Synthesis Gas to Gasoline ProductionChE 397 Senior DesignGroup Alpha
Ayesha RizviBernard HsuJeff TyskaMohammed ShehadehYacoub Awwad
2011.01.25
Group Members and Roles
Jeffrey Tyska Group Leader
Ayesha Rizvi Research
Bernard Hsu Technical Writer
Mohammed Shehadeh Webmaster
Yacoub Awwad Calculation Expert
Gasoline Prices
All Time High: $4.11/gal
http://www.eia.doe.gov/petroleum/data_publications/wrgp/mogas_home_page.html
General Increasing Trend
Defeyes, Kenneth S. Hubbert's Peak: the Impending World Oil Shortage. Princeton: Princeton UP, 2003. 113-131.
Peak Production 1970
World Oil Production
http://www.princeton.edu/hubbert/images/cera-chart.gif
Peak World Production
Methanol as a Feedstock Different Sources of Methanol
Natural Gas
CoalBiomass Municipal
Solid Waste
Why Syn Gas to make Methanol ?
Economical Efficient
Why Gasoline and Mobil Process?
Existing infrastructure Established demand Reduced SOx emissions Fairly easy to scale Fairly renewable feedstock Energy Independence
SO2
Environmental Review
http://www.usstcorp.com/solutions-environment.html
Competing Processes Fischer-Tropsch
Oil
Tar Sands
(2n+1) H2 + n CO → CnH(2n+2) + n H2O
http://portland.indymedia.org/media/images/2010/12/404850.jpg
http://tonto.eia.doe.gov/country/index.cfm?view=production
43%
Syngas to MethanolDehydration(Alumina Catalyst)
Dimethyl Ether
2H2 + CO
Synthesis
+ + +
2
Process Equations
ZSM-5
CH3OCH3 + H2O
dehydration
C5+ + H2O
Possible alternative fuel
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
http://image.absoluteastronomy.com/images/topicimages/z/zs/zsm-5.gif
Methane diffusion through zeolite catalysthttp://www.sciencephoto.com/images/download_lo_res.html?id=655060020
Gasoline grade
High Quality Similar
Properties Very low Sulfur 2% Durene
http://www.exxonmobil.com/Apps/RefiningTechnologies/files/sellsheet_09_mtg_brochure.pdf
Highly Exothermic
High concentration of durene that causes carburetor “icing”
Catalyst aging • Reversible- caused by coked catalyst• Irreversible- caused by the steam
Band aging• Allows the reactant to break through the bed unconverted
Unconverted methanol may be lost from dissolving in water
Inability to directly produce diesel and jet fuel.
Constraints of the MTG process
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
Block Flow Diagram
Methanol
Reactor
Wastewater
treatment
H2O, trace contaminants
CO
H2
MeOH DME
Reactor
Methanol to Gasoline Reactors
DME
H2O
MeOH
Distillation Columns
H2Heavy GasolineDurene
Reactor
Light Gasoline
HVP Gasoline
Heavy Gasoline (less durene)
StorageBlending
Additives
Final Storage
To consumer or refineries for final blending
Crude Gasoline
Light Gas
End!
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 catalysthttp://www.sciencephoto.com/images/download_lo_res.html?id=655060020
Oil Consumption in the USA
http://tonto.eia.doe.gov/country/country_energy_data.cfm?fips=US
18,686,223 (2009)
20,802,162 (2005)
MeOH reactor 270
C, 5 MPa
Syngas H2, CO, CO2, H2O
MeOHCooler
CO, H2, CO2
Crude MeOHFlash
separatorDME
Reactor
MTG
MTG
MTG
MTG
Hot EffluentCooled Effluent
Cool Effluent
Separator
Cooler
Water
Recycle Gas
Liquid HC
Liquid HC
Dist Col.
1
Dist Col.
2
Liquid HC
Cooler *2
*1 *1 *1 *1 *1
LPG
Dist Col.
3
Liquid HC
HVP Gasoline
HVP Gasoline
HVP Storage
Light Gasoline
Light Gasoline Storage
Durene Reactor
Heavy Gasoline
H2
Treated Heavy Gasoline
Heavy Gasoline Storage
Blending
Additives
Gasoline Storage
*1 – MTG Reactors*2 – Mix of gas, water and light HCs*3 – Boilers and Condensers not included
*3*3 *3
Gasoline
For Sale
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
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 catalysthttp://www.sciencephoto.com/images/download_lo_res.html?id=655060020
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
http://www.scribd.com/doc/7140653/Reactions-of-Synthesis-Gas
http://www.scribd.com/doc/7140653/Reactions-of-Synthesis-Gas