MEMO

To: Dr. Michael Cunningham, Xin Su

A B+C
The dehydrogenation of ethylbenzene to produce styrene follows elementary
rate laws in both the forward and reverse reactions. Therefore the rate law can
be written so that all concentration components have an exponent of 1.

r A=K c C A =K f C A K r C B CC
Since the reaction follows the ideal gas law, the equilibrium constant with
regards to concentration is equivalent to the equilibrium constant with regards to
pressure divided by the gas constant and temperature.

K C=

Kp
RT

Similarly ,

Kf =

Kf,p
RT

The equilibrium constant can be defined by the quotient of the forward rate constantthe reverse rate constant
Thiscan be rearranges substitute for the reverse rateequations .

Kr=

Kf
Kc

Subbing all of these values in gives a rate law expression of:

r A=K f C A K r C B CC =K f C A

Kf
C C
Kc B C

A stoichiometric table can be used to solve for the output flowrates of each
component. These can then be converted into concentrations and subbed into
the rate law.

Table 1: Stoicheometric Table

Input

Change

Output

FA 0

X A F A 0

1 X
( A) F A 0 =F A

X A F A0

X A F A0

X A F A 0=F C

FI 0 S F A0

S F A 0 =F I

Total

F0 =(1+ S)F A 0

X A F A0

FB

Ft =(1+ S+ X A )F A 0

Using the ideal gas law with the ratio of initial conditions to final conditions, the
volumetric flowrate can be found.

V Ft
=
V 0 F0
The initial and final flowrates can be subbed into this equation to give an
expression for the final volumetric flowrate.

V =V 0

Ft
( 1+ S+ X A ) F A 0
( 1+ S+ X A )
=V 0
=V 0
F0
(1+S )F A 0
(1+ S)

Now that the volumetric flowrate is solved for, this can be used with the final
flowrates found in the stoichiometric table to find the final concentrations of each
species.

1 X
1 X
1 X
( A) ( 1+ S ) C A 0
( 1+ S+ X A )
( A) ( 1+ S ) F A 0
=
( 1+S + X A ) V 0
( A ) F A 0
=
( 1+ S+ X A )
V0
(1+S )
F
C A = A =
V

C B=

FB
=
V

CC =C B=

V0

X A F A0
X C (1+ S)
= A A0
( 1+S + X A ) ( 1+ S+ X A )
(1+ S)

X A C A 0 (1+ S)
( 1+S + X A )

Each of the concentrations can now be subbed in for a completed rate law.

1X
( A) ( 1+ S ) C A 0 K f X A C A 0 ( 1+ S )

K c ( 1+ S+ X A )
( 1+ S+ X A )
r A =K f

At steady state:

dCA
=0
dt
Which implies that ,

1X
2
( A) ( 1+ S ) C A 0 K f X A C A 0 ( 1+ S )

=K c C A
K c ( 1+ S+ X A )
( 1+ S+ X A )
0=K f

As

K f =K r =

Kf
Kc

More detailed calculations are in Page 1 of the appendix.

Figure 1 Comparing the effect on conversion of varying temperature (a and b), varying
pressure (c and d) and varying steam ratio (e and f)

The conversion plots in Figure 1 were created by solving for Xa using the
quadratic equation. The equation from which the a, b, and c values were
obtained was as follows:

X A 2 ( C A 0 ( 1+ S ) + K C ) + X A ( S K C )( K C ( 1+S ) ) =0
In examining Figure 1, the effects of temperature, pressure, and steam ratio can
be compared. Plots a) and b) show that increased temperature increases the
conversion significantly past approximately 550K. These plots also show that
conversion is higher with a lower pressure and higher steam ratio, but these
changes are not as significant as the temperature changes. Plots c) and d) show

that with lower pressures, the conversion rate is higher, especially between 1atm
and approximately 3atm. Plot c) shows that higher steam ratios also contribute
to higher conversions. Plot d) shows that there is even more of a contribution
from temperature, seeing as how at very high temperatures and very low
temperature, the conversion is very high and very low (respectively), and the
pressure is almost insignificant to the conversion. Plots e) and f) show that as the
steam ratio increases, so does the conversion, and plot e) shows that at more
extreme temperatures, the steam ratio has less of an impact. With varying steam
ratio, as seen in plot f), the conversion is not affected greatly at different
pressures, except for at 1 atm. The conclusions to be drawn are that higher
steam ratios and low pressures increase conversion slightly, but temperature is
the main factor in conversion rate.

a)
600000
S=0 P=1atm
T=953.90K

400000

Fao/-ra [L] 200000

S=3 P=1atm
T=953.9K
0

0.2

0.4

0.6

0.8

Conversion, X [-]

b)
80000
60000

S=0 P=1atm
T=953.90K

Fao/-ra [L] 40000

s=0 P=1atm T=1000K

0.2 0.4 0.6 0.8

Conversion, X [-]

c)
80000
60000

S=0 P=1atm
T=953.90K

Fao/-ra [L] 40000

S=0 P=2atm
T=953.90K

20000
0

0 0.10.20.30.40.50.60.70.80.9 1

Conversion, X[-]

Figure 2 Levenspiel plots for varying S (plot a), varying T (plot b), and
varying S (plot c)

In Figure 2, the Levenspiel plot a) shows that with a higher S value, the volume
increased for both the CSTR and the PBR, which is not ideal for a reactor because
with increased volume comes increased cost. With lower pressure and higher
temperature (plots a and b), the volume of both the PBR and CSTR are
minimized. From the design equations for a PBR vs. a CSTR (PBR volume is area
under the curve and CSTR volume is area above the curve), the volume of a
CSTR is always larger than the volume of a PBR. Therefore, using a PBR would
minimize volume thereby decreased cost for a more optimized process.
Part c. Optimisation of product per volume of reactor.

70000
60000
50000
40000

Fao/-ra [ L]

30000

S=0 P=1atm T=953.90K

20000
10000
0

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Conversion, X [-]

Figure 3 Levenspiel plot for optimized reactor conditions

The Levenspiel plot for the optimized conditions shows an exponential trend so
that higher conversions always results in a much higher reactor volume. This is
especially true when the conversion is increased above 0.7. Therefore, if the
minimum required conversion is 0.7, the system needs to be optimized for that
value.
According to our Conversion vs T, P and S plots for section b), the conversion is
maximized when pressure is minimized and the temperature and steam ratio are
maximized.
However, according to our Levenspiel plots, in figure 2. It is possible to conclude
that a small increase in steam ratio results in a very high increase in volume.
This means that to maximize the product per L of reactor we would need to
diminish S. This is because the steam (inert) that enters the reactor also
occupies a volume, therefore the reactor needs to be bigger.
Therefore, it is possible to state that there is trade-off between conversion and
reactor volume for a change in S. Analysing the X vs S plot and the Levenspiel
plot with a change in S it is possible to determine that the change in conversion
can be neglected as a lower steam ratio does not diminish the conversion
coefficient nearly as much as a higher steam ratio increases the reactor volume.
As a consequence, our final theoretical optimization would be a steam ratio of 0,
a pressure of 1 atm and a temperature of 953.90K, which at steady state results
in a conversion of 0.7. The reactor volume for this system is 14752 L for CSTR
and 7663L for the PFR. This is expected as the PFR minimizes the volume as it
can be observed from the Levenspiel plot. The volume under the curve is the
volume corresponding to the PFR and the area of y-axis (1/-Ra) times x-axis(Xa)
is the volume for the CSTR. To calculate the volume from the PFR in Excel, the
sum of rectangles methodwas used as excel does not have a built-in function.

1+ S
F A 0 ()

V =

The inlet volumetric flowrate was calculated by

= 0.07827 cubic

meters per s
The residence time was calculated using the formula:

t=

V PFR
V

= 1m 37s.

This means that a particle entering the optimized reactor will take 1m 37s to exit
the reactor.
The maximum flowrate of Fb per L of reactor volume was found to be Fb/Vpfr =
9.17*10^-5 g/L/s.
This is just a theoretical approximation and it is important to take into account
other factors like to what extent temperature needs to be minimized as heating
the mixture requires energy and implies higher running costs. In this case the
steam ratio was set to zero to maximize the flowrate of product per L of reactor
but in an actual set up steam is required to heat up the gas mixture. If we
account for a reasonable steam ratio such as 10 [1] and want to diminish the
volume of the reactor, the pressure could be increased to 200Kpa [1] so that the
temperature would need to be at 885.5 K according to our optimization algorithm
for the conversion. This temperature is in the actual Temperature range that an
actual reactor that produces ST from EB would be at [1]. This would result in a
volume of 243000L for the CSTR and 126100L for the PFR, which give a
residence time of 311 seconds. With these conditions, Fb/Vpfr =5.55 * 10^-6
g/L/s.
It is clear from these results that the production rate of product B is not
maximised under these conditions as Fb/Vpfr is lower than it was with S=0, but
the volume is still reasonable, about 20 times less than an Olympic swimming
pool (2,500,000L).
Operating conditions are also going to be affected by costs of reactants, volume
available as well as the materials for the reactor. Another important factor would
be maximum temperature and pressure that the reactor can operate and the
conditions that the chemical compounds can withstand.
Appendix:
Table A 1 Optimization for Fb/Vpfr

Optimization
minimizing S

0
0

Kpa

101.
33
101.
33

953.
90
953.
90

Kc

CA0

X
a

0.0
12
4
0.0
12

mol/L
0.012
77627
1
0.012
77627

0.
0
5
0.
1

-ra
mol/L/
s
0.000
15025
6
0.000
14234

1/-ra

F
b

6.66
E+0
3
7.03
E+0

0.
0
5
0.
1

vPF
R

vCST
R

332
.8
674
.8

332.
77
702.
50

Fb/V

v0

mol/L
0.000
15025
6
0.000
14819

m^3/s
0.078
27010
1
0.078
27010

101.
33

953.
90

101.
33

953.
90

101.
33

953.
90

101.
33

953.
90

101.
33

953.
90

101.
33

953.
90

101.
33

953.
90

101.
33

953.
90

101.
33

953.
90

101.
33

953.
90

101.
33

953.
90

101.
33

953.
90

101.
33

953.
90

101.
33

953.
90

101.
33

953.
90

101.
33

953.
90

101.
33

953.
90

4
0.0
12
4
0.0
12
4
0.0
12
4
0.0
12
4
0.0
12
4
0.0
12
4
0.0
12
4
0.0
12
4
0.0
12
4
0.0
12
4
0.0
12
4
0.0
12
4
0.0
12
4
0.0
12
4
0.0
12
4
0.0
12
4
0.0
12
4

1
0.012
77627
1
0.012
77627
1
0.012
77627
1
0.012
77627
1
0.012
77627
1
0.012
77627
1
0.012
77627
1
0.012
77627
1
0.012
77627
1
0.012
77627
1
0.012
77627
1
0.012
77627
1
0.012
77627
1
0.012
77627
1
0.012
77627
1
0.012
77627
1
0.012
77627
1

0
0.
1
5
0.
2
0
0.
2
5
0.
3
0
0.
3
5
0.
4
0
0.
4
5
0.
5
0
0.
5
5
0.
6
0
0.
6
5
0.
7
0
0.
7
5
0.
8
0
0.
8
5
0.
9
0
0.
9
5

8
0.000
13444
0.000
12653
1
0.000
11862
3
0.000
11071
5
0.000
10280
7
9.489
85E05
8.699
03E05
7.908
21E05
7.117
39E05
6.326
57E05
5.535
75E05
4.744
93E05
3.954
1E-05
3.163
28E05
2.372
46E05
1.581
64E05
7.908
21E06

3
7.44
E+0
3
7.90
E+0
3
8.43
E+0
3
9.03
E+0
3
9.73
E+0
3
1.05
E+0
4
1.15
E+0
4
1.26
E+0
4
1.41
E+0
4
1.58
E+0
4
1.81
E+0
4
2.11
E+0
4
2.53
E+0
4
3.16
E+0
4
4.22
E+0
4
6.32
E+0
4
1.26
E+0
5

0
0.
1
5
0.
2
0
0.
2
5
0.
3
0
0.
3
5
0.
4
0
0.
4
5
0.
5
0
0.
5
5
0.
6
0
0.
6
5
0.
7
0
0.
7
5
0.
8
0
0.
8
5
0.
9
0
0.
9
5

103
6.4

1115
.74

141
9.9

1580
.64

182
8.2

2107
.51

226
4.8

2709
.66

273
3.8

3404
.45

324
0.4

4215
.03

379
1.2

5172
.99

439
4.7

6322
.54

506
2.1

7727
.55

580
8.5

9483
.82

665
5.3

1174
1.87

763
3.8

1475
2.60

879
2.9
102
15.
5
120
59.
6
146
93.
9
194
35.
9

1896
7.63
2529
0.18
3582
7.75
5690
2.90
1201
28.3
5

8
0.000
14473
8
0.000
14085
6
0.000
13674
5
0.000
13246
3
0.000
12802
9
0.000
12344
2
0.000
11869
6
0.000
11377
3
0.000
10865
1
0.000
10329
7
9.766
68E05
9.169
78E05
8.529
61E05
7.831
26E05
7.048
36E05
6.124
97E05
4.887
87E05

1
0.078
27010
1
0.078
27010
1
0.078
27010
1
0.078
27010
1
0.078
27010
1
0.078
27010
1
0.078
27010
1
0.078
27010
1
0.078
27010
1
0.078
27010
1
0.078
27010
1
0.078
27010
1
0.078
27010
1
0.078
27010
1
0.078
27010
1
0.078
27010
1
0.078
27010
1

Table A 2 Optimal conditions from data from Reference 1 (Optimal conditions for a real
life reactor)

Actual optimization accounting for the steam

requirement to heat up the

Kc

10

200

885.25

0.00387588

10

200

885.25

0.00387588

10

200

885.25

0.00387588

10

200

885.25

0.00387588

10

200

885.25

0.00387588

10

200

885.25

0.00387588

10

200

885.25

0.00387588

10

200

885.25

0.00387588

10

200

885.25

0.00387588

10

200

885.25

0.00387588

10

200

885.25

0.00387588

10

200

885.25

0.00387588

10

200

885.25

0.00387588

10

200

885.25

0.00387588

10

200

885.25

0.00387588

10

200

885.25

0.00387588

10

200

885.25

0.00387588

10

200

885.25

0.00387588

10

200

885.25

0.00387588

10

200

885.25

0.00387588

CA0
mol/L
0.002470
366
0.002470
366
0.002470
366
0.002470
366
0.002470
366
0.002470
366
0.002470
366
0.002470
366
0.002470
366
0.002470
366
0.002470
366
0.002470
366
0.002470
366
0.002470
366
0.002470
366
0.002470
366
0.002470
366
0.002470
366
0.002470
366
0.002470
366

Xa
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0.5
0.55
0.6
0.65
0.7
0.75
0.8
0.85
0.9
0.95
0.9

minus ra
mol/L/s
9.0961E06
8.61736E06
8.13862E06
7.65987E06
7.18113E06
6.70239E06
6.22365E06
5.74491E06
5.26616E06
4.78742E06
4.30868E06
3.82994E06
3.3512E06
2.87245E06
2.39371E06
1.91497E06
1.43623E06
9.57484E07
4.78742E07
9.57484E07

References:
(1) Material Balances Project Styrene Manufacture, West Virginia University.
http://www.che.cemr.wvu.edu/publications/projects/styrene/styrene-a.pdf
(accessed: Nov 6, 2014)

#NAME?

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