ChE 455

Major #1
Ethyl Benzene Process

Background

You have recently been assigned to the ethyl benzene (EB) plant at the XYZ petrochemical
facility. This facility produces a wide range of monomers, polymers, and solvents, all derived
from petroleum. The EB process produces 80,000 tonne/yr of 99.8 mol% ethyl benzene that is
totally consumed by the styrene facility on site. Like most EB/styrene facilities, there is
significant heat integration between the two plants. In order to decouple the operation of the two
plants, the energy integration is achieved by the generation and consumption of steam within the
two processes. The EB reaction is exothermic, so steam is produced, and the styrene reaction is
endothermic, so energy is used in the form of steam.

Several changes are anticipated within the EB process, and your job is to evaluate the effect
that each change will have on the processes (EB and styrene) and to recommend ways to
minimize upsets in current operation and maximize the positive economic impact of each
change.

Ethyl Benzene Production Reactions

The production of EB takes place via the direct addition reaction between ethylene and
benzene:

C6 H 6 + C2 H 4 → C6 H 5C2 H 5
(1)
benzene ethylene ethyl benzene

The reaction between EB and ethylene to produce diethyl benzene (DEB) also takes place:

C6 H 5C2 H 5 + C2 H 4 → C6 H 4 (C2 H 5 )2
(2)
ethyl benzene ethylene diethyl benzene

Additional reactions between DEB and ethylene yielding tri- and higher ethyl benzene are also
possible. However, in order to minimize these additional reactions, the molar ratio of benzene to
ethylene is kept high, at approximately 8:1. The production of diethyl benzene is undesirable,
and its value as a side product is low. In addition, even small amounts of DEB in EB cause
significant processing problems in the downstream styrene process. Therefore, the maximum
amount of DEB in EB is specified as 2 ppm. In order to maximize the production of the desired
EB, the DEB is separated and returned to a separate reactor in which excess benzene is added to
produce EB via the following equilibrium reaction:
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C6 H 4 (C2 H 5 ) 2 + C6 H 6 ↔ 2C6 H 5C2 H 5

(3)
diethyl benzene benzene ethyl benzene

The incoming benzene contains a small amount of toluene impurity. The toluene reacts with
ethylene to form ethyl benzene and propylene:

C6 H 5CH 3 + 2C2 H 4 → C6 H 5C2 H 5 + C3H 6

(4)
toluene ethyl benzene propylene

The reaction kinetics are of the form:

− ri = ko,i e − Ei / RT Cethylene
a b
CEB c
Ctoluene d
Cbenzene e
CDEB (5)

where i is the reaction number above, and

i Ei ko,i a b c d e
kcal/kmol
1 22,500 1.00×106 1 0 0 1 0

2 22,500 6.00×105 1 1 0 0 0

3 25,000 7.80×106 0 0 0 1 1

4 20,000 1.80×108 2 0 1 0 0

The units of ri are kmol/s/m3-reactor, the units of Ci are kmol/m3-gas and the units of ko,i vary
depending upon the form of the equation.

Process Description

The PFD is in Appendix 1. A refinery cut of benzene is fed from storage to an on-site
process vessel (V-301) where it is mixed with the recycled benzene. From V-301, it is pumped
to reaction pressure of approximately 2,000 kPa (20 atm) and sent to a fired heater (H-301) to
bring it to reaction temperature (approximately 400°C). The preheated benzene is mixed with
feed ethylene just prior to entering the first stage of a reactor system consisting of three adiabatic
packed bed reactors (R-301 to R-303) with inter-stage feed addition and cooling. Reaction
occurs in the gas phase and is exothermic. The hot, partially converted reactor effluent leaves
the first packed bed, is mixed with more feed ethylene, and is fed to E-301, where the stream is
cooled to 380°C prior to passing to the second reactor (R-302) where further reaction takes
place. High-pressure steam is produced in E-301, which is subsequently used in the styrene unit.
The effluent stream from R-302 is similarly mixed with feed ethylene and is cooled in E-302
(with generation of high-pressure steam) prior to entering the third and final packed bed reactor,
R-303. The effluent stream leaving the reactor contains products, by-products, unreacted
 3

benzene, and small amounts of unreacted ethylene and other non-condensable gases. The reactor
effluent is cooled in two waste-heat boilers (E-303 and E-304) in which high-pressure and low-
pressure steam are generated, respectively. This steam is also consumed in the styrene unit. The
two-phase mixture leaving E-304 is sent to a trim cooler (E-305), where the stream is cooled to
80°C, and then to a two-phase separator (V-302), where the light gases are separated and sent
overhead as fuel gas to be consumed in the fired heater. The condensed liquid is then sent to the
benzene tower, T-301, where the unreacted benzene is separated as the overhead product and
returned to the front end of the process. The bottoms product from the first column is sent to T-
302, where product ethyl benzene (at 99.8 mol% and containing less than 2 ppm DEB) is taken
as the top product and is sent directly to the styrene unit. The bottom product from T-302
contains all the diethyl benzene and trace amounts of higher ethyl benzenes. This stream is
mixed with recycle benzene and passes through fired heater (H-301) prior to being sent to a
fourth packed bed reactor (R-304) in which the excess benzene is reacted with the DEB to
produce EB and unreacted benzene. The effluent from this reactor is mixed with the liquid
stream entering the waste heat boiler (E-303).

The PFD for this process is shown in Figure 1 in Appendix 1, and a stream table indicating
current operation is given as Table 1 in Appendix 1. The utility summary is in Table 2 in
Appendix 1. Pertinent equipment information is given in Table 3 in Appendix 1.

Proposed Changes and Improvements

Several changes to the process have been suggested and your job is to determine which of the
proposed changes (if any) should be implemented.

Change 1: A new catalyst has been developed by your supplier that is claimed to suppress
the ethylation of EB to give DEB. Information on this new catalyst along with information on
the existing catalyst is given in Appendix 3. You are to determine what changes in the process
are required in order to utilize this new catalyst and what economic benefits would be achieved.

Change 2: An opportunity has arisen to purchase a lower of grade of benzene that contains a
significantly greater fraction of toluene than the existing feed. For this new feed (containing
10% toluene), you are to determine what changes, if any, are required to process this new feed
and the reduction in price of the benzene feed stream (currently $1.22/kg) that would make a
switch to the new feed economically attractive. You should assume an internal hurdle rate of
11% before taxes and a length of 5 years for these economic calculations.

Economic improvements: Although no specific recommendations or changes are suggested,

if you see anywhere that process improvements can be made, these should be evaluated using the
same hurdle rate and project time given above.
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Deliverables

A written report of your results, an analysis of your results, your conclusions, and your
recommendations is required by 9:00 am, Monday, November 14, 2005. There will be an oral
presentation of your results which will be scheduled between Monday, November 14, 2005 and
Friday, November 18, 2005. More details about the written and oral reports are given below.

Your report should address all of the following issues:

1. You should describe the changes in the process required in order to utilize the new
catalyst and the economic benefits that would be achieved

2. For the new feed, you are to determine the changes, if any, required to process the new
feed and the reduction in price of the benzene feed stream that would make a switch to
the new feed economically attractive.

3. Chemcad reports (that include stream compositions, equipment summaries, and

convergence results but without stream properties) for any new cases that you present
should be included as separate, labeled appendices.

4. PFD and stream tables for any new cases that you present should be included in the main
written report.

5. Cost-saving measures that you recommend for the plant should be suggested.

6. A written report, conforming to the guidelines, detailing the information in items 1-5
should be included.

7. A legible, organized set of calculations justifying your recommendations, including any

assumptions made should be included as an appendix.

8. A signed copy of the attached confidentiality statement should be included as the last
page of the report.

Report Format

This report should be brief and should conform to the guidelines. It should be bound in a
folder that is not oversized relative to the number of pages in the report. Figures and tables
should be included as appropriate. An appendix should be attached that includes items such as
the requested calculations. These calculations should be easy to follow. The confidentiality
statement should be the very last page of the report.

The written report is a very important part of the assignment. Reports that do not conform to
the guidelines will receive severe deductions and will have to be rewritten to receive credit.
Poorly written and/or organized written reports may also require re-writing. Be sure to follow
the format outlined in the guidelines for written reports.
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Oral Presentation

You will be expected to present and defend your results to XYZ’s management
representatives some time between November 14 and November 18, 2005. Your presentation
should be 15-20 minutes, followed by about a 30 minute question and answer period. Make
certain that you prepare for this meeting since it is an important part of your assignment. You
should also prepare a hard copy of your transparencies to be handed in at the beginning of your
report.

Other Rules

You may not discuss this major with anyone other than the instructors. Discussion,
collaboration, or any other interaction with anyone other than the instructors is prohibited.
Violators will be subject to the penalties and procedures outlined in the University Procedures
for Handling Academic Dishonesty Cases (begins on p. 47 of the Undergraduate Catalog).

Consulting is available from the instructors. Chemcad consulting, i.e., questions on how to
use Chemcad, not how to interpret results, is unlimited and free, but only from the instructors.
Each individual may receive five free minutes of consulting from the instructors. After five
minutes of consulting, the rate is 2.5 points deducted for 15 minutes or any fraction of 15
minutes, on a cumulative basis. The initial 15-minute period includes the 5 minutes of free
consulting.

Late Reports

Late reports are unacceptable. The following severe penalties will apply:

• late report on due date before noon: one letter grade (10 points)

• late report after noon on due date: two letter grades (20 points)

• late report one day late: three letter grades (30 points)

• each additional day late: 10 additional points per day

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Appendix 1

Figure 1 is a flowsheet of Unit 300 as it was designed. Table 2, the stream table, follows and
identifies design operating conditions, which, as far as we know, reflect the actual operating
conditions prior to the shut down. Table 3 provides a summary of available equipment
specifications. If information is missing or incomplete for a particular piece of equipment, it is
not available.
7
 8

Table 1: Stream Flow Table

Stream No. 1 2 3 4 5 6
Temp °C 25.0 25.0 58.5 25.0 25.0 383.3
Pres kPa 110.0 2000.0 110.0 2000.0 2000.0 1985.0
Vapor mole fraction 0.0 1.0 0.0 1.0 1.0 1.0
Total kmol/h 99.0 100.0 229.2 30.0 35.0 259.2
Total kg/h 7761.3 2819.5 17952.2 845.9 986.8 18797.9
Flowrates in kmol/h
Ethylene 0.0000 93.0000 0.0000 27.9000 32.5500 27.9000
Ethane 0.0000 7.0000 0.0000 2.1000 2.4500 2.1000
Propylene 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Benzene 97.0000 0.0000 226.5099 0.0000 0.0000 226.5077
Toluene 2.0000 0.0000 2.0000 0.0000 0.0000 2.0000
Ethylbenzene 0.0000 0.0000 0.7003 0.0000 0.0000 0.7003
1,4-DiEthBenzene 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000

Stream No. 7 8 9 10 11 12
Temp °C 444.1 380.0 453.4 25.0 380.0 449.2
Pres kPa 1970.0 1960.0 1945.0 2000.0 1935.0 1920.0
Vapor mole fraction 1.0 1.0 1.0 1.0 1.0 1.0
Total kmol/h 234.0 269.0 236.4 35.0 271.4 238.7
Total kg/h 18797.9 19784.7 19784.7 986.8 20771.5 20771.5
Flowrates in kmol/h
Ethylene 0.8510 33.4010 0.6226 32.5500 33.1726 0.5407
Ethane 2.1000 4.5500 4.5500 2.4500 7.0000 7.0000
Propylene 1.8129 1.8129 1.9974 0.0000 1.9974 2.0000
Benzene 203.9113 203.9113 174.9631 0.0000 174.9631 148.3445
Toluene 0.1871 0.1871 0.0026 0.0000 0.0026 0.0000
Ethylbenzene 24.2827 24.2827 49.9541 0.0000 49.9541 70.5669
1,4-DiEthBenzene 0.8268 0.8268 4.2881 0.0000 4.2881 10.2963
 9

Table 1: Stream Flow Table (cont’d)

Stream No. 13 14 15 16 17 18
Temp °C 497.9 458.1 73.6 73.6 81.4 145.4
Pres kPa 1988.0 1920.0 110.0 110.0 105.0 120.0
Vapor mole fraction 1.0 1.0 1.0 0.0 0.0 0.0
Total kmol/h 51.3 290.0 18.6 271.4 170.2 101.1
Total kg/h 4616.5 25387.9 1042.0 24345.9 13321.5 11024.5
Flowrates in kmol/h
Ethylene 0.0000 0.5407 0.5407 0.0000 0.0000 0.0000
Ethane 0.0000 7.0000 7.0000 0.0000 0.0000 0.0000
Propylene 0.0000 2.0000 2.0000 0.0000 0.0000 0.0000
Benzene 29.5018 177.8462 8.3819 169.4643 169.2948 0.1695
Toluene 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Ethylbenzene 21.6875 92.2546 0.7128 91.5419 0.9154 90.6265
1,4-DiEthBenzene 0.0705 10.3668 0.0132 10.3536 0.0000 10.3536

Stream No. 19 20 21 22 23
Temp °C 139.0 191.1 82.6 82.6 121.4
Pres kPa 110.0 140.0 2000.0 2000.0 2000.0
Vapor mole fraction 0.0 0.0 0.0 0.0 0.0
Total kmol/h 89.9 11.3 130.2 40.0 51.3
Total kg/h 9538.6 1485.9 10190.9 3130.6 4616.5
Flowrates in kmol/h
Ethylene 0.0000 0.0000 0.0000 0.0000 0.0000
Ethane 0.0000 0.0000 0.0000 0.0000 0.0000
Propylene 0.0000 0.0000 0.0000 0.0000 0.0000
Benzene 0.1695 0.0000 129.5100 39.7849 39.7849
Toluene 0.0000 0.0000 0.0000 0.0000 0.0000
Ethylbenzene 89.7202 0.9063 0.7003 0.2151 1.1214
1,4-DiEthBenzene 0.0001 10.3535 0.0000 0.0000 10.3535
 Table 2: Utility Summary

Stream Name bfw to E-301 bfw to E-302 bfw to E-303 bfw to E-304 cw to E-305
Temp °C 115 115 115 115 30
Pressure kPa 4,200 4,200 4,200 600 400
Flowrate in 103kg/h 0.851 1.121 4.341 5.424 118.3
Duty (MJ/h) -1,967 -2,592 -10,080 -12,367 -4,943

Stream Name lps to E-306 cw to E-307 hps to E-308* cw to E-309

Temp °C 160 30 254 30
Pressure kPa 600 400 4200 400
Flowrate in 103kg/h 4.362 174.1 3.124 125.9
Duty (MJ/h) 9,109 -7,276 5,281 -5,262

*throttled and desuperheated at exchanger

10
 11

Table 3
Partial Equipment Specifications Summary
Heat Exchangers
E-301 E-302
A = 62.6 m2 A = 80.1 m2
1-2 exchanger, floating head, carbon steel 1-2 exchanger, floating head, carbon steel
process stream in tubes process stream in tubes
Q = 1,967 MJ/h Q = 2,592 MJ/h
maximum pressure rating of 2,200 kPa maximum pressure rating of 2,200 kPa
E-303 E-304
A = 546 m2 A = 1,567 m2
1-2 exchanger, floating head, carbon steel 1-2 exchanger, fixed head, carbon steel
process stream in tubes process stream in tubes
Q = 10,080 MJ/h Q = 12,367 MJ/h
maximum pressure rating of 2,200 kPa maximum pressure rating of 2,200 kPa
E-305 E-306
A = 348 m2 A = 57.8 m2
1-2 exchanger, floating head, carbon steel 1-2 exchanger, fixed head, carbon steel
process stream in shell process stream in shell
Q = 4,943 MJ/h Q = 9,109 MJ
maximum pressure rating of 2,200 kPa maximum pressure rating of 2,00 kPa
E-307 E-308
A = 54.6 m2 A = 22.6 m2
1-2 exchanger, floating head, carbon steel 1-2 exchanger, fixed head, carbon steel
process stream in shell process stream in shell
Q = 7,276 MJ/h Q = 5,281 MJ/h
maximum pressure rating of 200 kPa maximum pressure rating of 200 kPa
E-309
A = 17.5 m2
1-2 exchanger, floating head, carbon steel
process stream in shell
Q = 5,262 MJ/h
maximum pressure rating of 200 kPa

Pumps
P-301 A/B P-302 A/B
Carbon steel – positive displacement Carbon steel - centrifugal
Actual power = 15 kW Actual power = unknown
Efficiency 75% Efficiency unknown
P-303 A/B P-304 A/B
Carbon steel - centrifugal Carbon steel - centrifugal
Actual power = unknown Actual power = 1.4 kW
Efficiency unknown Efficiency 80%
P-305 A/B
Carbon steel - Positive displacement
Actual power = 2.7 kW
Efficiency 75%
 12

Fired Heater
H-301
required heat load = 22,376 MJ/h
design (maximum) heat load = 35,000 MJ/h
75% thermal efficiency
maximum pressure rating of 2,200 kPa

Reactors
R-301 R-302
carbon steel packed bed, ZSM-5 mol. sieve catalyst carbon steel packed bed, ZSM-5 mol. sieve catalyst
V = 20 m3 V = 25 m3
11 m long, 1.72 m diameter 12 m long, 1.85 m diameter
maximum pressure rating of 2,200 kPa maximum pressure rating of 2,200 kPa
Maximum allowable catalyst temperature = 500°C Maximum allowable catalyst temperature = 500°C
R-303 R-304
carbon steel packed bed, ZSM-5 mol. sieve catalyst carbon steel packed bed, ZSM-5 mol. sieve catalyst
V = 30 m3 V = 1.67 m3
12 m long, 1.97 m diameter 5 m long, 0.95 m diameter
maximum pressure rating of 2,200 kPa maximum pressure rating of 2,200 kPa
Maximum allowable catalyst temperature = 500°C Maximum allowable catalyst temperature = 525°C

Vessels
V-301 V-302
7 m3 10 m3
Maximum operating pressure = 250 kPa Maximum operating pressure = 250 kPa
horizontal vertical
height = 4.35 m height = 4.90 m
Diameter = 1.45 m Diameter =1.62 m

Towers
T-301 T-302
carbon steel carbon steel
45 sieve trays plus reboiler and total condenser 76 sieve trays plus reboiler and total condenser
42% efficient trays 45% efficient trays
feed on tray 19 feed on tray 56
additional feeds ports on tray 14 and 24 additional feeds ports on 50 and 62
reflux ratio = 0.3874 reflux ratio = 0.6608
24 in tray spacing 15 in tray spacing
column height 27.45 m column height 28.96 m
diameter = 1.7 m diameter = 1.5 m
maximum pressure rating of 300 kPa maximum pressure rating of 300 kPa
 13

Appendix 2
Design Calculations

The following design calculations are available for this process. If information is not given, then
it is not available.

Heat Exchangers

E-301
Q = 1,967 MJ/h 423.9
ΔTlm = 146.9°C T 380
process fluid hi = 60 W/m2K
bfw to hps ho = 6000 W/m2K 254
U ≈ 1/hi + 1/ho = 59.4 W/m2K
A = 62.6 m2
Q
E-302
Q = 2,592 MJ/h 434.1
ΔTlm = 151.4°C T 380
process fluid hi = 60 W/m2K
bfw to hps ho = 6000 W/m2K 254
U ≈ 1/hi + 1/ho = 59.4 W/m2K
A = 80.1 m2
Q
E-303
Q = 10,080 MJ/h 458.1
ΔTlm = 86.4°C T 280
process fluid hi = 60 W/m2K
bfw to hps ho = 6000 W/m2K 254
U ≈ 1/hi + 1/ho = 59.4 W/m2K
A = 546 m2
Q

E-304
280
Q = 12,367 MJ/h
ΔTlm = 44.3°C T 170
process fluid hi = 50 W/m2K
160
bfw to lps ho = 5000 W/m2K
U ≈ 1/hi + 1/ho = 49.5 W/m2K
A = 1567 m2 Q
NOTE: for E-301 – E-304 duties include specific heat
change for bfw to saturation temperature but the shell side is assumed to be well mixed and
at the temperature of the saturated steam.
 14

E-305
Q = 4,943 MJ/h 170.
ΔTlm = 83.7°C
process fluid ho = 50 W/m2K T 80
40
cw hi = 1000 W/m2K
U ≈ 1/hi + 1/ho = 47.6 W/m2K 30
P = 90/10 = 9
R = 10/140 = 0.07 Q
F = 0.99
A = 348 m2

E-306 160
Q = 9,109 MJ/h T
ΔTlm = 14.6°C
process fluid ho = 6000 W/m2K 145.4
lps condensing hi = 6000 W/m2K
U ≈ 1/hi + 1/ho = 3000 W/m2K
A = 57.8 m2 Q
E-307
Q = 7,276 MJ/h 81.4
ΔTlm = 46.2°C T
40
process fluid ho = 4000 W/m2K
cw hi = 1000 W/m2K 30
U ≈ 1/hi + 1/ho = 800 W/m2K
A = 54.6 m2
Q
E-308
Q = 5,281 MJ/h 210
ΔTlm = 18.9°C T
process fluid ho = 8000 W/m2K
throttled hps condensing hi = 6000 W/m2K 191.1
U ≈ 1/hi + 1/ho = 3429 W/m2K
A = 22.6 m2
Q
E-309
Q = 5,262 MJ/h 139
ΔTlm = 103.92°C
T
process fluid ho = 4000 W/m2K 40
cw hi = 1000 W/m2K
30
U ≈ 1/hi + 1/ho = 800 W/m2K
A = 17.5 m2
Q
 15

T-301

tray/tower sizing done on Chemcad

efficiency from O’Connell correlation
run flash on distillate and bottom stream
at top αtop = Kbenzene/Kethylbenzene = 6.01
at bottom αbottom = Kbenzene/Kethylbenzene = 3.93
αavg = (αtopαbottom)0.5 = 4.9
from Chemcad μfeed = 0.003612 Pa s = 0.3612 cp
See Figure 12-14 in Wankat
efficiency ≈ 0.42

21 stages = 19 trays + condenser + reboiler

19/0.42 = 45 actual trays + condenser + reboiler
feed on stage 9 = tray 8
8/0.42 = 19 so feed on tray 19

T-302

tray/tower sizing done on Chemcad

efficiency from O’Connell correlation
run flash on distillate and bottom stream
at top αtop = Kethylbenzene/Kdi-ethylbenzene= 3.84
at bottom αbottom = Kethylbenzene/Kdi-ethylbenzene = 3.2
αavg = (αtopαbottom)0.5 = 3.5
from Chemcad μfeed = 0.003612 Pa s = 0.3612 cp
See Figure 12-14 in Wankat
efficiency ≈ 0.45

36 stages = 34 trays + condenser + reboiler

34/0.45 = 76 actual trays + condenser + reboiler
feed on stage 26 = tray 25
25/0.45 = 56 so feed on tray 56

V-301
from Chemcad, liquid throughput (volumetric rate of Stream 3) = 21.4 m3/h = 0.3567 m3/min
assume 10 min residence time, so volume = 3.567 m3
assume vessel size is approximately double this volume = 7 m3
horizontal vessel
V = πD2L/4, where D = diameter and L = length of vessel (as drawn on PFD)
L/D = 3
(4)(7)
D=3 = 1.45 m and L = 3D = 4.35 m
π(3)
P-301
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Flow of liquid at normal operating conditions, m& =17,912 kg/h, T = 58.4°C, pben* = 50.6 kPa
Vol flow of liquid, Q = 21.36 m3/h = 5.93 L/s
ρl = 839 kg/m3, μl = 0.000404 kg/m s

V-301 1 inch sch 40

3 inch sch 40 Q2 = 0.87 L/s PIC

1.5 m FIC
2.5 inch sch 40

4m

Q1 = 5.93 L/s V-302

P-301A/B

The pump curve and NPSH curves for P-301 are attached as Figures 2 and 3. Under normal
operating conditions, approximately 15% of the flow through P-301 A/B is recycled back to V-
301. The normal operating level of liquid is 1.5 m above the pump inlet. Pipe calculations for
100 ft of suction and discharge piping are

variable 2.5"sch 40 3" sch 40 units

D 2.469 3.0680 inch
D 0.062713 0.0779 m
Q 0.0068 0.0068 m3/s
v 2.207766 1.4298 m/s
μ 4.04×10 -4
4.04×10 -4
kg/m s
ρ 839 839 kg/m3
Re 287,533 231,395
e/D 0.000718 0.000577
f 0.004582 0.0044
L 30.48 30.48 m
ΔPf 9,107 2,937 Pa
 17

NPSHA = Psupply + hρg – (-ΔPf) – P* = 101,000 + (1.5)(839)(9.81) – 2937 – 50,600 = 59,810 Pa

= (59,810)/(839)/(9.81) = 7.3 m of liquid – cavitation is not a problem

Equivalent length of suction piping (Leq,suct) is approx 100 ft, discharge piping (Leq,disch) = 500 ft

−ΔPf = 2,937 + (500)(9,107)(5.93/6.8)2/(100) + ΔPH-301 + ΔPR-301 + ΔPR-302 + ΔPR-303 + ΔPE-301 +

ΔPE-302 + ΔPE-303 + ΔPE-304 + ΔPE-305 = 2,937 + 34,627 + 15,000 + 15,000 + 15,000 + 15,000 +
10,000 + 10,000 + 10,000 + 10,000 + 10,000 = 147,560 Pa

M E Balance from V-301 to V-302

ΔP12 + ρgΔz12 + 0.5ρΔv12 + (−ΔPf) + ΔPcv = -ρws

We require 2000 kPa at pump outlet thus (-ρws) + 101 + (1.5)(9.81)(839)/1000 – 2.937 = 2,000
-ρws = 1890 kPa

System Curve at normal flow = (110 - 101) + (839)(9.81)(4.0 - 1.5)/1000 + (0) + 147.6 = 177.2
kPa
∴ ΔPcv = 1890 – 177 = 1,723 kPa

3,000
Pressure increase across pump, kPa

2,500

2,000

1,500 ΔPcv at design

conditions
1,000

500

0
0 1 2 3 4 5 6 7 8
o
flow rate of benzene at 58 C, lit/s
 18

10

8
NPSHA
7
NPSH (m of liquid)

3
NPSHR

0
6 6.2 6.4 6.6 6.8 7
o
Flow rate of benzene at 58 C, lit/s

V-302
from Chemcad, liquid throughput (volumetric rate of Stream 16) = 29.7 m3/h = 0.495 m3/min
assume 10 min residence time, so volume = 4.95 m3
assume vessel size is approximately double this volume = 10 m3
Vapor flow (Stream 15) = 476 m3/h = 0.1322 m3/s, ρg = 2.17 kg/m3
vertical vessel
V = πD2h/4, where D = diameter and L = height of vessel (as drawn on PFD)
Assume L/D = 3
(4)(10)
D=3 = 1.62 m and L = 3D = 4.90 m
π(3)
Check gas velocity
4Q (4)(0.1322)
vgas = = = 0.064 m/s
πD 2 π(1.62) 2
ρl 821
Criterion for phase separators is vgas ≤ 0.11 − 1 = 0.11 − 1 = 2.14 m/s - no problem
ρg 2.17

Design of Fuel gas feed line from V-302 to H-301

Vapor from V-302 (Stream 15) is fuel gas that is consumed in H-301.
Available pressure drop across line from V-302 to H-301 is 10 kPa.
 19

Assume 2 kPa across regulating flow valve at heater.

Equivalent length of pipe from V-302 to H-301 is 110 ft.
2ρ g fv 2 Leq fv 2
−ΔPf = 8, 000 = = 2(2.17)(110)(0.3048)
D D
Choose values of D and calculate -ΔPf

Variable Units 2"sch 40 3" sch 40 4" sch 40

D inch 2.067 3.068 4.026
D m 0.0525 0.07792 0.10226
Q m3/s 0.1322 0.1322 0.1322
v m/s 61.0651 27.7181 16.0963
μ kg/m s 9.51×10-6 9.51×10-6 9.51×10-6
Re 7.32×105 4.93×105 3.76×105
e m 0.000045 0.000045 0.000045
e/D 0.000857 0.000577 0.000440
f 0.004748 0.004346 0.004108
-ΔPf Pa 49,068 6,235 1,515

Choose 3” sch 40 carbon steel

R-301
packed bed
Volume of reactor containing catalyst, Vreac = 20 m3
Vreac = 20 = Vcat/(1-ε)
Voidage, ε = 0.4
Vcat = 12 m3 of catalyst
Catalyst size = 2 mm approx spherical
Vertical vessel
V = πD2L/4, where D = diameter and L = height of vessel containing catalyst
Assume an L/D = 5

(4)(20)
D= 3 = 1.72 m
π(5)
L = 5D = 8.6 m
Add 1 m either end for vapor distribution, giving L = 11 m

R-302
packed bed
Volume of reactor containing catalyst, Vreac = 25 m3
Vreac = 25 = Vcat/(1-ε)
Voidage, ε = 0.4
Vcat = 15 m3 of catalyst
 20

Catalyst size = 2 mm approx spherical

Vertical vessel
Vreac = πD2L/4, where D = diameter and L = height of vessel containing catalyst
Assume an L/D = 5

(4)(25)
D= 3 = 1.85m
π(5)
L = 5D = 9.27 m
Add 1 m either end for vapor distribution, giving L = 12 m

R-303
packed bed
Volume of reactor containing catalyst, Vreac = 30 m3
Vreac = 30 = Vcat/(1-ε)
Voidage, ε = 0.4
Vcat = 18 m3 of catalyst
Catalyst size = 2 mm approx spherical
Vertical vessel
Vreac = πD2L/4, where D = diameter and L = height of vessel containing catalyst
Assume an L/D = 5

(4)(30)
D= 3 = 1.97 m
π(5)
L = 5D = 9.85 m
Add 1 m either end for vapor distribution, giving L = 12 m

R-304
packed bed
Volume of reactor containing catalyst, Vreac = 1.67 m3
Vreac = 1.67 = Vcat/(1-ε)
Voidage, ε = 0.4
Vcat = 1 m3 of catalyst
Catalyst size = 2 mm approx spherical
Vertical vessel
V = πD2L/4, where D = diameter and L = height of vessel containing catalyst, assume an L/D =
2.5

(4)(1.67)
D= 3 = 0.95m
π(2.5)
L = 2.5D = 2.37 m

Add 1 m either end for vapor distribution, giving L = 5 m

 21

Appendix 3

Pressure drop calculations for reactors R-301 – R-304 – Existing Conditions

Variable Units R-301 R-302 R-303 R-304

Vcat m3 12 15 18 1
Voidage, ε 0.4 0.4 0.4 0.4
volume of cat filled
reactor, Vreac m3 20.00 25.00 30.00 1.67
L/D 5 5 5 2.5
D m 1.72 1.85 1.97 0.95
Lcat m 8.60 9.27 9.85 2.37
Dcat m 0.002 0.002 0.002 0.002
gas density, ρg kg/m3 28.00 28.30 29.70 29.60
gas viscosity, (×10-5)μg kg/m s 1.80 1.75 1.70 1.82
Volumetric gas flow, Q m3/s 0.1889 0.1939 0.1936 0.0433
Superficial gas vel, v m/s 0.0812 0.0719 0.0636 0.0615
ΔP Ergun Equation Pa 15,700 13,600 11,900 2,700

Look at pore diffusion resistance in catalysts

Consider the main reaction (Reaction 1) only since this is the fastest reaction and will provide
the limiting case.
Since benzene is in high excess, we can consider this as pseudo-first-order reaction with respect
to ethylene

Use highest temperature in reaction system which is approx. 450°C = 723K

Mole fraction of benzene at reactor R-301 inlet (Stream 6) = 226.34/259.3 = 0.8729
Mole fraction of ethylene at reactor R-301 inlet (Stream 6) = 27.9/259.3 = 0.1076
Total molar concentration at reactor inlet (Stream 6) = P/RT = (1985000)/(8.314)/(383+273) =
363.9 mol/m3 = 0.3639 kmol/m3
Benzene concentration at reactor inlet = (0.8729)(0.3639) = 0.3177 kmol/m3
Pseudo first-order reaction rate constant, k1Cbenzene = 1.00×106exp(-22,500/1.986/723)(0.3177) =
0.04974 m3-gas/m3-reactor/s
Changing the basis to the volume of catalyst ⇒ k’1= k1/(1-ε) = (0.04974)/(1-0.4) = 0.08290 m3-
gas/m3-catalyst/s
Effective diffusivity of catalyst (from catalyst manufacturer) = 6×10-8 m3-gas/m-catalyst/s
Dcat k1' 0.002 0.0829
Thiele Modulus, M T = = = 0.39
6 Deff 6 6 ×10−8
This gives an effectiveness factor of approximately 0.95 – close to 1, so use of intrinsic kinetics
should be ok. Next, check for external mass transfer resistance.
 22

External mass transfer to surface of catalyst

Dcatρ g ubed (0.002)(28)(0.0812 / 0.4)
Particle Reynolds number, Re p = = = 632
μg (18 × 10−6 )
Estimate mass transfer coefficient from correlation due to Froessling [N. Froessling, Gerlands
Beitr. Geophys., 52, 170 (1938).]
1/ 3
km Dcat ⎛ μ ⎞
= 2.0 + 0.552 Re0.5
p ⎜ ⎟
y A DAB ⎝ ρDAB ⎠
At these conditions the diffusivity of ethylene in benzene, DAB, is estimated to be 1×10-2 cm2/s =
1×10-6 m2/s
1/ 3
km (0.002) 0.5 ⎛ (18 × 10−6 ) ⎞
∴ = 2.0 + 0.552(632) ⎜⎜ −6 ⎟
= 14.0
(0.1076)(1 × 10−6 ) ⎟
⎝ (28)(1 × 10 ) ⎠
km = 7.519 × 10−4 m/s
1 1
Fraction of resistance in the external film = = −4
= 0.035
1+ '
km 7.519 × 10
1+
k1 ( Dcat / 6) (0.0829)(0.002 / 6)

Therefore, the external mass transfer resistance is only 3.5% of the total and can be safely
ignored. Therefore, the reaction is controlled by the intrinsic kinetics of the reaction and these
should be used in the simulation.

Properties of new Catalyst

The new catalyst is available as a cylindrical extruded pellet with diameter 4 mm and length
8 mm. For the sake of calculations, you may assume that the catalyst behaves like a spherical
particle of diameter = 5.8 mm and packed bed voidage of 0.52. You should assume that the
maximum allowable catalyst temperature = 500°C.

According to the manufacturer, the intrinsic rates of reaction are given in the following table:

i Ei ko,i a b c d e
kcal/kmol
1 22,500 1.50×106 1 0 0 1 0

2 22,500 6.00×103 1 1 0 0 0

3 25,000 7.80×106 0 0 0 1 1

4 20,000 1.80×108 2 0 1 0 0
 23

The pore structure of the new catalyst is somewhat smaller than the existing catalyst and the
manufacturer gives the effective diffusivity as 1×10-8 m3-gas/m-catalyst/s. The bulk density of
the new catalyst is 1,200 kg/m3.
 24

Appendix 4
Cost Information

Raw Materials
Ethylene $0.77/kg
Benzene $1.22/kg

Products
Ethyl Benzene not available

Utility Costs

See Table 6.3 of text

Equipment Costs and Cost Factor

Use CAPCOST if needed

 25

Appendix 5
Chemcad Simulation

A Chemcad simulation is provided to aid in the solution of the current problem. The
simulation is for the current operating conditions. The thermodynamics models are K-val =
UNIFAC and Enthalpy = Latent Heat, these should not be changed.

It should be noted that, in the simulation, a component separator is placed after the high-
pressure flash drum (V-302) in order to remove non-condensables from Stream 16 prior to
entering T-301. This is done in order to avoid problems in simulating this tower. In practice, the
non-condensables would be removed from the overhead reflux drum, V-303 after entering T-
301.

Both towers are simulated as Shortcut columns in the main simulation but each is separately
simulated using the rigorous TOWER module. You should use the same approach in your
simulations. The rigorous TOWER module provides accurate design and simulation data and
should be used to assess column operation.