1. Maizeoline: Biomass to Diesel via Furfural Rebecca Paustian, Stephanie Callahan, Ross Warner, Ryan Felde-Vassallo May 2, 2015

2. What is Biodiesel  Biodiesel is a renewable, clean burning fuel made from plant- based products

3. Importance  6.57 billion barrels of petroleum products consumed in the US in 2013  ~18 million barrels/day  Import ~ 9.3 million barrels/day as of 2014 from 80 different countries  Eventually all known reserves will be depleted

4. Applications and Uses for Biodiesel  Can be used in all diesel engines.  Cleans out engines  Lubricates better then petro-diesel  Was licensed by the California Department of Fish and Game as a shoreline cleaning agent.  Paint and adhesive remover

5. Advantages of Biodiesel  Renewable feedstock  Meets the Clean Air Act Amendments  Comparable energy density and energy content to petro-diesel  Compatible with existing engines  Biodegradable

6. Properties of Biodiesel  Immiscible with water  High flash point  Low vapor pressure

7. Location and Market Opportunities  Plant Location: Spencer, Iowa  Fairly new technology that is being looked by several different companies  Can be blended with petro-diesel  Consumers  US Military  Disneyland  National Parks

8. Approximate Yield from Corn Stover (Mass Percent) 5.5% mass of Corn Stover can be converted into Diesel

9. Block Diagram

10. Biomass to Furfural Furfural Generation Biomass Grinding Furfural Separation Furfural Wastewater Corn Stover Sulfuric acid Ethanol Plant O-nitrotoluene Unused Biomass

11. Furfural Generation  MTC is a novel reactor designed at Delft University of Technology to minimize by-products and improve yield.  Only significant by product is acetic acid  72.7% yield (mass basis)

12. Furfural Separation  NaOH neutralizes the sulfuric acid and generates sodium sulfate ions  O-nitrotoluene is used to remove most of the water in the extraction tower.  Sodium sulfate ions compete with furfural for hydration  improved furfural separation from water  Two vacuum distillation towers isolate furfural from the organic solvent and residual water.

13. Ethanol Production Summary  Recombinant strain of Zymomonas mobilis ferments glucose and pentose sugars into ethanol and CO 2  Recovered as a 99.5% ethanol product  ~150,000 lb/hr is produced

14. Block Diagram

15. Furfural to 2-MethylFuran Furfural Separation/ Purification Reactor Hydrogen Furfural Hydrogen Furfuryl Alcohol 2-MethylFuran Waste Water Vent to Power Plant

16. Reactor  Exothermic Hydrogenation Reaction  Catalyst: Copper Chromite on Activated Charcoal  Temperature: 195-205 ⁰C  Pressure: 1atm  53.3% Yield Copper Chromite + +

17. Separation Process  Flash Drum  Separate Hydrogen from affluent of reactor  Series of 3 Distillation Columns  1 Vapor Liquid Liquid Column  2 for Furfuryl Alcohol Purification

18. Block Diagram

19. C15 Ketone 2-Methylfuran Reactor Water Separation: Decanter Water Recycle 2-Methylfuran Alkylation to C15 Ketone

20. 2-Methylfuran (C 5 H 6 O) + H2OH2O 3 + H2OH2O 2-Methylfuran Alkylation to C15 Ketone Water Is Not Consumed 5,5-bisylvyl-2-pentanone (C 15 H 18 O 3 )

21.  Packed Bed Reactor  60 o C and Atmospheric Pressure  Catalyst: ITQ-2 delaminated zeolite  C15 Ketone = 5,5-bisylvyl-2-pentanone  94% Yield 2-Methylfuran Alkylation to C15 Ketone

22. Block Diagram

23. C15 Ketone Hydrodeoxygenation to Diesel Separation: Decanter C15 Ketone Heat Exchanger Hydrogen Reactor Diesel Byproducts Water Vent Organic Phase Separation: Distillation Diesel Overhead

24.  Packed Bed Reactor  350 o C and 5 MPa  Catalyst: Platinum on Active Carbon  92.6% Yield H2H2 C15 Ketone Hydrodeoxygenation to Diesel 6-butyl Undecane (C 15 H 32 )

25. Byproducts  From Decanter:  Dirty Water  Vented Hydrocarbons  From Distillation:  Gaseous Hydrocarbons  Hydrocarbons = C 1 to C 8 Range  Propane = C 1 to C 4 Representative  n-Hexane = C 5 to C 8 Representative

26. Block Diagram

27. Power Plant Electricity Purge Steam Firing Duty Unused Biomass Combustor Waste Boiler Vent Overhead Vent Turbines Steam Electricity Process To Grid

28. Power Plant  $66 MM Capital Investment  Capture 80% of Firing Duty for Steam  1.6 MM lb/hr Generated (540 o C, 600 psia)  85% Efficient Turbines  180 o C, 145 psia Steam Sent to the MTC  81 MW of Electricity Generated  40 MW to the Grid

29. Aspen Modeling Properties  NRTL Property Method  Joback  Pure Component Estimation  T c, P c, T B, V c, Z c, and DHFORM  UNIFAC  Estimate Missing Activity Coefficients

30. Waste Water Treatment  Ames Water Pollution Control Facility  Uses physical and biological treatment methods  Remove organic materials, solids, ammonia, and meet oxygen demand before discharging to Skunk River  Include a Non-Domestic Waste Pretreatment Program  Total wastewater cost: $12.26 MM per year

31. Feed Stock Analysis  Corn Stover required to meet Biodiesel requirement  7.491 Billion lb/year  Will need approximately 5.853 million bales/year  Area required: ~ 1million acres  Corn Production in Iowa  13.7 million acres

32. Costs Cost DescriptionTotal Cost MM$ Feed Streams $300.3 Capital Cost $163.9 Waste water $12.3 Catalysts $8.5 Total Cost $485.0 o Catalysts and Capital costs are a one time cost. o Yearly cost averages $312.6 MM$

33. Revenue/ Profits DescriptionYearly Profits MM$ Ethanol $470.8 Furfuryl Alcohol $385.9 Biodiesel $209.9 Electricity Credit $22.04 Total Revenue $1,088.7 By-products are the most profitable.

34. Profitability Analysis This process is not very sensitive to changes in interest rates Summary NPV0 $7.23 MMM$ IRR 32% Pay Back Period ~3.0 years NPV10 $2.35 MMM$ IRR19% Pay Back Period~3.7 years NPV12$1.91 MMM$ IRR17% Pay Back Period~3.95 years

35. Conclusion  Feed:  900,000 lb/hr Corn Stover  Production:  50,000 lb/hr Biodiesel  52,000 lb/hr Furfuryl Alcohol  150,000 lb/hr Ethanol  40 MW Electricity  Profits:  1,088 MM$/year  Pay Back Period: 3.7 years  IRR: 19%  This plant is profitable

36. Acknowledgements  John Myers  Joseph Holles  David Bell  BP Energy Bioscience Institute, Berkeley, CA

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