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1 Auburn UniversityBiomass Refining CAFI Corn stover Wood chip Bagasse Rice straw Sawdust Biomass Ethanol Fuel
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2 Auburn UniversityBiomass Refining CAFI Comparison among various feedstock Lose lot of sugars In liquid stream/Low pretreatment yield (considering solid only) Very hard to treat Optimum Corn Stover Low Lignin Hybrid Poplar High Lignin Hybrid Poplar (Courtesy: US-DOE website) http://www.eere.energy.gov/biomass/progs/search1.cgi
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3 Auburn UniversityBiomass Refining CAFI Substrate Dependency on the Effect of Pretreatment by Aqueous Ammonia Rajesh Gupta, Tae Hyun Kim and Y. Y. Lee Department of Chemical Engineering Auburn University
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4 Auburn UniversityBiomass Refining CAFI Outline Difference in physical & chemical features of biomass responsible for different results in pretreatment. Effect of xylanase supplementation on ARP treated biomass. How the cellulosic part in biomass affected during different pretreatment.
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5 Auburn UniversityBiomass Refining CAFI Comparison among various feedstock Low lignin Poplar seems the best choice among three feed stocks.
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6 Auburn UniversityBiomass Refining CAFI Corn Stover Low Lignin PoplarHigh Lignin Poplar Comparison among various feedstock
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7 Auburn UniversityBiomass Refining CAFI Processes with Ammonia SAA (Soaking in Aqueous Ammonia) Batch Reactor Low Temperature Long Pretreatment time (several hours) ARP (Ammonia Recycle Percolation) Flowthrough Reactor High Temperature Short Pretreatment time (several min.)
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8 Auburn UniversityBiomass Refining CAFI Effect of SAA treatment Treatment Conditions: 15% Ammonia, 1:6 S:L & 12 hrs soaking time Enzyme Loading: Cellulase (15FPU/g glucan) + Cellobiase (30CBU/g glucan)
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9 Auburn UniversityBiomass Refining CAFI Effect of SAA treatment Treatment Conditions: 15% Ammonia, 1:10 S:L & 24hrs soaking time Effective treatment temperature for SAA is much higher for Hybrid poplar than Corn stover. Enzyme Loading: Cellulase (15FPU/g glucan) + Cellobiase (30CBU/g glucan)
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10 Auburn UniversityBiomass Refining CAFI Effect of SAA treatment In comparison to Corn stover, higher delignification / xylan removal is required in case of High lignin Poplar for attaining the good digestibility. ~15-20% Xylan removal ~50% Delignification Enzyme Loading: Cellulase (15FPU/g glucan) + Cellobiase (30CBU/g glucan)
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11 Auburn UniversityBiomass Refining CAFI ARP (Ammonia Recycle Percolation) Treatment Optimum chosen treatment condition: Corn Stover: Temperature : 170°C Reaction time : 20min. Ammonia Conc.: 15% Liquid : Solid : 3.33 : 1 Hybrid Poplar: Temperature : 185°C Reaction time : 27.5min. Ammonia Conc.: 15% Liquid : Solid : 3.667 : 1
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12 Auburn UniversityBiomass Refining CAFI Effect of ARP Treatment (15FPU + 30 CBU)
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13 Auburn UniversityBiomass Refining CAFI Effect of Reaction time on Hybrid Poplar (High Lignin Poplar) during ARP treatment
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14 Auburn UniversityBiomass Refining CAFI Effect of Ammonia flow on Hybrid Poplar (High Lignin Poplar) during ARP treatment Digestibility seems more sensitive towards xylan removal than delignification.
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15 Auburn UniversityBiomass Refining CAFI Effect of Temperature on Hybrid Poplar (High Lignin Poplar) during ARP treatment
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16 Auburn UniversityBiomass Refining CAFI Effect of Temperature on Hybrid Poplar (Low Lignin Poplar) during ARP treatment Enzyme Loading: Cellulase (15FPU/g glucan) + Cellobiase (30CBU/g glucan) Increase of temperature from 170°C to 185°C does not affect xylan/lignin removal, but increases cellulase accessibility to cellulosic part in biomass
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17 Auburn UniversityBiomass Refining CAFI Effect of xylanase supplementation on ARP treated Corn Stover Enzyme Loading: C+β-G : Cellulase (15FPU/g glucan) + Cellobiase (30CBU/g glucan) C+ β-G +X : Cellulase (15FPU/g glucan) + Cellobiase (30CBU/g glucan) + Xylanase (31.3mg protein/g glucan) Xylan DigestibilityGlucan Digestibility
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18 Auburn UniversityBiomass Refining CAFI Effect of xylanase supplementation on Glucan Digestibility of Hybrid Poplar High Lignin Poplar Low Lignin Poplar Enzyme Loading: C+β-G : Cellulase (15FPU/g glucan) + Cellobiase (30CBU/g glucan) C+ β-G +X : Cellulase (15FPU/g glucan) + Cellobiase (30CBU/g glucan) + Xylanase (31.3mg protein/g glucan)
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19 Auburn UniversityBiomass Refining CAFI Enzyme Loading: C+β-G : Cellulase (15FPU/g glucan) + Cellobiase (30CBU/g glucan) C+ β-G +X : Cellulase (15FPU/g glucan) + Cellobiase (30CBU/g glucan) + Xylanase (31.3mg protein/g glucan) High Lignin Poplar Low Lignin Poplar Effect of xylanase supplementation on Xylan Digestibility of Hybrid Poplar Near 100% Glucan & xylan digestibility can be achieved for ARP treated Low lignin Poplar with xylanase supplementation.
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20 Auburn UniversityBiomass Refining CAFI Effect of xylanase loading Cellulase loading: 15FPU/g glucan β-G loading : 30CBU/g glucan In ARP treated Low lignin Poplar, there is some easily digestible xylan. In High lignin Poplar, minimum amount of xylan removal is required for better accessibility of cellulase.
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21 Auburn UniversityBiomass Refining CAFI Basis: 100g dry biomass Enzyme Loading Without xylanase : Cellulase (15FPU/g glucan) + Cellobiase (30CBU/g glucan) With xylanase : Cellulase (15FPU/g glucan) + Cellobiase (30CBU/g glucan) + Xylanase (31.3mg protein/g glucan) Yield from different ARP treated Biomass * Processing of liquid stream is eliminated. * High fermentation efficiency due to absence of inhibitor/toxins * There is a need to increase the xylanase activity in cellulase * Low pretreatment severity/Low pretreatment cost
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22 Auburn UniversityBiomass Refining CAFI Treatment Conditions : ARP treatment: 15% NH 3, 175°C & 20min Rx. Time (Flow through) Acid treatment: 0.05% H 2 SO 4, 175°C & 30min Rx Time (Batch) How Cellulose is Affected in Pretreatment
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23 Auburn UniversityBiomass Refining CAFI How Cellulose is Affected in Pretreatment Enzyme loading: 15FPU Cellulase + 30CBU β-G
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24 Auburn UniversityBiomass Refining CAFI How Cellulose is Affected in Pretreatment
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25 Auburn UniversityBiomass Refining CAFI How Cellulose is Affected in Pretreatment Untreated Cotton(77.1) ARP treated Cotton(83.4) Acid treated Cotton(81.35) XRD Plots Lower CrystallinityMore Endo glucanase action Higher Digestibility (a.u.)
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26 Auburn UniversityBiomass Refining CAFI How Cellulose is Affected in Pretreatment Any pretreatment reagent( Ammonia/Acid) first attacks the amorphous part of cellulose & increase the crystallinity. Ammonia, being a weak base, cannot hydrolyse the crystalline part of cellulose and removes very little cellulose. H 2 SO 4, being a strong acid, hydrolyze the crystalline cellulose as well and that’s why more cellulose is lost into liquid. Ammonia Does not affect Cellulosic part in biomass Better sugar yield in pretreatment
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27 Auburn UniversityBiomass Refining CAFI Summary Lignin/xylan content plays an important role in pretreatment of lignocellulosic biomass. Without xylanase supplementation, the overall sugar yield with ARP treatment is seen in the order: Corn Stover > Low-lignin poplar > High-lignin poplar (~68%) (~61%) (~43%) With xylanase supplementation, the overall sugar yield with ARP treatment is seen in the order: Low-lignin poplar> Corn Stover> High-lignin poplar (~90%) (~73%) (~62%)
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28 Auburn UniversityBiomass Refining CAFI Summary Without xylanase supplementation, a certain degree of xylan/lignin removal is necessary in pretreatment to achieve acceptable level of digestibility. With xylanase supplementation, high digestibility and overall yield can be attained without removing much xylan/lignin during the ARP treatment. Higher xylanase activity in cellulase will improve the overall yield and economics of cellulosic ethanol process drastically.
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29 Auburn UniversityBiomass Refining CAFI Future Work To compare the economics of following two bio-ethanol production processes using ARP pretreatment: *Severe pretreatment conditions/Processing of liquid stream/No xylanase supplementation *Mild pretreatment conditions/No sugars in liquid stream/ xylanase supplementation To optimize the ARP pretreatment conditions for different feedstocks with xylanase supplementation. To characterize the changes in biomass during ARP pretreatment using FTIR.
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30 Auburn UniversityBiomass Refining CAFI Acknowledgements US Department of Energy Office of the Biomass Program, Contract DE-FG36-04GO14017 CAFI Team: *University of California, Riverside *Michigan State *Purdue *Texas A&M *University of British Columbia *National Renewable Energy Laboratory Genencor International
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