Group Ass

INTRODUCTION AND BACKGROUND TO THE PROBLEM
Ever since the discovery of crude oil, its processing into finished products has always been adjusted
to meet supply, demand and environmental regulations. This discovery also has made a lot of
economic and technological impacts such that researches are continually done to improve the
quality of products, reduce processing costs and maximizing profits. Hence, Present-day refineries
produce a variety of products that are vastly used as feedstock for almost all the petrochemical
industries (Meyers, 2003; Prasad, 2002).
Crude oil refining is simply the conversion of crude oil into useful products such as gasoline,
kerosene, diesel, lubricants and feedstock in petrochemical process (Lu, 2017). This process starts
from the distillation and then followed by petrochemical process, including cracking, reforming,
isomerization, etc., up to the downstream processes which includes purification and blending.
Blending is the process that combines intermediate stream products and additives in various
proportions resulting in finished products that meet regulatory/market specifications. (Lu, 2017).
A lot of requirements are expected of a gasoline blend; the two most important are Reld Vapor
Pressure (RVP) and Octane number. The RVP is the vapor pressure of the gasoline blend when
the temperature is 100 degrees Fahrenheit and varies between summer (lower) and winter (higher).
For any blend, the major contributor to the RVP are the light-end hydrocarbons (i.e., butane,
pentane and isopentane) as they exhibit high vapor pressure. (Lu, 2017).
Octane numbers are measures of whether a gasoline will cause knocking in an engine and defined
as the percent of isooctane in the isooctane/normal heptane blend that knocks at the same
compression ratio as the gasoline. (Leffler, 2008). The Octane number also depend on the
component of the gasoline and is greatly influenced by the amount of short alkane chain in the
product., hence a lot of processes are being undergone to ensure having the optimum amount for
best performance.
Furthermore, the discovery of biofuels, such as ethanol, are used as blend additives as they have
short chains, hence reducing the reliance on fossil fuels.
This paper explores the effect of blending of methanol (a short chain) at different proportion with
hydrocarbon (propane) through detailed chemical kinetic modeling using ANSYS CHEMKIN.
SIMULATION
The simulation was done using ANSYS CHEMKIN for 3 different blends of methanol
1. Pure Hydrocarbon (100% Propane)
2. M10: 10% Methanol, 90% Propane (by volume)
3. M85: 85% Methanol, 15% Propane (by volume)
The GRI-Mech 3.0 kinetics and thermodynamic databases were used for the elementary
mechanism parameters. For the 3 cases examined, operating conditions are as follow:
 Reaction Temperature = 1500oC
 Reaction Pressure = 1atm
 Residence Times = 10ms
 Fuel equivalence ratio: 20% excess oxygen (based on complete propane combustion to
CO 2 and H 2 O)
Calculations
Pure Hydrocarbon (100% Propane by Volume)
𝐶𝐶3 𝐻𝐻8 + 5𝑂𝑂2 → 3𝐶𝐶𝑂𝑂2 + 4𝐻𝐻2 𝑂𝑂
Basis = 100ml of Fuel
Density of Propane = 0.68g/ml
Mass of Propane = 0.68g/ml x 100ml = 68g
Molar Mass of Propane = 44g/mol
68𝑔𝑔
Number of moles of Propane = 44𝑔𝑔/𝑚𝑚𝑚𝑚𝑚𝑚 = 1.54545𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚
Stoichiometrically, 1 mole of Propane requires 5 moles of O 2 .
Hence, 1.54545moles of Propane will require 1.54545 x 5 moles = 7.72727moles of O 2 .
As per requirement, 20% of oxygen is being supplied, hence
Amount of O 2 supplied = 1.2 x 7.72727 moles = 9.27273 moles of O 2 .
In terms of mole fractions,
Total moles = 1.54545mole of Propane + 9.27273 moles of O2 = 10.81818 moles
1.54545
Mole fraction of Propane = 10.81818 = 0.1429
9.27273
Mole fraction of Oxygen = 10.81818 = 0.8571
For the three cases of fuel composition considered,
Residence time = 10ms = 1x10-2s.

Diameter of Tubular Reactor = 1x10-25cm
Length of Tubular Reactor = 4x10-19cm
4x10−19 𝑐𝑐𝑐𝑐
Velocity = 1𝑥𝑥10−2 𝑠𝑠
= 4𝑥𝑥10−17 𝑐𝑐𝑐𝑐/𝑠𝑠
10% Methanol and 90% Propane (By Volume)
2𝐶𝐶𝐶𝐶3 𝑂𝑂𝑂𝑂 + 3𝑂𝑂2 → 2𝐶𝐶𝑂𝑂2 + 4𝐻𝐻2 𝑂𝑂
Still using 9.27273 moles of Oxygen as required.
10% of Methanol = 10ml of methanol.
Density of Methanol = 0.792g/ml
Mass of Methanol = 0.792g/ml x 10ml = 7.92g
Molar Mass of Methanol = 36g/mol
7.92𝑔𝑔
Number of moles of Methanol = 32𝑔𝑔/𝑚𝑚𝑚𝑚𝑚𝑚 = 0.2475𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚
90% of Propane = 90ml of Propane.
Mass of Propane = 0.68g/ml x 90ml = 61.2g
61.2𝑔𝑔
0.2475
Mole fraction of Methanol = 9.27273+0.2475+1.3909 = 0.02268
1.3909
Mole fraction of Propane = 9.27273+0.2475+1.3909 = 0.12748
9.27273
Mole fraction of Oxygen = 9.27273+0.2475+1.3909 = 0.84984
85% Methanol and 15% Propane (By Volume)
2𝐶𝐶𝐶𝐶3 𝑂𝑂8 + 3𝑂𝑂2 → 2𝐶𝐶𝑂𝑂2 + 4𝐻𝐻2 𝑂𝑂
Still using 9.27273 moles of Oxygen as required.
85% of Methanol = 85ml of methanol.
Density of Methanol = 0.792g/ml
Mass of Methanol = 0.792g/ml x 85ml = 67.32g
Molar Mass of Methanol = 36g/mol
67.32𝑔𝑔
Number of moles of Methanol = 32𝑔𝑔/𝑚𝑚𝑚𝑚𝑚𝑚 = 1.87𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚
15% of Propane = 15ml of Propane.
Mass of Propane = 0.68g/ml x 15ml = 10.2g

10.2𝑔𝑔
1.87
Mole fraction of Methanol = 9.27273+1.87+0.23182 = 0.16440
0.23182
Mole fraction of Propane = 9.27273+1.87+0.23182 = 0.02038
9.27273
Mole fraction of Oxygen = 9.27273+1.87+0.23182 = 0.81522
Results and Discussion
Pure Hydrocarbon (100% Propane by Volume)
Sensitivity Analysis and Reaction Pathway were taken at Distance X = 8 x 10-21
 Concentration Profile of Main Reactants and Products.
As shown in the figure below, virtually all the propane was consumed as soon as it enters the
reactor. The mole fraction of CO 2 and H 2 O coming out of the reactor are 0.375 and 0.499
respectively.
mole fraction of C3H8 with length

1.60E-01
1.40E-01
1.20E-01
mole fraction of C3H8
1.00E-01
8.00E-02
6.00E-02
4.00E-02
2.00E-02
0.00E+00
0.E+00 1.E-22 2.E-22 3.E-22 4.E-22 5.E-22 6.E-22 7.E-22 8.E-22
Length
mole fraction of CO2 with length
4.00E-01
3.50E-01
mole fraction of CO2 3.00E-01

2.50E-01
2.00E-01
1.50E-01
1.00E-01
5.00E-02
0.00E+00
0.E+00 2.E-20 4.E-20 6.E-20 8.E-20 1.E-19
Length
mole fraction of H2O with length

6.00E-01
5.00E-01
mole fraction of H2O
4.00E-01
3.00E-01
2.00E-01
1.00E-01
0.00E+00
0.E+00 1.E-20 2.E-20 3.E-20 4.E-20 5.E-20 6.E-20 7.E-20
Length
 Sensitivity Analysis of C 3 H 8 , CO 2 and H 2 O
𝜕𝜕𝜕𝜕𝜕𝜕𝑥𝑥𝑖𝑖
𝑆𝑆𝑖𝑖𝑖𝑖 =
𝜕𝜕𝜕𝜕𝜕𝜕𝑘𝑘𝑗𝑗
As shown in the Figure below, C 3 H 8 concentration in the reactor is mostly sensitive to 2 reactions,
Reaction 315 (𝑂𝑂𝑂𝑂 + 𝐶𝐶3 𝐻𝐻8 = 𝐶𝐶3 𝐻𝐻7 + 𝐻𝐻2 𝑂𝑂) and Reaction 312 (𝐶𝐶𝐶𝐶3 + 𝐶𝐶2 𝐻𝐻5 (+𝑀𝑀) = 𝐶𝐶3 𝐻𝐻8 ).
Reaction 315 consumes C 3 H 8 to produce C 3 H 7 while Reaction 312 produces C 3 H 8 . Reaction 315
produces C 3 H 7 which could be a precursor for more C 3 H 8 production as simply adding H to it
gives C 3 H 8 (+ve sensitivity), hence increasing the k j decreases the availability of C 3 H 8 in the
reactor. Reaction 312 produces more C 3 H 8 which makes it more available in the reactor, hence
increasing the k j decreases the availability of C 3 H 8 in the reactor.
For CO 2 , its availability in the reactor is sensitive to Reaction 312 (𝐶𝐶𝐶𝐶3 + 𝐶𝐶2 𝐻𝐻5 (+𝑀𝑀) = 𝐶𝐶3 𝐻𝐻8 )
and Reaction 173 (𝐶𝐶2 𝐻𝐻3 + 𝑂𝑂2 = 𝐻𝐻𝐻𝐻𝐻𝐻 + 𝐶𝐶𝐶𝐶2 𝑂𝑂). Reaction 312 produces more C 3 H 8 , hence
giving room for more combustion to produce CO 2 meaning increasing its kj would be more
favorable for CO 2 production. Reaction 173 consumes the O 2 that would be needed for combusting
C 3 H 8 so increasing its k j would not favor CO 2 production, which will tend to reduce the amount
of CO 2 produced.
For H 2 O, its availability in the reactor is sensitive to Reaction 312 (𝐶𝐶𝐶𝐶3 + 𝐶𝐶2 𝐻𝐻5 (+𝑀𝑀) = 𝐶𝐶3 𝐻𝐻8 )
and Reaction 314 (𝐻𝐻 + 𝐶𝐶3 𝐻𝐻8 = 𝐶𝐶3 𝐻𝐻7 + 𝐻𝐻2 ). Reaction 312 produces more C 3 H 8 which gets
combusted to produce more H 2 O so increasing its k j would influence H 2 O production positively,
Reaction 314 consumes C 3 H 8 to produce H 2 so increasing its k j reduces H 2 O production.

C3H8 Sensitivity Chart (100% Propane)
4.E+01 C3H8_Sens_GasRxn#38_()
C3H8_Sens_GasRxn#57_()
C3H8 Sensitivity
0.E+00
0.0E+00 5.0E-20 1.0E-19 1.5E-19 2.0E-19 2.5E-19 3.0E-19 3.5E-19 4.0E-19 4.5E-19
-1.E+01
-2.E+01
-3.E+01
Distance
CO2 Sensitivity Chart (100% Propane)

CO2_Sens_GasRxn#38_()
2.0E+00 CO2_Sens_GasRxn#96_()
1.5E+00 CO2_Sens_GasRxn#119_()
1.0E+00
CO2 Sensitivity
5.0E-01 CO2_Sens_GasRxn#294_()
0.0E+00
0.00E+00 5.00E-21 1.00E-20 1.50E-20 2.00E-20
-5.0E-01
-1.0E+00
Distance
1.5E+00
H2O Sensitivity Chart (100% Propane)
1.0E+00 H2O_Sens_GasRxn#38_() H2O_Sens_GasRxn#74_()

H2O_Sens_GasRxn#74_() H2O_Sens_GasRxn#119_()
5.0E-01 H2O_Sens_GasRxn#314_() H2O_Sens_GasRxn#315_()

H2O Sensitivity
0.0E+00
0.E+00 1.E-21 2.E-21 3.E-21 4.E-21 5.E-21 6.E-21 7.E-21 8.E-21 9.E-21
-5.0E-01
-1.0E+00 Distance
 Reaction Path Diagrams
Reaction Pathway diagrams for the 3-main species (C 3 H 8 , CO 2 and H 2 O) are as shown below.
The major producer is the thickest arrow in the pathways.
The Reaction 315, i.e. 𝑂𝑂𝑂𝑂 + 𝐶𝐶3 𝐻𝐻8 = 𝐶𝐶3 𝐻𝐻7 + 𝐻𝐻2 𝑂𝑂 is the major consumer of C 3 H 8 in the reactor
(Absolute Rate of Production, ARP = -1.07e-14), for CO 2 , its major producer is the Reaction 99,
i.e. 𝑂𝑂𝑂𝑂 + 𝐶𝐶𝐶𝐶 = 𝐻𝐻 + 𝐶𝐶𝐶𝐶2 (ARP = 7.1e-4) while for H 2 O, its major producer is the Reaction 84,
i.e. 𝑂𝑂𝑂𝑂 + 𝐻𝐻2 = 𝐻𝐻 + 𝐻𝐻2 𝑂𝑂 (ARP = 3.09e-4).

 Rate of Production
As shown in the chart below, the major consumer of C3H8 is the reaction 315 𝑂𝑂𝑂𝑂 + 𝐶𝐶3 𝐻𝐻8 =
𝐶𝐶3 𝐻𝐻7 + 𝐻𝐻2 𝑂𝑂, which corresponds to its reaction pathway. For CO 2 , its major producer is the
Reaction 99, i.e. 𝑂𝑂𝑂𝑂 + 𝐶𝐶𝐶𝐶 = 𝐻𝐻 + 𝐶𝐶𝐶𝐶2 while for H 2 O, its major producer is the Reaction 84, i.e.
𝑂𝑂𝑂𝑂 + 𝐻𝐻2 = 𝐻𝐻 + 𝐻𝐻2 𝑂𝑂.

5.00E-02
C3H8 Rate of Production
0.00E+00
0.00E+00 5.00E-21 1.00E-20 1.50E-20 2.00E-20
-5.00E-02 Distance
-1.00E-01
-1.50E-01
-2.00E-01
C3H8_ROP_GasRxn_Total_(mole/cm3-sec) C3H8_ROP_GasRxn#312_(mole/cm3-sec)
C3H8_ROP_GasRxn#313_(mole/cm3-sec) C3H8_ROP_GasRxn#314_(mole/cm3-sec)
C3H8_ROP_GasRxn#323_(mole/cm3-sec)
CO2 Rate of Production

1.40E-01
1.20E-01
1.00E-01
8.00E-02
6.00E-02
4.00E-02
2.00E-02
0.00E+00
0.00E+00 5.00E-21 1.00E-20 1.50E-20 2.00E-20
Distance
CO2_ROP_GasRxn_Total_(mole/cm3-sec) CO2_ROP_GasRxn#12_(mole/cm3-sec)
CO2_ROP_GasRxn#14_(mole/cm3-sec) CO2_ROP_GasRxn#30_(mole/cm3-sec)
CO2_ROP_GasRxn#305_(mole/cm3-sec)
H2O Rate of Production
3.50E-01
3.00E-01
2.50E-01
2.00E-01
1.50E-01
1.00E-01
5.00E-02
0.00E+00
0.00E+00 5.00E-21 1.00E-20 1.50E-20 2.00E-20
-5.00E-02
Distance
H2O_ROP_GasRxn_Total_(mole/cm3-sec) H2O_ROP_GasRxn#84_(mole/cm3-sec)
H2O_ROP_GasRxn#86_(mole/cm3-sec) H2O_ROP_GasRxn#89_(mole/cm3-sec)
M10 (10% Methanol, 90% Propane by Volume)
As shown in the figure below, virtually all the propane and methanol was consumed as soon as
they entered the reactor but propane was consumed faster. The mole fraction of CO 2 and H 2 O
coming out of the reactor are 0.355 and 0.487 respectively.

Mole fraction of C3H8 with Length
1.4E-01
1.2E-01
1.0E-01
8.0E-02
6.0E-02
4.0E-02
2.0E-02
0.0E+00
0.00E+00 1.00E-22 2.00E-22 3.00E-22 4.00E-22 5.00E-22 6.00E-22 7.00E-22 8.00E-22
Length
Mole fraction of CH3OH with length

2.50E-02
mole fraction of CH3OH
2.00E-02
1.50E-02
1.00E-02
5.00E-03
0.00E+00
0.00E+00 5.00E-22 1.00E-21 1.50E-21 2.00E-21 2.50E-21 3.00E-21 3.50E-21
Length
Mole fraction of CO2 with Length
4.0E-01
3.5E-01
mole fraction of CO2
3.0E-01
2.5E-01
2.0E-01
1.5E-01
1.0E-01
5.0E-02
0.0E+00
0.00E+00 5.00E-21 1.00E-20 1.50E-20 2.00E-20 2.50E-20 3.00E-20
Length
Mole Fraction of H2O with Length

6.E-01
5.E-01
Mole Fraction of H2O
4.E-01
3.E-01
2.E-01
1.E-01
0.E+00
0.E+00 1.E-20 2.E-20 3.E-20 4.E-20 5.E-20 6.E-20 7.E-20
Length
 Sensitivity Analysis of C 3 H 8 , CH 3 OH, CO 2 and H 2 O
As shown in the Figure below, C 3 H 8 concentration in the reactor is mostly sensitive to 2 reactions,
Reaction 315 (𝑂𝑂𝑂𝑂 + 𝐶𝐶3 𝐻𝐻8 = 𝐶𝐶3 𝐻𝐻7 + 𝐻𝐻2 𝑂𝑂) and Reaction 318 (𝐶𝐶𝐶𝐶3 + 𝐶𝐶2 𝐻𝐻4 (+𝑀𝑀) = 𝐶𝐶3 𝐻𝐻7 ).
Reaction 315 consumes C 3 H 8 to produce C 3 H 7 which is a precursor for the complete combustion,
hence reducing its availability in the reactor (-ve sensitivity). Increasing the k j decreases the
availability of C 3 H 8 in the reactor. Reaction 318 produces C 3 H 7 which would deter reaction 315
from occurring, hence the +ve sensitivity. Increasing the k j increases the availability of C 3 H 8 in
the reactor
For CH 3 OH, its availability in the reactor is sensitive (+ve and –ve) to Reaction 57 (𝐶𝐶𝐶𝐶3 +
𝐶𝐶2 𝐻𝐻5 (+𝑀𝑀) = 𝐶𝐶3 𝐻𝐻8 ) and Reaction 147 (𝐶𝐶𝐻𝐻2 (𝑆𝑆) + 𝐻𝐻2 𝑂𝑂(+𝑀𝑀) = 𝐶𝐶𝐶𝐶3 𝑂𝑂𝑂𝑂(+𝑀𝑀)). Reaction 57
produces C 3 H 8 which in-turn consumes O 2 that can be used by CH 3 OH making CH 3 OH more
available (+ve sensitivity), while the –ve sensitivity would mean that the C 3 H 8 being produced
might at some point in the reactor reduce the availability of CH 3 OH. Increasing or decreasing the
k j increases or decrease the availability of CH 3 OH at almost the same length of the reactor.
Reaction 147 produces more CH 3 OH (+ve sensitivity) but along the same length of the reactor, it
changes to –ve sensitivity, meaning it influences CH 3 OH availability negatively. Increasing or
decreasing the k j increases or decrease the availability of CH 3 OH at almost the same length of the
reactor.
For CO 2 , its availability in the reactor is mostly sensitive to Reaction 312 (𝐶𝐶𝐶𝐶3 + 𝐶𝐶2 𝐻𝐻5 (+𝑀𝑀) =
𝐶𝐶3 𝐻𝐻8 ) and Reaction 168 (𝐻𝐻𝐻𝐻𝐻𝐻 + 𝑂𝑂2 = 𝐻𝐻𝑂𝑂2 + 𝐶𝐶𝐶𝐶). Reaction 312 produces C 3 H 8 which is a
precursor for more CO 2 production from complete combustion (+ve sensitivity), hence increasing
the k j increases the availability of CO 2 in the reactor while reaction 168 consumes O 2 that to
produce CO that could have been used to produce CO 2 (–ve sensitivity), increasing its k j reduces
the availability of CO 2 in the reactor.
and Reaction 314 (𝐻𝐻 + 𝐶𝐶3 𝐻𝐻8 = 𝐶𝐶3 𝐻𝐻7 + 𝐻𝐻2 ) . Reaction 312 produces C 3 H 8 which is a precursor
for more H 2 O production from complete combustion (+ve sensitivity), hence increasing the k j
increases the availability of H 2 O in the reactor, while reaction 314 makes C 3 H 8 react with H to
produce H 2 instead of reacting with O 2 to produce H 2 O (–ve sensitivity), hence increasing its k j
reduces the availability of H 2 O in the reactor.
C3H8 Sensitivity Chart (90% Propane)

1.50E+02
1.00E+02
CH3OH Sensitivity
5.00E+01
0.00E+00
0.00E+00 5.00E-20 1.00E-19 1.50E-19 2.00E-19 2.50E-19 3.00E-19 3.50E-19 4.00E-19 4.50E-19
-5.00E+01
-1.00E+02
-1.50E+02
Distance
C3H8_Sens_GasRxn#35_() C3H8_Sens_GasRxn#38_() C3H8_Sens_GasRxn#99_()

CH3OH Sensitivity Chart (90% Propane)

1.E+02
CH3OH Sensitivity
5.E+01
0.E+00
0.0E+00 5.0E-20 1.0E-19 1.5E-19 2.0E-19 2.5E-19 3.0E-19 3.5E-19 4.0E-19 4.5E-19
-5.E+01
-1.E+02
Distance
CH3OH_Sens_GasRxn#38_() CH3OH_Sens_GasRxn#57_()
CO2 Sensitivity Chart (90% Propane)
2.50E+00
2.00E+00
1.50E+00
CO2 Sensitivity
1.00E+00
5.00E-01
0.00E+00
0.00E+00 5.00E-21 1.00E-20 1.50E-20 2.00E-20 2.50E-20 3.00E-20
-5.00E-01
-1.00E+00
Distance
CO2_Sens_GasRxn#38_() CO2_Sens_GasRxn#57_() CO2_Sens_GasRxn#85_()

1.6E+00
H2O Sensitivity Chart (90% Propane)
1.4E+00
1.2E+00
1.0E+00
8.0E-01
H2O Sensitivity
6.0E-01
4.0E-01
2.0E-01
0.0E+00
0.0E+00 2.0E-21 4.0E-21 6.0E-21 8.0E-21 1.0E-20 1.2E-20 1.4E-20 1.6E-20 1.8E-20
-2.0E-01
Distance
-4.0E-01 H2O_Sens_GasRxn#38_() H2O_Sens_GasRxn#74_()
-6.0E-01 H2O_Sens_GasRxn#119_() H2O_Sens_GasRxn#147_()
Reaction Pathway diagrams for the 4-main species (C 3 H 8 , CH 3 OH, CO 2 and H 2 O) are as shown
below. The major producer is the thickest arrow in the pathways.
(ARP = -1.0e-14), for CH 3 OH, its major producer is the Reaction 105, i.e. 𝑂𝑂𝑂𝑂 + 𝐶𝐶𝐶𝐶3 𝑂𝑂𝑂𝑂 =
𝐶𝐶𝐶𝐶3 𝑂𝑂 + 𝐻𝐻2 𝑂𝑂 (ARP = 4.76e-12), for CO 2 , its major producer is the Reaction 99, i.e.
𝑂𝑂𝑂𝑂 + 𝐶𝐶𝐶𝐶 = 𝐻𝐻 + 𝐶𝐶𝐶𝐶2 (ARP = 5.86e-4) while for H 2 O, its major producer is the Reaction 84, i.e.
𝑂𝑂𝑂𝑂 + 𝐻𝐻2 = 𝐻𝐻 + 𝐻𝐻2 𝑂𝑂 (ARP = 2.7e-4).

As shown in the chart below, the Reaction 315, i.e. 𝑂𝑂𝑂𝑂 + 𝐶𝐶3 𝐻𝐻8 = 𝐶𝐶3 𝐻𝐻7 + 𝐻𝐻2 𝑂𝑂 is the major
consumer of C 3 H 8 in the reactor. For CH 3 OH, its major producer is the Reaction 105, i.e. 𝑂𝑂𝑂𝑂 +
𝐶𝐶𝐶𝐶3 𝑂𝑂𝑂𝑂 = 𝐶𝐶𝐶𝐶3 𝑂𝑂 + 𝐻𝐻2 𝑂𝑂. For CO 2 , its major producer is the Reaction 99, i.e. 𝑂𝑂𝑂𝑂 + 𝐶𝐶𝐶𝐶 = 𝐻𝐻 +
𝐶𝐶𝐶𝐶2 while for H 2 O, its major producer is the Reaction 84, i.e. 𝑂𝑂𝑂𝑂 + 𝐻𝐻2 = 𝐻𝐻 + 𝐻𝐻2 , all of which
corresponds to the Reaction pathway figures

2.00E-02
0.00E+00 Distance
0.00E+00 5.00E-21 1.00E-20 1.50E-20 2.00E-20
-2.00E-02
-4.00E-02
-6.00E-02
-8.00E-02
-1.00E-01
-1.20E-01
-1.40E-01
-1.60E-01
CH3OH Rate of Production
5.00E-03
0.00E+00
0.00E+00
-5.00E-03 5.00E-21 1.00E-20 1.50E-20 2.00E-20
Distance
-1.00E-02
-1.50E-02
-2.00E-02
-2.50E-02
-3.00E-02
CH3OH_ROP_GasRxn_Total_(mole/cm3-sec) CH3OH_ROP_GasRxn#18_(mole/cm3-sec)
CH3OH_ROP_GasRxn#19_(mole/cm3-sec) CH3OH_ROP_GasRxn#68_(mole/cm3-sec)
CH3OH_ROP_GasRxn#163_(mole/cm3-sec)

1.40E-01
1.20E-01
1.00E-01
8.00E-02
6.00E-02
4.00E-02
2.00E-02
0.00E+00
0.00E+00 5.00E-21 1.00E-20 1.50E-20 2.00E-20
-2.00E-02
Distance
3.50E-01
3.00E-01
2.50E-01
2.00E-01
1.50E-01
1.00E-01
5.00E-02
0.00E+00
0.00E+00 5.00E-21 1.00E-20 1.50E-20 2.00E-20
-5.00E-02
Distance
H2O_ROP_GasRxn#315_(mole/cm3-sec)
M85 (85% Methanol, 15% Propane by Volume)
As shown in the figure below, virtually all the propane and methanol was consumed as soon as
they enter the reactor and roughly all done at the same length of reactor. The mole fraction of CO 2
and H 2 O coming out of the reactor are 0.204 and 0.371 respectively.
Mole fraction of C3H8 with length
2.50E-02
2.00E-02
1.50E-02
1.00E-02
5.00E-03
0.00E+00
0.00E+00 5.00E-22 1.00E-21 1.50E-21 2.00E-21
lenght
Mole fraction of CH3OH with length

2.0E-01
Mole fraction of CH3OH
1.5E-01
1.0E-01
5.0E-02
0.0E+00
0.0E+00 5.0E-22 1.0E-21 1.5E-21 2.0E-21 2.5E-21
Length
Mole fraction of CO2 with length

2.5E-01
mole fraction of CO2
2.0E-01
1.5E-01
1.0E-01
5.0E-02
0.0E+00
0.0E+00 5.0E-21 1.0E-20 1.5E-20 2.0E-20 2.5E-20
length
Mole fraction of H2O with length
4.0E-01
3.5E-01
mole fraction of H2O

3.0E-01
2.5E-01
2.0E-01
1.5E-01
1.0E-01
5.0E-02
0.0E+00
0.0E+00 5.0E-21 1.0E-20 1.5E-20 2.0E-20 2.5E-20 3.0E-20
Length
 Sensitivity Analysis of C 3 H 8 , CH 3 OH, CO 2 and H 2 O
As shown in the Figure below, C 3 H 8 concentration in the reactor is mostly sensitive Reaction 85
(2𝑂𝑂𝑂𝑂(+𝑀𝑀) = 𝐻𝐻2 𝑂𝑂2 (+𝑀𝑀)) and Reaction 89 (𝑂𝑂𝑂𝑂 + 𝐻𝐻2 𝑂𝑂2 = 𝐻𝐻𝑂𝑂2 + 𝐻𝐻2 𝑂𝑂). Reaction 85 produces
H 2 O 2 and probably inhibiting consumption of C 3 H 8 in the reactor (+ve sensitivity), hence increase
in its k j means more C 3 H 8 in the reactor while reaction 89 consumes H 2 O 2 , hence the reverse of
what reaction 85 is doing (-ve sensitivity), hence increase in its k j means less C 3 H 8 in the reactor
For CH 3 OH, its availability in the reactor is sensitive to Reaction 97 (𝑂𝑂𝑂𝑂 + 𝐶𝐶𝐻𝐻3 = 𝐶𝐶𝐻𝐻2 (𝑠𝑠) +
𝐻𝐻2 𝑂𝑂) and Reaction 98 (𝑂𝑂𝑂𝑂 + 𝐶𝐶𝐻𝐻4 = 𝐶𝐶𝐻𝐻3 + 𝐻𝐻2 𝑂𝑂). Reaction 97 was first favorable for CH 3 OH
availability (+ve sensitivity) but later serves as a precursor for its consumption down the length of
the reactor, hence the –ve sensitivity.
For CO 2 , its availability in the reactor is sensitive to Reaction 85 (2𝑂𝑂𝑂𝑂(+𝑀𝑀) = 𝐻𝐻2 𝑂𝑂2 (+𝑀𝑀)) and
Reaction 89 (𝑂𝑂𝑂𝑂 + 𝐻𝐻2 𝑂𝑂2 = 𝐻𝐻𝑂𝑂2 + 𝐻𝐻2 𝑂𝑂). Reaction 85 produces H 2 O 2 and probably a precursor
for more CO 2 production in the reactor, so increase in its k j means more CO 2 (+ve sensitivity)
while reaction 89 consumes H 2 O 2 , hence the reverse of what reaction 85 is doing, so increase in
its k j means less CO 2 (-ve sensitivity).
and Reaction 89 (𝑂𝑂𝑂𝑂 + 𝐻𝐻2 𝑂𝑂2 = 𝐻𝐻𝑂𝑂2 + 𝐻𝐻2 𝑂𝑂). Reaction 312 produces C3H8 which in-turn will
be combusted to produce H2O, so increasing its k j will be more favorable (+ve sensitivity) while
reaction 89, although looks like it produces more H2O might have actually been a precursor for
more H2O consumption, so increasing its k j would not be favorable, (-ve sensitivity)
For the 4 major reactants and products, changing parameters like temperature, which in turn affects
rate constants can influence how much of complete combustion we can have in the reactor.
C3H8 Sensitivity (15% Propane)

5.E+02
4.E+02
3.E+02
2.E+02
C3H8 Sensitivity
1.E+02
0.E+00
0.0E+00 5.0E-21 1.0E-20 1.5E-20 2.0E-20
-1.E+02
-2.E+02
-3.E+02
-4.E+02
C3H8_Sens_GasRxn#38_() Distance
C3H8_Sens_GasRxn#57_() C3H8_Sens_GasRxn#85_()
CH3OH Sensitivity (15% Propane)
4.E+02
2.E+02
0.E+00
CH3OH Sensitivity
0.0E+00 5.0E-20 1.0E-19 1.5E-19 2.0E-19 2.5E-19 3.0E-19 3.5E-19 4.0E-19 4.5E-19
-2.E+02
-4.E+02
-6.E+02
-8.E+02
Distance
CH3OH_Sens_GasRxn#10_() CH3OH_Sens_GasRxn#11_() CH3OH_Sens_GasRxn#85_()
CH3OH_Sens_GasRxn#284_()
4.E+00
CO2 Sensitivity (15% Propane)
3.E+00
2.E+00
CO2 Sensitivity
1.E+00
0.E+00
0.0E+00 2.0E-21 4.0E-21 6.0E-21 8.0E-21 1.0E-20 1.2E-20 1.4E-20
-1.E+00
-2.E+00
-3.E+00 Distance
H2O Sensitivity (15% Propane)
1.2E+00
1.0E+00
8.0E-01
6.0E-01
H2O Sensitivity
4.0E-01
2.0E-01
0.0E+00
0.E+00 1.E-21 2.E-21 3.E-21 4.E-21 5.E-21 6.E-21 7.E-21 8.E-21 9.E-21
-2.0E-01
-4.0E-01
-6.0E-01
Distance
H2O_Sens_GasRxn#38_() H2O_Sens_GasRxn#85_() H2O_Sens_GasRxn#89_()

H2O_Sens_GasRxn#312_()
Reaction Pathway diagrams for the 4-main species (C 3 H 8 , CH 3 OH, CO 2 and H 2 O) are as shown
below. The major producer is the thickest arrow in the pathways.
(ARP = -1.0e-14), for CH 3 OH, its major producer is the Reaction 105, i.e. 𝑂𝑂𝑂𝑂 + 𝐶𝐶𝐶𝐶3 𝑂𝑂𝑂𝑂 =
𝐶𝐶𝐶𝐶3 𝑂𝑂 + 𝐻𝐻2 𝑂𝑂 (ARP = 4.76e-12), for CO 2 , its major producer is the Reaction 99, i.e.
𝑂𝑂𝑂𝑂 + 𝐶𝐶𝐶𝐶 = 𝐻𝐻 + 𝐶𝐶𝐶𝐶2 (ARP = 5.86e-4) while for H 2 O, its major producer is the Reaction 84,
i.e.𝑂𝑂𝑂𝑂 + 𝐻𝐻2 = 𝐻𝐻 + 𝐻𝐻2 𝑂𝑂 (ARP=2.7e-4).

The Reaction 315, i.e. 𝑂𝑂𝑂𝑂 + 𝐶𝐶3 𝐻𝐻8 = 𝐶𝐶3 𝐻𝐻7 + 𝐻𝐻2 𝑂𝑂 is the major consumer of C 3 H 8 in the reactor.
For CH 3 OH, its major producer is the Reaction 105, i.e. 𝑂𝑂𝑂𝑂 + 𝐶𝐶𝐶𝐶3 𝑂𝑂𝑂𝑂 = 𝐶𝐶𝐶𝐶3 𝑂𝑂 + 𝐻𝐻2 𝑂𝑂. For CO 2 ,
its major producer is the Reaction 99, i.e. 𝑂𝑂𝑂𝑂 + 𝐶𝐶𝐶𝐶 = 𝐻𝐻 + 𝐶𝐶𝐶𝐶2 , while for H 2 O, its major producer
is the Reaction 84, i.e.𝑂𝑂𝑂𝑂 + 𝐻𝐻2 = 𝐻𝐻 + 𝐻𝐻2 𝑂𝑂, all of which corresponds to the reaction pathway
figures.

1.00E-03
0.00E+00
0.00E+00
-1.00E-03 5.00E-21 1.00E-20 1.50E-20 2.00E-20
-2.00E-03
-3.00E-03
-4.00E-03
-5.00E-03
-6.00E-03
-7.00E-03
-8.00E-03
-9.00E-03
-1.00E-02
Distance
5.00E-03
0.00E+00
0.00E+00 5.00E-21 1.00E-20 1.50E-20 2.00E-20
-5.00E-03
-1.00E-02
-1.50E-02
-2.00E-02
-2.50E-02
Distance

8.00E-02
7.00E-02
6.00E-02
5.00E-02
4.00E-02
3.00E-02
2.00E-02
1.00E-02
0.00E+00
0.00E+00
-1.00E-02 5.00E-21 1.00E-20 1.50E-20 2.00E-20
Distance
1.40E-01
1.20E-01
1.00E-01
8.00E-02
6.00E-02
4.00E-02
2.00E-02
0.00E+00
0.00E+00 5.00E-21 1.00E-20 1.50E-20 2.00E-20
-2.00E-02
Distance
-4.00E-02
H2O_ROP_GasRxn#287_(mole/cm3-sec)
References
Lu, J. (2017). ‘Sub-surface Gasoline “Blending” and Forensic Implications’. Journal of
Environmental Protection, 8, 714-732.
Leffler, W.L. (2008). ‘Petroleum Refining in Non-Technical Language’. 4th Edition, PennWell
Corporation, Tulsa.

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INTRODUCTION AND BACKGROUND TO THE PROBLEM

industries (Meyers, 2003; Prasad, 2002).

short chains, hence reducing the reliance on fossil fuels.

1. Pure Hydrocarbon (100% Propane)

2. M10: 10% Methanol, 90% Propane (by volume)

3. M85: 85% Methanol, 15% Propane (by volume)

 Reaction Temperature = 1500oC

 Reaction Pressure = 1atm

 Residence Times = 10ms

Pure Hydrocarbon (100% Propane by Volume)

𝐶𝐶3 𝐻𝐻8 + 5𝑂𝑂2 → 3𝐶𝐶𝑂𝑂2 + 4𝐻𝐻2 𝑂𝑂

Basis = 100ml of Fuel

Density of Propane = 0.68g/ml

Mass of Propane = 0.68g/ml x 100ml = 68g

Molar Mass of Propane = 44g/mol

Stoichiometrically, 1 mole of Propane requires 5 moles of O 2 .

Hence, 1.54545moles of Propane will require 1.54545 x 5 moles = 7.72727moles of O 2 .

As per requirement, 20% of oxygen is being supplied, hence

Amount of O 2 supplied = 1.2 x 7.72727 moles = 9.27273 moles of O 2 .

In terms of mole fractions,

Total moles = 1.54545mole of Propane + 9.27273 moles of O2 = 10.81818 moles

For the three cases of fuel composition considered,

Residence time = 10ms = 1x10-2s.

Length of Tubular Reactor = 4x10-19cm

10% Methanol and 90% Propane (By Volume)

𝐶𝐶3 𝐻𝐻8 + 5𝑂𝑂2 → 3𝐶𝐶𝑂𝑂2 + 4𝐻𝐻2 𝑂𝑂

2𝐶𝐶𝐶𝐶3 𝑂𝑂𝑂𝑂 + 3𝑂𝑂2 → 2𝐶𝐶𝑂𝑂2 + 4𝐻𝐻2 𝑂𝑂

Still using 9.27273 moles of Oxygen as required.

Basis = 100ml of Fuel

10% of Methanol = 10ml of methanol.

Density of Methanol = 0.792g/ml

Mass of Methanol = 0.792g/ml x 10ml = 7.92g

Molar Mass of Methanol = 36g/mol

90% of Propane = 90ml of Propane.

Density of Propane = 0.68g/ml

Mass of Propane = 0.68g/ml x 90ml = 61.2g

Molar Mass of Propane = 44g/mol

85% Methanol and 15% Propane (By Volume)

𝐶𝐶3 𝐻𝐻8 + 5𝑂𝑂2 → 3𝐶𝐶𝑂𝑂2 + 4𝐻𝐻2 𝑂𝑂

2𝐶𝐶𝐶𝐶3 𝑂𝑂8 + 3𝑂𝑂2 → 2𝐶𝐶𝑂𝑂2 + 4𝐻𝐻2 𝑂𝑂

Still using 9.27273 moles of Oxygen as required.

Basis = 100ml of Fuel

85% of Methanol = 85ml of methanol.

Density of Methanol = 0.792g/ml

Mass of Methanol = 0.792g/ml x 85ml = 67.32g

Molar Mass of Methanol = 36g/mol

15% of Propane = 15ml of Propane.

Density of Propane = 0.68g/ml

Mass of Propane = 0.68g/ml x 15ml = 10.2g

Molar Mass of Propane = 44g/mol

Results and Discussion

Pure Hydrocarbon (100% Propane by Volume)

Sensitivity Analysis and Reaction Pathway were taken at Distance X = 8 x 10-21

 Concentration Profile of Main Reactants and Products.

mole fraction of C3H8 with length

mole fraction of CO2 3.00E-01

mole fraction of H2O with length

 Sensitivity Analysis of C 3 H 8 , CO 2 and H 2 O

increasing the k j decreases the availability of C 3 H 8 in the reactor.

combusted to produce more H 2 O so increasing its k j would influence H 2 O production positively,

Reaction 314 consumes C 3 H 8 to produce H 2 so increasing its k j reduces H 2 O production.

CO2 Sensitivity Chart (100% Propane)

1.0E+00 H2O_Sens_GasRxn#38_() H2O_Sens_GasRxn#74_()