Synthesis Gas to Gasoline Production

1. Synthesis Gas to Gasoline Production ChE 397 Senior Design Group Alpha Ayesha Rizvi Bernard Hsu Jeff Tyska Mohammed Shehadeh YacoubAwwad 2011.01.25

2. Group Members and Roles

3. Gasoline Prices All Time High: $4.11/gal General Increasing Trend http://www.eia.doe.gov/petroleum/data_publications/wrgp/mogas_home_page.html

4. Peak Production 1970 Defeyes, Kenneth S. Hubbert's Peak: the Impending World Oil Shortage. Princeton: Princeton UP, 2003. 113-131.

5. World Oil Production Peak World Production http://www.princeton.edu/hubbert/images/cera-chart.gif

6. Methanol as a Feedstock • Different Sources of Methanol Natural Gas Biomass Municipal Solid Waste Coal Why Syn Gas to make Methanol ? Economical Efficient

7. Why Gasoline and Mobil Process? SO2 • Existing infrastructure • Established demand • Reduced SOx emissions • Fairly easy to scale • Fairly renewable feedstock • Energy Independence

8. Environmental Review http://www.usstcorp.com/solutions-environment.html

9. Competing Processes (2n+1) H2 + n CO → CnH(2n+2) + n H2O • Fischer-Tropsch • Oil • Tar Sands 43% http://portland.indymedia.org/media/images/2010/12/404850.jpg http://tonto.eia.doe.gov/country/index.cfm?view=production

10. Syngas to Methanol Dehydration (Alumina Catalyst) Dimethyl Ether 2H2 + CO Synthesis + + +

11. Possible alternative fuel Process Equations dehydration 2 CH3OCH3 + H2O ZSM-5 C5+ + H2O

12. Zeolite Socony Mobil 5 • First synthesized in 1972 • U. S. Patent 3,702,886 (Mobil Oil Company 1975) • NanAlnSi96–nO192·16H2O (0<n<27) • Pentasil unit = 8 five-membered rings • Isomerization Methane diffusion through zeolite catalyst http://www.sciencephoto.com/images/ download_lo_res.html?id=655060020 http://image.absoluteastronomy.com/images/topicimages/z/zs/zsm-5.gif

13. Gasoline grade • High Quality • Similar Properties • Very low Sulfur • 2% Durene http://www.exxonmobil.com/Apps/RefiningTechnologies/files/sellsheet_09_mtg_brochure.pdf

14. Constraints of the MTG process • Highly Exothermic • High concentration of durenethat causes carburetor “icing” • Catalyst aging • Reversible- caused by coked catalyst • Irreversible- caused by the steam • Band aging • Allowsthe reactant to break through the bed unconverted • Unconverted methanol may be lost from dissolving in water • Inabilitytodirectlyproduce diesel and jet fuel.

15. Scale • 1800 metric tons syngas / day • 900 metric tons gasoline / day • Newton County Landfill • 265 Acres • Next to gasifier • 50-60% plant thermal efficiency • Losses mainly from methanol production

16. Block Flow Diagram DME Light Gas CO Methanol to Gasoline Reactors MeOH H2O Methanol Reactor DME Reactor H2 MeOH Crude Gasoline H2O, trace contaminants Heavy Gasoline Wastewater treatment H2 Durene Reactor Distillation Columns HVP Gasoline Light Gasoline Heavy Gasoline (less durene) Final Storage Blending Storage To consumer or refineries for final blending Additives

17. End!

18. ZSM-5 • In the 1970's, Mobil synthesized a new zeolite catalyst (ZSM-5), which became a key element in the MTG process. • Zeolites are porous, crystalline materials with three dimensional framework composed of AlO4 and SiO4 tetrahedral. • ZSM-5 catalyst produces the right kind of shape and size selectivity properties suitable for gasoline synthesis. Methane diffusion through zeolite catalyst http://www.sciencephoto.com/images/ download_lo_res.html?id=655060020

19. Oil Consumption in the USA 20,802,162 (2005) 18,686,223 (2009) http://tonto.eia.doe.gov/country/country_energy_data.cfm?fips=US

20. H2, CO, CO2, H2O Syngas MeOH reactor 270 C, 5 MPa Crude MeOH DME Reactor Flash separator Cooler MeOH CO, H2, CO2 Hot Effluent Cooled Effluent Additives MTG MTG MTG *1 *1 MTG Gasoline Storage *1 *1 *1 Separator Gasoline Blending Water HVP Storage Liquid HC Cooler Light Gasoline Storage HVP Gasoline Cool Effluent For Sale Recycle Gas Liquid HC Heavy Gasoline Storage Light Gasoline LPG Cooler Dist Col. 2 *2 Dist Col. 1 Dist Col. 3 HVP Gasoline Liquid HC Treated Heavy Gasoline Durene Reactor H2 *3 *1 – MTG Reactors *2 – Mix of gas, water and light HCs *3 – Boilers and Condensers not included *3 *3 Liquid HC Heavy Gasoline

21. Environmental Review • Production of methanol from synthesis gas generates a limited pressure to the environment. • Methanol is a compound of relative low toxicity. • All plant waste effluents will be regularly analyzed and checked to meet environmental restrictions and conditions. Environmental & Global Safety sintankimya.com

22. ZSM-5 Catalyst • In the 1970's, Mobil synthesized a new zeolite catalyst (ZSM-5), which is a key element in the MTG process. • Zeolites are porous, crystalline materials with three dimensional framework composed of AlO4 and SiO4 tetrahedral. • ZSM-5 catalyst produces an unusual shape and has size selectivity properties suitable for gasoline synthesis. Methane diffusion through zeolite catalyst http://www.sciencephoto.com/images/ download_lo_res.html?id=655060020

23. Syngas to Methanol • The overall reaction in which methanol is produced from synthesis gas is summarized by the following equation: + + → + + heat • Cu-Zn is the Copper – Zinc Catalyst used in the reaction. • The methanol produced contains a large range of impurities which have to be removed to produce methanol of chemical grade quality. • In addition, side reactions occur during methanol production, such as the generation of higher alcohols (ethanol, propanol, butanol) and alkanes. • http://nzic.org.nz/ChemProcesses/energy/7D.pdf Cu-Zn

24. http://www.scribd.com/doc/7140653/Reactions-of-Synthesis-Gas

25. http://www.scribd.com/doc/7140653/Reactions-of-Synthesis-Gas