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

2. Group Members and Roles
Jeffrey Tyska
Group Leader
Ayesha Rizvi
Research
Bernard Hsu
Technical Writer
Mohammed Shehadeh
Webmaster
Yacoub Awwad
Calculation Expert

3. Gasoline Prices All Time High: $4.11/gal General Increasing Trend

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

5. World Oil Production Peak World Production

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?
Existing infrastructure
Established demand
Reduced SOx emissions
Fairly easy to scale
Fairly renewable feedstock
Energy Independence

8. Environmental Review

9. Competing Processes Fischer-Tropsch Oil Tar Sands 43%
(2n+1) H2 + n CO → CnH(2n+2) + n H2O
43%

10. Syngas to Methanol 2H2 + CO Synthesis + + + Dimethyl Ether Dehydration
(Alumina Catalyst)
Dimethyl Ether
2H2 + CO
Synthesis
The compressed synthesis gas enters the converter reactor containing copper zinc and catalyst and the synthesis reaction occurs, according to the equation:
2𝐻 CO CH3OH ∆rH = -92 kJ 𝑚𝑜𝑙 −1
This reaction is highly exothermic and the low temperatures and increasing pressure favors the conversion to methanol formation.
The final conditions used involve a copper oxide based catalyst at about 5 MPa (50 atmospheres) pressure and about 270ºC. + + +

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

12. Zeolite Socony Mobil 5 Isomerization 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
download_lo_res.html?id=

13. Gasoline grade High Quality Similar Properties Very low Sulfur
2% Durene

14. 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.

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 CO Methanol to Gasoline Reactors Methanol Reactor
DME CO
Light Gas
Methanol to Gasoline Reactors
MeOH
Methanol
Reactor
DME Reactor
H2O H2
MeOH
H2O, trace contaminants
Crude Gasoline
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
download_lo_res.html?id=

19. Oil Consumption in the USA
20,802,162 (2005)
18,686,223 (2009)

20. Gasoline Storage Blending Dist Col. 3 Dist Col. 2 Dist Col. 1
Syngas
MeOH reactor 270 C, 5 MPa
H2, CO, CO2, H2O
Crude MeOH
DME Reactor
Cooler
Flash separator
MeOH
CO, H2, CO2
Hot Effluent
Cooled Effluent
Additives
Gasoline Storage *1 *1
MTG *1
MTG *1
MTG *1
MTG
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
Dist Col. 3
Cooler
Dist Col. 2 *2
Dist Col. 1
HVP Gasoline
Treated Heavy Gasoline
Liquid HC
Durene Reactor H2
*1 – MTG Reactors
*2 – Mix of gas, water and light HCs
*3 – Boilers and Condensers not included *3 *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
download_lo_res.html?id=

23. Syngas to Methanol
The overall reaction in which methanol is produced from synthesis gas is summarized by the following equation:
𝐂𝐎 𝟐 + 𝐂𝐎+ 𝟓𝐇 𝟐 → 𝟐𝐂𝐇 𝟑 𝐎𝐇 + 𝐇 𝟐 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.
Cu-Zn
The compressed synthesis gas enters the converter reactor containing copper zinc and catalyst and the synthesis reaction occurs, according to the equation:
2𝐻 CO CH3OH ∆rH = -92 kJ 𝑚𝑜𝑙 −1
This reaction is highly exothermic and the low temperatures and increasing pressure favors the conversion to methanol formation.
The final conditions used involve a copper oxide based catalyst at about 5 MPa (50 atmospheres) pressure and about 270ºC.

26. Methanol as a Feedstock
Different Sources of Methanol
Natural Gas
Coal
Biomass Conversion to Syn-Gas ( Partial Oxidation)
Municipal Solid Waste
Why Syn Gas to make Methanol ?
More Economical
Better Methanol Purity
More Efficient