FACULTY OF CHEMICAL ENGINEERING

UNIVERSITI TEKNOLOGI MARA

CPE 614 – PROCESS INTEGRATION

PRODUCTION OF ETHYLBENZENE

PREPARED BY: EH2206A & EH2206B

1 NUR FATIHAH BINTI ZULKEFLI 2016595727

2 AMNI BINTI SAUFIAN 2016718381

3 MUHAMMAD SYAHSAIFULLAH BIN OSMAN 2016577903

4 TENGKU MUHAMMAD AMIRUL ASHRAF BIN 2016565633

TENGKU NASIR

DATE OF SUBMISSION:

18th December 2019

NAME OF LECTURER:
DR. SITI SHAWALLIAH IDRIS
TABLE OF CONTENTS

1.0 INTRODUCTION ........................................................................................................ 3

2.0 PROCESS FLOW DIAGRAM FOR ETHYLBENZENE PLANT ................................... 4

2.1 STREAM TABLE .................................................................................................... 5

3.0 Problem Table Cascade (PTA) ................................................................................... 7

4.0 HEAT EXCHANGER NETWORK ............................................................................. 10

5.0 FEASIBILITY STUDY ............................................................................................... 13

5.1 TH DIAGRAM ABOVE PINCH .............................................................................. 13

5.2 TH DIAGRAM BELOW PINCH.............................................................................. 15

6.0 LOOP AND PATH IDENTIFICATION ....................................................................... 16

6.1 LOOP 1 INVOLVING HEAT EXCHANGER 3 & 11............................................... 16

6.2 LOOP 2 INVOLVING HEAT EXCHANGER 5, 6, 7 & 10 ........................................ 17

6.3 PATH 1 INVOLVING HEAT EXCHANGER 5 ........................................................ 18

6.4 PATH 2 INVOLVING HEAT EXCHANGER 3 ........................................................ 19

7.0 GRAND COMPOSITE CURVE ................................................................................. 20

7.1 DISTILLATION COLUMN INTEGRATION ............................................................ 21

8.0 ESTIMATION OF UTILITIES COST ......................................................................... 23

9.0 CONCLUSION ......................................................................................................... 24

10.0 REFERENCES ......................................................................................................... 25

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1.0 INTRODUCTION

Ethylbenzene (EB) with the formula of C₆H₅CH₂CH₃ is an organic compound and is highly
flammable, colorless liquid with an odor similar to that of gasoline. Other than that,
Ethylbenzene is an alkylbenzene that carrying an ethyl substituent. This monocyclic aromatic
hydrocarbon is major use is in the petrochemical industry as an intermediate compound for
the production of styrene. Ethylbenzene is used primarily to make another chemical, styrene
(Medicine, 2019). Ethylbenzene is produced by the catalytic alkylation of benzene with
ethylene, or from mixed xylenes by isomer separation and catalytic isomerisation, or from 1,3-
butadiene in a two-step process where the butadiene is converted to vinylcyclohexane which
is then dehydrogenated. In the early 1980s, Mobil/Badger developed an alternative zeolite-
based process using vapour phase alkylation, offering higher yields and purity. More recently,
liquid phase processes using zeolite catalysts have been introduced. These latest
technologies offer low benzene-to-ethylene ratios, which reduces the size of equipment, and
lowers the production of byproducts. Dow Chemical and Snamprogetti are developing a
process for making ethylbenzene/styrene from ethane and benzene. The process combines
the dehydrogenation of ethane and ethylbenzene in one unit and integrates the processes for
preparing ethylene, ethylbenzene and styrene. This process is claimed to have lower costs
than the conventional route to styrene, largely stemming from the low cost of ethane in relation
to ethylene. A pilot plant has been operating since 2002 and commercialisation could be
possible by the end of the decade. (Services, 2010)

In the chemical industry, more than 90% of Ethylbenzene is used in the synthesis of
styrene, while the remaining of ethylbenzene is used in the production of cellulose acetate,
diethylbenzenes (DEBs), acetophenone, ethylanthraquinone and α-methylbenzyl alcohol (T.
Vazhnova, K.S Wong, S.P Rigby, & D. Lukyanoy, 2013) Ethylbenzene is a component of
tobacco smoke, incense smoke and has been reported in the air emitted from grain and alfalfa
silage. Ethylbenzene is an important commercial chemical used to make other chemicals. It is
a component of automotive and aviation fuels. It is also used in paints, wood stains, sealants,
and automotive products. Workers that use ethylbenzene may breathe in vapors or have direct
skin contact. The general population may be exposed by breathing in air, smoking cigarettes,
ingestion of food and drinking water, and dermal contact with gasoline and other consumer
products containing ethylbenzene. If ethylbenzene is released to the environment, it will be
broken down eventually in air. It is not expected to be broken down by sunlight. It will move
into air from moist soil and water surfaces. It is expected to move moderately through soil. It
may be broken down by microorganisms, and is not expected to build up in fish. (Medicine,
2019)

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2.0 PROCESS FLOW DIAGRAM FOR ETHYLBENZENE PLANT

FIGURE 1: ETHYLBENZENE PRODUCTION PLANT PROCESS FLOW DIAGRAM

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 2.1 STREAM TABLE

Stream 1 2 3 4 5 6 7 8 9 10 11 12
Number
Temperatur 25.0 25.0 58.5 25.0 25.0 383.3 444.1 380.0 453.4 25.0 380.0 449.2
e (℃)
Pressure 110.0 2000.0 110.0 2000.0 2000.0 1985.0 1970.0 1960.0 1945.0 2000.0 1935.0 1920.0
(kPa)
Vapor mole 0.0 1.0 0.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0
fraction
Total kg/h 10574.08 3426.95 22271.59 1075.38 1180.70 23311.73 23312.02 24439.66 24202.20 1180.70 25331.09 24338.08
99 76 68 91 93 87 68 68 67 93 08 61
Total kmol/h 134.8850 121.909 284.3611 38.1460 41.8819 322.5071 289.8719 331.7538 289.8309 41.8819 331.7128 282.6111
8

Component Flowrates (kmol/h)

Ethylene 0.00 118.252 0.00 35.4758 38.9502 35.4758 1.0643 39.8105 0.7404 38.9502 39.8055 0.6488
5
Ethane 0.00 3.6573 0.00 2.6702 2.9317 2.6133 2.6123 6.6351 6.6351 2.9317 9.9514 9.9514
Propylene 0.00 0.00 0.00 0.00 0.00 0.00 2.2533 2.2327 0.2310 0.00 2.4447 3.1778E-
03
Benzene 132.16 0.00 281.0237 0.00 0.00 280.5812 252.5792 252.1329 216.3300 0.00 212.2962 180.0059
Toluene 2.7249 0.00 2.4813 0.00 0.00 2.4898 0.2365 0.2342 3.2085E- 0.00 3.1778E- 0.00
03 03
Ethylbenzen 0.00 0.00 0.8685 0.00 0.00 0.8708 29.2236 29.8578 63.0855 0.00 59.7083 85.1418
e
1,4- 0.00 0.00 0.00 0.00 0.00 0.00 1.9027 1.0716 2.8057 0.00 6.6343 6.8600
Diethylbenz
ene

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 Stream 13 14 15 16 17 18 19 20 21 22 23
Number
Temperature 497.9 458.1 73.6 73.6 81.4 145.4 139.0 191.1 82.6 82.6 121.4
(℃)
Pressure 1988.0 1920.0 110.0 110.0 105.0 120.0 110.0 140.0 2000.0 2000.0 2000.0
(kPa)
Vapor mole 1.0 1.0 1.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
fraction
Total kg/h 6016.351 30494.512 1117.496 38909.296 15387.912 14281.078 12360.750 1922.886 11699.017 3694.310 5562.406
1 2 4 5 5 7 9 5 6 7 3
Total kmol/h 66.8542 349.4653 21.6668 327.7985 196.6791 131.1194 116.4951 14.6243 149.4761 47.2030 61.8273

Component Flowrates (kmol/h)

Ethylene 0.00 0.6507 0.6290 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Ethane 0.00 8.4354 8.1542 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Propylene 0.00 2.4101 2.3298 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Benzene 38.4444 214.3186 9.7617 326.3733 195.5581 1.6815E- 0.2203 0.00 148.6839 46.9434 47.9433
03
Toluene 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Ethylbenzene 28.2664 111.1661 0.8271 110.5625 1.0631 117.5406 116.2619 1.1777 0.8036 0.2596 1.3498
1,4- 0.0925 12.4964 0.0151 12.5008 0.00 13.4232 1.2958E- 13.3948 0.00 0.00 12.4739
Diethylbenze 04
ne
TABLE 1: STREAM TABLE FOR PRODUCTION OF ETHYLBENZENE

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3.0 Problem Table Cascade (PTA)
In order to optimize the energy utilization and reducing the cost for additional utilities, the required minimum heat utilities and the possible heat
recovered need to be determine. Thus, PTA was used since this method is more accurate compared to composite curve as composite curve is
more complicated and less accuracy to the pinch temperature point with the minimum heat utilities.

Table 2: Stream Data Extracted from PFD EthylBenzene Plant, 𝜟𝑻min = 10⁰C

Supply Target Temperature Heat Capacity Shifted Supply Shifted Target

Temperature, Temperature, Difference, Flowrate, CP Enthalpy, Temperature, Temperature,
Stream Type
TS (⁰C) TT (⁰C) 𝜟𝑻 (⁰C) (kJ/⁰C) 𝜟H (kW) TS (⁰C) TT (⁰C)
7→8 Hot 444.1 380 64.1 30.68 1966.59 439.1 375
9→11 Hot 453.4 380 73.4 35.31 2591.75 448.4 375
13→15* Hot 479.9 80 399.9 82.36 32935.76 474.9 75
14→15* Hot 458.1 80 378.1 43.07 16284.77 453.1 75
3→6 Cold 58.5 383.3 325.2 48.81 15873.01 63.5 388.3
5→8 Cold 25 380 355 5.54 1966.70 30 385
18*→18 Cold 127.6 140.3 12.7 77.24 980.95 132.6 145.3
20*→20 Cold 183.9 191.3 7.4 63.65 471.01 188.9 196.3
17→23* Cold 81.4 500 418.6 43.45 18188.17 86.4 505
20→23* Cold 191.1 500 308.9 62.44 19287.72 196.1 505
Shifting rule;
∆𝑻𝒎𝒊𝒏
Hot Stream = − = −𝟓℃
𝟐
∆𝑻𝒎𝒊𝒏
Hot Stream =+ 𝟐
= +𝟓℃

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 Table 3: Problem Table Cascade 𝜟𝑻min = 10⁰C

Infeasibility Cascade Feasibility Cascade

∆T ∑ 𝐶𝑃𝐻 − 𝐶𝑃𝐶 ∆H

505 0 4819.98
30.1 -105.89 -3187.29
474.9 -3187.29 1632.69
21.8 -23.53 -512.95
453.1 -3700.24 1119.74
4.7 19.54 91.84
-3608.41 1211.58
448.4 9.3 54.85 510.11
-3098.30 1721.68
439.1 50.8 85.53 4344.92
1246.62 6066.60
388.3 3.3 36.72 121.18
1367.80 6187.78
385 10 31.18 311.80
375 1679.60 6499.58
178.7 -34.81 -6220.55
196.3 -4540.95 279.03
0.2 -98.46 -19.69
196.1 -4560.64 259.34
7.2 -36.02 -259.34
188.9 -4819.98 0.00
43.6 27.63 1204.67
145.3 -3615.32 1204.67
12.7 -49.61 -630.05
132.6
46.2 27.63 1276.51 -4245.36 574.62
86.4 -2968.86 1851.12
11.4 71.08 810.31
75 -2158.54 2661.44
11.5 -54.35 -625.03
63.5 -2783.57 2036.41
33.5 -5.54 -185.59
30 -2969.16 1850.82

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The pinch temperature = 188.9 ⁰C

The hot pinch temperature= 193.9⁰C

The cold pinch temperature= 183.9⁰C

The minimum hot utilities, Qhmin= 4819.98 kW

The minimum cold utilities, Qcmin= 1850.82 kW

The Heat Load for Cold Stream, ∆Hc

∆𝐻𝑐 = 15869.8 + 1966.7 + 980.44 + 471.38 + 18209.1 + 19275.4 = 56772.74𝑘𝑊

The Heat Load for Hot Stream, ∆HH

∆𝐻𝑐 = 1967.87 + 2591.02 + 32951.8 + 16296.1 = 53806.76 𝑘𝑊

The heat recovered from the process, Qrec

𝑄𝑟𝑒𝑐 = ∆𝐻𝑐 − 𝑄ℎ, 𝑚𝑖𝑛 = 56772.74 − 4819.98 = 51952.76 𝑘𝑊

The heat recovered from the process, Qrec

𝑄𝑟𝑒𝑐 = ∆𝐻𝐻 − 𝑄𝑐, 𝑚𝑖𝑛 = 53806.76 − 1850.82 = 51955.94 𝑘𝑊

∴ 𝑸𝒓𝒆𝒄 ≅ 𝟓𝟏𝟗𝟓𝟎 𝒌𝑾

The PTA resulting in threshold problem where the cold utilizes is fully utilized nut the minimum
hot utilities is still present. Hence, this show that this process needs additional heat utilities to
be supplied. Since, the recovered heat is still sufficient so there are possibilities for
improvement for the ethylbenzene process plant. Therefore, heat exchanger network, HEN is
required to oversee the possibilities.

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4.0 HEAT EXCHANGER NETWORK
Heat exchanger was designed to achieve the optimal energy target in the process by utilizing the heat released from the hot stream and being
absorbed by the cold stream. This is to ensure the heat exchanger was placed accordingly and consistent to the rules.

Figure 2: Heat Exchanger Network at 𝜟𝑻min = 10⁰C

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 Figure 3: Heat Exchanger Network for Above Pinch at 𝜟𝑻min = 10⁰C

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 Figure 4: Heat Exchanger Network for Above Pinch at 𝜟𝑻min = 10⁰C

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5.0 FEASIBILITY STUDY
5.1 TH DIAGRAM ABOVE PINCH

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All heat exchanger for above pinch was feasible since all the matches for heat exchanger have
obeyed the CP rule where for above pinch is 𝐶𝑃𝐻 ≤ 𝐶𝑃𝐶 .

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 5.2 TH DIAGRAM BELOW PINCH

All the heat exchanger for below pinch are also feasible since the temperature doesn’t across
the pinch and all of the matches of heat exchanger have followed the CP rule 𝐶𝑃𝐻 ≥ 𝐶𝑃𝐶 .

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6.0 LOOP AND PATH IDENTIFICATION

6.1 LOOP 1 INVOLVING HEAT EXCHANGER 3 & 11

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 6.2 LOOP 2 INVOLVING HEAT EXCHANGER 5, 6, 7 & 10

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 6.3 PATH 1 INVOLVING HEAT EXCHANGER 5

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 6.4 PATH 2 INVOLVING HEAT EXCHANGER 3

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7.0 GRAND COMPOSITE CURVE

T*℃
2995 Hot oil

HPS

LPS

CW

∆𝐻 (𝑘𝑊)

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 7.1 DISTILLATION COLUMN INTEGRATION

T*℃
2995

For distillation column 1 the column was

appropriately placed below the pinch hence the
reboiler duty can be supplied by integration with
the process. For the condenser part of the duty
must be integrated, while the remainder of the
REB condenser duty can be rejected to cold utility.
DC1
CON

∆𝐻 (𝑘𝑊)

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 HEAT INTEGRATION OF DISTILLATION COLUMN 2

T*℃
540
530
520
510
500
490
480
470
460
450
440
430
420
410
400
390
380
370
360
350
340
330
320
310
300
290
280
270
260
250
240
230
220
210 Distillation column 2 has the same outcome as
200 distillation 1 where it was placed below the
190
180 pinch hence the reboiler duty can be supplied by
170 integration with the process. For the condenser
160
DC2
150 part of the duty must be integrated, while the
140 remainder of the condenser duty can be rejected
130
120 to cold utility.
110
100
90
80
70
60
50
40
30
20
10
0
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000 6500 7000
∆𝐻 (𝑘𝑊)
∆𝐻 (𝑘𝑊)

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8.0 ESTIMATION OF UTILITIES COST

Type Temperature (℃) 𝑼𝑺𝑫

Cost ( )
𝑮𝑱
Cooling water 25-35 0.354
Low pressure steam 160 7.78
High pressure steam 254 9.88
Hot oil 3000 14.2

∆𝑇𝑚𝑖𝑛 = 10

Cost for utility

Below pinch
1
𝑇 + ∆𝑇𝑚𝑖𝑛
2
1. Cooling water= 30 − 40℃
∆𝐻 = 1276.58 𝑘𝑊
0.354 𝑈𝑆𝐷 𝑅𝑀 4.13 1 𝐺𝐽 𝑅𝑀 6.72
Cooling water = 𝐺𝐽
× 1 𝑈𝑆𝐷 × 277.78 𝑘𝑊ℎ × 1276.58 𝑘𝑊 = ℎ

2. Low pressure steam= 165℃

∆𝐻 = 574.62 𝑘𝑊
7.78 𝑈𝑆𝐷 𝑅𝑀 4.13 1 𝐺𝐽 𝑅𝑀 66.47
LPS = 𝐺𝐽
× 1 𝑈𝑆𝐷
× 277.78 𝑘𝑊ℎ × 574.62 𝑘𝑊 = ℎ

Above pinch
1
𝑇 − ∆𝑇𝑚𝑖𝑛
2
1. High pressure steam= 249℃
∆𝐻 = 1119.74 𝑘𝑊
9.88 𝑈𝑆𝐷 𝑅𝑀 4.13 1 𝐺𝐽 𝑅𝑀 164.48
HPS = 𝐺𝐽
× 1 𝑈𝑆𝐷
× 277.78 𝑘𝑊ℎ × 1119.74kW = ℎ

2. Hot oil= 2995℃

∆𝐻 = 3700.24𝑘𝑊
14.2 𝑈𝑆𝐷 𝑅𝑀 4.13 1 𝐺𝐽 𝑅𝑀 781.21
Hot oil= 𝐺𝐽
× 1 𝑈𝑆𝐷
× 277.78 𝑘𝑊ℎ × 3700.24kW = ℎ

Total cost of utility per hour= 6.72 + 66.47 + 164.48 + 781.21 = 𝑅𝑀1018.88

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9.0 CONCLUSION

Total heat exchanger unit required for this Ethylbenzene production plant is nine units.
Surprisingly after doing heat integration analysis by constructing heat exchanger network the
amount of heat exchanger unit was increasing from nine units to twelve units but by further
inspection we could identify two loops and two path that could have the potential to reduce the
amount of total heat exchanger units required. The additional utility required for this process
include hot oil and high pressure steam as hot utility while low pressure steam and cooling
water as cold utility. The calculated cost for the additional utility was 𝑅𝑀1018.88 per hour.

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10.0 REFERENCES

Medicine, U. N. (2019). Ethylbenzene. Retrieved from PubChem:

https://pubchem.ncbi.nlm.nih.gov/compound/ethylbenzene#section=Atmospheric-
Concentrations

ScienceDirect. (2013). Composite CUrve. Retrieved from Heat Integration: Targets and Heat
Exchanger Network Design:
https://www.sciencedirect.com/topics/engineering/composite-curve

Services, I. C. (27 April, 2010). Ethylbenzene(EB) Production and Manufacturing Process.

Retrieved from
https://www.icis.com/explore/resources/news/2007/11/02/9075695/ethylbenzene-eb-
production-and-manufacturing-process

T. Vazhnova, K.S Wong, S.P Rigby, & D. Lukyanoy. (2013). Temperatre Effects in Benzene
Alkylation with Ethane into Ethylbenzene over a PtH-MFI Bifunctionalcatalyst. Applied
Catalysis A: General, 137-144.

Zuckerman, M. (2015). Process Design. Retrieved from Pinch Analysis:

https://processdesign.mccormick.northwestern.edu/index.php/Pinch_analysis

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