1. Production of Gasoline Components from Synthesis Gas ChE 397 Senior Design Group Alpha Ayesha Rizvi Bernard Hsu Jeff Tyska Mohammad Shehadeh Yacoub Awwad 2011.04.26

2. Overview  Process Basics  Block Flow Diagram  Plant and Equipment Layout  General Economics  Conclusions and Further Improvements

3. Our Process H2H2

4. Process Equation 2H 2 + CO ZSM-5 C 5 + + H 2 O + LPG (C3/C4)

5. Why Gasoline and Mobil Process?  Existing infrastructure  Established and high demand product  Great amount of C5+ gasoline in the final product  Lower Gasoline Price  Reduced Sox/GHG emissions  Easy to scale  Renewable feedstock  Energy Independence SO 2

6. Competing Processes  Fischer-Tropsch  Oil  Tar Sands (2n+1) H 2 + n CO → C n H(2n+2) + n H 2 O http://portland.indymedia.org/media/image s/2010/12/404850.jpg http://tonto.eia.doe.gov/country/index.cfm?view=production 43%

7. Process Summary  Syngas  Methanol  Methanol  Water/Hydrocarbons  Water/Hydrocarbons  Water + Hydrocarbons  Hydrocarbons  Gasoline and Liquefied Petroleum Gas (LPG)

8. Block Flow Diagram Methanol Reactor CO H2H2 MeOH H 2, CO Cooling and Separation MeOH H 2, CO Methanol to Gasoline (MTG) Reactors Water Separation Hydrocarbons Water Hydrocarbons Deethanizer (Dist. Col.) C1/C2 Distillation Columns Heavy Hydrocarbons Liquefied Petroleum Gas Gasoline Purge

9. Methanol Reactor Cooling and Separation T (518F) P (725psi) CO 15,967 lbmol/hr H2 31,935 lbmol/hr T (518F) P (725psi) CO 23,059 lbmol/hr H2 58,373 lbmol/hr MeOH 15,948 lbmol/hr T (345F) P (725psi) CO 22,464 lbmol/hr H2 57,182 lbmol/hr MeOH 576 lbmol/hr T (518F) P (725psi) CO 23,059 lbmol/hr H2 58,373 lbmol/hr MeOH 15,948 lbmol/hr T (364F) P (435psi) T (364F) P (435psi) MeOH 5 lbmol/hr CO 136 lbmol/hr H2 23 lbmol/hr Rec Syngas Syngas Syngas & MeOH Syngas MeOH

10. Methanol to Gasoline (MTG) Reactors Water Separation T (716F) P (362psi) H2O 15,111 lbmol/hr L.G(C1,C2) 211.8 lbmol/hr LPG(C3,C4) 792.5 lbmol/hr C5+(gasoline)2290.8 lbmol/hr MeOH 5 lbmol/hr T (364F) P (435psi) H2O 15,109 lbmol/hr T (305F) P (72psi) H2O 2 lbmol/hr L.G(C1,C2) 211.8 lbmol/hr LPG(C3,C4) 792.5 lbmol/hr C5+(gasoline)2290.8 lbmol/hr T (68F) P (391psi) MeOH Hydrocarbons/ Water Water Hydrocarbons

11. Deethanizer (Dist. Col.) Distillation Columns H2O 2 lbmol/hr L.G(C1,C2) 211.8 lbmol/hr LPG(C3,C4) 792.5 lbmol/hr C5+(gasoline)2290.8 lbmol/hr L.G(C1,C2) 209.2 lbmol/hr LPG(C3,C4) 121.5 lbmol/hr C5+(gasoline) 0.02 lbmol/hr H2O 2 lbmol/hr LPG(C3,C4) 670 lbmol/hr C5+(gasoline)2290.1 lbmol/hr T (68F) P (391psi) T (71F) P (391psi) T (365F) P (363psi) H2O 1.3 lbmol/hr LPG(C3,C4) 663 lbmol/hr C5+(gasoline)485 lbmol/hr H2O 0.30 lbmol/hr LPG(C3,C4) 7.6 lbmol/hr C5+(gasoline)1,805 lbmol/hr T (101F) P (96psi) T (77F) P (73psi) GasolineLPG C1/C2 Heavy Hydrocarbons

12. Design Basis  6000 Short tons syngas/day  518 °F (270 °C)  725 psi (5 Mpa)  Product  Gasoline – 15,974 barrels/day  LPG – 4,263 barrels/day

13. MTG Reactor Sizing   10 Ft/Sec

14. General Plant Layout

15. Site Plan

16. Process Building

17. Economics  Capital Cost = $374 Million  Syngas cost = $250/ton  Gasoline Sold at $2.75 / gallon  LPG sold at $1.00 / gallon  Plant is profitable  30% IRR  $1.473 billion NPV  $104 Million in profit / year

18. Gasoline Price Dependence

19. Future of the Mobil Process  Coal to gasoline  Plants are starting to be built  Primus Green – Pennsylvania  Biomass to Gasoline  South Dakota – New plant in 2012

20. Process Overview  6000 Short Tons / Day Syngas Feed  Gasoline- 15,974 barrels/day @ $2.75/gal  LPG – 4,263 barrels/day @ $1.00/gal  Newton County, Indiana  Adjacent to Gasification Plant  Plant is profitable  Capital Cost = $374 Million  Syngas cost = $250/ton  30% IRR  $1.473 billion NPV  $104 Million in profit / year

21. Conclusions & Further Improvements Further Improvements  Reacting out Durene to increase gasoline quality.  Alkylation of C4 olefins.  Air coolers to reduce cooling water loads.  New methods of catalyst regeneration for ZSM-5.  Different distillation column set-ups.  Pinch analysis for the process. Durene

22. Questions From Last Presentation  Our catalyst regeneration for the MTG results in higher alcohols. Is this okay?  Yes, they will also be converted to gasoline components  You should decouple the reboiler heat duty from the flow of the feed to the distillation columns  We will be using bias control

23. Important References  Phillips, S. D., Tarud, J. K., Biddy, M. J., & Dutta, A. (2010, January). Gasoline from Wood via integrated gasification, synthesis and methanol to gasoline technology. Retrieved from nrel.gov: http://www.nrel.gov/docs/fy11osti/47594.pdf http://www.nrel.gov/docs/fy11osti/47594.pdf  (1994). Kirk-Othmer Encyclopedia of Chemical Technology. In Volume 22 (pp. p 166-168).  Exxon Mobil Research and Engineering. (2009). Methanol to Gasoline: Production of clean gasoline from coal.  Kooy, P., & Kirk, D. C. (n.d.). The production of methanol and gasoline. Retrieved from http://nzic.org.nz/ChemProcesses/energy/7D.pdf Questions?