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