Synthesis Gas
to Gasoline
Production
ChE 397 Senior Design
Group Alpha
Ayesha Rizvi
Bernard Hsu
Jeff Tyska
Mohammed Shehadeh
Yacoub 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
General
Increasing Trend
http://www.eia.doe.gov/petroleum/data_publications/wrgp/mogas_home_page.html
Peak
Production
1970
Defeyes, Kenneth S. Hubbert's Peak: the Impending World Oil Shortage. Princeton: Princeton
UP, 2003. 113-131.
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
Coal
Biomass
Why Syn Gas to make Methanol ?
Economical
Efficient
Municipal
Solid Waste
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/solutionsenvironment.html
Competing Processes
 Fischer-Tropsch
(2n+1) H2 + n CO → CnH(2n+2) + n H2O
 Oil
 Tar
Sands
43%
http://portland.indymedia.org/media/ima
ges/2010/12/404850.jpg
http://tonto.eia.doe.gov/country/index.cfm?view=production
Syngas to Methanol
Dehydration
(Alumina Catalyst)
Dimethyl Ether
2H2 + CO
Synthesis
+
+
+
Process Equations
Possible
alternative fuel
dehydration
2
CH3OCH3 + H2O
ZSM-5
C5+ + H2O
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/topicima
ges/z/zs/zsm-5.gif
Gasoline grade
 High
Quality
 Similar Properties
 Very low Sulfur
 2% Durene
http://www.exxonmobil.com/Apps/RefiningTechnologies/files/sellsheet_09_mtg_brochure.pdf
Constraints of the MTG process

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.
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
CO
H2
Methanol
Reactor
MeOH
DME
DME
Reactor
H 2O
MeOH
Methanol to
Gasoline
Reactors
Crude
Gasoline
H2O, trace
contaminants
Wastewater
Durene
Reactor
H2
treatment
Heavy Gasoline
(less durene)
Final
Storage
To consumer or
refineries for final
blending
Light
Gas
Blending
Additives
Heavy
Gasoline
Distillation
Columns
HVP
Gasoline
Storage
Light
Gasoline
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 catalyst
http://www.sciencephoto.com/images/
download_lo_res.html?id=655060020
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
Syngas
MeOH
reactor 270
C, 5 MPa
H2, CO, CO2, H2O
MeOH
Crude MeOH
DME
Reacto
r
Flash
separator
Cooler
CO, H2, CO2
Hot Effluent
Cooled Effluent
Additives
*1
Gasoline
Storage
Gasoline
Separator
Blending
Liquid HC
Cooler
HVP Gasoline
Cool Effluent
For Sale
Recycle Gas
Liquid HC
Heavy Gasoline
Storage
Light Gasoline
H2
LPG
*2
Cooler
Treated Heavy Gasoline
*1 – MTG
Reactors
*2 – Mix of gas,
water and light
HCs
*3 – Boilers and
Condensers not
M
*1
T
G
Water
HVP
Storage
Light
Gasoline
Storage
*1
M
T
G
M
*1
T
G
Durene
Reacto
r
Dis
t
Col.
3
HVP Gasoline
*3
Dis
t
Col.
2
*3
Liquid HC
Heavy Gasoline
Liquid HC
Dis
t
Col.
1
*3
M
*1
T
G
Environmental Review
• Production of methanol from synthesis gas
generates a limited pressure to the
environment.
• Methanol is a compound of relative low
toxicity.
Environmental &
• All plant waste effluents will be regularly
analyzed and checked to meet environmental
restrictions and conditions.
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 catalyst
http://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:
𝐂𝐎𝟐 + 𝐂𝐎+ 𝟓𝐇𝟐 Cu-Zn
→ 𝟐𝐂𝐇𝟑 𝐎𝐇 + 𝐇𝟐 𝐎 + 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
http://www.scribd.com/doc/7140653/Reactions-of-Synthesis-Gas
http://www.scribd.com/doc/7140653/Reactions-of-Synthesis-Gas