Production of Gasoline Components from Synthesis Gas ChE 397 Senior Design Group Alpha Ayesha Rizvi Bernard Hsu Jeff Tyska Mohammed Shehadeh Yacoub Awwad

Recap H2H2

Block Flow Diagram Methanol Reactor Wastewater treatment H 2 O, trace contaminants CO H2H2 MeOH DME Reactor Methanol to Gasoline Reactors DME H2OH2O MeOH Distillation Columns Heavy Gasoline Light Gasoline Storage Crude Gasoline Light Gas

Overall Flowsheet Mass Balance Basis: 3307 Tons per Day Syn Gas

Syngas to Methanol CO: lbmol/hr H 2 : lbmol/hr CO: lbmol/hr H 2 : lbmol/hr CO: lbmol/hr H 2 : lbmol/hr Mass Balance Basis: 3307 Tons per Day Syn Gas MeOH: lbmol/hr

DME reaction MeOH: lbmol/hr MeOH: lbmol/hr DME and H 2 O: lbmol/hr Mass Balance Basis: 3307 Tons per Day Syn Gas

Methanol to Gasoline Effluent: lbmol/hr

After the MTG Reaction

Cooling Separator

End Refining LPGPRG

Final Recycle

Material Balance Methanol Reactor

Material Balance DME Reactor

Material Balance Component Profile Assumptions 1.All H2 is taken away in the light gas 2.All CH4 is taken away in the light gas 3.All ethane is taken away in the light gas 4.30% of the propane is taken away in the light gas 5.None of the butane is taken away in the light 6.All CO/CO2 is lost in the light gas 7.All water is immiscible with the other components, leaves completely 8.Remaining components are in the second liquid phase Continued above

Liquid Hydrocarbon Components

Material Balance LPG Flowrates Assumptions 1.All of the remaining propane goes out the vapor stream 2.All of the remaining butane goes out the vapor stream 3.10% of the pentane goes out the vapor stream 4.The liquid component out the stripper is our final product

Material Balance Product Composition

Energy Balance rxn MeOH DME H2O Heat of formation: ΔHF= m DME,out ΔHF(DME)+m MeOH,out ΔHF(MeOH)+ m H2O,out ΔHF(H 2 O)- m MeOH,in ΔHF(MeOH) = ΔHF=Σm*cp*(Tout-Tin)+Q Q:heat loss to surroundings Tin=590°F MM Btu/hr

Energy Balance  At heat loss of 3400 Btu Tout= 860 °F Heat loss to surroundings negligible  Reactor Sizing: PV=nRT V=315.6 Ft 3 diameter d=8 Ft, height h=25 Ft considering the reactor as a cylinder Area=2*pi*(d/2)*h+2*pi*(r 2 /4) =729 Ft 2  Residence Time: 5 seconds for MeOH and Durene Reactor. 10 seconds for MTG Reactors.

Equipment Costs

What affects the Gasoline Prices  Seasonal Switch in Gasoline blends  Crude Oil Cost  Taxes and Fees  Supply and Demand  Transportation and Distribution Cost Pricing Gasoline ad/PumpPriceUpdate.pdf

Economics of Oil  For 2011, crude oil is averaged out to be $93 per barrel $2.21 per gallon  Average gasoline price in the city of Chicago is $3.29 per gallon  Nationwide the average is $3.13 per gallon  Our gasoline price with low olefin and low Durene is roughly about $ 2.63 per gallon

Economics of Products  Average gasoline price in the city of Chicago is $3.29 per gallon  Nationwide the average is $3.13 per gallon  Our gasoline price with low olefin and low Durene is roughly about $ 2.63 per gallon  Product: $84.6 Million / year  LPG : $5.4 Million / year

Major Components of Gasoline Components Total Percentage Composition n-AlkanesC 5, C 6, C 7, C 9, C 10 - C % Branched AlkanesC 4, C 5, C 6, C 7, C 8, C 9, C 10 -C % CycloalkanesC 6, C 7, C 8 5.0% OlefinsC6C6 1.8% AromaticsBenzene, Toluene, Xylenes, Ethylbenzene, C 3 – Benzenes, C 4 - Benzenes 30.5%

Properties of Gasoline Blends Octane Number (MON/RON)ranges (83/96 – 90/102) Reid Vapor Pressure (psi)ranges (5 - 12) Final Boiling Point (°C)ranges ( ) Sulfur (ppm)ranges ( ) Mixtures of C5-C10 Hydrocarbons Major Components of Gasoline

Newton County MTG Process, IN Refinery Joliet, IL Refinery Whiting, IN

Transporting to Refineries  Key supplier of refined petroleum products to the Midwest.  250,000 barrels of crude per day  Produces ~9 million gallons of gasoline, diesel fuel/day. Joliet, IL _brochure.pdf Whiting, IN  405,000 barrels of raw crude oil/day  Produce 15 million gallons refining products.  Whiting Refinery Modernization Project yId= &contentId= #

Transport of Gasoline  Pipeline transport  Railroad transport  Gasoline truck transportation

Major Blending Components of Gasoline: - Total of n-Alkanesabout 17.3% - Total of Branched Alkanesabout 32.0% - Total of Cycloalkanesabout 5.0% - Total of Olefinsabout 1.8% - Total of Aromaticsabout 30.5% Gasoline Blending Components

Our Gasoline’s Composition

Gasoline Blending Conversion process in petroleum refining Fluid Catalytic Cracker (FCC) AlkylateCatalytic Reforming Cracking hydrocarbons by vaporization breaking long chained high- boiling hydrocarbon molecules presence of a fluidized powdered catalyst Isobutane is alkylated with low molecular weight alkenes presence of a strong acid catalyst sulfuric acid or hydrofluoric acid Petroleum refinery naphtha low octane high octane liquid products

Questions from Presentation 1  Catalysts: How long do they last?  ZSM-5: Pressure and temp (305 psi, 350ºC) is 52 days  Is gasoline >10% olefins?  No, our product is 3.73 wt% olefins.  May change with other conditions

Durene  High melting point  3-6% from literature  2% Limit  1% in our gasoline  Blending  Other Methods

End!

Questions From Last Presentation  Removal of the water is desirable because the catalyst may tend to become deactivated by the presence of the water vapor at the reaction temperatures employed, but this step is by no means essential

Sulfuric Acid Alkylation  The Alkylation reaction combines Isobutane with light Olefins primarily a mix of Butylene and Propylene in the presence of a strong acid catalyst, Sulfuric Acid  This process results in upgrading the gasoline blend to a high octane blending component.  Low Olefin Content (3.73 wt%)