Example of Process Synthesis: 50,000 Metric Tonnes per Annum

Production of Cumene from Alkylation of Benzene

Instruction

The reaction stoichiometry undergoes as follows

1. C3H6 + C6H6  C9H12

propylene (P) benzene (B) cumene (C)

2. C3H6 + C9H12  C12H18

P C p-diisopropyl benzene (PDIPB)

and the reaction kinetics are based on the power law model

r 1=k 1 C P C B (i)

r 2=k 2 C P C C (ii)

where both reaction rates are in kmol kgcat -1 s-1, CP is concentration of propylene in kmol m -3,
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

∆ E1
k 1=A 1 exp ( ) RT
(iii)

∆ E2
k 2=A 2 exp ( ) RT
(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.

Reaction Ai Ei
6 -1 -1 -1
(m kgcat kmol s ) (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 28 oC 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 28 oC). 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.
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

FB Process 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 Purity (%) Boiling Points (oC) Price/ Cost

Propylene 95.2 -42.7 $167/kmol
Benzene 99.9 80.1 $267/kmol
Cumene 99.9 152.4 $1200/kmol
PDIPB Not necessary 203 $0.1/kW fuel
Propane Not necessary -46 $0.1/kW fuel

2
Prepared by Ir. Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
Table of Contents

1. Introduction......................................................................................................................4
2. Level 2 Decision: Input-Output Structure of the Process Flowsheet.................................4
2.1. Mole Balances in Term of Extent of Reaction...........................................................5
2.1.1. Reaction Selectivity, Yield and Stoichiometry...................................................6
2.2. Economic Potential...................................................................................................9
3. Level 3 Decision: Recycle Structure of the Flowsheet.....................................................11
3.1. Mole Balances for the Reactor................................................................................11
3.2. Reactor Design........................................................................................................13
3.2.1. Thermal Effect: Adiabatic or not.....................................................................13
3.2.2. Reactor Design................................................................................................14
3.2.3. Reactor Cost....................................................................................................16
3.3. Compressor Design and Costs.................................................................................16
3.3.1. Efficiency.........................................................................................................17
3.3.2. Annualized Installed Cost................................................................................17
3.3.3. Operating Cost................................................................................................18
3.4. Economical Potential..............................................................................................18
4. References......................................................................................................................18
5. Appendix A

6. Appendix B

7. Appendix C

8. Appendix D

3
Prepared by Ir. 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.

2. Level 2 Decision: Input-Output Structure of the Process Flowsheet

Raw Material and Impurities Management

The available raw materials for the process must be sought out from local or overseas
market. Their prices are usually based on the place of origin (Biegler, Grossmann, &
Westberg, 1997; Poling, THompson, Friend, Rowley, & Wilding, 2008) (incurring shipment
cost) and purity. Nevertheless, in this project, they are all readily given for the sake of
brevity.

From the project instruction, the benzene liquid is fed to the process in pure form. Thus,
there is no need to pre-treat anything. However, the propylene feed is having 4.8% propane.
Boiling point of propane is about 5 oC higher than propylene. Thus, propane can be
separated in a cryogenic system from propylene as the first guess. Further discussion on this
separation can be made in the Level 4 decision especially related to the relative volatility of
propylene-propane that is close to unity.

Output Decision

The raw materials costs normally fall in the range from 33 to 85% of the total processing
cost, and these costs are essential to be estimated before any other detail is added to the
design (Douglas, 1988). At this level, the impurity comes from the fresh propylene feed,
which is propane.

As the rule of thumb in a process design, it is desirable to recover more than 99% of all
valuable materials. Thus, at this level of decision, the mole balances are calculated for the
overall system in which the limiting reactant is assumed to convert all due to the recycle.
The recycle streams will not appear because it comes out and goes in again into the process,
except for the recycle and purge, which is not in this case.

As referred to the heuristics of the destination code in Table 5.1-3 of the Douglas textbook,
the destination of products and impurity of the process are classified based on the boiling
point at the atmospheric pressure of all species in the process as can be summarised in
Table 2 .1.

4
Prepared by Ir. Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
 Table 2.1 Destination Code for Toluene HDA Process

Component Boiling Point (oC) Destination Code

s
Propylene -47.6 Recycle
Propane -42 Fuel
Cumene 152.4 Primary product
Benzene 111 Recycle
PDIPB 203 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

2 Benzene Process 4 p-diisopropyl benzene

(a)

FFPA

FFP, FFPA
PC

FFB Process
PPDIPB

(b)

Figure 2.1 Input-Output Stream and the Respective Nomenclatures of the Benzene
Alkylation Process

2.1. Mole Balances in Term of Extent of Reaction

The benzene alkylation occurs in gas phase with a side reaction of p-diisopropyl benzene
synthesis as follows

C3H6 + C6H6  C9H12 ( 2 .1a)

propylene (P) benzene (B) cumene (C)

C3H6 + C9H12  C12H18 (2.1b)

5
Prepared by Ir. Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
 P C p-di-isopropyl benzene (PDIPB)

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

ṅ i=n˙0 + ν i ξ1

where ṅ 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 Inlet Change Outlet

Benzene FFB - 1 0
Propylene FFP - 1 - 2 0
Cumene 0 1 - 2 PC
p-diisopropyl benzene 0 2 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 4

2 Independent reactions +2
4 equation of extent of reactions -4
Composition of inert propane in the feed and purge (4.8%) -1
Total (Variables can be calculated by specifying any one of them) 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.

2.1.1. Reaction Selectivity, Yield and Stoichiometry

The extent of reaction will be calculated in the stoichiometric manner employing the
conversion and flow of limiting reactant. The limiting reactant can first be identified from the
scheme of reactor through selectivity analysis. Thus,

rC r C 1 +r C 2 k 1 C P C B−k 2 C P C C k 1 C B
SC / PDIPB = = = = −1 (2.2)
r PDIPB r PDIPB k2 C P C C k 2CC

From the equation, the selectivity is declined by cumene concentration.

Physically, the reaction can be simultaneously optimized by the different phase of

components appeared. To check it, vapour pressure of cumene at 300 oC can be computed
from the logarithmic equation given in Perry Handbook (Poling et al., 2008)

6
Prepared by Ir. Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
Ln PP = C1 + C2/T + C3 ln T + C4TC5

where for cumene: C1 = 102.81, C2 = -8674.6, C3 = -11.922, C4 = 7.0048 x 10 -6 and C5 = 2

thus, PP = 571,318 Pa or 5.71 bar. This means cumene exist in liquid phase at 30 bar, the
minimum pressure of the reaction. Benzene, however, by using the same method, its vapour
pressure at 300oC is 54.76 bar, reveals that its phase is gas. Hence, due to this pressure and
temperature conditions the concentration of benzene is always high at reactive gas phase to
have effective contact with propylene thus securing the maximum selectivity.

The selectivity equations (Equation 2.2) cannot simply quantify the difference between both
reactant feed flows required as taught in the BKF2453 subject. Hence, some detail analyses
by using the batch reactor algorithm is necessary to delineate the effects of feed ratios of
propylene:benzene. From calculations using Ordinary Differential Equation (ODE) in
Polymath (Appendix A) the results for various ratios can be summarised and plotted as
depicted in Figure 2 .2. All selectivities clearly decrease as the conversion of propylene
increase. The graph also shows that propylene cannot be excess as it will render the
selectivity to be almost zero at nearly half of the limiting reactant mole and thus high
selectivity is attributed to excess benzene whereby the ratio of 1:4 shows the maximum. It
also implies that the limiting reactant of the process will be propylene.

1.00E+03
9.00E+02
8.00E+02
7.00E+02
6.00E+02
Selectivity

5.00E+02 1:1
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 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

moles of desired product

overall yield, Ý = (2.3)
moles of limiting reactant consumed
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

7
Prepared by Ir. Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
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 selectivity’s 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

0.95
0.9

0.85 1:1
Yield

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 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 (alternatively, students can directly use
yield value in the Polymath ODE solver by writing the process mole balance there)

Y  1  0.0193 X P1.6321 (2.4)

For a production of PC mol/hr (52.08 kmol/hr), the propylene fed to the process FFP must be

PC
F FP= (2.5)
Ý
The molar flow of propane corresponds to the fresh propylene feed through the purity
percentage. Thus

8
Prepared by Ir. Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
 F PA
=0.048
F PA + F FP

0.048
∴ F PA = F (2.6)
0.952 FP
If a fraction Y of propylene is converted to cumene, 1-Y must be lost to p-diisopropyl
benzene. From the stoichiometry of the reactions (Equation 2.1), the amount of PDIPB ,
PPDIPB, must be

PC
P PDIPB=F FP ( 1−Ý )= ( 1−Ý ) (2.7)
Y
Unlike propylene, benzene is only involved in the desired reaction. Final cumene (P c), which
is not involved in the side reaction and is expressed as F FPY, can be written in the desired
reaction as follows:-

Propylene + benzene  cumene

Whereas p-diisopropyl benzene (PDIPB), as expressed as F FP(1-Ý ), is synthesized through

both the desired and side reactions and can be written as follows:-

Overall: 2 propylene + benzene  p-diisopropyl benzene

When the overall reaction is normalised to propylene, the limiting reactant, the reaction will
be

Propylene + ½ benzene  ½ p-diisopropyl benzene

Therefore the required benzene input is from both way of writing and is equated as follows

F FP F P
F Fb =F FP Ý + ( 1−Ý ) = FP ( 1+ Ý )= C ( 1+ Ý ) (2.8)
2 2 2 Ý
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 1 2 3 4 5
Propylene PC/Y 0 0 0 0
0.048 P C 0.048 P C
Propane 0 0 0
0.952 Y 0.952 Y
PC
Benzene 0 ( 1+ Ý ) 0 0 0
2 Ý
Cume 0 0 PC 0 0
PC
P-diisopropyl benzene 0 0 0 (1−Y ) 0
2Y
Temperature (oC) 28 28 28 28 28
Pressure (bar) 12 1 1 1 1

9
Prepared by Ir. Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
Where Y = 1 – 0.0193XP1.6321 ;

2.2. 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. (2.9)

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 Price/ Cost

Propylene $167/kmol
Benzene $267/kmol
Cumene $1200/kmol
PDIPB $0.1/kW fuel
Propane $0.1/kW fuel

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

PC ( 1−Ý ) 0.048 P C P P
[
E P2=$ 1200 P C + $ 0.1 ( −H oC−PDIPB )
Ý
+ ( −H oC−PA )(0.952 Ý )]
− $ 267 C ( 1+ Ý )−$ 167 C
2 Ý Ý
(2.10)

where Y can be calculated from Equation 2.5.

Figure 2 .4 shows the result of economic potential for the benzene alkylation process. All
range of conversion yields positive potential and the minimum is $902 mil per year at XP = 1.
The highest profit is indicated by the XP = 0.

As this economic potential is the annual profit that does not have to pay anything for capital
costs and utilities costs, all the analyses are just catering the sale of products (including
byproducts) and the purchasing of raw materials. The next level of decisions would use the
positive range obtained from this level.

10
Prepared by Ir. Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
 3.84E+10

3.82E+10

3.80E+10

3.78E+10

3.76E+10

3.74E+10

3.72E+10

3.70E+10
0 0.2 0.4 0.6 0.8 1 1.2
Xp

Figure 2.4 Economic Potential – Level 2

3. Level 3 Decision: Recycle Structure of the Flowsheet

At the third level, the recycle stream is focused including the reactor. A compressor, as the
major utility (due to its significant cost), is necessary here to recycle the unconverted
propylene gas increasing pressure from 1 bar to the liquefying pressure at 28 oC that is 15
bar. Recycling benzene, on the other reactant, transfers liquid by using a pump of which the
cost is relatively low and negligible at the conceptual design stage.

Figure 3 .5 shows the reactor and recycle streams for the process. The unconverted
reactants are expressed by using stoichiometry.

Propylene Recycle FP
 Compressor
RG and yPH

Propylene feed
FFP and FPA1 Propane FPA
FP, PC, FPA
FP0, FPA Reactor Separators Cumene PC
2 FB, PPDIPB PDIPB PPDIPB
Benzene Feed FB0

FFB Benzene recycle

FB

Figure 3.5 Benzene Alkylation Process with Liquid and Gas Recycle Streams

3.1. Mole Balances for the Reactor

11
Prepared by Ir. Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
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 .5 can be tabulated as in
Table 3 .5.

Table 3.5 Degree of freedom analyses for unit and junctions appeared at level 2 decision

Unit or junction 1 2 Reactor

Unknown variables FFP, FPA, FPO and FP: 4 FFB, FB and FB0: 3 FP0, FPA, FP, FB0, FB and
PPDIPB: 6
Independent reactions - - 2
Balance FFP +FP = FP0: -1 FFB + FB = FB0: -1 Independent extent of
reactions: -4
Feed condition Purity percentage: -1 - Molar feed ratio, B: -1
Information from the FFP = PC/Y: -1 FFB = PC/Y: -1 FPA: -1
2nd level of decision
Variables to be 1 ( variable XP) 1 ( variable XP) 2 ( variable XP and FP0)
specified

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)

F FP PC
 F P 0= = (3.11)
XP Y XP

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 .6.

Propylene Recycle FP0 (1-X)

Compressor
RG and yPH

Propylene feed
FFP and FPA1 FP0 Propane FPA
Reactor FP0 (1-X) Separators Cumene PC
FP (B -X) PDIPB PPDIPB
2
Benzene Feed BFP
FFB
Benzene recycle
FP (B -X)

3.6 Block flow diagram of the benzene alkylation at the 2 nd level of decision: recycle
structure.

12
Prepared by Ir. Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
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 .7 where the liquid phase will
flow downward of the catalyst packing.

P, B and PA

P, B, C, PDIPB and PA

3.7 Schematic diagram of tubular reactor

3.2.1. Thermal Effect: Adiabatic or not

The thermal effect of the reactor can be observed from the energy balance calculation via
the plot of reaction temperature versus propylene conversion. From various references,
heat capacities of the involving components are not unique and changed with respect to
absolute temperature as tabulated in Table 3 .6.

Table 3.6 Heat capacities of components:

Components C1 x 1e-5 C2 x 1e-5 C3 x 1e-3 C4 x 1e-5 C5

Benzene* 0.44767 2.3085 1.4792 1.6836 677.66
Propylene* 0.43852 1.506 1.3988 0.74754 616.46
Propane* 0.5192 1.9245 1.6265 1.168 723.6
Cumene* 1.081 3.7932 1.7505 3.0027 794.8
C1 C2 C3 C4 C5
PDIB** -30.99e-5 1.01728 -6.0 e-4 1.312e-7
2 2
C 3/T C 5/T
* C 0P =C 1+C 2
[ ] [
sinh ( C 3/T )
+C 4
cosh ( C 5 /T ) ] the unit is J/kmol – from Perry

Handbook 8th ed.

13
Prepared by Ir. Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
 0 2
**C P =C 1+C 2 T +C 3 T + C 4 T 3, the unit is J/mol – from chemical property website
http://chemeo.com/cid/56-152-1

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 50 oC, 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 .8. 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.

1
0.9
0.8
0.7
0.6
0.5
Xo

0.4
0.3
0.2
0.1
0
570 620 670 720 770
T

Figure 3.8 The conversion versus reaction temperature for adiabatic reactor

The X-T plot in Figure 3 .8 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.

3.2.2. Reactor Design

The pack bed reactor is designed by using the desired production rate where the feed is
changed by the conversion of propylene following Equation 3.1. The algorithm of reactor for
multiple reactions is thus employed here with several molar flow rates calculated from the
conversion specified in the range of 0  1.

The mole balance of a pack bed reactor is

d Fi
=r ' i where i = P, B, C and PDIPB
dW

14
Prepared by Ir. Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
The net rate laws are calculated as following

r ' 1=k '1 C P C B for Reaction 1

r ' 2=k '2 C P C PDIPB for Reaction 2

where
N
r ' i= ∑ ν j r ' i where  is stoichiometric coefficient and j is the reaction.
j

and

k’1 = 3.5 x 104 exp[-1.04 x 103/(RT)]

k’2 = 2.9 x 106 exp[-1.47 x 103/(RT)]

Energy Balance of adiabatic PBR changing the reaction temperature

dT r ' p Δ H rxn (T )
= where -HRxn(T) = Y[-HRxn1(T)] + (1-Y)[ -HRxn2(T)] which Y is
dW ∑ F i C Pi
reaction yield as Y = 1 – 0.0193 XP1.6321 and XP = (FP0 – FP)/FP0

C Pi is heat capacity for respective components of which all change with temperature.
However, in this project average heat capacities between 300 – 350 oC are used in
Polymath Educational Edition.

Stoichiometry:-

From the selectivity analysis, propylene was identified as the limiting reactant

FiT 0
C i=CT 0 y where CT0 = P0/(RT); FT =  Fi and y = P/P0
FT T

Pressure drop:-

dy −α F T T
=
dW 2 y F T 0 T 0

where FT0 = 3FP0 as for FB0 = 2FP0

2β G (1−ϕ ) 150 ( 1−ϕ ) μ

and α =
A c ρ b P0
whilst β=
ρ 0 g c D p ϕ3 Dp [ +1.75 G
]
with 0 = 19.1 kg m-3, gC = 1, DP =0.01 m,  = 2.914 x 10 -5 Pa.s,  = 0.5 and G =
FP0*MWP/Ac. Ac is the cross sectional area for 1.5” schedule 40 pipe, which is
approximately 0.0013 m2.

15
Prepared by Ir. Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
From various conversions, the weight of catalyst obtained from the algorithm (can refer
Appendix D) is plotted as can be seen in Figure 3 .9. Besides, the volume of the reactor can
be obtained from the weight of the catalyst by using its bulk density.

Figure 3.9 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.

3.2.3. Reactor Cost

The plug flow reactor cost estimation follows the shell and tube method. From the graph of
purchased cost versus tube surface area ¼” schedule 40 pipes in Figure 15-13 (Peters &
Timmberhaus, 1991), the following correlation (readily included inflation for 2014) was
obtained.

Purchased Cost,

CA0 = 125933V + 651508 (3.12)

3.3. Compressor Design and Costs

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.

16
Prepared by Ir. Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
The design equation for the theoretical horsepower (hp) for the centrifugal gas compressor
(for various pressure loads) is as follows

 3.03 105    P  
hp    PinQin    1
out

     P  
 in
(3.13)

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 
(3.14)

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 3.7 Values of  for respective type of gasesr

Values of 
Monotomic gases 0.40
Diatomic gases 0.29
More complex gases (CO2, CH4) 0.23
Other gasses R/Cp

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.

3.3.2. Annualized Installed Cost

The brake horsepower, bph, is obtained by introducing the compressor efficiency into Eq.
4.9:

bph = hp/0.9 (3.15)

Then, Guthrie’s correlation can be used to calculate the installed cost for various types of
compressors:

 M &S 
 517.5bhp  2.11  Fc 
0.82

Installed Cost =  280  (3.16)

17
Prepared by Ir. Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
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).

3.3.3. Operating Cost

By dividing the brake horsepower by the driver efficiency (80%) , the utility requirement can
be calculated. Then from the utility cost ($0.1/kW for 2014) and using 8000 hr/yr, the
operating cost can be obtained.

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

 M &S 
EP3 ($/yr)  EP2 ($/yr)  W  Catalyst cost   V  installation cost     517.5bhp  2.11  Fc 
0.82

 280 
Compressor Operating Cost

as shown from the graph in Figure 3 .10, indicates that the optimum conversion of
propylene, at the stage where no separators are considered yet, is 0.9.

$350,000,000

$300,000,000

$250,000,000

$200,000,000
$/yr

$150,000,000

$100,000,000

$50,000,000

$0
0 0.2 0.4 0.6 0.8 1 1.2
Xp

Figure 3.10 The Profitability of the Process at Level 3 Decision versus Propylene
Conversion.

18
Prepared by Ir. Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject
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.

19
Prepared by Ir. Dr. Mohd Sabri Mahmud, the lecturer of the chemical reaction engineering subject