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propylene (P)
2. C3H6
C6H6
C9H12
benzene (B)
cumene (C)
C9H12
C12H18
and the reaction kinetics are based on the power law model
(i)
(ii)
where both reaction rates are in kmol kgcat-1 s-1, CP is concentration of propylene in kmol m3
, CB is concentration of benzene in kmol m-3 and CC is concentration of cumene in kmol m-3.
The specific rate constants (m6 kgcat-1 kmol-1 s-1) are given by
(iii)
(iv)
Subscript numbers denote the number of reaction and the values of the parameters can be
seen in Table 1
Table 1: parameters of the reaction between from 300 350 oC and 30 40 bar.
Ai
Ei
(m kgcat kmol-1 s-1) (kJ kmol-1)
1
3.5 x 104
-1.04 x 105
6
2
2.9 x 10
-1.47 x 105
The reaction occurs in gas phase with the feed of pure benzene liquid at 28oC and 1 bar and
the feed of propylene liquid at the same temperature and 12 bar (from the vapour pressure
graph, the gaseous propylene liquefied at 10.17 bar for the temperature of 28oC). However
propylene feed contains 4.8% propane (PA) which does not involve in any reaction with
components of the reaction. The catalyst is zeolite-base type costed $1.8/kg with void
fraction, = 0.5, particle diameter, DP = 1 cm and bulk density, b = 2,500 kg m-3. For the
ease of calculation in this particular BKF2453 miniproject, the feed flow is assumed similar to
the air properties at 300oC and 30 bar.
Reaction
-1
The unreacted propylene will be separated under cryogenic condition from the inert
propane. Although the separation is costly, propane cannot be recycled together
continuously as it will accumulate in the reactive unit. Thus, propylene will recycled
internally and propane will be incinerated so as to generate steam for the process.
The block flow diagram of the process proposed at level 2 can be seen in Figure 1. F is molar
rate of input, P is molar flow rate of output for the respective components where,
additionally, the subscript G denotes the outlet gas of unconverted propylene and propane
and the subscript PA denotes propane.
FPA
FP, FPA
PC
Process
FB
PPDIPB
Figure 1
The prices of material involved in the components are as in Table 2.
Table 2: Physical property and prices of components
Components
Propylene
Benzene
Cumene
PDIPB
Propane
Purity (%)
95.2
99.9
99.9
Not necessary
Not necessary
Price/ Cost
$167/kmol
$267/kmol
$1200/kmol
$0.1/kW fuel
$0.1/kW fuel
Prepared by Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
Table of Contents
1.
Introduction ....................................................................................................................... 4
2.
2.1.1.
2.2.
3.
3.2.
3.2.1.
3.2.2.
3.2.3.
3.3.
3.3.1.
Efficiency.......................................................................................................... 17
3.3.2.
3.3.3.
3.4.
4.
References ....................................................................................................................... 18
5. Appendix A
6. Appendix B
7. Appendix C
8. Appendix D
Prepared by Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
1. Introduction
Conceptual design should normally start with decision on the mode of operation. Since the
BKF2453 students do not learn the process economics in attaining right production rate and
detail qualitative analysis in order to decide either batch or continuous, the mode of
operation for the projects has thus been set to continuous one. The process runs for 8000 hr
yearly with the remaining hours are for plant turn-around and cleaning.
Prepared by Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
Components
Propylene
Propane
Cumene
Benzene
PDIPB
Destination Code
Recycle
Fuel
Primary product
Recycle
Fuel
Outlet components exit the process at the ambient condition. From the boiling point, the
purge stream of propane is in gas phase while both cumene and p-diisopropyl benzene exit
as in liquid phase. However, cumene is the main product and must exit separately at a
standard purity to a particular price which, in this case, it is 99.9%. Figure 2.1 shows the
streams of input and output materials of the process.
5 propane
1 Propylene, propane
3 Cumene
Process
2 Benzene
4 p-diisopropyl benzene
(a)
FFPA
FFP, FFPA
PC
Process
FFB
PPDIPB
(b)
Figure 2.1 Input-Output Stream and the Respective Nomenclatures of the Benzene
Alkylation Process
2.1.
The benzene alkylation occurs in gas phase with a side reaction of p-diisopropyl benzene
synthesis as follows
C3H6
propylene (P)
C3 H 6
P
C 6 H6
benzene (B)
+
C9H12
C
C9H12
(2.1a)
cumene (C)
C12H18
(2.1b)
Prepared by Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
Analysis of mole balance follows the extent of reaction method (Felder & Rousseau, 2005).
The symbols 1 and 2 are used to denote the extents of reaction for the first and second
reactions (Eq. (2.1), respectively. The mole balance of all chemical species are generally
computed using the correlation as follows
i = +
where i is molar flow rate of the species i and I is the stoichiometric coefficient. Hence,
the final flow rate from Figure 3.1 can be summarised as in Table 2.2.
Table 2.2 Mole Balance for the Second Level of Decision
Species
Benzene
Propylene
Cumene
p-diisopropyl benzene
Inlet
FFB
FFP
0
0
Change
- 1
- 1 - 2
1 - 2
Outlet
0
0
PC
PPDIPB
In total, other than PC, there are 5 unknown variables. Information available to solve those
variables can be detailed based on the material and energy balance textbook as follows
(Felder & Rousseau, 2005)
Number of unknown variables in the process
2 Independent reactions
4 equation of extent of reactions
Composition of inert propane in the feed and purge (4.8%)
Total (Variables can be calculated by specifying any one of them)
4
+2
-4
-1
1
From the degree of freedom, one variable, any of FFP, FFB, or PPDIPB, must first be specified
before the others can be calculated. In chemical reaction engineering, they can be expressed
in conversion of the limiting reactant, which is the reactor design variable and thus will be
the variable to calculate the mole balance.
/ =
(2.2)
Prepared by Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
Selectivity
7.00E+02
6.00E+02
1:1
5.00E+02
1:2
4.00E+02
2:1
3.00E+02
1:4
2.00E+02
1.00E+02
0.00E+00
0
0.2
0.4
0.6
0.8
1.2
Xp
Figure 2.2 selectivity as functions of propylene conversion at various molar feed ratio,
propylene:benzene
The reaction yields are defined as
instantaneous yield =
overall yield =
(2.3)
(2.4)
Since, in this project, only two reactions involve in the process (or in other words, only one
side reaction exists), Equation 2.3 is thus same as Equation 2.4.
7
Prepared by Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
The yield is the fraction of propylene converted in the reactor that corresponds to the
cumene flow at the reactor outlet. Also, this cumene is all recovered and taken (assuming
100% separation efficiency for the second level of decision) from the process. Using the
same algorithm for the selectivity (Appendix A), the resulting yield of the reaction can be
plotted as shown in Figure 2.3. The results of yield from various feed ratios show a good
agreement with the selectivitys whereby the excess propylene clearly declines the yield to
zero before XP = 0.6. The feed with equal molar ratio exhibits significant drop up to 0.85 of
yield. The molar ratios of 1:2 and 1:4 do not have much difference, implies that further
excess of benzene is no longer sensitive to yield enhancement. Therefore the feed ratio,
propylene:benzene, of 1:2 is probably preferable for this process.
1.1
1.05
1
0.95
Yield
0.9
1:1
0.85
1:2
0.8
2:1
0.75
1:4
0.7
0.65
0.6
0
0.2
0.4
0.6
0.8
1.2
Xp
Figure 2.3 Reaction yields against the conversion of propylene for various feed ratio,
propylene:benzene
The equation of the yield against the conversion of propylene for the P:B feed ratio of 1:2 (as
exhibited in Figure 2.3) can be derived by using the Regression function in Polymath on the
data of the results from the batch reactor algorithm (Appendix B). The equation of power
with 0.99 R-square fits the correlation as follows
Y = 1 0.0193XP1.6321
(2.5)
For a production of PC mol/hr (52.08 kmol/hr), the propylene fed to the process FFP must be
=
(2.6)
The molar flow of propane corresponds to the fresh propylene feed through the purity
percentage. Thus
= 0.048
8
Prepared by Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
(2.7)
If a fraction Y of propylene is converted to cumene, a faction 1-Y must be lost to pdiisopropyl benzene. From the stoichiometry of the reactions (Equation 2.1), the amount of
PDIPB , PPDIPB, must be
= 1 =
(2.8)
The benzene input is identical to propylene input because benzene also involves indirectly
with the second reaction. Hence,
(2.9)
In summary, the above variables can be calculated for respective streams as tabulated in
Table 2.3.
Table 2.3 Stream Table of Mole Balance of Benzene Alkylation Process
Component
Propylene
2
0
3
0
4
0
Benzene
Cume
1
PC/Y
0.048
0.952
0
0
PC/Y
0
0
PC
P-diisopropyl benzene
28
12
28
1
28
1
0
0
28
1
Propane
Temperature (oC)
Pressure (bar)
Where Y = 1 0.0193XP1.6321
2.2.
5
0
0.048
0.952
0
0
0
28
1
Economic Potential
Since the practical values of the design variables depend on the process economics, the
stream costs are calculated where all of the costs of all raw materials and product streams
equated in term of design variables. The potential of economics (EP) at the second level is
therefore
EP ($/yr) = Cumene Value + Fuel Value of PDIPB + Fuel Value of Propane
Propylene Cost Benzene Cost.
(2.10)
The prices of materials and fuel value for cost estimation are as tabulated in Table 3.4
Table 2.4 Price Data for Benzene Alkylation
Components
Propylene
Benzene
Cumene
PDIPB
Propane
Price/ Cost
$167/kmol
$267/kmol
$1200/kmol
$0.1/kW fuel
$0.1/kW fuel
Prepared by Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
Power of fuel can be calculated from the enthalpies of combustion of PDIPB and propane: HC-PDIPBo = 6.82 kJ/kmol (Turton, Bailie, Whiting, & Shaeiwitz, 2008) and -HC-PAo = 2.2
kJ/kmol (Poling et al., 2008).
The economic potential in Eq 3.12 would finally be
= $1200 + $0.1
$167
+
$267
.
(2.11)
$/yr
9.10E+08
9.08E+08
9.06E+08
9.04E+08
9.02E+08
9.00E+08
0
0.2
0.4
0.6
0.8
1.2
Xp
10
Prepared by Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
Propylene
Recycle
RG and yPH
Propylene feed
FFP and FPA 1
FP0, FPA
Benzene
Feed
FP
Compressor
Reactor
FB0
Propane
Cumene
PDIPB
FPA
PC
PPDIPB
Benzene recycle
FFB
FB
Figure 3.1 Benzene Alkylation Process with Liquid and Gas Recycle Streams
3.1.
Before solving the mole balance, the unknown variables must be ensured that they can be
solved by using specifications and equations available from the process. The degrees of
freedom of 2 recycle junctions and a reactor based on Figure 3.1 can be tabulated as in
Table 3.1.
Table 3.1 Degree of freedom analyses for unit and junctions appeared at level 2 decision
Unit or junction
Unknown variables
1
FFP, FPA, FPO and FP: 4
2
FFB, FB and FB0: 3
Independent reactions
Balance
FFB + FB = FB0: -1
Feed condition
Purity percentage: -1
Information from the FFP = PC/Y: -1
2nd level of decision
Variables
to
be 1 ( variable XP)
specified
FFB = PC/Y: -1
Reactor
FP0, FPA, FP, FB0, FB and
PPDIPB: 6
2
Independent extent of
reactions: -4
Molar feed ratio, B: -1
FPA: -1
1 ( variable XP)
From the analysis, the solution must start at Junction 1 as it has the lowest degree and it
deals with the limiting reactant. Thus,
FFP +FP = FP0
But FP = FP0(1 XP)
=
(3.1)
The feed information is essential in estimating the cost of the reactor and corresponding to
the fixed production rate. Unlike the BKF2453 activities, in this project, the reactor design
based on the production rate and conversion not from the feed rate and conversion. The
block flow diagram will be as 3.2.
11
Prepared by Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
RG and yPH
Propylene feed
FFP and FPA 1
Propylene
Recycle
Compressor
FP0
Reactor
FP0 (1-X)
FP (B -X)
FP0 (1-X)
Separator
s
Propane
Cumene
PDIPB
FPA
PC
PPDIPB
Benzene recycle
FP (B -X)
3.2 Block flow diagram of the benzene alkylation at the 2nd level of decision: recycle
structure.
3.2.
Reactor Design
Since both rate laws are the power law models and the reaction occurs irreversibly in
gaseous phase (assuming the mass transfer limitation is deemed negligible), the right and
economical reactor is thus the pack bed reactor as can be clearly seen from the plot of the
Levenspiel.
Based on the selectivity analysis, propylene feed must be limited at any cost. High selectivity
can be sustained if the concentration of cumene is low. This probably can be attained by
having continuous exit flow of cumene along the reactor length. In fact, it is critical as the
reactor has potential of distribution problem in the catalyst packing due to the multiplicity of
phases. The reactor scheme suggestion can be illustrated in 3.3 where the liquid phase will
flow downward of the catalyst packing.
P, B and PA
P, B, C, PDIPB and PA
12
Prepared by Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
C1 x 1e-5
0.44767
0.43852
0.5192
1.081
C1
-30.99e-5
PDIB**
* = +
ed.
C2 x 1e-5
2.3085
1.506
1.9245
3.7932
C2
1.01728
C3 x 1e-3
1.4792
1.3988
1.6265
1.7505
C3
-6.0 e-4
C4 x 1e-5
1.6836
0.74754
1.168
3.0027
C4
1.312e-7
C5
677.66
616.46
723.6
794.8
C5
th
In using ODE of Polymath, only one dependant variable is allowed for one program. In
particular, for the batch reactor design algorithm, the variable is time. If differential
equation of enthalpy against absolute temperature is inputted, the program will then not
allow running. Normally, Matlab software is used to solve it. Since this BKF2453 project
encourages students to use Polymath and the range of reaction temperature is just 50oC, the
average heat capacities are used.
The previous algorithm is again employed here with the addition of heat effect, (Appendix
C), the differential equation, dT/dt (for the batch reactor Equation T8-1.H page 477, Fogler
Textbook 4th Ed with exclusion of the heat exchange term) using the average heat capacities.
The result of the propylene conversion against the reaction temperature can be seen in
Figure 3.4. The batch reactor algorithm is used here because the temperature is plotted
against conversion and not against the reactor size variable such as retention time or volume
or weight of catalyst. The temperature increase is only 0.3oC.
13
Prepared by Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
Figure 3.4 The conversion versus reaction temperature for adiabatic reactor
The X-T plot in Figure 3.4 shows temperature increase due to the exothermic of the reaction
and the final temperature is not too high. There is no run away reaction occurs at any
temperature. Thus, adiabatic condition is preferable for the reactor of choice, the pack bed
reactor because of simpler design and cost incurred.
for Reaction 1
for Reaction 2
where
and
Prepared by Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
is heat capacity for respective components of which all change with temperature.
However, in this project average heat capacities between 300 350oC are used in
Polymath Educational Edition.
Stoichiometry:From the selectivity analysis, propylene was identified as the limiting reactant
Pressure drop:
whilst =
+ 1.75
15
Prepared by Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
Figure 3.5 the weight of catalyst and volume for PBR against the propylene conversion.
Two trends of weight and volume plotted at the same line but their values are referred at
left and right axes, respectively.
3.3.
(3.2)
A compressor is required as the process has a gas recycle stream. Compressors are so
expensive that spares are seldom provided for centrifugal units (although reciprocating
compressors may have spares because of a lower service factor). In practice, one standby
compressor would also be purchased to accommodate for any failure and breakdown.
The design equation for the theoretical horsepower (hp) for the centrifugal gas compressor
(for various pressure loads) is as follows
P
3.03 105
out
hp =
P
Q
1
in in
P
in
(3.3)
where Pin = lbf/ft3, Qin = ft3/min (calculate from gas real law equation for RG) and = (Cp/Cv
1)/(Cp/Cv). The exit temperature from a compressor stage is
Tout Pout
=
Tin Pin
(3.4)
where the temperatures and pressure must be in the Rankine absolute units. Values of
that can be used for first estimates are given in Table
Table 3.3 Values of for respective type of gasesr
Values of
Monotomic gases
Diatomic gases
More complex gases (CO2, CH4)
Other gasses
0.40
0.29
0.23
R/Cp
16
Prepared by Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
The compressor will be designed pressures Pin = 1 bar to Pout = 15 bar which is identical to
the feed of fresh propylene. The pressure is enough to liquefy the propylene flow. The flow
of both propylene and benzene liquids will be dosed by pumps equipped with non-return
valves.
3.3.1. Efficiency
At this level, the compressor has 90% of efficiency to account for fluid friction in suction and
discharge valves, ports, friction or moving metal surfaces, fluid turbulence, etc. The driver is
also assumed to have 90% of efficiency to account for the conversion of the input energy to
shaft work.
bph = hp/0.9
Then, Guthries correlation can be used to calculate the installed cost for various types of
compressors:
M &S
0.82
517.5bhp ( 2.11 + Fc )
280
Installed Cost =
(3.6)
where Fc is the correction factor (Fc = 1 in this case) and M&S (Marshall and Swift inflation
index) those are obtainable from the Peters textbook (Peters & Timmberhaus, 1991).
3.4.
Economical Potential
The previous economic analysis for the input-output structure considered only the stream
costs, i.e., products plus by-products minus raw material costs. At the second level decision
where the reactor system complete with the recycle streams, the previous economic
potential will be minus to the cost of reactor and catalysts, and the cost of multistage
compressor elevating pressure from 1 bar to 15 bar of propylene recycle. The result of the
calculation
EP ($/yr) = Cumene value + Fuel Value of PDIPB and Propane Propylene Cost Benzene
Cost Reactor Cost Catalyst Cost Compressor Installation Cost Compressor Operation
Cost
17
Prepared by Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
M &S
0.82
EP3 ($/yr) = EP2 ($/yr) W ( Catalyst cost ) V ( installation cost )
517.5bhp ( 2.11 + Fc )
280
Compressor Operating Cost
as shown from the graph in Figure 3.6, indicates that the optimum conversion of propylene,
at the stage where no separators are considered yet, is 0.6.
$920,000,000
$900,000,000
$/yr
$880,000,000
$860,000,000
$840,000,000
$820,000,000
$800,000,000
0
0.2
0.4
0.6
0.8
1.2
Xp
Figure 3.6 The Profitability of the Process at Level 3 Decision versus Propylene
Conversion.
4. References
Biegler, L. T., Grossmann, I. E., & Westberg, A. W. (1997). Systematic Methods of Chemical
Process Design: Prentice-Hall.
Douglas, J. M. (1988). Conceptual Design of Chemical Processes. New York: McGraw Hill.
Felder, R. M., & Rousseau, R. W. (2005). Elementary Principles of Chemical Processes (3 ed.).
New York: John Wiley & Sons.
Peters, M. S., & Timmberhaus, K. D. (1991). Mass Transfer and Reactor Equipment - Design
and Costs. In J. J. Carberry, J. R. Fair, W. P. Schowalter, M. Tirrell & J. Wei (Eds.),
Plant Design and Economics for Chemical Engineers (4th ed.). New York: McGraw
Hill.
Poling, B. E., THompson, G. H., Friend, D. G., Rowley, R. L., & Wilding, W. V. (2008). Physical
and Chemical Data. In D. W. Green & R. H. Perry (Eds.), Perry's Chemical Engineers'
Handbook (Vol. 8th). New York: McGraw-Hill.
Turton, R., Bailie, R. C., Whiting, W. B., & Shaeiwitz, J. A. (2008). Analysis, synthesis and
design of chemical processes: Prentice Hall.
18
Prepared by Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
APPENDIXA
ALGORITHMUSINGBATCHREACTORDESIGNTOANALYSESELECTIVITYOFREACTIONS
Appendix A.txt
APPENDIX A
# mole balance
d(Cp)/d(t) = rp
Cp(0) = 209.911
d(Cb)/d(t) = rb
Cb(0) = 419.822
d(Cc)/d(t) = rc
Cc(0) = 0
d(Cpdib)/d(t) =
Cpdib(0) = 0
# propylene
# benzene
# cumene
rpdib # p-diisopropyl benzene
# rate law
r1prime = k1prime * Cp * Cb
r2prime = k2prime * Cp * Cc
rp = -r1prime - r2prime
rb = -r1prime
rc = r1prime - r2prime
rpdib = r2prime
k1prime = 3.5e4 * exp(-1.04e5 / R / T)
k2prime = 2.9e6 * exp(-1.47e5 / R / T)
R = 8.314
T = 300 + 273
# Selectivity, Yield and Conversion
S = (r1prime - r2prime + 0.00001) / (r2prime + 0.00001)
Y = (r1prime - r2prime + 0.00001) / (r1prime + r2prime + 0.00001)
Xp = 1 - Cp * Nt * P0 / (Cp0 * Nt0 * P)
Xb = theta - Cb * Nt * P0 / (Cp0 * Nt0 * P)
Nt = (Cp + Cb + Cc + Cpdib) * V
V = 1
Nt0 = (Cp0 + Cb0) * V
P0 = (Cp0 + Cb0) * R * T
P = (Cp + Cb + Cc + Cpdib) * R * T
Cp0 = 209.911
Cb0 = 419.822
theta = Cb0 / Cp0
t(0) = 0
t(f) = 3600
Page 1
AppendixA2:ResultsofcalculationusingPolymath
Xp
Xb
1:1
Xp
Xb
1:2
Xp
Xb
2:1
Xp
Xb
1:4
0.000106
0.000106
1.15E+04
-5.28E-05
-5.28E-05
1.02E+04
-5.28E-05
-5.28E-05
1.02E+04
-4.44E-16
7.34E+04
0.216636
0.216448
490.0172
0.996218
0.260285
0.130052
847.1249
0.997949
0.133008
0.265771
378.1073
0.995044
0.333162
0.333015
1078.336
0.998193
0.299081
0.298696
321.8495
0.994176
0.390574
0.19511
535.5406
0.996677
0.18507
0.369562
236.5181
0.991992
0.425405
0.425163
825.0834
0.997635
0.338552
0.338041
269.312
0.993022
0.474277
0.236882
420.1637
0.995748
0.238872
0.476623
153.2114
0.987598
0.556166
0.555742
608.1531
0.996793
0.413499
0.412679
196.3647
0.990416
0.514351
0.256874
377.339
0.995267
0.264198
0.526928
125.4529
0.984859
0.596507
0.596016
560.075
0.996521
0.447597
0.446602
171.0495
0.989003
0.590067
0.294633
311.1418
0.994286
0.287163
0.572476
104.4269
0.981834
0.671164
0.670533
485.8866
0.996
0.478079
0.476906
151.4028
0.987589
0.625468
0.312281
285.1946
0.99379
0.30736
0.612472
88.48478
0.978604
0.737089
0.736318
432.2227
0.99552
0.505402
0.50405
135.7608
0.986178
0.658786
0.328887
263.018
0.993301
0.34111
0.679137
66.00185
0.971477
0.766553
0.765714
410.9241
0.9953
0.552357
0.550649
112.4235
0.983365
0.716179
0.35748
228.8828
0.9924
0.355296
0.707078
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2.102787
0.992808
0.524045
0.999732
-0.89912
-0.86479
0.999999
0.998504
1.038043
0.999756
0.928014
0.917269
10.44826
0.861884
0.999809
0.498563
1.95854
0.993284
0.524271
0.99975
-0.90161
-0.8693
0.999999
0.998504
1.033529
0.999784
0.928681
0.917888
10.34477
0.860865
0.999822
0.498569
1.893612
0.993523
0.524496
0.999766
-0.90393
-0.87354
0.998504
1.029551
0.999809
0.929336
0.918497
10.24315
0.859849
0.999834
0.498575
1.833058
0.993761
0.52472
0.999781
-0.9061
-0.87753
0.998505
1.022955
0.999851
0.929981
0.919097
10.14336
0.858837
0.999845
0.498581
1.776586
0.993997
0.525167
0.999808
-0.91002
-0.88477
0.998505
1.020231
0.999868
0.931241
0.920266
9.949031
0.856825
0.999866
0.498591
1.674818
0.994464
0.52539
0.99982
-0.91178
-0.88806
0.998505
1.017831
0.999883
0.931856
0.920836
9.854415
0.855825
0.999875
0.498596
1.629029
0.994693
0.525612
0.999832
-0.91343
-0.89115
0.998505
1.015715
0.999897
0.932462
0.921397
9.761438
0.854828
0.999883
0.4986
1.586335
0.994919
0.525833
0.999843
-0.91498
-0.89404
0.998505
1.012207
0.99992
0.933059
0.92195
9.670059
0.853835
0.999891
0.498604
1.546529
0.995141
0.526274
0.999862
-0.91776
-0.8993
0.998505
1.010758
0.999929
0.934225
0.923028
9.491938
0.851861
0.999906
0.498611
1.474815
0.995571
0.526494
0.999871
-0.91901
-0.90168
0.998505
1.009482
0.999937
0.934795
0.923555
9.405121
0.850879
0.999912
0.498614
1.442558
0.995779
0.526713
0.999879
-0.92018
-0.90391
0.998505
1.008357
0.999945
0.935356
0.924074
9.319749
0.849902
0.999918
0.498617
1.412486
0.995981
0.526932
0.999887
-0.92127
-0.906
0.998505
1.006491
0.999957
0.936074
0.924737
9.210807
0.848636
0.999925
0.498621
1.374996
0.996246
0.527295
0.999899
-0.92292
-0.90918
0.998505
1.005723
0.999962
APPENDIXB
REGRESSIONRESULTOFCORRELATIONBETWEENYIELDANDCONVERSIONOFPROPYLENE
Page 1 of 2
POLYMATH Report
03-May-2014
Model: Y = 1-A*Xp^B
Variable Initial guess Value
95% confidence
0.008
0.0192825 7.782E-05
1.74
1.63208
0.0341333
0.9978368
R^2adj 0.9977975
Rmsd
2.869E-05
Variance 4.861E-08
General
Sample size 57
Model vars 2
Indep vars 1
Iterations
Y calc
Delta Y
1.
about:blank
3/5/2014
Page 2 of 2
about:blank
3/5/2014
APPENDIXC
ALGORITHMUSINGBATCHREACTORDESIGNTOANALYSEHEATEFFECTOFREACTIONS
APPENDIXD
ALGORITHMUSINGPACKEDBEDREACTORDESIGNTOESTIMATETHEWEIGHTOFCATALYSTAND
VOLUMEOFTHEREACTOR
ECONOMICPOTENTIALCALCULATIONSATLEVEL3DECISIONS
#APPENDIX D-1
# Mole Balance of PBR
d(Fp)/d(W) = rp # Propylene balance
Fp(0) = 1.446681718
d(Fb)/d(W) = rb # benzene
Fb(0) = 2.893363436
d(Fc)/d(W) = rc # cumene
Fc(0) = 0
d(Fpdipb)/d(W) = rpdib # p-diisopropyl benzene
Fpdipb(0) = 0
Ft0 = Fp0 * 3
Y = 1 - 0.0193 * Xp ^ 1.6321
Xp = (Fp0 - Fp) / Fp0
Fp0 = 1.446681718
# Rate Law
r1prime = k1prime * Cp * Cb
r2prime = k2prime * Cp * Cc
rp = -r1prime - r2prime
rb = -r1prime
rc = r1prime - r2prime
rpdib = r2prime
k1prime = 3.5e4 * exp(-1.04e5 / R / T0) * exp(1.04e5 / R * (1 / T0 - 1 / T))
k2prime = 2.9e6 * exp(-1.47e5 / R / T0) * exp(1.47e5 / R * (1 / T0 - 1 / T))
R = 8.314 # kJ/kmol/K
T0 = 300 + 273
# Stoichiometry
Cp = Ct0 * Fp / Ft * y * T0 / T
Cb = Ct0 * Fb / Ft * y * T0 / T
Cc = Ct0 * Fc / Ft * y * T0 / T
Cpdipb = Ct0 * Fpdipb / Ft * y * T0 / T
Ft = Fp + Fb + Fc + Fpdipb
Ct0 = P0 / (1000 * R * T0) # kmol/m^3
P0 = 30e5 # Pa
# Energy balance
delHrxn = -99000 - (Y * Cpc + (1 - Y) * Cppdipb - Cpb - Cpp) * (T - T0)
Cpb = 118301.05 # J/kmol mean heat capacity between 300-350C
Cpp = 75645.53 # J/kmol mean heat capacity between 300-350C
Cppa = 103155.16 # J/kmol mean heat capacity between 300-350C
Cpc = 237763.42 # J/kmol mean heat capacity between 300-350C
Cppdipb = 421721.13 # J/kmol mean heat capacity between 300-350C
d(T)/d(W) = rp * delHrxn / (Fb * Cpb + Fp * Cpp + Fc * Cpc + Fpdipb * Cppdipb + 0.0001) # Energy Balance for PBR
T(0) = 573 # K
AppendixD2
Xp
0.000000001
0.00085
0.001000001
0.010000001
0.020000001
0.100000001
0.200000001
0.300000001
0.400000001
0.500000001
0.600000001
0.700000001
0.800000001
0.900000001
0.950000001
0.970000001
0.980000001
0.990000001
1.000000001
Y
1
1
1
0.999989
0.999967
0.99955
0.998604
0.997295
0.995674
0.993773
0.991615
0.989217
0.986591
0.983749
0.98225
0.981636
0.981326
0.981014
0.9807
EP2
911917967
911917870
911917841
911912549
911901171
911685603
911197040
910518832
909676778
908685939
907556315
906294986
904907135
903396616
902596284
902267834
902101835
901934655
901766298
Ffp
Fp0
Fb0
0.014467 14466667 28933333
0.014467 17.01961 34.03922
0.014467 14.46666 28.93331
0.014467 1.446682 2.893363
0.014467 0.723357 1.446714
0.014473 0.144732 0.289464
0.014487 0.072434 0.144869
0.014506 0.048353 0.096706
0.01453 0.036324 0.072648
0.014557 0.029115 0.058229
0.014589 0.024315
0.04863
0.014624 0.020892 0.041784
0.014663 0.018329 0.036658
0.014706
0.01634 0.032679
0.014728 0.015503 0.031007
0.014737 0.015193 0.030386
0.014742 0.015043 0.030086
0.014747 0.014896 0.029791
0.014751 0.014751 0.029503
G
264957265
311.714488
264.9570649
26.49600216
13.24829393
2.65076614
1.326637805
0.885586389
0.665271076
0.533234732
0.445329311
0.382636367
0.335697893
0.299260198
0.28394238
0.278261821
0.275509419
0.272813233
0.270171576
alfa
5.88798E+14
815.7470646
589.4782606
5.956185192
1.506131881
0.065743789
0.018169804
0.008853173
0.005421388
0.003754896
0.002807558
0.002211117
0.001807719
0.001520047
0.001405764
0.001364383
0.001344527
0.0013252
0.001306382
W(kg)
V(m3)
1.85E+04
7.4
1.83E+04
7.3
1.60E+04
6.404
1.44E+04
5.764
1.51E+04
6.02
1.51E+04
6.02
1.57E+04
6.276
1.66E+04
6.628
1.76E+04
7.044
1.89E+04
7.564
2.06E+04
8.24
2.31E+04
9.244
2.68E+04
10.7
3.46E+04
13.828
4.20E+04 16.78949
4.80E+04
19.216
5.25E+04
20.988
6.11E+04
24.44
2.15E+05
85.92