984

4.

5.
6.
7.
8.

9.
10.

11.

CHEMICAL ENGINEERING

far as possible in the corrected evaluation. The diagram should show all major pipe
lines and the instrumentation of the reactor and the cooler/scrubber system.
Prepare an equipment schedule listing all major items of equipment and
giving sizes, capacities, operating pressures and temperatures, materials of
construction, etc.
Present a specimen pipeline sizing calculation.
Work out the full chemical engineering design of the reactor and cooler/scrubber
systems.
Calculate the height and diameter of the expeller.
Prepare a mechanical design of the cooler/scrubber showing by dimensioned
sketches suitable for submission to a draughtsman how:
(a) The tower packing is to be supported.
(b) The liquid is to be distributed in the tower.
(c) The shell is to be constructed so as to withstand the severely corrosive conditions inside it.
Discuss the safety precautions involved in the operation of the plant, and the
procedure to be followed in starting the plant up and shutting it down.
Develop the mechanical design of the reactor and prepare a key arrangement
drawing, supplemented by details to make clear the essential constructional features.
The study should include recommendations for the design of the bed and means of
separation and disposal of dust from the exit gas stream, and should take account
of needs connected with thermal expansion, inspection, maintenance, starting and
stopping, inlet gas distribution, insertion and removal of catalyst, and the positioning
and provision for reception of instruments required for control and operational
safety. Written work should be confined, as far as possible, to notes on engineering
drawings, except for the design calculations, the general specification and the justification of materials of construction.
Assuming that the plant throughout may vary by 10 per cent on either side of its
normal design value due to changes in demand, specify control systems for:
(i) regulation of the necessary recycle flow from the cooler/scrubber base, at the
design temperature; and
(ii) transfer of the cooler/scrubber make liquor to the expeller.

REFERENCES
ARNOLD, C. W. and KOBE, K. A. (1952) Chem. Engng Prog. 48, 293.
FLEURKE, K. H. (1968) Chem. Engr., Lond., p. CE41.
QUANT, J., VAN DAM, J., ENGEL, W. F., and WATTIMENA, F. (1963) Chem. Engr., Lond., p. CE224.
SCONCE, J. S. (1962) Chlorine: Its Manufacture, Properties, and Uses (New York: Rheinhold Publishing Corporation).

F.8 ANILINE FROM NITROBENZENE

The project
Design a plant to make 20,000 tonnes per annum of refined aniline by the hydrogenation
of nitro-benzene. The total of on-stream operation time plus regeneration periods will be
7500 hours per year.

APPENDIX F

985

Materials available:
Nitrobenzene containing < 10 ppm thiophene.
Hydrogen of 99.5 per cent purity at a pressure of 50 psig (350 kN/m2 ).
Copper on silica gel catalyst.

Services available:
Steam at 200 psig (1400 kN/m2 ) 197 C, and 40 psig (280 kN/m2 ) 165 C.
Cooling water at a maximum summer temperature of 24 C.
Towns water at 15 C.
Electricity at 440 V, three-phase 50 Hz.

Product specification:
Aniline
Nitrobenzene
Cyclohexylamine
Water

99.9 per cent w/w min.

2 ppm max.
100 ppm max.
0.05 per cent w/w max.

The process
Nitrobenzene is fed to a vaporiser, where it is vaporised in a stream of hydrogen (three
times stoichiometric). The mixture is passed into a fluidness bed reactor containing copper
on silica gel catalyst, operated at a pressure, above the bed, of 20 psig (140 kN/m2 ). The
contact time, based on superficial velocity at reaction temperature and pressure and based
on an unexpanded bed, is 10 seconds. Excess heat of reaction is removed to maintain the
temperature at 270 C by a heat-transfer fluid passing through tubes in the catalyst bed.
The exit gases pass through porous stainless-steel candle filters before leaving the reactor.
The reactor gases pass through a condenser/cooler, and the aniline and water are
condensed. The excess hydrogen is recycled, except for a purge to maintain the impurity
level in the hydrogen to not more than 5 per cent at the reactor inlet. The crude aniline
and water are let down to atmospheric pressure and separated in a liquid/liquid separator,
and the crude aniline containing 0.4 per cent unreacted nitrobenzene and 0.1 per cent
cyclo-hexylamine as well as water, is distilled to give refined aniline. Two stills are used,
the first removing water and lower boiling material, and the second removing the higher
boiling material (nitrobenzene) as a mixture with aniline. The vapour from the first column
is condensed, and the liquid phases separated to give an aqueous phase and an organic
phase. A purge is taken from the organic stream to remove the cyclo-hexylamine from the
system, and the remainder of the organic stream recycled. The cyclo-hexylamine content
of the purge is held to not greater than 3 per cent to avoid difficulty in phase separation.
In the second column, 8 per cent of the feed is withdrawn as bottoms product.
The purge and the higher boiling mixture are processed away from the plant, and the
recovered aniline returned to the crude aniline storage tank. The aniline recovery efficiency
in the purge unit is 87.5 per cent, and a continuous stream of high-purity aniline may be
assumed.

986

CHEMICAL ENGINEERING

The aqueous streams from the separators (amine-water) are combined and steam stripped
to recover the aniline, the stripped water, containing not more than 30 ppm aniline or
20 ppm cyclo-hexylamine, being discharged to drain.
Regeneration of the catalyst is accomplished in place using air at 250 350 C to burn
off organic deposits. Regeneration takes 24 hours, including purging periods.
The overall yield of aniline is 98 per cent theory from nitrobenzene, i.e. from 100 mols
of nitrobenzene delivered to the plant, 98 mols of aniline passes to final product storage.

Scope of design work required

1. Prepare a material balance on an hourly basis for the complete process in weight
units.
2. Prepare a heat balance for the reactor system, comprising vaporiser, reactor and
condenser/cooler.
3. Draw a process flow diagram for the plant. This should show all items of equipment
approximately to scale and at the correct elevation. The catalyst regeneration.
equipment should be shown.
4. Chemical engineering design.
(a) Vaporiser
Give the detailed chemical engineering design, and give reasons for using the
type chosen. Specify the method of control.
(b) Reactor
Give the detailed chemical engineering design for the fluidness bed and heat
transfer surfaces. Select a suitable heat transfer fluid and give reasons for your
selection. Do not attempt to specify the filters or to design the condenser/cooler in
detail.
(c) Crude aniline separator
Specify the diameter, height and weir dimensions and sketch the method of
interface level control which is proposed.
(d) Amine water stripper
Give the detailed chemical engineering design of the column.
5. Prepare a full mechanical design for the reactor. Make a dimensioned sketch suitable
for submission to a drawing office, which should include details of the distributor,
and show how the heat transfer surfaces will be arranged. An indication of the
method of supporting the candle filters should be shown, but do not design this in
detail.
6. Prepare an equipment schedule detailing all major items of equipment, including
tanks and pumps. A specimen pipeline sizing calculation for the reactor inlet pipe
should be given. All materials of construction should be specified.
7. Describe briefly how the plant would be started up and shut down, and discuss
safety aspects of operation.
8. Write a short discussion, dealing particularly with the less firmly based aspects of
the design, and indicating the semi-technical work which is desirable.

987

APPENDIX F

Data
1. Catalyst properties:
(a) Grading:
0 20
20 40
40 60
60 80
80 100
100 120
120 140
140 150
> 150

m:
m:
m:
m:
m:
m:
m:
m:
m:

3
7
12
19
25
24
10

Negligible
per cent w/w
per cent w/w
per cent w/w
per cent w/w
per cent w/w
per cent w/w
per cent w/w
Negligible.

(b)
(c)
(d)
(e)

Voidage at minimum fluidisation, 0.45.

Shape factor, 0.95.
Bulk density at minimum fluidisation, 50 lb/ft3 (800 kg/m3 ).
Life between regenerations 1500 tonne of aniline per ton of catalyst, using the
feedstock given.
2. Exothermic heat of hydrogenation.
H298 D 132, 000 CHU/lb mol (552,000 kJ/k
mol).
3. Mean properties of reactor gases at reactor conditions:
Viscosity
0.02 centipoise (0.02 mNs/m2 )
Heat capacity at constant pressure 0.66 CHU/lb C (2.76 kJ/kg C)
Thermal conductivity
0.086 CHU/hr ft2 ( C/ft) (0.15 W/m C)
4. Pressure drop through candle filters D 5 psi35 kN/m2 .
5. Density of nitrobenzene:
Temp. C

Density g/cm3

0
15
30
50

1.2230
1.2083
1.1934
1.1740

6. Latent heat of vaporisation of nitrobenzene:

Temp. C

Latent heat CHU/lb

(kJ/kg)

100
125
150
175
200
210

104
101
97
92.5
85
79

(434)
(422)
(405)
(387)
(355)
(330)

988

CHEMICAL ENGINEERING

7. Latent heat of vaporisation of aniline:

Temp. C

Latent heat CHU/lb

(kJ/kg)

100
125
150
175
183

133.5
127
120
110
103.7

(558)
(531)
(502)
(460)
(433)

8. Specific heat of aniline vapour D 0.43 CHU/lb C (1.80 kJ/kg C).

9. Solubility of aniline in water:
Temp. C

per cent w/w aniline

20
40
60
100

3.1
3.3
3.8
7.2

10. Solubility of water in aniline:

Temp. C

per cent w/w water

20
40
60
100

5.0
5.3
5.8
8.4

11. Density of aniline/water system:

Density g/cm3
Temp. C

Water layer

Aniline layer

0
10
20
30
40
50
60
70

1.003
1.001
0.999
0.997
0.995
0.991
0.987
0.982

1.035
1.031
1.023
1.014
1.006
0.998
0.989
0.982

12. Partition of cyclo-hexylamine between aniline and water at 30 C:

w/w per cent cyclohexylamine in
aniline

w/w per cent water

in aniline

w/w per cent cyclohexylamine in

water

w/w per cent aniline

in water

1.0
3.0
5.0

5.7
6.6
7.7

0.12
0.36
0.57

3.2
3.2
3.2

13. Partition coefficient of nitrobenzene between aniline layer and water layer:
Ca.l. /Cw.l. D 300.

989

APPENDIX F

14. Design relative velocity in crude aniline-water separator: 10 ft/h (3 m/h).

15. Equilibrium data for water-aniline system at 760 mm Hg abs:
Mole fraction water
Temp C

Liquid

Vapour

184
170
160
150
140
130
120
110
105
100
99

0
0.01
0.02
0.03
0.045
0.07
0.10
0.155
0.20
0.30
0.35 0.95
0.985
0.9896
0.9941
0.9975
0.9988

0
0.31
0.485
0.63
0.74
0.82
0.88
0.92
0.94
0.96
0.964
0.9641
0.9642
0.9735
0.9878
0.9932

16. Equilibrium data for cyclo-hexylamine-water system at 760 mm Hg abs:

Mole fraction cyclo-hexylamine
Liquid

Vapour

0.005
0.010
0.020
0.030
0.040
0.050
0.100
0.150
0.200
0.250

0.065
0.113
0.121
0.123
0.124
0.125
0.128
0.131
0.134
0.137

17. Temperature coefficient for aniline density

0 100 C).

0.054 lb/ft3 C(0.86 kg/m3 C) (range

REFERENCES
1. U.S. Patent 2,891,094 (American Cyanamid Co.).
2. PERRY, R. H., CHILTON, C. H. and KIRKPATRICK, S. D. (eds) Chemical Engineers Handbook, 1963, 4th edn,
Section 3 (New York: McGraw-Hill Book Company, Inc.).
3. LEVA, M. Fluidization, 1959 (New York: McGraw-Hill Book Company, Inc.).
4. ROTTENBURG, P. A. Trans. Instn. Chem Engrs, 1957, 35, 21.
As an alternative to Reference 1 above, any of the following may be read as background information to the
process:
5. Hyd. Proc. and Pet. Ref., 1961, 40, No. 11, p. 225.
6. STEPHENSON, R. M. Introduction to the Chemical Process Industries, 1966 (New York: Reinhold Publishing
Corporation).
7. FAITH, W. L., KEYES, D. B. and CLARK, R. L. Industrial Chemicals, 3rd edn, 1965 (New York: John Wiley
& Sons Inc.).
8. SITTIG, M. Organic Chemical Processes, 1962 (New York: Noyes Press).