing the A/F ratio that maximizes syngas production in each feed, another analysis was performed to examine the effect of gasifier pressure on the composition of the synthesis gas when each feedstock was fed at its respective optimal air to fuel ratio. As gasifier pressure increases, the flows of hydrogen and carbon monoxide both decrease, while the flows of methane, carbon dioxide, and water all increase. This same phenomenon is observed in the other three feedstocks as well. Thus, further evaluation of the economics of capital costs versus operating costs may be warranted depending on the intended use of the gasifier. Though lower operating gasifier pressures would require a larger vessel to obtain the same throughput, the increased production of hydrogen and carbon monoxide may offer an advantage in some circumstances. As previously noted, there is a specific air to fuel ratio that produces the maximum flow of both hydrogen an carbon monoxide for a given system pressure. Analyses performed relate gasifier pressure to the production of four key components in a gasification system (H2, CO, CO2, and CH4) between the four studied feedstocks, when each feedstock is fed to the gasifier at 1000 kg/h with the optimum air flow as previously listed in Table 3. Though it might seem more logical to compare each feedstock using the same air flow to the gasifier, this method would not yield a fair comparison of each feedstock due to the varying chemical composition of each feedstock, which necessitates that each feed requires a different amount of oxygen to optimize syngas production. Our initial modeling efforts were focused on the development of a flexible model that could provide a representation of coal and biomass gasification. We continued these efforts by examining the effects of varying the percentage of oxygen in air. Montana sub-bituminous coal, Illinois bituminous coal, southern pine wood, and switchgrass continue to be the feedstocks of interest in these continued modeling efforts. All models were generated by assuming a flow of 1000 kg/h of the feedstock of choice. The initial studies of the impact of air-to-fuel ratio and gasifier pressure on component flows in the product stream were conducted assuming standard air composition (78 mole% nitrogen, 21 mole% oxygen, and 1 mole% argon). Newly created models look at the impact of increasing the oxygen percentage in the air feed to the gasifier from 21% to 100%, or pure oxygen. Data points were created with the assumption that the balance of nitrogen and argon decreased in proportion to the ratio of nitrogen to argon in standard air. For each feedstock, this analysis was performed at four different gasifier pressures: 1, 5, 30, and 100 bar. It should also be noted that the optimal air feed rates as determined in the initial models were used for each feedstock. The following figures show the data that was generated for Montana sub-bituminous coal.

Figure 14: Mole percent oxygen in air vs. hydrogen

flow rate in syngas for Montana Coal

Figure 15: Mole percent oxygen in air vs. carbon monoxide flow rate in syngas for Montana Coal

The data shows that as the fraction of oxygen in the air feed to the gasifier increases, the quality of the synthesis gas decreases, with hydrogen and carbon monoxide flows decreasing dramatically. One noteworthy exception to this, is in the range of values where the oxygen content is 30% or less. In this

18

range, the model at the lowest pressure of 1 bar shows a successive decrease in component flows as the mole fraction of oxygen in the air is increased. At 5 bar gasifier pressure, the flow of hydrogen decreases steadily while the flow of carbon monoxide is very slightly greater at 22% oxygen than at 21% oxygen, and then it decreases steadily as the oxygen percentage is increased. At the higher pressures of 30 bar and 100 bar, there is a noticeably more pronounced effect of slightly increasing the mole fraction of oxygen in the air. The flows of hydrogen and carbon monoxide predicted at 21% oxygen exactly match the values found in earlier models where gasifier pressure was varied; however, as the oxygen content of the air is increased, the flows of H2 and CO increase up to a maximum and then decrease subsequently from that point. Models of the other three feedstocks all showed these same general trends. The aforementioned effects on the gasifier product stream at oxygen values less than 30 mole percent are further examined in the following tables. These tables compare H2 and CO component flows in the synthesis gas generated assuming standard air composition and the highest value obtained for the flows while varying oxygen content of the air. The highest value for the flows of hydrogen and carbon monoxide are not necessarily at the same mole fraction of oxygen for each feedstock and pressure, but all values occurred at oxygen mole fractions of less than thirty, with the maximum flow of CO for switchgrass feed at 100 bar gasifier pressure occurring at 29% oxygen, and all of the remaining maxima occurring at 27% oxygen or less. The general trend of the data is that carbon monoxide flow increases more than hydrogen flow as a result of slightly increasing the mole fraction of oxygen in the air feed. This phenomenon should be a candidate for further evaluation in the research gasifier once it is operational. If empirical data supports the model data, slightly enriching the oxygen content of the air feed to high-pressure gasification systems could be an effective means of increasing desired syngas products at marginal capital and operating costs. A sensitivity analysis has been performed to examine the effects of varying oxidation air temperature to the gasifier. The general trend regardless of feedstock was that CO flow increased with increasing oxidation air temperature, while H2, CO2, and CH4 flows all decreased. The increase in the molar flow of CO is almost equal to the decrease in flow of CO2. This behavior can be explained by a shift in the water-gas shift reaction equilibrium. The WGS reaction is exothermic, thus increasing the heat in the system will push the reaction back towards CO and water. The H2O flow in the product gas also increased with increasing air temperature, further supporting this explanation. It is noted that the H2 flow does not decrease proportionally with the increase in CO flow and the decrease in CO2 flow. The reason for this behavior can be attributed to the endothermic nature of the steam reforming of methane present in the gasifier. Table 4: Component flows at standard air composition vs. component flow maxima at varied oxygen mole fraction of air feed to gasifier for Montana coal

Table 5: Component flows at standard air composition vs. component flow maxima at varied oxygen mole fraction of air feed to gasifier for Illinois coal

Gasifier Pressure (bar)

Standard Air Composition

Increasing O2 Composition

% Increase Flow

1 17.733 17.733 0.0%5 16.853 16.853 0.0%30 13.410 13.942 4.0%

100 10.699 11.729 9.6%

Gasifier Pressure (bar)

Standard Air Composition

Increasing O2 Composition

% Increase Flow

1 27.051 27.051 0.0%5 26.570 26.756 0.7%30 24.040 26.130 8.7%

100 20.684 25.616 23.8%

CO Flow (kmol/h)

Montana Sub-Bituminous Coal

H2 Flow (kmol/h)Gasifier

Pressure (bar)Standard Air Composition

Increasing O2 Composition

% Increase Flow

1 21.471 21.471 0.0%5 20.480 20.480 0.0%30 17.201 17.983 4.5%

100 14.500 16.052 10.7%

Gasifier Pressure (bar)

Standard Air Composition

Increasing O2 Composition

% Increase Flow

1 38.928 38.928 0.0%5 38.355 38.355 0.0%30 34.606 37.580 8.6%

100 30.919 36.813 19.1%

CO Flow (kmol/h)

Illinois Bituminous Coal

H2 Flow (kmol/h)

19

Table 6: Component flows at standard air composition vs. component flow maxima at varied oxygen mole fraction of air feed to gasifier for pine wood

Table 7: Component flows at standard air composition vs. component flow maxima at varied oxygen mole fraction of air feed to gasifier for switchgrass

Gasifier Pressure (bar)

Standard Air Composition

Increasing O2 Composition

% Increase Flow

1 24.208 24.208 0.0%5 23.677 23.677 0.0%30 20.889 21.509 3.0%

100 17.945 19.713 9.9%

Gasifier Pressure (bar)

Standard Air Composition

Increasing O2 Composition

% Increase Flow

1 27.975 28.064 0.3%5 27.776 28.058 1.0%30 26.677 27.987 4.9%

100 25.399 27.835 9.6%

CO Flow (kmol/h)

Switchgrass

H2 Flow (kmol/h)

Thus, the effects of increasing oxidation air temperature on the four main subcomponents can all be attributed to a shift in the equilibrium of two main governing reactions in the system. Increased temperature favors CO in both of the reactions, thus it shows the greatest response of the four subcomponents. H2 flow decreases over the range of studied temperatures, but the decrease is noticeably less than the decrease in the flow of CO2. It should be noted that the stoichiometry of the reforming reaction causes any shift toward CO and H2 to show a greater effect in H2 because of the 3:1 stoichiometric ratio of the two products. These parametric studies illustrate that although the gasifier itself is modeled by minimization of Gibbs free energy, the resulting behavior is supported by fundamental reaction engineering, thus lending further confidence in the performance of the model. Also, we have performed integration studies of the gasifier models with downstream Fischer-Tropsch models for gas-phase FTS and the supercritical phase FTS in Dr. Roberts laboratory. This work was summarized in a short manuscript (Yuan et al., 2011) that was published in Computer Aided Chemical Engineering in 2011. Recent work on the coal and biomass gasification model has been focused on completing modifications to simulate a liquid slurry feed and repeating the sensitivity analyses that were previously performed assuming a dry feed under slurry-feed conditions. All previously generated data was produced under the assumption that the gasifier was operated as a dry-feed system, but recently the model has been augmented to allow the same analyses that have been previously performed for a dry-feed setup to be performed for slurry-feed systems. The following data shows the effects of varying the percent solids of the slurry to the gasifier by adjusting the makeup water flow. As the slurry feed proceeds to a lower percent-solids by increasing the flow of make-up water, H2 flow increases slightly over part of the range, probably due to shifting the equilibrium of the water-gas shift reaction into favoring H2 and CO2 generation, but then as make-up water flow is increased beyond this point, H2 flow begins to decrease, and CH4 flow begins to increase. As the flow of liquid water into the gasifier increases, the heat needed to vaporize this water, begins to rob the methane-steam reforming reaction of its necessary heat, and this effect begins to overwhelm the effect of the water-gas shift reaction.

Gasifier Pressure (bar)

Standard Air Composition

Increasing O2 Composition

% Increase Flow

1 22.787 22.787 0.0%5 22.351 22.351 0.0%30 19.683 20.075 2.0%

100 16.761 18.238 8.8%

Gasifier Pressure (bar)

Standard Air Composition

Increasing O2 Composition

% Increase Flow

1 27.301 27.496 0.7%5 27.140 27.493 1.3%30 26.095 27.443 5.2%

100 24.806 27.302 10.1%

CO Flow (kmol/h)

Southern Pine Wood

H2 Flow (kmol/h)

20

Figure 16. Effect of slurry-feed conditions on gasifier product

For further models of slurry-feed systems, it was assumed that the slurry would be feed to the gasifier as 60% solids, by weight. This value falls within the range of commonly given values for percent solids in operating a slurry-feed gasifier. The following charts show the response of the four studied feedstocks to varying the air-to-fuel ratio (AFR). As shown earlier, when determining the effect of AFR on syngas product substreams for dry-feed operation, the values of the AFR that yielded the maximum production of both H2 and CO were so near to one another that a common value to be used to as the optimum AFR for both H2 and CO production; however, this is not the case with the slurry-feed system. In the dry-feed setup, the air flow rate the yielded the maximum CO generation was an average of 5.1% greater than the air flow rate the maximized H2 production. With the slurry-feed setup, the CO maximizing air flow was on average 26.5% larger than the H2 maximizing air flow rate. Thus, for slurry-feed gasification systems, the desired usage of the syngas (e.g. IGCC, Fischer-Tropsch, etc.) and the associated H2/CO ratio required would dictate the set point of the AFR since both H2 and CO flows cannot be maximized by the same air flow as was the case in the dry-feed systems. Also, the flow of CO2 in the synthesis gas at both the H2 and CO maxima is noticeably higher than in the dry-feed system. Both of these phenomena can be directly attributed to additional water in the slurry driving the equilibrium of the water-gas shift reaction away from water and CO toward H2 and CO2. One benefit of this is that the H2/CO ratio of the syngas leaving the gasifier is considerably higher at the H2 maximizing AFR over the optimal AFR for the dry-feed systems. Between the four feedstocks, the average H2/CO ratio of the syngas leaving the gasifier in the slurry models was 2.27 versus 0.71 in the dry-feed cases.

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Figure 17. Effect of air/fuel ratio on gasifier products for slurry feeds

Also of note in this data is that the AFR for maximum H2 production, the production of CH4 is noticeably greater than when AFR is optimized for H2 production in the dry-feed gasifier. At the H2 optimizing AFR, for the dry-feed systems, the flow of CH4 was on average 0.56% of the total molar flow between the four feedstocks, but in the slurry-feed systems, this value increased to 2.08%. Finally, we are working on a capital cost analysis of an alternative adiabatic reactor design for operation of the supercritical phase Fischer-Tropsch Synthesis. The results look promising and the design offers added process flexibility and potential operational benefits compared to conventional reactor configurations. This work was summarized in a short manuscript (Durham et al., 2012) that was published in Computer Aided Chemical Engineering in 2012, and a more complete version (Durham et al., 2013) has been accepted for publication in Industrial & Engineering Chemistry Research Mixture Design of Experiments (MDOE) is a technique for determining the optimum combination of chemical constituents that deliver a desired response using a minimum number of experimental runs. Conventional MDOE methods employ either polynomial or canonical models to predict the property response. Once identified, the properties are evaluated using response surface plots, which utilizes simplex (ternary) diagrams to visually interpret the data. Unfortunately, this method very quickly suffers from combinatorial explosion making it impractical for complex systems such as fuel mixture design. For example, in Figure 18, a four component mixture design of experiments was conducted and a response surface was generated to describe a single property. Six separate charts have to be used to visualize the response surface of each property. If additional components and/or properties are added to the design space, even more response plots are needed to describe the responses. Furthermore, interpretation of the impact of each mixture component on the overall properties of the solution is difficult since some colinearities exist between the components.

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Figure 18: Various simplex diagrams of one response for four components. A total of 18 diagrams need to be evaluated simultaneously to identify the optimal solution for 3 properties.

Figure 19: Single property cluster diagram, where all 3 properties and all components can be evaluated. Pure components are represented as single dots, while product targets are a region.

Eden’s group has shown that viewing the problem in the property space avoids combinatorial explosion while also offering insights into the effectiveness of the design. To transform the data into the property space, the property clustering technique is employed to convert the properties into conserved surrogate property clusters that are described by property operators, which have linear mixing rules, even if the operators themselves are nonlinear. Using this technique, the four component – three property mixture design mentioned above can be visualized in a single plot as shown in Figure 19. Identification of optimal mixtures can be performed visually using lever-arm analysis or algebraically by solving a finite set of equations. In this project, we will further develop these techniques to identify optimal fuel mixtures and aid the experimental researchers to maximize the information that can be inferred from their research. Initial work has begun on the development of characterization based methods for fuel additives design. The proof of concept method was tested on a biodiesel additive and the work was summarized in a short manuscript (Hada et al., 2011) that was published in Computer Aided Chemical Engineering in 2011. 5. Discuss Project Outcomes and Impact: This SunGrant project consisted of five interrelated research topics: Biomass fractionation, biomass gasification, supercritical phase Fischer-Tropsch Synthesis, catalyst characterization, as well as process and product design, integration and optimization. As the project progressed our work focused on primarily on biomass gasification, supercritical Fischer-Tropsch Synthesis (SCF-FTS) as well as various aspects of process and product design. The biomass gasification studies were focused on understanding the effects of biomass characteristics on syngas composition and tar concentration in a downdraft gasifier. In addition, the effects of thermal treatment (torrefaction) on the physicochemical properties of three different biomass types were studied. We were planning to conduct gasification studies in a fluidized-bed reactor, but due to delays in getting this gasifier running we have used a downdraft gasifier to perform our gasification studies. Although gasification results will vary depending upon the type of gasifier, we have learned important operational issues that one can encounter during gasification of biomass. We have also acquired important information on how the biomass type would affect synthesis gas composition. We were unable to perform gasification studies of fractionated biomass because of some operational issues with the fractionation unit. Large amounts of fractionated biomass could not be obtained because of intermittent operation of the fractionation unit. The Fischer-Tropsch synthesis aspect of the project has proceeded largely as planned with the single exception of not being able to run the FTS reactions on actual syngas from the fluidized bed gasifier as noted above. However, studies were performed using simulated syngas in order to determine proper operational parameters in preparation for obtaining actual syngas from the gasifier in the near future. We have illustrated that by modifying the FTS process to operate under dense phase conditions (including

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supercritical fluid recycle, supercritical fluid phase FTS or SCF-FTS) and optimizing the operating conditions, a significant enhancement of middle distillate products and simultaneous reduction of undesirable methane production can be achieved along with significantly prolonging catalyst lifetime. We were able to utilize undesired light products to enhance heat and mass transfer within the media and perform SCF-FTS in a simple fixed bed reactor system. Additionally, we worked on integrating various product upgrading stages including, oligomerization and cracking/isomerization following the SCF-FTS bed to further increase the fuel range product yield. We have developed generic process simulation models of biomass gasification along with both gas-phase and supercritical phase Fischer-Tropsch Synthesis processes. The models were developed using a combination of information available in the open literature and data collected as part of this project. We have illustrated that the SCF-FTS process results in significantly increased production of fuel range products and that while there is an accompanying increase in operating cost (due to the higher pressure), the SCF-FTS process still shows favorable performance compared to the gas-phase process. 6. Publications: Peer-Reviewed Articles – Published: 1. Gopal Gautam, Sushil Adhikari and Sushil Bhavnani, 2010. Estimation of biomass synthesis gas

composition using equilibrium modeling. Energy & Fuels 24 (4), pp. 2692–2698 2. Suchithra T. Gopakumar, Sushil Adhikari, Harideepan Ravindran, Ram B. Gupta, Oladiran Fasina,

Maobing Tu and Sandun Fernando, 2010. Physiochemical properties of bio-oil produced at various temperatures from pine wood using an auger reactor. Bioresource Technology 101, pp. 8389–8395.

3. Elbashir, N.O.; Bukur, D.B.; Durham, E.; Roberts, C.B.; “Advancement of Fischer-Tropsch Synthesis

via Utilization of Supercritical Fluid Reaction Media.” AIChE Journal, 56(4), 2010. 4. Durham, E.; Roberts, C.B., “Diesel-Length Aldehydes and Ketones via Supercritical Fischer Tropsch

Synthesis on an Iron Catalyst.” Applied Catalysis A., 386 (1-2), 2010. 5. Durham, E.; Roberts, C.B., “Diesel-length aldehydes from supercritical Fischer Tropsch Synthesis on

an iron catalyst.” Preprints of Symposia - American Chemical Society: Division of Fuel Chemistry, 2010.

6. Yuan W., Vaughan G.C., Roberts C.B., Eden M.R. (2011): “Modeling and Optimization of

Supercritical Phase Fischer-Tropsch Synthesis”, Computer Aided Chemical Engineering 29B, pp. 1929-1933.

7. Hada S., Solvason C.C., Eden M.R. (2011): “Molecular Design of Biofuel Additives for Optimization of

Fuel Characteristics”, Computer Aided Chemical Engineering 29B, pp. 1633-1637. 8. Gopal Gautam, Sushil Adhikari, Suchithra Thangalazhy-Gopakumar, Christian Brodbeck, Sushil

Bhavnani, and Steven Taylor. Tar analysis in syngas derived from pelletized biomass in a commercial stratified downdraft gasifier. BioResources. Vol. 6(4), pp. 4652-4661.

9. Gopal Gautam, Sushil Adhikari, Christian Brodbeck, Sushil Bhavnani, Oladiran Fasina, and Steven

Taylor. Gasification of wood chips, agricultural residues and waste using a downdraft commercial gasifier. Trans of ASABE, 54(5), pp. 1801-1807.

10. Durham E., Zhang S., Xu R., Eden M.R., Roberts C.B. (2012): “Novel Adiabatic Reactor Design for

Supercritical Fischer-Tropsch Synthesis”, Computer Aided Chemical Engineering, 30B, pp. 1098-1102.

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11. Hada S., Chemmangattuvalappil N.G., Roberts C.B., Eden M.R. (2012): “Product and Mixture Design in Latent Variable Space by Chemometric Techniques”, Computer Aided Chemical Engineering, 30A, pp. 147-151.

12. Hada S., Chemmangattuvalappil N.G., Roberts C.B., Eden M.R. (2012): “Optimization of Product

Formulation through Multivariate Statistical Analysis”, Computer Aided Chemical Engineering, 31B, pp. 1361-1365.

13. Durham E., Xu R., Zhang S., Eden M.R., Roberts C.B. (2013): “Supercritical Adiabatic Reactor for

Fischer-Tropsch Synthesis”, Industrial & Engineering Chemistry Research (published online October 10, 2012, DOI: 10.1021/ie3008677).

14. Zhang, S.; Xu, R.; Durham, E.; Roberts, C.B.; “Advancement of Fischer-Tropsch Synthesis with

Integrated Product Upgrading via Utilization of Supercritical Fluid Reaction Media,” Proceedings of the 10th International Symposium on Supercritical Fluids, paper 236_004, 2012.

Peer-Reviewed Articles – In Press: 1. Suchithra T. Gopakumar, Sushil Adhikari, Ram B. Gupta, Maobing Tu and Steven Taylor. Production

of hydrocarbon fuels from biomass using catalytic pyrolysis under helium and hydrogen environments. Bioresource Technology (accepted for publication).

2. Sadhwani N., Liu Z., Eden M.R., Adhikari S. (2013): “Simulation, Analysis and Assessment of CO2 Enhanced Biomass Gasification”, Computer Aided Chemical Engineering (accepted for publication January 2, 2013).

Oral and Poster Presentations – Presented: 1. Gopal Gautam and Sushil Adhikari. Biomass synthesis gas composition estimation using

thermodynamic equilibrium modeling presented at Annual International Meeting of American Society of Agricultural and Biological Engineers, June 20-June 23, 2010, Pittsburgh, PA

2. Sushil Adhikari, Christian Brodbeck, Gopal Gautam, Steven Taylor and Mark Hall. Biomass gasification for heat and power: synthesis gas composition, tar concentration and engine emissions analyses presented at 18th European Biomass Conference and Exhibition, May 3-7, 2010, Lyon, France.

3. Zhang, S.; Durham, E.; Xu, R.; Roberts, C.B.; “Production of middle distillate range transportation fuels from synthesis gas using Fischer-Tropsch synthesis technology under supercritical phase.” 2010 American Institute of Chemical Engineers Annual Meeting, paper 570s, November 7-12, Salt Lake City, UT, 2010.

4. Xu, R.; Zhang, S.; Roberts, C.B.; “Synthesis of higher alcohols from syngas over K promoted Cu-Co-Zn catalyst in supercritical n-hexane.” 2010 American Institute of Chemical Engineers Annual Meeting, paper 570r, November 7-12, Salt Lake City, UT, 2010.

5. Saunders, S.R.; Roberts, C.B.; “Tuning the precipitation and fractionation of nanoparticles in gas-expanded liquids.” 2010 American Institute of Chemical Engineers Annual Meeting, paper 649d, November 7-12, Salt Lake City, UT, 2010.

6. Durham, E.; Zhang, S.; Roberts, C.B.; “Diesel Length Aldehydes From Iron-Based Fischer Tropsch Synthesis,” American Institute of Chemical Engineers Spring Meeting: Topical 6 - 10th Topical Conference on Gas Utilization: Coal, Biomass and Natural Gas to Liquids II Section, presentation 33b, San Antonio, TX, March 21-25, 2010.

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7. Durham, E.; Roberts, C.B.; “Diesel-length aldehydes from supercritical Fischer Tropsch Synthesis on

an iron catalyst,” 239th American Chemical Society National Meeting: FUEL Division, Green Chemistry on Fuels of the Future, presentation 123, San Francisco, March 21-25, 2010.

8. Eden M.R., Roberts C.B., Adhikari S., Taylor S.E. (2010): “Co-Production of High Value Oxygenates

and Olefins through Integrated Biomass Fractionation, Gasification and Advanced Catalytic Conversion”, Invited Lecture, Frontiers in Biorefining: Biobased Products from Renewable Carbon, St. Simons Island, GA.

9. Eden M.R. (2010): “New Approaches to Evaluation of Economic and Environmental Impact of Biorefineries”, Invited Plenary Lecture, 5th Mississippi State University Biofuels Conference, Jackson, MS.

10. Hada S., Solvason C.C., Eden M.R. (2010): "Design of Biofuel Additives using Molecular Design

Techniques", Paper 238d, AIChE Annual Meeting, Salt Lake City, UT.

11. Yuan W., Eden M.R. (2010): "Modeling of Fischer-Tropsch Fuels Production from Polygeneration Facilities", Paper 443c, AIChE Annual Meeting, Salt Lake City, UT.

12. Hada S., Solvason C.C., Eden M.R. (2010): "Molecular Design of Biofuel Additives for Feedstock Flexibility", Paper 375aa, AIChE Annual Meeting, Salt Lake City, UT.

13. Yuan W., Eden M.R. (2010): "Process Modeling and Integration of Fischer-Tropsch Fuels Production

Strategies", Paper 375w, AIChE Annual Meeting, Salt Lake City, UT.

14. Eden M.R., Roberts C.B., Taylor S.E. (2011): “Production of Transportation Fuels and High Value Co-Products through Integrated Biomass Fractionation, Gasification and Advanced Catalytic Conversion”, Invited Lecture, 2nd International Congress on Sustainability Science and Engineering, Tucson, AZ.

15. Durham J.E., Eden M.R., Roberts C.B. (2011): "Reactor Design for Supercritical Fischer-Tropsch",

AIChE Spring Meeting, Chicago, IL.

16. Zhang, S.; Xu, R.; Durham, E.; Roberts, C.B.; “Production of Middle Distillate Range Transportation Fuels From Synthesis Gas Using Fischer Tropsch Synthesis Technology Under Supercritical Phase Conditions,” paper 56d, American Institute of Chemical Engineers Spring National Meeting, Chicago, IL, March 15, 2011.

17. Xu, R.; Zhang, S.; Durham, E.; Roberts, C.B.; “Synthesis of Higher Alcohols From Syngas Over a K Promoted Cu-Co-Zn Catalyst In Supercritical n-Hexane,” paper 100c, American Institute of Chemical Engineers Spring National Meeting, Chicago, IL, March 16, 2011.

18. Yuan W., Vaughan G.C., Roberts C.B., Eden M.R. (2011): “Modeling and Optimization of

Supercritical Phase Fischer-Tropsch Synthesis”, ESCAPE-21, Chalkidiki, Greece.

19. Hada S., Solvason C.C., Eden M.R. (2011): “Molecular Design of Biofuel Additives for Optimization of Fuel Characteristics”, ESCAPE-21, Chalkidiki, Greece.

20. Gopal Gautam, Christian Broadbeck, Sushil Adhikari, Suchithra Thangalazhy-Gopakumar. Tar

analysis in syngas from a commercial stratified downdraft gasifier, Annual International Meeting of American Society of Agricultural and Biological Engineers, August 7-11, 2011, Louisville, KY.

21. Durham J.E., Eden M.R., Roberts C.B. (2011): “Supercritical Adiabatic Reactor for Fischer-Tropsch

Synthesis”, Paper 265e, AIChE Annual Meeting, Minneapolis, MN.

26

22. Hada S., Solvason C.C., Eden M.R. (2011): “Characterization Based Molecular Design of Biofuel Additives for Feedstock Flexibility”, Paper 620x, AIChE Annual Meeting, Minneapolis, MN.

23. Hada S., Solvason C.C., Eden M.R. (2011): “Systematic Molecular Design of Biofuel Additives using

Hybrid Characterization and Group Contribution Based Techniques”, Paper 767c, AIChE Annual Meeting, Minneapolis, MN.

24. Hada S., Solvason C.C., Eden M.R. (2011): “Design of Biofuel Additives using Chemometric

Modeling and Molecular Design Techniques”, Paper 519f, AIChE Annual Meeting, Minneapolis, MN.

25. Sushil Adhikari, Christian Brodbeck and Steven Taylor, 2012. Biomass gasification for heat and power applications presented at Annual International Meeting of American Society of Agricultural and Biological Engineers, July 29- August 1, Dallas, TX.

26. Nourredine Abdoulmoumine and Sushil Adhikari, 2012. Effect of gasification parameters on syngas

contaminants presented at Annual International Meeting of American Society of Agricultural and Biological Engineers, July 29- August 1, Dallas, TX.

27. Avanti Kulkarni, Sushil Adhikari and Sushil Bhavnani, 2012. Gasification of torrefied biomass using a bench scale fluidized bed gasifier presented at Annual International Meeting of American Society of Agricultural and Biological Engineers, July 29- August 1, Dallas, TX.

28. Hada S., Chemmangattuvalappil N.G., Roberts C.B., Eden M.R. (2012): “Optimization of Product

Formulation through Multivariate Statistical Analysis”, 11th International Symposium on Process Systems Engineering (PSE-2012), Singapore, Singapore.

29. Hada S., Chemmangattuvalappil N.G., Roberts C.B., Eden M.R. (2012): “Product and Mixture Design

in Latent Variable Space by Chemometric Techniques”, ESCAPE-22, London, United Kingdom.

30. Durham E., Zhang S., Xu R., Eden M.R., Roberts C.B. (2012): “Novel Adiabatic Reactor Design for Supercritical Fischer-Tropsch Synthesis”, ESCAPE-22, London, United Kingdom.

31. Hada S., Herring R.H., Haser J.C., Chemmangattuvalappil N.G., Eden M.R. (2012): “Optimization of

Product Formulations using Multivariate Analysis and Property Clustering”, Paper 604b, AIChE Annual Meeting, Pittsburgh, PA.

32. Hada S., Herring R.H., Haser J.C., Chemmangattuvalappil N.G., Eden M.R. (2012): “Multivariate Analysis of Process Data for Product Formulation Optimization in Property Cluster Space”, Paper 544b, AIChE Annual Meeting, Pittsburgh, PA.

33. Sadhwani N., Adhikari S., Eden M.R. (2012): “Effect of Temperature and Oxidizing Medium on Tar

Formation in Southern Pine Gasification”, Paper 383e, AIChE Annual Meeting, Pittsburgh, PA.

34. Roe, D.; Zhang, S.; Xu, R.; Stewart, C.; Durham, E.; Roberts, C.B. “Production of Middle Distillate Range Liquid Fuels From Syngas Using Fischer-Tropsch Synthesis and Associated Upgrading Technology Under Supercritical Phase Conditions and Multiple Reactor Configurations,” AIChE Annual Meeting, Pittsburgh, PA, October 31, 2012.

35. Zhang, S.; Roe, D.; Xu, R.; Roberts, C.B.; “Advancement in Iron-Based Low Temperature Fischer-

Tropsch Synthesis with Integrated Product Upgrading Via Utilization of Supercritical Fluid Reaction Media,” AIChE Annual Meeting, Pittsburgh, PA, October 29, 2012.

27

Oral and Poster Presentations – In Preparation: 1. Sadhwani N., Liu Z., Eden M.R., Adhikari S. (2013): “Simulation, Analysis and Assessment of CO2

Enhanced Biomass Gasification”, ESCAPE-23, Lappeenranta, Finland (accepted for presentation). 7. Licenses/Inventions: None 8. Students Funded on Project: Student Name: Nishanth G. Chemmangattuvalappil Department: Chemical Engineering Institution: Auburn University Thesis/Dissertation Title: A Systematic Property Based Approach for Molecular Synthesis using

Higher Order Molecular Groups and Molecular Descriptors Degree Obtained/Date Ph.D. (December 2010) Program Area Process/Product Design and Optimization Student Name: Charles C. Solvason Department: Chemical Engineering Institution: Auburn University Thesis/Dissertation Title: Integrated Multiscale Chemical Product Design using Property Clustering

and Decomposition Techniques in a Reverse Problem Formulation Degree Obtained/Date Ph.D. (December 2011) Program Area Process/Product Design and Optimization Student Name: Subin Hada Department: Chemical Engineering Institution: Auburn University Thesis/Dissertation Title: Chemical Product Formulation through Multivariate Characterization,

Modeling, and Design in Property Cluster Space Degree Obtained/Date Ph.D. (August 2013) Program Area Process/Product Design and Optimization Student Name: Gopal Gautam Department: Biosystems Engineering Institution: Auburn University Thesis/Dissertation Title: Parametric study of a commercial-scale downdraft gasifier: experiments and

modeling work Degree Obtained/Date M.S. (2010) Program Area Biomass Resources and Conversion Student Name: Harideepan Ravindran Department: Biosystems Engineering Institution: Auburn University Thesis/Dissertation Title: Production of high pH value and stable bio-oil from woody biomass and

poultry litter Degree Obtained/Date M.S. (2011) Program Area Biomass Resources and Conversion Student Name: Gregory C. Vaughan Department: Chemical Engineering Institution: Auburn University

28

Thesis/Dissertation Title: Modeling and Optimization of Biomass Gasification Degree Obtained/Date M.S. (expected December 2013) Program Area Biomass Resources and Conversion Student Name: Susilpa Bommareddy Department: Chemical Engineering Institution: Auburn University Thesis/Dissertation Title: Property Integration for Simultaneous Process and Product Design Degree Obtained/Date Ph.D. (expected December 2013) Program Area Process/Product Design and Optimization Student Name: Pranav S. Vengsarkar Department: Chemical Engineering Institution: Auburn University Thesis/Dissertation Title: Understanding the Size-Selective Fractionation of Magnetic Nanoparticles

Using Gas-Expanded Liquids for use in Pickering Emulsions and Fischer-Tropsch Catalysis

Degree Obtained/Date Ph.D. (expected May 2014) Program Area Biomass Conversion and Fuels Production Student Name: Stephen Wahl Department: Chemical Engineering Institution: Auburn University Thesis/Dissertation Title: Not Applicable – Undergraduate Researcher Degree Obtained/Date N/A Program Area Biomass Conversion and Fuels Production Student Name: Whitney N. Bell Department: Biosystems Engineering Institution: Auburn University Thesis/Dissertation Title: Not Applicable – Undergraduate Researcher Degree Obtained/Date N/A Program Area Biomass Resources and Conversion 9. Collaborators and/or Partners: None 10. Educational Programs Conducted None 11. Internal and External Grants and Contracts Related to this Project Proposals Submitted: 1. IGERT: Integrated Biorefining for Sustainable Production of Fuels and Chemicals, National Science

Foundation (NSF-IGERT), PI: M.R. Eden, Co-PIs: C.B. Roberts, S. Taylor, P.K. Raju, T. Gallagher, $3,000,000, 08/15/2011 – 08/15/2016.

2. Fuel and Oxygenate Co-Products From Biomass Fractionation and Advanced Catalytic Conversion Processes, USDA-AFRI, PI: M.R. Eden, Co-PIs: C.B. Roberts, S. Taylor, S. Adhikari, $1,000,000, 01/01/2011 – 12/31/2015.

29

3. Biomass Gasification Research, Electric Power Research Institute (EPRI), PI: S. Adhikari, Co-PIs: O.

Fasina, S. Taylor, M.R. Eden, C.B. Roberts, $374,995, 08/01/2011 – 07/31/2013. Portion for Dr. Eden’s part of the project: $96,559.

4. Biomass to Liquid Fuels and Electrical Power, Department of Energy, PI: S. Taylor, Co-PIs: M.R.

Eden, C. Roberts, $1,500,000, 06/01/2011 – 09/01/2013. Portion for Dr. Eden’s part of the project: $451,709.

5. Southeastern Partnership for Integrated Biomass Supply Systems (IBSS), USDA-AFRI, PI: T. Rials

(U. Tennessee), Lead PI for Auburn: S.E. Taylor, $15,008,000 (Total amount for AU: $4,519,000) 01/01/2012 – 12/31/2017. Note: This project is a major center grant proposal led by U. Tennessee. M.R. Eden, C.B. Roberts and S. Adhikari are the lead investigators on the conversion task and associated education, extension and outreach efforts. The total budget for the conversion task at AU is $1,115,379.

6. Coal to biomass using micro fibrous entrapped catalysts and Supercritical phase FT processing,

Department of Energy – National Energy Technology Laboratory, PI: S. Adhikari, Co-PIs: M.R. Eden, C.B. Roberts, S.E. Taylor, B.J. Tatarchuk, $1,200,000.

7. From Forest to Fuels – Integrated Systems for Production of Biofuels and Bioproducts from Woody

Biomass, USDA-DOE-BRDI, PI: M.R. Eden, Co-PIs: C.B. Roberts, S.E. Taylor, B.J. Tatarchuk, $6,750,000

Proposals Funded: 1. IGERT: Integrated Biorefining for Sustainable Production of Fuels and Chemicals, National Science

Foundation (NSF-IGERT), PI: M.R. Eden, Co-PIs: C.B. Roberts, S. Taylor, P.K. Raju, T. Gallagher, $3,000,000, 08/15/2011 – 08/15/2016. Note: This is the first ever NSF-IGERT program awarded to Auburn University. IGERT is the National Science Foundation's flagship interdisciplinary training program for educating U.S. Ph.D. scientists and engineers. This program will provide funding for a total of 35 Ph.D. students across the Auburn University campus.

2. Fuel and Oxygenate Co-Products From Biomass Fractionation and Advanced Catalytic Conversion Processes, USDA-AFRI, PI: M.R. Eden, Co-PIs: C.B. Roberts, S. Taylor, S. Adhikari, $1,000,000, 01/01/2011 – 12/31/2015.

3. Biomass Gasification Research, Electric Power Research Institute (EPRI), PI: S. Adhikari, Co-PIs: O.

Fasina, S. Taylor, M.R. Eden, C.B. Roberts, $374,995, 08/01/2011 – 07/31/2013.

4. Biomass to Liquid Fuels and Electrical Power, Department of Energy Award No. DE-EE003115, PI: S. Taylor, Co-PIs: M.R. Eden, C. Roberts, $1,500,000, 06/01/2011 – 09/01/2013. Portion for Dr. Eden’s part of the project: $451,709.

5. Southeastern Partnership for Integrated Biomass Supply Systems (IBSS), USDA-AFRI, PI: T. Rials

(U. Tennessee), Lead PI for Auburn: S.E. Taylor, $15,008,000 (Total amount for AU: $4,519,000) 01/01/2012 – 12/31/2017. Note: This project is a major center grant proposal led by U. Tennessee. M.R. Eden, C.B. Roberts and S. Adhikari are the lead investigators on the conversion task and associated education, extension and outreach efforts. The total budget for the conversion task at AU is $1,115,379.

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ACKNOWLEDGMENT Support for this research was provided in part by a grant from the Southeastern Sun Grant Center with funds provided by the U.S. Department of Transportation Research and Innovative Technology Administration (DTOS59-07-G-00050).