Final Report
Final Report
Final Report
College of Engineering
PCE Department
Chemical Reaction Engineering
88805
89672
Abstract
These papers illustrate a reactor design to produce Phthalic anhydride (PAN) in
continuous plant through the oxidation of o-xylene. Maleic anhydride is also obtained
as by-product in this process. Pressure drop, side reactions and maintaining a
relatively constant driving force for heat transfer are considered in this design. The
production of phthalic anhydride is approximately 20,000 tons/year as required. The
process was simulated using the process simulator Aspen plus.
Table of Contents
Abstract ................................................................................................................................. I
Table of Contents .................................................................................................................. II
List of Tables ....................................................................................................................... III
List of figures ....................................................................................................................... IV
Introduction .......................................................................................................................... 1
Uses .................................................................................................................................. 1
Manufacturing company .................................................................................................... 2
The feed stock ................................................................................................................... 2
Process description ............................................................................................................ 3
Reactions path way............................................................................................................ 3
Type of reactors ................................................................................................................ 4
Catalyst ............................................................................................................................. 5
Kinetics ............................................................................................................................. 6
First Design: Reactor Volume Using Simple Reaction Rate Expression .................................... 7
Mass balance: .................................................................................................................... 8
Calculating the volume ...................................................................................................... 8
The simulation .................................................................................................................. 9
Second Design: Pressure Drop and Reactor Configuration .................................................... 11
Splitting the Reactor into Tubes ....................................................................................... 13
Tube Length effect .......................................................................................................... 13
Particle Diameter effect ................................................................................................... 14
The simulation ................................................................................................................ 16
Third Design: Multiple Reactions ........................................................................................ 18
Plot Flow ........................................................................................................................ 19
Effect of Temperature in Selectivity ................................................................................ 20
Aspen simulation............................................................................................................. 21
Final Design: Energy Balance............................................................................................. 23
Temperature profile ......................................................................................................... 23
Dynamic stability ............................................................................................................ 24
Aspen Simulation ................................................................................................................ 25
Economic analysis............................................................................................................... 30
Design summary.................................................................................................................. 31
Conclusion .......................................................................................................................... 31
II
References........................................................................................................................... 32
Appendix ............................................................................................................................. 33
List of Tables
Table 1: Component Price ..................................................................................................... 2
Table 2: Fixed-Bed. vs. Fluidized-Bed Reactors for Selective Hydrocarbon Oxidation
Reactions .............................................................................................................................. 4
Table 3:Catalyst Properties and Behavior in o-Xylene Oxidation .......................................... 5
Table 4: Mass Balance Results .............................................................................................. 8
Table 5:Polymath design results ............................................................................................ 8
Table 6: Heat and material balance ...................................................................................... 9
Table 7: Design Results without Sipliting to Tube ................................................................ 11
Table 8: Heat and material balance .................................................................................... 16
Table 9: Heat and material balance .................................................................................... 17
Table 10: Third Design Results ........................................................................................... 19
Table 11: Heat and Material Results in Aspen Plus ............................................................. 21
Table 12: Components Properties ....................................................................................... 23
Table 13: Gain Calculation ................................................................................................. 24
Table 14: Gain Calculation after Modification .................................................................... 25
Table15 :Aspen Results ....................................................................................................... 29
Table 16: Total Cost Results................................................................................................ 30
Table 17: Reactor Configurations ....................................................................................... 31
Table 18: Feed Rates........................................................................................................... 31
Table 19: Products Rates .................................................................................................... 31
Table 20 : Coolant Specification ......................................................................................... 31
III
List of figures
IV
Introduction
Phthalic anhydride (PAN) is an organic compound with the formula C6H4(CO)2O. It is
the anhydride of phthalic acid. This colorless solid is an important industrial chemical.
It is one of the most important products of modem large-scale organic synthesis, and
it has a wide application in various branches of chemical industry.
Uses
PAN is an intermediate petrochemical used for the production of plasticizers
especially for polyvinylchloride (PVC), unsaturated Polyesters, dyes and alkyd resins
which are used in the manufacture of reinforced plastics and in specialized
applications such as surface coatings. It is trade in either molten form or as a white
powder. About 50% of all phthalic anhydride produced is used in the manufacture of
plasticizers for PVC processing. Unsaturated polyester resins are uses (15-20) % of all
PAN produced and (10-15) % used in alkyd resins.[1]
The figure below shows the major product chain of phthalic anhydride in chemical
industry.
Manufacturing company
PAN is currently produced in many region of the world. In Australia one company
has two plants were built in 1960s and use naphthalene as the feed. Several large
producers of PAN operate in Japan, Korea, and Taiwan. The major company that
produce PAN are NCP coatings inc , Arkema inc, Esco company and Durcon inc .
In 2006, the worldwide production of PAN has slowly increased with production
approaching the estimated capacity of 3,600,000 tones/year.[2]
The selling price has varied due fluctuating demands and production rates but is
currently around $(850-950)/ton with purity of 99.5%.[3]
The feed stock
PAN is produced from o-xylene feedstock or naphthalene. In 1896 the feed stock for
the liquid phase oxidation was naphthalene. In the United State and Germany they try
to come up with process to oxide naphthalene using vapor phase and they success in
1930.The shortage of naphthalene with availability of o-xylene the company forced to
use it. Since the 1960s o-xylene has replaced naphthalene as feedstock more and
more. The selling price of pure o-xylene around $5.05/kg while the price for
naphthalene around $5.96/kg[1].Currently 90% of phthalic anhydride is produced
from o-xylene because of the yield since it is the main factor affecting the choice of
the feed stock and the price.
Table 1: Component Price
Component
O-xylene
Naphthalene
Price($)
5.05/kg
5.96/kg
Process description
The manufacturing of Phthalic Anhydride (PAN) is done in several steps. As
simplicity, mixture of O-xylene and air is preheated and converting o-xylene to vapor
knowing that the boiling point of the o-xylene is 144.4 C. Then, the mixture is fed to a
catalytic reactor. The reaction is highly exothermic, so to maintain the temperature,
the reactor is designed as packed bed reactor with heat exchanger. Water is used to
cool the reactor. The products then purified using other units like distillation.
There are five reactions happen beside the production of phthalic anhydride by
oxidation of o-xylene. These reactions are listed below.[6]
+
+
+ .
+ .
+
+
+
The first reaction is the main reaction and it is assumed 70% selectivity. The second
Reaction refers to the formation of the by-product maleic anhydride (MA) and a 10%
selectivity is considered. The third and the fourth reactions represent the complete and
incomplete combustions of o-xylene with 15% and 5% selectivity, respectively.
Type of reactors
In the past, phthalic anhydride (PAN) was produced in a slurry. After o-xylene has
replaced naphthalene as feedstock, the reactors were developed and fluidized bed and
fixed bed reactors were used. Naphthalene-based feedstock is made up of vaporized
naphthalene and compressed air. It is transferred to the fluidized bed reactor and
oxidized in the presence of a catalyst.
In PAN production using o-xylene as the basic feedstock, filtered air is preheated,
compressed, and mixed with vaporized o-xylene and fed into the fixed-bed tubular
reactors. Nowadays, fixed bed catalytic reactor is commonly used. The table below
shows comparison between fluidized bed and fixed bed for many parameters.[5]
Table 2: Fixed-Bed. vs. Fluidized-Bed Reactors for Selective Hydrocarbon Oxidation Reactions
Hydrocarbon
concentration
Oxygen concentration
Temperature control
Catalyst effectiveness
Catalyst cost
Capital investment
Raw material Cost
Raw material availability
CO2 emission
PAN Yield
Fixed-bed
reactor
Below flammability
Large excess
Hot spot
Poor to average
Least expensive
Expensive
Lower
More available
Less
Higher
Near stoichiometric
Nearly isothermal
Good
More expensive
Less expensive
Higher
Less available
More
Lower
Fluidized-bed reactor
Catalyst
There are different types of catalysts which are used for the oxidation of o-xylane to
PAN. Types that contain V2O5 supported on TiO2 are common and affective
catalysts for this process. The amount of V2O5 is used affects the selectivity of PAN
and carbon dioxide and the temperature for total conversion. Table (3) shows some
comparison. It seems that the catalyst contain 5.6% is more active. It has selectivity of
50% PAN when 100% conversion of o-xylene and the best temperature is 553K.[8]
Table 3:Catalyst Properties and Behavior in o-Xylene Oxidation
Catalyst
Vanadium
(wt%)
VPTGA(1)
0.68
VPTGA(5)
2.85
VPTGA(10) 5.6
VPTGB
0.58
VP25
0.13
Surface
(m2/g)
111
96
104
152
56
area Yield of PA
(%)
26
17
50
25
18
Temp.
(K)
558
513
553
568
593
Kinetics
The kinetic of the five reactions are:[7]
+ 3O C H O + 3H O
A catalyst weight of a packed bed reactor model is obtained and then converts the
weight to a reactor volume using catalyst bulk density. In this design we will explore
a reactor with a single reaction. However, reactions to byproducts will be added in the
third design.
The designing of fixed bed reactor depend on the following rate of the reaction that
obtained from literature:
r
= k P P
ln
+ 19.837
k =4.1219e8 kmole /(kg catalyst).atm2 hr. The activation energy is 27000 cal/mol[1].
The design differential mole balance equation is
d(x) r
=
d(w) Fa
P=3atm
W (f) =21071kg
Polymath solved the differential equation and gave the relation between the weight of
catalyst and the conversion. The typical conversion is 85%. The calculations were
repeated at different temperatures to visualize the effect of temperature in the
conversion and the weight of the catalyst required to achieve the specified conversion.
The calculations can be obtained in matlab which is easier and the code is in the
appendix. Table (4) shows the results at 400 C and 3 atm. Figure (4) shows the effect
of temperature in the conversion. From figure (4), the weight of the catalyst required
to reach 85% conversion decrease with increasing in temperature. At 633 K, 75 000
kg of catalysts is needed however; 21000 kg is only required to achieve the specified
conversion.
Mass balance:
Table 4: Mass Balance Results
species
Total
Initial
(Kmol/s)
0.0523
0.7259
0
0
2.7308
3.509
Change
(kmol/s)
-0.04453
-0.1333
0.0444
0.1333
0
0
Final
(Kmol/s)
7.858 10
0.5925
0.0444
0.1333
2.7308
3.509
1
2
3
4
Variable
w (kg)
X
T (K)
P (atm)
Final value
2.107E+04
0.8500067
673
3
w
21071
=
= 12.55m
(1 ) 3357(1 0.5)
The simulation
We simulate the packed bed reactor in Aspen Plus using the RPLUG reactor. The
specifications of the feed are 673K and 3 atm. The table below shows the result
obtained of heat and material balance.
Table 6: Heat
balance
Heaand
t anmaterial
d Material
Ba la nce Table
Strea m ID
Tem perature C
P ressure
Vap or Frac
ba r
Mole Flo w
Ma ss Flo w
FEED
P RODUCT
39 9. 9
399. 9
3.040
1.000
3.00 0
1.00 0
km ol/hr
kg/hr
12 686.36 0
38 0541.6 02
12686.360
380541 .602
23 3529.3 66
236623 .630
37 .683
-4.82 6
188. 597
2612.819
30 .1 43
21 37.456
Enthalpy
Mole Flo w
C8H10 -01
O2
Gca l/hr
km ol/hr
C8H4O-01
H2O
N2
15 8. 454
47 5. 363
9884.945
98 84.945
The conversion can be calculating using the flow rate of the o-xylene obtained from
aspen plus by the equation below, and we get very close answer to the calculated
result.
x=
188.597 30.143
= 0.84
188.597
To construct the plot of conversion versus heat duty we use the data composition
obtained and multiplied by the total flow of the outlet and use it to find the
conversion.
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0
10000
20000
30000
40000
50000
60000
Q (KW)
Figure6 : conversion versus heat duty
The figure above shows the relationship between the conversions versus heat duty. As
can be seen from the figure, as we increase the conversion the heat duty increase.
Actually there is a proportional linear relationship between them.
10
( )
(1+x)
P=3atm
W (f) =21071kg
= y (0) =1
Polymath solved the differential equations and gave the relation between the weight
of catalyst and the conversion. The calculations were repeated at different
temperatures to visualize the effect of temperature in the conversion with
consideration of pressure drop and compare it with the result of previous design.
Table 7: Design Results without Sipliting to Tube
1
2
3
4
5
6
7
8
9
Variable
w (kg)
x
y
T (K)
N
P0 (atm)
D (m)
V (m3)
L (m)
Final value
2.107E+04
0.7044096
0.4936886
673
1
3
3.5
12.55347
1.304257
11
Weight VS conversion
0.8
0.7
0.6
T=673K
T=650K
T=630K
T=600K
T=573K
0.5
0.4
0.3
0.2
0.1
0
0
5000
10000
15000
20000
W(kg)
25000
Figure (7) above shows the effect of catalyst weight on the conversion at different
range of temperature with consideration of pressure drop. As can be seen, the
conversion increases as the catalyst weight increase. When the pressure drop
increased the concentration decreased resulting in a decreased rate of reaction. As a
result of this smaller reaction rate, the conversion will be less with pressure drop than
without pressure drop as we observed that on figure (8).
Weight VS conversion
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0
5000
10000
15000
W(kg)
20000
12
25000
14
1
2
3
4
5
6
7
8
9
Variable
w (kg)
x
y
T (k)
N
P0 (atm)
D (in)
L (m)
Vt (m3)
Final value
2.152E+04
0.8507969
0.9009362
617
2.514E+04
3
1.5
0.653
86.87042
The number of tubes is considered to be 25140 tubes and contains 5.8 kg of catalyst in
each one. The conversion is calculated and gives 85% and the pressure ratio is 0.9.
Figure (13) shows the catalyst weight effects in pressure drop and conversion. The
tube diameter of each tube is 1.5 inches and a length of 0.653 meter.
Figure 13: Shows the Catalyst Weight Effects in Pressure Drop and Conversion
15
The simulation
Based on the simulation done in memo 2 of packed bed reactor in Aspen Plus using
the RPLUG reactor, the pressure drop was including in this memo. We specify Ergun
friction correlation to calculate process steam pressure drop. The specifications of the
feed in the first run are 673K and 3 atm with the following configurations and catalyst
weight.
N (number of tube) =1
W=21071kg
D=3.5m
L=1.304257m
The table below shows the result obtained of heat and material balance.
Table 8: Heat and material balance
FEED
P ROD UCT
Temperature
399 .9
399 .9
P res sure
bar
3.0 40
1.4 95
1.0 00
1.0 00
126 86.3 60
126 86.3 60
Vapor Frac
Mole Flow
kmol/hr
Mass Flow
kg/hr
Gcal/hr
Mole Flow
kmol/hr
C8H10-0 1
O2
37.683
2.3 01
188 .597
56.708
261 2.81 9
221 7.15 3
C8H4O-01
131 .889
H 2O
395 .666
N2
988 4.94 5
988 4.94 5
The conversion can be calculating using the flow rate of the o-xylene obtained from
aspen plus by the equation below, and we get very close answer to those obtained in
POLYMATH.
x=
188.597 56.708
= 0.699
188.597
The conversion obtained using POLMATH was 0.704. As we observed the difference
between them is 0.7%.
16
In the second run, the specifications of the feed are 617K and 3 atm with the
following configurations and catalyst weight that give us the desired conversion
which is 0.85.
N (number of tube) =25140
L=3.03m
The table below shows the result obtained of heat and material balance.
Table 9: Heat and material balance
FEE D
PRODUCT
Temperature
343. 9
343. 9
Pressure
bar
3. 040
2. 738
1. 000
1. 000
12686. 360
12686. 360
Vapor Frac
Mole Flow
kmol/hr
Mass Flow
kg/hr
Gcal/hr
Mole Flow
kmol/hr
C8H10-01
O2
-10. 926
188. 597
28. 761
2612. 819
2133. 313
C8H4O-01
159. 835
H2O
479. 506
N2
9884. 945
9884. 945
The calculated conversion using flow rate of the o-xylene obtained from Aspen is
0.848 with the difference of 0.2% from POLYMATH result.
In both trails the ratio of the pressure (P/Po) is exactly the same we obtained in
POLYMATH.
17
( )
( )
( )
=r
=r
( )
=r
(
( )
(
=r
=r
( )
d(y) F T
=
d(w) 2y F T
18
=r
1
2
3
4
5
6
7
8
Variable
w (kg)
y
T (k)
N
P0 (atm)
D (in)
L (m)
Vt (m3)
Final value
23055
0.9005
673
2.25E+04
3
1.5
0.653
86.87042
Plot Flow
Figure 14: Molar flow rate of each component versus the catalyst weight
Figure (14) shows the molar flow of each component with the weight of catalyst. The
molar flow rate of all products is always increasing. Water is produced with high
amount. Pressure drop was fixed to be 10% only.
19
3
2.5
T=673K
sd_pa
T=655K
1.5
T=640K
1
0.5
0
0
5000
10000
W(kg)
15000
20000
25000
sd_ma Vs W
0.3
0.25
T=673K
sd_ma
0.2
T=655K
0.15
T=640K
0.1
0.05
0
0
5000
10000
W(kg)
15000
20
20000
25000
Aspen simulation
Based on the simulation done in memo 3 of packed bed reactor in Aspen Plus using
the RPLUG reactor, the four side reactions are added in the configuration with their
kinetics. The specifications of the feed are 673K and 3 atm with the following
configurations and catalyst weight.
N (number of tube) =1
W=21071kg
D=5.35m
L=0.558m
The table below shows the result obtained of heat and material balance.
Table 11: Heat and Material Results in Aspen Plus
Heat and Material Balance Table
Stream ID
FEED
PRODUCT
Temp erature
399.9
399.9
Pressure
bar
3.040
2.737
1.000
1.000
22547.160
22626.729
Vap or Frac
M ole Flow
kmol/hr
M ass Flow
kg/hr
676363.053
676363.053
Volume Flow
cum/hr
415046.066
462533.781
Enthalp y
Gcal/hr
66.980
-47.109
M ole Flow
kmol/hr
335.520
92.947
4646.160
3432.062
C8H10-01
O2
C8H4O-01
160.015
H2O
848.566
N2
17565.480
17565.480
CO2
483.391
C4H2O-01
44.268
The conversion can be calculating using the flow rate of the o-xylene obtained from
aspen plus by the equation below, and we get very close answer to those obtained in
POLYMATH.
x=
335.520 92.947
= 0.722
335.520
The conversion obtained using POLMATH was 0.726. As we observed the difference
between them is 0.5%.However in this memo we care more about the exit flow rate of
21
our product (phthalic anhydride) to get the desired amount specified (20,000
tons/year). The outlet flow rate obtained using Aspen is 160.0 kmol/hr which is very
close answer calculated by POLYMATH(160.5 kmol/hr).
Figure (17) shows the flow rate of all species except the flow rate of O2 in the
primary axis with reactor length. As can be seen, the reactant flow rate (O-xylene and
Oxygen) are decreasing with the reactor length while the product species increasing
with the reactor length. These results are expected from the reactions since all it are
producing water and four reactions producing CO2
and only one reaction are
producing phthalic anhydride.
5000
800
4500
700
4000
3500
600
3000
500
2500
400
2000
300
1500
200
1000
100
500
0
0
0.1
0.2
0.3
L(m)
0.4
0.5
0.6
Figure 17: Molar Flow of each Component with Reactor Length obtained from Aspen
22
900
f_O-xylene
f_phthalic
f_water
f_CO2
f_o2
Component
o-xylene
Maleic
anhydride
269.9
Carbon
dioxide
48.96
Water
Nitrogen
458.6
Oxygen Phthalic
anhydride
32.73
723.5
Cp
(KJ/kmol.K)
H
(KJ/mol)
37.23
30.6
19.1
-398.2
-393.5
-241.80
-371.4
The overall heat transfer coefficient was found in literature to be 58 (W/m2.K). the
coolant inlet temperature is 655 K. the pressure drop was maintained not to exceed
10%.
Temperature profile
Figure (18) shows the temperature gradient with the weight of catalyst. A hot spot
appear in the reactor. The hot spot temperature which is the highest temperature is
calculated to be 672.8 oC. Then the temperature decreases and goes to constant. The
outlet temperature of the reactor is 656.1 oC which is almost acceptable. Coolant
temperature increases along the reactor and Figure (19) shows the relation.
23
Dynamic stability
The reactor was tested dynamically by considering the gain. The inlet temperature of
the coolant was changed to study the effect of changing in the hot spot temperature.
The following results were obtained:
Table 13: Gain Calculation
Ta ( K )
638
636
Th ( K )
715.2
689.1
24
Gain
17
9.1
From the results, the design is not stable dynamically since the gain is more than 2. As
a solution the amount of inert component should be increased and in this case the ratio
of the air to o-xylene was increased from 20 to 25 ( kg.air/kg.xylene). After the air
amount was changed and other parameters were optimized, the dynamic results were
shown in table (14). The coolant inlet temperature was set to be 643 K and hot spot
temperature was found to be 688.1.
Table 14: Gain Calculation after Modification
Ta ( K )
642
644
Th ( K )
681.2
684.8
Gain
1.9
1.7
Aspen Simulation
After the reactor was designed to obtain the target production of phtalic anhydride, the
reactor was simulated in Aspen Plus. The flow sheet of the model was shown in figure
(21). PBR model was used with co-current coolant and specified heat transfer
coefficient U of 3.5 (kw/m2.K). Figure (22) shows the model specification. The
reactor configuration used in Aspen is the calculated dimensions. A length of 0.6 m,
1.5 in diameter and 36000 tubes was considered.
25
The inlet reactor pressure is specified to be 3 atm. The Ergun equation was used to
calculate the pressure drop in the reactor. Catalyst weight, porosity and particles
diameter were added in the model specification. Figures (24) and (25) show the
progress.
26
The five reactions were added to the design. POWERLAW type of kinetics was
considered and the all kinetics were added. Rate phase, basis and activation energies
were specified for each reaction. Figure (27) explains the kinetics specification way.
27
After running the simulation, the results were tabulated and then compared with the
calculated values. The production of phthalic anhydride is consistent. The calculated
phthalic anhydride is 163 kmol/hr and Aspen calculated to be 160 kmol/hr. The
pressure drop was 0.3 atm as same as the calculated value. The temperature profile
through the reactor was plotted and a hot spot can be determined. The hot spot
temperature is 391.5 C, 665 K and calculated is 670 K. The results were shown
below.
28
392
391
Temperature (c)
390
389
388
387
386
385
384
0
0.1
0.2
0.3
0.4
Tube Length (m)
29
0.5
0.6
0.7
Economic analysis
The cost of production phthalic anhydride per year depends on purchase cost of the
packed bed reactor with heat exchanger, annual cost of the raw material (air and oxylene); cooling cost and catalyst cost (V2O5).The cost of production of
20000tons/year can be calculated using the following equation
Cost=Purchase cost of the reactor + Annual cost of raw material + Annual cooling
cost + catalyst cost- annual revenue of by product (malic anhydride)- Annual revenue
of phthalic anhydride
Purchase cost of the packed bed reactor with heat exchanger can be calculated using
the following equation [1] ($) =1.25*1600(As) .
Where N is number of tubes
As = DLN
Cooling cost calculated by obtained first the heat duty then calculate mass flow rate
using the following equation
m =
Q
C T
Annual cost of the raw material and revenue of by product and the product depend on
the flow rates multiply by it price.
Table 16: Total Cost Results
Total
17,145,104
30
Design summary
Table 17: Reactor Configurations
N (tubes)
36000
D (in)
1.5
L (m)
0.6
W ( kg )
40000
T(K)
656
P ( atm)
3
Component
Rate ( kg/s)
O-xylene
10
Air
250
Component
Rate (kmol/s)
O-xylene
0.0256
Oxygen
1.4706
PAN
0.0454
MAN
0.0125
CO2
0.1352
Water
0.2395
Type of coolant
Water
Conclusion
The packed bed reactor design that used for phtalic anhydride production has been
done. Pressure drop, side reactions, temperature variation were considered. After
optimizing all parameters to achieve 20 ton/year of phthalic anhydride, reactor
configurations listed in table (15). The reactor looks like a double pipe heat exchanger
with 36000 tubes with 1.5 in. water steam at 640 K was used to maintain the
temperature with a flow rate of 0.18 kg/s per tube. The feed rates to the reactor shown
in table (16) and products rate tabulated in table (17).
31
References
1.
2.
3.
4.
5.
6.
32
Appendix
function main ()
clear all;close all;clc
%----------------------------------------------% OPERATING CONDITION
%----------------------------------------------To=656;
% k
R1=1.987;
% cal/mol.k
Po=3;
% atm
N=36000;
% Tubes
Ta0=640;
% K
m_c=.01;
% kmol/s
U=3.5;
% Kw/m2.k
Tr=298;
% K
D=.0254*1.5;
% m
w=40000;
% kg
%-----------------------------------------------% O-Xylene FEED
%-----------------------------------------------m_xy=10/N;
% kg/s
%-----------------------------------------------%----------------------------------------------%Reactions
%----------------------------------------------% (1) XY + 3
O2 --->
PA + 3 H2O
% (2) PA + 7.5 O2 ---> 8 CO2 + 2 H2O
% (3) XY + 10.5 O2 ---> 8 CO2 + 5 H2O
% (4) XY + 7.5 O2 --->
MA + 4 CO2 + 4 H2O
% (5) MA + 3
O2 ---> 4 CO2 +
H2O
%
% Stoic
%
XY
O2
PA MA CO2 W
v=[ -1
-3
1
0
0
3
0
-7.5 -1
0
8
2
-1
-10.5 0
0
8
5
-1
-7.5
0
1
4
4
0
-3
0 -1
4
1];
%---------------------------------------------% Cp
%
XY
O2
PA
MA
CO2
Cp=[ 458.588
32.7362
723.474
269.858
48.96
Cpn2=30.5798;
%-----------------------------------------------dCp=v*Cp';
%---------------------------------------------% H
%
XY
O2
PA
MA
CO2
W
Ho=[19.1
0
-371.4
-398.2 -393.51 -241.83]*1e3;
dHrx_o=v*Ho';
%----------------------------------------------% K CALCULATION
%----------------------------------------------ko=[19.837 20.86 18.98 19.23 20.47];
E=[27000 31000 28600 27900 30400];
%-----------------------------------------------%================================================
% CALCULATION
%-----------------------------------------------m_air=m_xy*25;
% kg/s
m_o2=0.232*m_air;
% kg/s
m_n2=(1-.232)*m_air;
% kg/s
%
XY
O2
N2
PA
Mr=[106.16 32 28.02 148.1];
n_xy=m_xy/Mr(1);
% kmol/s
n_o2=m_o2/Mr(2);
n_n2=m_n2/Mr(3);
% kg/kmol
% kmol/s
% kmol/s
33
W
37.23 ];
% KJ/kmol.K
% KJ/kmol
Ft0=n_xy+n_o2+n_n2;
% kmol/s
%
N2
XY
O2
y0=[n_n2 n_xy n_o2]/Ft0;
%-----------------------------------------------------% Alpha Calculation
%-----------------------------------------------wf=w/N;
P0=Po*101325;
%
R=8.314;
%
por=0.5;
Dp=.006;
%
Vis=(-1e-08*To^2+5e-5*To+0.0039)/1000;
rho_c=3357;
%
rho_b=rho_c*(1-por);
%
V=wf/(rho_c*(1-por));
%
L=4*V/(pi*D^2);
%
M_avg=y0(3)*Mr(1)+y0(1)*Mr(3)+y0(3)*Mr(2);
%
Ac=pi/4*D^2;
%
m=Ft0*M_avg;
%
G=m/Ac;
%
rho_o=P0*M_avg/(R*To)/1000;
%
B0=G/(rho_o*Dp)*(1-por)/por^3*(150*(1-por)*Vis/Dp+1.75*G);%
a=2*B0/(rho_c*Ac*(1-por)*P0);
%
%-----------------------------------------------%-----------------------------------------------------Fn=n_n2;
Fi=[ Ft0*y0(2) Ft0*y0(3) 0 0 0 0 1 To Ta0];
Pa
kPa.m3/kmol.k
m
% Pa.s
kg/m3
kg/m3
m3
m
kg/kmol
m2
kg/s
kg/m2.s
kg/m3
kg/m2.s2
1/kg
ws=0:10/N:wf; n=length(ws);
[w,z]=ode45(@(w,z)rate(w,z,Po,a,v,Ft0,dHrx_o,dCp,rho_b,D,Cp,Fn,Cpn2,To,ko,E,R1,m_c,U,T
r,Ta0),ws,Fi);
%-----------------------------------------------------%======================================================
% RESULTS
%------------------------------------------------------disp('
Fxy
Fo2
table=[z(:,1:6)*N z(:,7:9)]
yf=z(n,7)
Th=max(z(:,8))
D
L
x=(z(1,1)-z(n,1))/(z(1,1))
mp=z(n,3)*Mr(4)*(30326400/1000)*N
q=[z(:,1:6)*N];
plotyy(w,q,w,z(:,7))
plot(w,z(:,8:9))
Vt=V*N
end
Fpa
Fma
Fco2
Fw
% ton/year
%==========================================================================
%==========================================================================
%==========================================================================
function
dzdw=rate(w,z,Po,a,v,Ft0,dHrx_o,dCp,rho_b,D,Cp,Fn,Cpn2,To,ko,E,R1,m_c,U,Tr,Ta0)
for i=1:6
F(i)=z(i);
end
y=z(7);
T=z(8);
Ta=z(9);
Ft=sum(F)+Fn;
34
y ')
% Heat
dHrx=(dHrx_o+dCp*(T-Tr));
% KJ/kmol
k=exp(ko - E/(R1*T))/3600;
% kmol/(kgcat.atm2.s)
Pxy=F(1)/Ft*Po*y*To/T;
Po2=F(2)/Ft*Po*y*To/T;
Ppa=F(3)/Ft*Po*y*To/T;
Pma=F(4)/Ft*Po*y*To/T;
%
%
%
%
atm
atm
atm
atm
% Reactions
rs(1)=k(1)*Pxy*Po2;
rs(2)=k(2)*Ppa*Po2;
rs(3)=k(3)*Pxy*Po2;
rs(4)=k(4)*Pxy*Po2;
rs(5)=k(5)*Pma*Po2;
%
%
%
%
%
kmol/kgcat.s
kmol/kgcat.s
kmol/kgcat.s
kmol/kgcat.s
kmol/kgcat.s
% Rates Evaluation
for i=1:6
r(i)=0;
for j=1:5
r(i)=r(i)+rs(j)*v(j,i);
end
end
% differential
for i=1:6
dzdw(i)=r(i);
end
dzdw(7)=-a/(2*y)*(Ft/Ft0)*(To/T);
dzdw(8)=(((4*U)*(Ta-T)/(D*rho_b))+(sum(-rs.*dHrx')))/(sum(F.*Cp)+Fn*Cpn2);
dzdw(9)=((4*U)*(T-Ta)/(D*rho_b))/(m_c*Cp(6));
dzdw=dzdw';
end
35