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Appendix B Information for the Preliminary Design of Fifteen Chemical Processes 89

Table B.4.3 Major Equipment Summary for Unit 500 (Continued)

Towers
T-501 T-502
Stainless steel Stainless steel
56 sieve trays plus reboiler and condenser 35 sieve trays plus reboiler and condenser
25% efficient trays 52% efficient trays
Total condenser Total condenser
Feed on tray = 32 Feed on tray = 23
Reflux ratio = 0.15 Reflux ratio = 0.52
12-in tray spacing, 2.2-in weirs 12-in tray spacing, 2.8-in weirs
Column height = 17 m Column height = 11 m
Diameter = 2.1 m below feed and 0.65 m Diameter = 0.45 m
above feed

Vessels
V-501 V-503
Horizontal Horizontal
Carbon steel Stainless steel
L/D = 3 L/D = 3
V = 2.3 m3 V = 2.3 m3
V-502 V-504
Vertical Horizontal
Stainless steel Carbon steel
L/D = 5 L/D = 3
V = 3 m3 V = 0.3 m3

B.4.4 Reference
1. Smith, J. M., Chemical Engineering Kinetics, 3rd ed. (New York: John Wiley and Sons,
1981), 224–228.

B.5 PRODUCTION OF MALEIC ANHYDRIDE FROM BENZENE, UNIT 600

Currently, the preferred route to maleic anhydride in the United States is via isobutene in
fluidized-bed reactors. However, an alternative route via benzene may be carried out
using a shell-and-tube reactor, with catalyst in the tubes and a cooling medium being cir-
culated through the shell [1, 2].
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90 Appendix B Information for the Preliminary Design of Fifteen Chemical Processes

B.5.1 Process Description

A process flow diagram for the reactor section of the maleic anhydride process is shown
in Figure B.5.1. Benzene is vaporized in E-601, mixed with compressed air, and then
heated in a fired heater, H-601, prior to being sent to a packed-bed catalytic reactor,
R-601, where the following reactions take place:

k
C6H6  4.5O2 S C4H2O3  2CO2  2H2O
1
(B.5.1)
benzene maleic anhydride

k2
C6H6  7.5O2 S 6CO2  3H2O (B.5.2)
benzene

C4H2O3  3O2 S 4CO2  H2O

k3
.(B.5.3)
maleic anhydride

k4
C6H6  1.5O2 S C6H4O2  2H2O (B.5.4)
benzene quinone

All the reactions are highly exothermic. For this reason, the ratio of air to benzene
entering the reactor is kept very high. A typical inlet concentration (Stream 6) of approxi-
mately 1.5 vol% of benzene in air is used. Cooling is achieved by circulating molten salt (a
mixture of sodium nitrite and sodium nitrate) cocurrently through the shell of the reactor
and across the tubes containing the catalyst and reactant gases. This molten salt is cooled
in two external exchangers—E-602 and E-607—prior to returning to the reactor.
The reactor effluent, Stream 7—containing small amounts of unreacted benzene,
maleic anhydride, quinone, and combustion products—is cooled in E-603 and then sent
to an absorber column, T-601, which has both a reboiler and condenser. In T-601, the
vapor feed is contacted with recycled heavy organic solvent (dibutyl phthalate), Stream 9.
This solvent absorbs the maleic anhydride, quinone, and small amounts of water. Any
water in the solvent leaving the bottom of the absorber, T-601, reacts with the maleic an-
hydride to form maleic acid, which must be removed and purified from the maleic anhy-
dride. The bottoms product from the absorber is sent to a separation tower, T-602, where
the dibutyl phthalate is recovered as the bottoms product, Stream 14, and recycled back to
the absorber. A small amount of fresh solvent, Stream 10, is added to account for losses.
The overhead product from T-602, Stream 13, is sent to the maleic acid column, T-603,
where 95 mol% maleic acid is removed as the bottoms product.
The overhead stream is taken to the quinone column, T-604, where 99 mol%
quinone is taken as the top product and 99.9 mol% maleic anhydride is removed as the
bottoms product. These last two purification columns are not shown in Figure B.5.1 and
are not included in the current analysis.
Stream summaries, utility summaries, and equipment summaries are presented in
Tables B.5.1–B.5.3.
 V-601 C-601 P-601A/B E-601 H-601 P-602 A/B E-602 R-601 P-603A/B E-603 T- 601 E-604 V-602 P-604 A/B E-605
Benzene Inlet Air Benzene Benzene Feed Molten Molten Reactor Dibutyl Reactor MA MA Tower MA MA MA
Feed Compressor Feed Feed Heater Salt Circ. Salt Makeup Effluent Scrubber Condenser Reflux Reflux Reboiler
Turton_AppB_Part1.qxd

Drum Pumps Vaporizer Pumps Cooler Pumps Cooler Drum Pumps

T- 602 E-606 V-603 P-605 A/B E-607 P-606 A/B

Dibutyl Phthalate Make-up Dibutyl Dibutyl Dibutyl Dibutyl Dibutyl Dibutyl
Scrubber Tower Reflux Reflux Reboiler Recycle
5/11/12

10 Condenser Drum Pumps Pumps

P-603 A/B
5
12:21 AM

Air
FIC
4
Products of
116 Combustion
C-601 9 E-604 Off-Gas to
Incinerator
Page 91

H-601
~
E-601
cw 12

PIC ~
lps
T- 601
LIC V-602

6
Benzene air ng
3 FIC
1 P-604A/B E-606
R-601 E-605
15 LIC
V-601 FIC
hps T- 602 cw
E-602
2 hps
hps
16 8 FIC LIC To Maleic
V-603
7 Anhydride
P-601 A/B
Purification
11
bfw
~ 13
P-602 A/B E-603 P-605A/B ~
Temperature °C bfw
E-607 LIC
14

P-606 A/B

Figure B.5.1 Unit 600: Maleic Anhydride Process Flow Diagram

91
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92 Appendix B Information for the Preliminary Design of Fifteen Chemical Processes

Table B.5.1 Stream Table for Unit 600

Stream Number 1 2 3 4 5 6 7 8
Temperature (°C) 30 30 30 30 170 460 608 270
Pressure (kPa) 101 101 280 101 250 235 220 215
Total kg/h 3304 3304 3304 80,490 80,490 83,794 83,794 83,794
Total kmol/h 42.3 42.3 42.3 2790.0 2790.0 2832.3 2825.2 2825.2
Component Flowrates (kmol/h)
Maleic anhydride 0.0 0.0 0.0 0.0 0.0 0.0 26.3 26.3
Dibutyl phthalate 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Nitrogen 0.0 0.0 0.0 2205.0 2205.0 2205.0 2205.0 2205.0
Water 0.0 0.0 0.0 0.0 0.0 0.0 91.5 91.5
Oxygen 0.0 0.0 0.0 585.0 585.0 585.0 370.2 370.2
Benzene 42.3 42.3 42.3 0.0 0.0 42.3 2.6 2.6
Quinone 0.0 0.0 0.0 0.0 0.0 0.0 0.7 0.7
Carbon dioxide 0.0 0.0 0.0 0.0 0.0 0.0 129.0 129.0
Maleic acid 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Sodium nitrite 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Sodium nitrate 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0

Stream Number 9 10 11 12 13 14 15 16
Temperature (°C) 330 320 194 84 195 330 419 562
Pressure (kPa) 82 100 82 75 80 82 200 200
Total kg/h 139,191.6 30.6 141,866 81,225 2597 139,269 391,925 391,925
Total kmol/h 500.1 0.1 526.2 2797.9 26.2 500.0 5000.0 5000.0
Component Flowrates (kmol/h)
Maleic anhydride 0.0 0.0 4.8 0.5 24.8 0.0 0.0 0.0
Dibutyl phthalate 500.1 0.1 500.0 0.0 0.0 500.0 0.0 0.0
Nitrogen 0.0 0.0 0.0 2205.0 0.0 0.0 0.0 0.0
Water 0.0 0.0 0.0 91.5 0.0 0.0 0.0 0.0
Oxygen 0.0 0.0 0.0 370.2 0.0 0.0 0.0 0.0
Benzene 0.0 0.0 0.0 2.6 0.0 0.0 0.0 0.0
Quinone 0.0 0.0 0.4 0.4 0.4 0.0 0.0 0.0
Carbon dioxide 0.0 0.0 0.0 129.0 0.0 0.0 0.0 0.0
Maleic acid 0.0 0.0 1.0 0.0 1.0 0.005 0.0 0.0
Sodium nitrite 0.0 0.0 0.0 0.0 0.0 0.0 2065.6 2065.6
Sodium nitrate 0.0 0.0 0.0 0.0 0.0 0.0 2934.4 2934.4
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Appendix B Information for the Preliminary Design of Fifteen Chemical Processes 93

Table B.5.2 Utility Summary Table for Unit 600

E-601 E-602 E-603 E-604 E-605 E-606
lps bfw → hps bfw → hps cw hps cw
1750 MJ/h 16,700 MJ/h 31,400 MJ/h 86,900 MJ/h 19,150 MJ/h 3050 MJ/h
841 kg/h 7295 kg/h 13,717 kg/h 2.08 × 106 kg/h 11,280 kg/h 73,000 kg/h

Table B.5.3 Major Equipment Summary for Unit 600

Compressor and Drives
C-601 D-601A/B (not shown on PFD)
Centrifugal/electric drive Electric/explosion proof
Carbon steel W = 3200 kW
Discharge pressure = 250 kPa 98% efficient
Efficiency = 65%
Power (shaft) = 3108 kW
MOC carbon steel
Fired Heater
H-601
Total (process) heat duty required = 26,800 MJ/h
Design capacity = 32,000 kW
Carbon steel tubes
85% thermal efficiency
Design pressure = 300 kPa
Heat Exchangers
E-601 E-605
A = 14.6 m2 A = 131 m2
1-2 exchanger, floating head, stainless steel 1-2 exchanger, floating head, stainless steel
Process stream in tubes Process stream in shell
Q = 1750 MJ/h Q = 19,150 MJ/h
Design pressure = 600 kPa Design pressure = 4100 kPa
E-602 E-606
A = 61.6 m2 A = 11.7 m2
1-2 exchanger, floating head, stainless steel 1-2 exchanger, floating head, stainless steel
Process stream in shell Process stream in shell
Q =16,700 MJ/h Q = 3050 MJ/h
Design pressure = 4100 kPa Design pressure = 300 kPa
E-603 E-607
A = 1760 m2 A = 192 m2
1-2 exchanger, floating head, stainless steel 1-2 exchanger, floating head, stainless steel
Process stream in shell Molten salt in tubes
Q = 31,400 MJ/h Q = 55,600 MJ/h
Design pressure = 4100 kPa Design pressure = 4100 kPa
E-604
A = 1088 m2
1-2 exchanger, fixed head, stainless steel
Process stream in tubes
Q = 86,900 MJ/h
Design pressure = 300 kPa

(continued)
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94 Appendix B Information for the Preliminary Design of Fifteen Chemical Processes

Table B.5.3 Major Equipment Summary for Unit 600 (Continued)

Pumps
P-601 A/B P-604 A/B
Centrifugal/electric drive Centrifugal/electric drive
Carbon steel Stainless steel
Power = 0.3 kW (actual) Power = 6.75 kW (actual)
65% efficient 65% efficient
Design pressure = 300 kPa Design pressure = 200 kPa
P-602 A/B P-605 A/B
Centrifugal/electric drive Centrifugal/electric drive
Stainless steel Stainless steel
Power = 3.8 kW (actual) Power = 0.7 kW (actual)
65% efficient 65% efficient
Design pressure = 300 kPa Design pressure = 400 kPa
P-603 A/B P-606 A/B
Reciprocating/electric drive Centrifugal/electric drive
Stainless steel Stainless steel
Power = 0.1 kW (actual) Power = 2.4 kW (actual)
65% efficient 65% efficient
Design pressure = 200 kPa Design pressure = 150 kPa
Reactor
R-601
Shell-and-tube vertical design
Stainless steel
L = 7.0 m
D = 3.8 m
12,100 1-in diameter, 6.4 m length catalyst-
filled tubes
Design pressure = 300 kPa
Towers
T-601 T-602
Stainless steel Stainless steel
14 sieve trays plus reboiler and condenser 42 sieve trays plus reboiler and condenser
50% efficient trays 65% efficient trays
Partial condenser Total condenser
Feeds on trays 1 and 14 Feed on tray 27
Reflux ratio = 0.189 Reflux ratio = 1.24
24-in tray spacing, 2.2-in weirs 15-in tray spacing, 1.5-in weirs
Column height = 10 m Column height = 18 m
Diameter = 4.2 m Diameter = 1.05 m
Design pressure = 110 kPa Design pressure = 110 kPa
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Appendix B Information for the Preliminary Design of Fifteen Chemical Processes 95

Table B.5.3 Major Equipment Summary for Unit 600 (Continued)

Vessels
V-601 V-603
Horizontal Horizontal
Carbon steel Stainless steel
L = 3.50 m L = 3.90 m
D = 1.17 m D = 1.30 m
Design pressure = 110 kPa Design pressure = 110 kPa
V-602
Horizontal
Stainless steel
L = 13.2 m
D = 4.4 m
Design pressure = 110 kPa

B.5.2 Reaction Kinetics

The reactions and reaction kinetics [3] given in Equations (B.5.1)–(B.5.4) are given by the
expression
−ri  kiCbenzene or −r3  k3Cmaleic anhydride (B.5.5)
where
k1  7.7  106 exp(−25,143RT) (B.5.6)

k2  6.31  107 exp(−29,850RT) (B.5.7)

k3  2.33  104 exp(−21,429RT) (B.5.8)

k4  7.20  105 exp(−27,149RT) (B.5.9)

The units of reaction rate, ri, are kmol/m3(reactor)s, the activation energy is given in
cal/mol (which is equivalent to kcal/kmol), the units of ki are m3(gas)/m3 (reactor)s, and
the units of concentration are kmol/m3(gas).
The catalyst is a mixture of vanadium and molybdenum oxides on an inert support.
Typical inlet reaction temperatures are in the range of 350°C to 400°C. The catalyst is
placed in 25 mm diameter tubes that are 3.2 m long. The catalyst pellet diameter is 5 mm.
The maximum temperature that the catalyst can be exposed to without causing
irreversible damage (sintering) is 650°C. The packed-bed reactor should be costed as a
shell-and-tube exchanger. The heat transfer area should be calculated based on the total
external area of the catalyst-filled tubes required from the simulation. Because of the high
temperatures involved, both the shell and the tube material should be stainless steel. An
overall heat transfer coefficient for the reactor should be set as 100 W/m2°C. (This is the
value specified in the simulation.)
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96 Appendix B Information for the Preliminary Design of Fifteen Chemical Processes

B.5.3 Simulation (CHEMCAD) Hints

The CHEMCAD simulation used to generate the PFD shown in Figure B.5.1 has several
simplifications that are valid for this system. The removal of trace amounts of noncon-
densables is achieved after the absorber using a component separator, which avoids prob-
lems with column convergence downstream. The formation of maleic acid is simulated by
using a stoichiometric reactor and setting the conversion of water to 1.
Tower T-601, the maleic anhydride scrubber, is simulated using the rigorous tower
simulator. Tower T-602, the dibutyl phthalate tower, is simulated using the Shortcut col-
umn module. Currently, there is no experimental vapor pressure data for the components
in this simulation. It appears that the vapor pressures of the components differ widely,
and no azeotropes are known at this time. For this reason, the ideal vapor pressure
K-value option and the latent heat enthalpy option are used.
In order to simulate the temperature spike in the reactor, the reactor is simulated as
a cocurrent, packed-bed kinetic reactor, with a molten salt stream as the utility. This con-
figuration provides a greater temperature differential at the front end of the reactor,
where the reaction rate is highest. Countercurrent flow could be investigated as an alter-
native. The kinetics given above are used in the simulation. Dimensions of the reactor
tubes are given in Section B.5.2.

B.5.4 References
1. Felthouse, T. R., J. C. Burnett, B. Horrell, M. J. Mummey, and Y-J Kuo, “Maleic Anhy-
dride, Maleic Acid, and Fumaric Acid,” Kirk-Othmer Encyclopedia of Chemical Technol-
ogy, online version (New York: John Wiley and Sons, 2001).
2. “Maleic Acid and Anhydride,” Encyclopedia of Chemical Processing and Design, Vol.
29, ed. J. J. McKetta (New York: Marcel Dekker, 1984), 35–55.
3. Wohlfahrt, Emig G., “Compare Maleic Anhydride Routes,” Hydrocarbon Processing,
June 1980, 83–90.

B.6 ETHYLENE OXIDE PRODUCTION, UNIT 700

Ethylene oxide is a chemical used to make ethylene glycol (the primary ingredient in an-
tifreeze). It is also used to make polyethylene oxide, and both the low-molecular-weight
and high-molecular-weight polymers have many applications including as detergent addi-
tives. Because ethylene oxide is so reactive, it has many other uses as a reactant. However,
because of its reactivity, danger of explosion, and toxicity, it is rarely shipped outside the
manufacturing facility but instead is often pumped directly to a nearby consumer.

B.6.1 Process Description [1, 2]

The process flow diagram is shown in Figure B.6.1. Ethylene feed (via pipeline from a
neighboring plant) is mixed with recycled ethylene and mixed with compressed and dried
air (drying step not shown), heated, and then fed to the first reactor. The reaction is
exothermic, and medium-pressure steam is made in the reactor shell. Conversion in the re-
actor is kept low to enhance selectivity for the desired product. The reactor effluent is
cooled, compressed, and sent to a scrubber, where ethylene oxide is absorbed by water.
The vapor from the scrubber is heated, throttled, and sent to a second reactor, followed by
a second series of cooling, compression, and scrubbing. A fraction of the unreacted vapor