Simulation of Process Plants Module Report - ASPEN PLUS

SIMULATION AND OPTIMIZATION OF ETHYLBENZENE

PRODUCTION PLANT

By

Vamsidhar Gannavarapu, 34278

Under the guidance of

M.Sc. Hubert Stell

Hochschule Bremerhaven
LIST OF CONTENTS:
Introduction: ..............................................................................................................................................................4
Literary background: .................................................................................................................................................4
ASPEN Plus Simulation: ............................................................................................................................................6
Preliminary Results: ...................................................................................................................................................6
Reactors 1&2: ........................................................................................................................................................6
Distillation Columns – DCBENZ & DCETHYBE: ..................................................................................................7
Sensitivity Analysis and Optimization: ....................................................................................................................9
Temperature and Pressure in Reactors 1&2:......................................................................................................9
Fractional Conversion in Reactors 1&2:..............................................................................................................9
Reflux ratio in Distillation Column - DCBENZ: ................................................................................................. 11
Recovery in Distillation Column: ....................................................................................................................... 11
Sizing and Economics: ........................................................................................................................................... 13
Heat Analysis and Heat integration: ..................................................................................................................... 15
Discussion: .............................................................................................................................................................. 16
References: .............................................................................................................................................................. 17

LIST OF TABLES

Table 1: Stream Results after optimization ........................................................................................................................................ 12

Table 2: Sizing of the plant, design parameters ............................................................................................................................... 13
Table 3 :Equipment costs........................................................................................................................................................................ 13
Table 4: Summary of Plant economics ................................................................................................................................................. 15
Table 5: Heat Analysis summary ........................................................................................................................................................... 15

LIST OF FIGURES

Figure 1: Standard flowsheet of ethylbenzene production .............................................................................................................. 4

Figure 2 : ASPEN Simulation of the process ........................................................................................................................................ 6
Figure 3 : Stream data from Simulation ................................................................................................................................................ 6
Figure 4 : Distillation column-Benzene results.................................................................................................................................... 7
Figure 5 : Theoretical stages vs Reflux ratio profile of first column .............................................................................................. 7
Figure 6 : Distillation column-Ethylbenzene results ........................................................................................................................... 8
Figure 7 : Theoretical stages vs Reflux ratio profile of second column ........................................................................................ 8
Figure 8 : Plot of S1 Analysis .................................................................................................................................................................. 9
Figure 9 : Plot of S2 Analysis .................................................................................................................................................................. 9
Figure 10: Plot of S3 Analysis ............................................................................................................................................................... 10
Figure 11: Plot of S5 Analysis ............................................................................................................................................................... 11
Figure 12: Stream Price data ................................................................................................................................................................. 14
Figure 13: Utilities data ........................................................................................................................................................................... 14
Figure 14 : Heat Analysis........................................................................................................................................................................ 15
Figure 15: Saving potentials of the process plant ........................................................................................................................... 16

ABRREVATIONS

EB – Ethylbenzene (C8H10)

DEB – Diethylbenzene (C10H14)

Frac. Conv. – Fractional Conversion

Introduction:

Ethylbenzene (C₆H₅CH₂CH₃) is an organic compound and an important commodity chemical used as an

intermediate in the production of styrene. It has also some important uses in petrochemical industry, also in
production of paints and solvents. To produce ethylbenzene, ethylene and benzene are reacted at high
temperatures and pressures. The process involves two reactor columns and two distillation columns in series. The
reaction with ethylene and benzene is slightly sensitive, as it forms an undesired product Diethylbenzene (C10H14)
along with the desired product Ethylbenzene (C8H10). The undesired product is again recycled into the reactor to
react with the excess of benzene, converting it into desired product.

Literary background:
The arrangement of the two reactors and distillation columns are arranged in the way shown below in Figure 1
taken from (Douglas, 1988). As mentioned earlier the two reactors need to be maintained at high pressures
(20atm) to keep the ethylene in liquid phase at the high temperatures (430+ K) required for reasonable reaction
rates (L., 2010). A large benzene stream is fed to the first reactor along with the liquid ethylene stream. The
effluent from the first reactor is fed into the second reactor along with a recycle stream of DEB. This reactor
works in adiabatic condition.

Figure 1: Standard flowsheet of ethylbenzene production

The effluent from the second reactor is fed to a distillate column which produces a distillate that is mostly
benzene, which can be recycled into the first reactor along with the fresh feed of benzene. This second recycle
could not be simulated due to solver errors, because of inadequate Ethylene feed into REACTOR1. The bottoms
of this first column is mixture of EB and DEB that is fed into the second distillation column. The second column
produces the final product, an EB distillate of 99% purity and a DEB bottoms which is recycled back into the
second reactor.

The reason for using a two reactor flow sheet is to achieve high conversion of ethylene in first reactor and to bring
back EB from DEB in the second reactor. The three reactions that occur in series during this process are:

The production of EB involves mainly the liquid phase reaction of ethylene with benzene. Ethylene and Benzene
can form Ethylbenzene (EB) as:

C2 H4 + C6 H6 → C8 H10 (1)

The undesirable reaction is represented by this reaction in which Ethylbenzene (EB) and rest of Ethylene form
Diethylbenzene (DEB):

C8 H10 + C2 H4 → C10 H14 (2)

The third reaction makes it possible to recycle the DEB back to reactor in which excess Benzene and
Diethylbenzene (DEB) form Ethylbenzene (EB) again as:

C6 H6 + C10 H14 → 2C8 H10 (3)

It is essential to maintain negligible DEB content in the final product of this system. For this reason, there are a
few considerations for the reactor design. The amount of ethylene in the first reactor should be kept minimum to
avoid the reaction 2 to occur, therefore reducing the DEB content. The amount of benzene in the second reactor
must be more, to increase the selectivity of the reaction 3 and to recycle DEB back to useful product.

Also, from the kinetics of the above three reactions states that the activation energy of the undesired reaction
(E_r2=20,000 col/mol) is more than the desired reaction (E_r1=17,000cal/mol) (L., 2010). So, at low
temperatures and in low concentrations of ethylene and EB in the reactor can improve the selectivity. Ethylene
conversion is set to maximum in all the reactors.
ASPEN Plus Simulation:

The EB production process is then simulated using ASPEN PLUS environment, using the operating conditions
mentioned in the process diagram (L., 2010). Choa-Seader property method is used in simulation.

Figure 2 : ASPEN Simulation of the process

Preliminary Results:

Reactors 1&2:
The stream results with the input data are available after a successful run. The results table below has been
compressed to focus only on the molar flows of the inlet and outlet streams.

Figure 3 : Stream data from Simulation

The first reactor operates at 434K and 20 atm and about 15.538kmol/hr of DEB is generated along with
401.768kmol/hr of EB. So, the per-pass EB yield of the first reactor is 96%.

EB Flow rate 401.768

EB Yield = = = 0.96
EB Flow rate+DEB Flow rate 401.768+15.538

The second reactor also operates at similar conditions, at 432K and 20 atm and about 6.99kmol/hr of recycle
DEB from the bottom of the second column is fed into the reactor. The DEB leaving in effluent is about
6.999kmol/hr, which means the DEB from the first reactor (15.538kmol/hr) has been completely extinguished.
Therefore, the second reactor can successfully convert the DEB generated in the first reactor to EB.

Distillation Columns – DCBENZ & DCETHYBE:

The effluent from the second reactor enters the first distillation column DCBENZ at high pressure and
temperature. The heat duty of the condenser(3.1MW) is more than that of the reboiler (2.57MW) because of the
high temperature of the feed stream. The first column has a reflux ratio of 0.3209 and the number of stages is 6.
The reflux ratio profile is shown below. The distillate obtained is mostly benzene and bottom is a mixture of EB
and DEB.

Figure 4 : Distillation column-Benzene results

Figure 5 : Theoretical stages vs Reflux ratio profile of first column

The second column has a reflux ratio of 0.672 and the boiler and condenser pressure are at 0.1 atm. The reflux
ratio profile is shown below. The different parameters of the second column are also shown in the table below.
The distillate is pure EB (99.8%). The bottoms is recycled again into the second reactor.

Figure 6 : Distillation column-Ethylbenzene results

Figure 7 : Theoretical stages vs Reflux ratio profile of second column

It is evident from the above profiles that the reflux ratio of the specific column decreases in a certain range, with
the increasing number of theoretical stages. So a range of reflux ratio is selected, such that the number of stages
will be economically feasible, using less energy (utilities), production of distillate is more. For the first column
the reflux ratio should be in the range of 0.25-1.25 and for the second column it is 0.2-0.8.
Sensitivity Analysis and Optimization:

The simulation is done using the parameters mentioned in the literature. There is a scope for improvement of the
entire process and it is done by varying different parameters against the production rate of the desired product.

Temperature and Pressure in Reactors 1&2:

From the sensitivity analysis S1 and S2 from the ASPEN file, it is evident that the pressure and temperature
change in the REACTOR s 1 and 2, within the range of 0-30atm has no change in the production rate of the
resultant components in stream 2. In the first figure, pressure in atm vs molar flow rate of benzene in stream 2 is
plotted. The second figure contains the molar fraction of EB vs the change in temperature of REACTOR 1 in
between 300-500K.

Figure 8 : Plot of S1 Analysis

Figure 9 : Plot of S2 Analysis

Fractional Conversion in Reactors 1&2:

It becomes interesting from these following sensitivity analysis, S3 and S4, from which it is evident that the
production quality changes with the amount of fractional conversion of the three different reactions mentioned
earlier. To know the exact amount of fractional conversion, the value of fractional conversion of reactions 1,3 of
REACTOR 1 are varied with the production rate of distillate in first and second columns. The desired component
in those distillate streams DIST-B and DIST-EB are Benzene and Ethylbenzene respectively.

The reason only the first and the last reaction are varied, is because the fraction of component that should be
converted in both the first and second reactions is the same.

The plot from the sensitivity analysis S3 is plotted with Row/case against the molar production rate of Benzene
and Ethylbenzene in kmol/hr in the streams DIST-B and DIST-EB respectively. Fractional conversion of reaction
1 is varied 21 times within the range of 0.34-0.87, and 21 times within 0.1-1 for reaction 3. There are 21x21
permutations available, and row/case is defined for each permutation in a sequence. The plot is as below.

Figure 10: Plot of S3 Analysis

It can be observed that between the case 211-231 in the middle, the production rate is optimal. It is related to the
frac. conv. of 0.65 with reaction 1 and between 0.1-1 with reaction 3. There exists another point in the last
iteration 442, with frac. conv. of 0.44 with reaction 1 and 0.9 with reaction 3, which cannot be seen in the plot.
The reason for this iteration to converge at the very end is unknown, but the production rate seems to be more
balanced than in the range of case 211-231. This result has been considered for further calculations and hence an
optimization of the original value has been achieved.

For the case of REACTOR2, the condition that the amount of DEB in the output stream 2 should be equal to that
of the stream 6. It means that the amount of DEB produced in the previous REACTOR1 should be completely
exhausted. Same as before, reaction 1 is varied between 0.31-0.4, reaction 2 between 0.25-0.9. These are varied
against the DEB content in streams 2,6 and the data can be observed in the EXCEL file attached. The difference
between the two values is calculated and the least difference is then considered to be the best value using MIN
function in EXCEL. It is found to be 0.4 of reaction 1 and 0.9 of reaction 3.

Reflux ratio in Distillation Column - DCBENZ:

With the sensitivity analysis S5, the reflux ratio is varied vs the condenser and reboiler duty of the distillation
column DCBENZ. As the feed stream entering the distillation column is of high temperature, the condenser duty
should be more than reboiler duty. But from the plot, it is evident that the reflux ratio has no influence on the
difference of duties. So another parameter should be selected for this optimization.

Figure 11: Plot of S5 Analysis

Recovery in Distillation Column:

For the S6 analysis, the recovery of light and heavy components are varied against the condenser and reboiler
duty. The recovery of light component is varied between 0.28 and 0.99, and the heavy component is varied
against 0.01 and 0.1. The results are exported to excel and the difference between those duties are calculated. The
iterations which could not be converged are avoided using the sort function, and the results which turned out to be
ERRORS are avoided. The maximum difference is found using MAX function in excel and it was found with the
condition of 0.99 and 0.1.

For ease of use, the sensitivity analysis S6 has been deactivated in the ASPEN file, as it contains errors. It can be
activated again during observation when needed. After the optimization has been applied, the stream results
obtained be observed in the following table.
 Units 1 2 4 6 DIST-B DIST-EB C2H4 C6H6
Description
From REACTOR1 REACTOR2 DCBENZ DCETHYBE DCBENZ DCETHYBE
To REACTOR2 DCBENZ DCETHYBE REACTOR2 REACTOR1 REACTOR1
Stream Class CONVEN CONVEN CONVEN CONVEN CONVEN CONVEN CONVEN CONVEN
Maximum Relative Error
Cost Flow $/hr 84434.61 21450.73 48325.36
MIXED Substream
Phase Liquid Phase Liquid Phase Liquid Phase Liquid Phase Liquid Phase Liquid Phase Vapor Phase Liquid Phase
Temperature K 434 432 473.6456 354.8289 147.1999 337.6755 320 320
Pressure atm 20 19 4.053 0.1 0.3 0.1 20 20
Molar Vapor Fraction 0 0 0 0 0 0 1 0
Molar Liquid Fraction 1 1 1 1 1 1 0 1
Molar Solid Fraction 0 0 0 0 0 0 0 0
Molar Enthalpy cal/mol 9196.596 5919.574 6141.411 -8270.16 3200.24 -1142.14 12567.13 12533.42
Mass Enthalpy cal/gm 113.7887 61.756 57.6608 -67.559 46.98012 -10.7619 447.9661 160.451
Molar Entropy cal/mol-K -61.1657 -76.8951 -82.687 -125.58 -85.5846 -101.251 -18.3806 -59.7807
Mass Entropy cal/gm-K -0.7568 -0.80221 -0.77634 -1.02586 -1.2564 -0.95404 -0.65519 -0.7653
Molar Density mol/cc 0.008103 0.007376 0.006467 0.006609 0.013191 0.00781 0.000846 0.01088
Mass Density gm/cc 0.654902 0.707056 0.688795 0.809048 0.89854 0.828866 0.023732 0.849901
Enthalpy Flow cal/sec 2116127 1173823 879813.3 -27729.2 176128.6 -159792 2201343 2195437
Average MW 80.82171 95.85423 106.5093 122.414 68.11903 106.1281 28.05376 78.11364
Mole Flows kmol/hr 828.3562 713.8627 515.733 12.07053 198.1298 503.6624 630.6 630.6
ETHYLENE kmol/hr 197.7562 71.19222 2.94E-14 0 71.19222 0 630.6 0
BENZENE kmol/hr 213.2941 71.20085 0.712009 2.72E-08 70.48884 0.712009 0 630.6
EB kmol/hr 401.7679 564.4707 5.08E+02 5.080182 56.44707 502.9434 0 0
DEB kmol/hr 15.53798 6.998981 6.997343 6.99E+00 0.001638 0.006997 0 0
WATER kmol/hr 0 0 0 0 0 0 0 0
Mole Fractions
Mass Flows kg/hr 66949.16 68426.76 54930.36 1477.602 13496.41 53452.75 17690.7 49258.46
Mass Fractions
Volume Flow l/min 1703.796 1612.951 1329.142 30.4391 250.3397 1074.817 12423.91 965.9643

Table 1: Stream Results after optimization

Sizing and Economics:
The reactor sizing has not been included as RSTOIC reactor has been used in the simulation. If in case a RCSTR
block was used, the reactor size is 200 m3 as mentioned in the literature. The reactor temperature would change
according to the size of the reactor and the conversion rate of the products. To satisfy the economics of the project
in real time, different parameters related to the sizing of the equipment have been considered. A list of these
sizing parameters is shown below.

REACTOR1 REACTOR2
Liquid volume [l] 11120.0599 11120.0599
Vessel diameter [meter] 1.524 1.524
Vessel tangent to tangent height [meter] 6.096 6.096
Design gauge pressure [barg] 22.69921077 22.69921077
Design temperature [K] 461.7777778 461.7777778
- -
DCBENZ DCETHYBE
Diameter Bottom section [meter] 1.2192 3.9624
Bottom tangent to tangent height [meter] 12.8016 12.8016
Design gauge pressure Bottom [barg] 21.6859608 4.817163067
Design temperature Bottom [K] 501.4233839 501.4233839
Operating temperature Bottom [K] 473.6456061 473.6456061
Number of trays Bottom section 15 15
Bottom Tray type SIEVE SIEVE
Bottom Tray spacing [meter] 0.6096 0.6096
Molecular Wt Overhead Prod. 68.119033 106.128131
Table 2: Sizing of the plant, design parameters

The equipment costs that have been calculated using the above parameters are as follows. The costs have been in
dollar ($). And this is the base currency of the following economic analysis.

Name Equipment Cost Installed Cost [USD] Equipment Weight Installed Weight
[USD] [LBS] [LBS]
DCBENZ 99100 284800 24600 52636
DCETHYBE 285900 640600 97700 172928
REACTOR1 169800 327600 28200 48477
REACTOR2 169800 327600 28200 48477
Table 3 :Equipment costs
The stream price of the feed streams and the product stream are considered from the literature available online.
They are entered in the stream price section in ASPEN Plus. They are as follows:

Figure 12: Stream Price data

The utility costs have also been included. As there are two reactors which require WATER as utility, they have
been included in the economic analysis. The two distillation columns would require HEAT utility which is
essential to know the total heat duty required and the energy savings of the whole plant. The utilities added have
been shown below.

Figure 13: Utilities data

From the above data, the net costs of the utilities per hour and the net cost flow of the feed stream and the product
stream have been calculated. The operating profit of this process is equal to around $14600 per hour of operation.

[𝑂𝑝𝑒𝑟𝑎𝑡𝑖𝑛𝑔 𝑝𝑟𝑜𝑓𝑖𝑡𝑠] = [𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑠𝑎𝑙𝑒𝑠] − [𝑟𝑎𝑤 𝑚𝑎𝑡𝑒𝑟𝑖𝑎𝑙𝑠 𝑐𝑜𝑠𝑡] − [𝑢𝑡𝑖𝑙𝑖𝑡𝑦 𝑐𝑜𝑠𝑡𝑠]

= 84434.6 $⁄ℎ𝑟 − 69776.1 $⁄ℎ𝑟 − 10.29 $⁄ℎ𝑟 = $ 14648.29⁄ℎ𝑟

The assumptions taken for sizing of the equipment and economic analysis were mostly considered by the default
libraries in ASPEN Plus Economic Analyzer (APEA). Upon running the economic analyzer function, the
economic analysis has been successfully done. The desired rate of return is considered to be 20% per year. The
results are shown below. The payback period has been calculated as 6 years.

Total Capital Cost [USD] 4762420

Total Operating Cost [USD/Year] 662276000
Total Raw Materials Cost [USD/Year] 611542000
Total Product Sales [USD/Year] 740014000
Total Utilities Cost [USD/Year] 96361.1
Desired Rate of Return [Percent/'Year] 20
P.O. Period [Year] 6.06402
 Equipment Cost [USD] 724600
Total Installed Cost [USD] 1580600
Table 4: Summary of Plant economics

Heat Analysis and Heat integration:

Apart from the economics of the plant, it is essential to know the saving potential of every plant in terms of
energy usage. The heat utilization in the reboiler and condenser sections of the distillation, the cooling water in
reactors are the major sources. It is shown below the quantities of energy utilization to this specific plant.

Figure 14 : Heat Analysis

The potential for savings has been directly calculated by the ASPEN Energy Analyzer module. The potential for
savings is shown below. It is estimated at around 30% of energy can be saved by changing the operating
parameters and the inlet temperatures of the process.

Property Actual Target Available Savings % of Actual

Total Utilities [cal/sec] 7705000 5337000 2368000 30.74
Heating Utilities [cal/sec] 1662000 478100 1184000 71.24
Cooling Utilities [cal/sec] 6043000 4859000 1184000 19.6
Carbon Emissions [kg/hr] 1648 473.8 1174 71.25

Table 5: Heat Analysis summary

 Figure 15: Saving potentials of the process plant

Discussion:

The production of Ethylbenzene has been successfully simulated in ASPEN Plus. It is a good example of multiunit
complex process that is typical of many chemical plants found in industry. As this process involves undesired and
desired products which are produced simultaneously, it is essential to minimize the undesired to improve the
yield and economic efficiency of the plant.

From the sensitivity analysis S1, S2 it was evident that the temperate and pressure has no direct effect on the
production quality, but from S3, S4, as the fractional conversion of the base reactions has a greater influence on
the fraction of desirable component in final product. There has been an improvement of about 15% in the molar
flow rate of Ethylbenzene produced in the process. The benzene that could be recovered has also been
increased by 6%. The final amount of Ethylbenzene produced after optimization was 502.9 kmol/hr with around
99.3% purity.

The economic analysis has been done for the plant and it was estimated that the pay-off period for this plant in
a real time would be around 6 years. This was considered when the Ethylbenzene product would sell at the cost
of 1433$/ton. Energy analysis has revealed a possibility of around 30% of energy savings in the whole process
considering the working period of 20 years with all the utility costs included.
References:

1. Douglas, J. M. (1988). Conceptual Design of Chemical Processes,. New York: McGraw-Hill.

2. Kalyanee Ambatkar, P. N. (n.d.). ASPEN SIMULATION AND OPTIMIZATION OF ETHYLBENZENE PRODUCTION.

3. L., L. W. (2010). Design and control of Ethylbenzene process. AIChE Journal - 655Volume 57, 655-670.

4. ASPEN, ASPEN Working Manual and Help Section.