Production of
Gasoline
Components
from Synthesis
Gas
ChE 397 Senior Design
Group Alpha
Ayesha Rizvi
Bernard Hsu
Jeff Tyska
Mohammed Shehadeh
Yacoub Awwad
2011.02.15
Recap
H2
Block Flow Diagram
CO
H2
Methanol
Reactor
MeOH
DME
DME
Reactor
H 2O
MeOH
Methanol to
Gasoline
Reactors
Crude
Gasoline
H2O, trace
contaminants
Wastewater
treatment
Light
Gas
Heavy
Gasoline
Distillation
Columns
Storage
Light
Gasoline
Overall Flowsheet
Mass Balance Basis: 3307 Tons per Day Syn Gas
Syngas to Methanol
MeOH: 8226.65 lbmol/hr
CO: 8611.72 lbmol/hr
H2: 17223.45 lbmol/hr
CO: 141.09 lbmol/hr
H2: 18.48 lbmol/hr
CO: 243.98 lbmol/hr
H2: 594.88 lbmol/hr
Mass Balance Basis: 3307 Tons per Day Syn Gas
DME reaction
MeOH: 8226.65 lbmol/hr
MeOH: 2468.00 lbmol/hr
DME and H2O: 2879.33 lbmol/hr
Mass Balance Basis: 3307 Tons per Day Syn Gas
Methanol to Gasoline
Effluent: 8226.65 lbmol/hr
After the MTG Reaction
Cooling Separator
End Refining
LPGPRG
Final Recycle
Material Balance
Methanol Reactor
In
Syn Gas: CO:
H2:
Recycle: CO:
H2:
8612
17223
12199
29744
Out
lbmol/hr
lbmol/hr
lbmol/hr
lbmol/hr
purge:
CO:
H2:
product: CO:
H2:
244
594.9
141.1
18.48
lbmol
lbmol
lbmol
lbmol
MeOH: 8227 lbmol
2.207505519
Material Balance
DME Reactor
MeOH:
H2O:
2.207505519
In:
8227 lbmol/hr
0 lbmol/hr
MeOH:
H2O:
Out:
2468 lbmol/hr
2879 lbmol/hr
DME:
2879 lbmol/hr
Material Balance
Component Profile
Component lbmol/hr Component lbmol/hr Assumptions
58.87856 1. All H2 is taken away in the light gas
H2
0 C5's
C6's
7.870113 2. All CH4 is taken away in the light
C1
27.55832
C7's
3.148045
gas
CO
0 C8's
1.83636 3. All ethane is taken away in the light
CO2
0 C9's
0.655843
gas
0.131169 4. 30% of the propane is taken away
C2 =
7.873805 C10's
9.610079
in the light gas
C2
8.818661 Benzene
50.32388 5. None of the butane is taken away
C3 =
10.49841 Toluene
C8 AROM
74.84642
in the light
C3
162.3435 C9 AROM
4.842082 6. All CO/CO2 is lost in the light gas
iC4
142.1629 C10 AROM
1.832139 7. All water is immiscible with the
C4 =
10.23595 C11 AROM
other components, leaves
0.261734
completely
0
nC4
42.57285 Methanol
Continued
above
DME
H20
Total
0 8. Remaining components are in the
second liquid phase
2818.389
3444.69
lbmol/hr
Liquid Hydrocarbon
=
Components C3
C3
iC4
C4 =
nC4
C5's
C6's
C7's
C8's
C9's
C10's
Benzene
Toluene
C8 AROM
C9 AROM
C10 AROM
C11 AROM
Total
7.34888
113.64
142.163
10.2359
42.5728
58.8786
7.87011
3.14805
1.83636
0.65584
0.13117
9.61008
50.3239
74.8464
4.84208
1.83214
0.26173
530.2
lbmol/hr
Material Balance
LPG Flowrates
lbmol/hr
C1
C2 =
C2
C3 =
C3
iC4
C4 =
nC4
C5's
Total
0
0
0
7.348884
113.6405
142.1629
10.23595
42.57285
5.887856
321.8489
lbmol/hr
%
0
0
0
2.283334
35.30864
44.1707
3.180358
13.22759
1.829385
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
C5's
C6's
C7's
C8's
C9's
C10's
Benzene
Toluene
C8 AROM
C9 AROM
C10 AROM
C11 AROM
Total
52.9907
7.870113
3.148045
1.83636
0.655843
0.131169
9.610079
50.32388
74.84642
4.842082
1.832139
0.261734
208.3486
lbmol/hr
Energy Balance
MeOH
rxn
ΔHF=Σm*cp*(Tout-Tin)+Q
Heat of formation:
ΔHF= m DME,outΔHF(DME)+m
MeOH
DME
H2O
Q:heat loss to surroundings
Tin=590°F
MeOH,outΔHF(MeOH)+
mH2O,outΔHF(H2O)- mMeOH,inΔHF(MeOH) = -29.2 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 Ft3
diameter d=8 Ft , height h=25 Ft
considering the reactor as a cylinder
Area=2*pi*(d/2)*h+2*pi*(r2 /4)
=729 Ft2
 Residence Time: 5 seconds for MeOH and Durene
Reactor. 10 seconds for MTG Reactors.
Component Name
Component Type
DMEREACT
FLASH-flash vessel
GASMEHX
HCCOOLER
HEATER
HEATEX
MEOHRXN
3PHASESP-flash vessel
ACCMLTR-flash vessel
GASPROD1
GASPROD2
GASPROD3
HCSHEAT
HEATER2
HEATER3
HEATER4
STRIPPER-cond
STRIPPER-cond acc
STRIPPER-reb
STRIPPER-reflux pump
STRIPPER-tower
Catalyst
DAT REACTOR
DVT CYLINDER
DHE FLOAT HEAD
DHE FLOAT HEAD
DHE FLOAT HEAD
DHE FLOAT HEAD
DAT REACTOR
DVT CYLINDER
DVT CYLINDER
DAT REACTOR
DAT REACTOR
DAT REACTOR
DHE FLOAT HEAD
DHE FLOAT HEAD
DHE FLOAT HEAD
DHE FLOAT HEAD
DHE FIXED T S
DHT HORIZ DRUM
DRB U TUBE
DCP CENTRIF
DTW TRAYED
Catalyst
Totals:
Equipment Cost Total Direct Cost
(USD)
(USD)
162000
450000
143000
295100
25900
102000
20200
98200
791300
1.21E+06
47200
157800
170000
450000
47000
178200
42700
155700
2.00E+06
6.00E+06
2.00E+06
6.00E+06
2.00E+06
6.00E+06
16000
77100
14800
77700
14800
77700
14800
77700
15800
77300
13100
69200
13900
69900
4200
30000
89900
243700
10000000
10000000
1.76E+07
USD
3.19E+07
USD
Equipment
Costs
Pricing Gasoline
What affects the Gasoline Prices

Seasonal Switch in Gasoline blends

Crude Oil Cost

Taxes and Fees

Supply and Demand

Transportation and Distribution Cost
http://www.api.org/aboutoilgas/gasoline/uplo
ad/PumpPriceUpdate.pdf
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
Total Percentage
Composition
Components
n-Alkanes
Branched Alkanes
C5, C6, C7, C9, C10C13
17.3%
C4, C5, C6, C7, C8, C9,
C10-C13
32.0%
Cycloalkanes
C6, C7, C8
Olefins
C6
5.0%
1.8%
Aromatics
Benzene, Toluene,
Xylenes,
Ethylbenzene, C3 –
Benzenes, C4Benzenes
30.5%
Major Components of Gasoline
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 (180 - 210)
Sulfur (ppm)
ranges (10 - 50)
Mixtures of C5-C10 Hydrocarbons
Refinery
Whiting, IN
Refinery
Joliet, IL
Newton
County MTG
Process, IN
Transporting to Refineries
Joliet, IL



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.
http://www.exxonmobil.com/Corporate/Files/joliet
_brochure.pdf
Whiting, IN



405,000 barrels of raw
crude oil/day
Produce 15 million gallons
refining products.
Whiting Refinery
Modernization Project
http://www.bp.com/sectiongenericarticle.do?categor
yId=9030203&contentId=7055766#7205736
Transport of Gasoline

Pipeline transport

Railroad transport

Gasoline truck
transportation
Gasoline Blending
Conversion process in petroleum refining
Fluid Catalytic
Cracker (FCC)
• Cracking
hydrocarbons by
vaporization
• breaking long
chained highboiling
hydrocarbon
molecules
• presence of a
fluidized
powdered
catalyst
Alkylate
Catalytic Reforming
• Isobutane is
• Petroleum refinery
alkylated with low
naphtha
molecular weight
• low octane
alkenes
• presence of a
strong acid catalyst
• high octane
• sulfuric acid or
liquid products
hydrofluoric
acid
Questions from Presentation 1
 Catalysts:

 Is


How long do they last?
ZSM-5: Pressure and temp (305 psi, 350ºC) is
52 days
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
Butylene
with light Olefins primarily a mix of
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%)