PRODUCTION OF ANILINE BY REDUCTION

OF NITROBENZENE
Group#2

Group Members:

Muhammad Mudassar Aslam 2016-CH-420

Saqib Sabir 2016-CH-405

Ahmad Hussain Chishti 2016-CH-417

Mansab Ali 2016-CH-424

Introduction:
Aniline is colorless, oily liquid, which darkens on exposure to air and light. It has a characteristic
amine odour and burning taste. Aniline is miscible with alcohol, benzene, choloroform, carbon
tetrachloride acetone and most organic solvents. Aniline also combines with acids to form salts
and is combustible.

Physical Properties of Aniline:

Molecular Weight 93.128 g/gmol

Boiling Point 184 – 186oC

Melting Point -6.3oC

Flash Point 76oC

Vapor Density 3.22

Specific Gravity 1.022

Vapor Pressure 0.489 mmHg

Water Solubility 36.070mg/lit at 25oC

History:

Aniline was first isolated from the destructive distillation of indigo in 1826 by Otto Unverdorben
who named it crystalline. In 1834, F.Runge isolated from coal tar a substance which produced a
beautiful blue color on treatment with chloride of lime, this he named kyanol or cyanol. In 1841,
C.J. Fritzsche showed that by treating indigo with caustic potash it yielded an oil, which he named
aniline, from the specific name of one of the indigo yielding plants. About the same time N.N.Zinin
found that on reducing nitrobenzene, a base was formed which he named benzidam. August
Wilhelm von Hofmann investigated these substances and proved them to be identical and named
them aniline or phenyl amine.

Its first industrial scale use was in the manufacture of manuveine, a purple dye discovered in
1856 by William Henry Perkin.

Uses:

 MDI (4, 4 – Methylene Diphenyl Diisocyanate): 85%

 Rubber processing Chemials: 9%

 Herbicides: 2%

 Specific Fibers: 1%

 Miscellaneous: including explosives, epoxy curling agents and pharmaceuticals 1%

RubberProcessing

Herbicides

Fibers

Miscellaneous

MDI
Synthesis of Aniline:
Manufacturing Techniques

1. From Nitrobenzene by Reduction

2. From Chlorobenzene by Ammonolysis
3. From Phenol by Ammonolysis

1. From Nitrobenzene by Reduction:

Reaction:

4C6 H5 NO2 + 9 Fe + 4 H2O → 4 C6 H5 NH 2 + 3 Fe3 O4

Process Description:

Crude nitrobenzene is charged into a reducer (reactor) fitted with an efficient reflux condenser.
The reducer is a steam – jacketed cast – iron enclosed cylindrical vessel coating an agitator. Cast
– iron borings (turnings) or powder (free from oil and nonferrous metals), water and catalyst are
added gradually, in small quantities to the nitrobenzene. Generally 10-20% of the total iron is
added at the beginning and the mixture is heated by steam to reflux temperature(c.a 2000C).The
remaining iron is added over a period of time at a rate determined by the proper temperature -
pressure balance. The addition rate is fast enough to maintain lively reflux by the heat generated
from the exothermic reaction, yet slow enough to prevent excessive hydrogen pressure buildup.

The water required for the reaction is generally in the form of aniline water recovered from the
separator or column and is added to the reducer either in bulk at the start or in small quantities
along with the iron additions. Dilute (30%) HCl is added along with the water as catalyst. The acid
reacts with the iron borings, forming catalytically active iron salts. Subsequent runs may utilize
the aniline –HCl mother liquor as the source of the catalyst and some of the reaction water. The
weight ratio of reactants is approximately 115 parts of iron boring, 0.27 part of 100% HCl and 60
parts of water per 100 parts of nitrobenzene. After the last iron addition, the reaction is heated
with steam to maintain lively reflux.

At the end of reduction (about 10 hr for a 5000 lb charge) the aniline is separated from the
reducer charge by one of more of several methods. The liquid water-aniline mixture may be
separated from the solid iron oxide-iron hydroxide sludge by steam distillation, vacuum
distillation, centrifugation, or siphoning. For example, the finished reduction product may be
neutralized with a small amount of sodium carbonate (about equal to the amount of HCl in the
charge) and allowed to settle. Most of the aniline and some water are siphoned off, and the
residual aniline is separated from the sludge by steam distillation. The sludge consisting of ferric
oxide, water and small amounts of ferric hydroxide is dumped and may be marketed after drying.

The water – aniline mixture from the reducer is run to a separator, where the heavier aniline
separated and is withdrawn from the bottom. The top layer, which contains 3 -5% aniline, is
partially distilled until the aniline content in the water is low. The residual aniline water is
returned to the reducer for subsequent runs. The aniline in the distillate is separated by
decantation and the water layer is redistilled to obtain the remaining aniline. An alternate the
procedure is to extract the aniline from the aniline water with nitrobenzene. The aniline streams
from the separator and decanter are united and vacuum distilled to yield purified aniline.
Process Flow Diagram:
Equipment Selection
 Vaporizer
 Fluidized Bed Reactor
 Condenser
 Knock Out Drum
 Decanter
 Distillation Tower (I)
 Distillation Tower (II)

Specifications of the Components

Vaporizer:

Vaporizers are devices which heat and vaporize a working fluid. In many cases, they are similar
to industrial boilers except that they do not build up high pressures. Vaporizer units are most
commonly used for low pressure heat transfer by incorporating the vaporized stream as the heat
exchange fluid. They can also be used to vaporize liquid fuels or cryogenic liquids.

These are specified on the basis of;

1. Type of source
2. Capacity
3. Max. Temperature
4. Power Requirements
5. Operating Pressure
In our process feed is fed to the vaporizer on 25oC and 344.5 KPa. The vaporizer which we are
using is well suited for our process as all parameters are considered while its selection.

Fluidized Bed Reactor:

A fluidized bed reactor (FBR) is a type of reactor device that can be used to carry out a variety
of multiphase chemical reactions. In this type of reactor, a fluid (gas or liquid) is passed through a
solid granular material (usually a catalyst possibly shaped as tiny spheres) at high
enough velocities to suspend the solid and cause it to behave as though it were a fluid. This
process, known as fluidization, imparts many important advantages to an FBR. As a result, FBRs
are used for many industrial applications.
These are specified on the basis of;

1. Nature of fluids
2. Temperature Ranges
3. Size of Reactor
4. Flow Rates
The FBR which we are using is operating at 20 psig (140 kN/m2) and 270oC. Our FBR is well suited
for the type of our reaction as we selected it after a whole study.

Cooler:

Coolers are the devices which removes heat from the process fluid and cools it down to a required
temperature. Coolers are considered to be one of the very basic equipments being used in
Chemical Industries.

These may be specified on the basis of;

1. Required Temperature
2. Size
3. Flow Rates
The condenser we are using is receiving water of 120oC and is cooling down it to 90oC. Like all
other equipments, our cooler is also well suited for this process as its material and size is well
compatible with the temperature and the pressure of the process.

Knock Out Drum:

The Knock out drum is a vessel in the flare header designed to remove & accumulate condensed
& entrained liquids from the relief gases. Both the horizontal & vertical design is a common
consideration for the Knock out drum, which is determined based on the operating parameters
as well as other plant conditions.

These may be differentiated on the basis of;

1. Types of gases to separated

2. Other process conditions
Here in our process excess Hydrogen is separated from the reactor gases and then is recycled
back to maintain impurity level in the feed.

Decanter:
Now we need a liquid-liquid separator to separate crude aniline and water. It gives us two layers.
One is the aqueous layer and the other one is the organic layer and now we are able to separate
both of them.

Distillation Tower/Fractionating Column:

A fractionating column is an essential item used in distillation of liquid mixtures so as to separate

the mixture into its component parts, or fractions, based on the differences in volatilities.
Fractionating columns are used in small scale laboratory distillations as well as for large scale
industrial distillations.

These are specified on the basis of;

1. Size
2. Process Fluid
3. Operating Conditions
We are using two distillation towers in our process according to the process requirements. Both
of them are well suited for our process with their temperature ranges and material to withstand
the process conditions.
 Design of Distillation Column

Distillation
Multicomponent Distillation:

For a binary mixture under constant pressure conditions the vapor liquid equilibrium curve for
either component is unique so that if the concentration of either component is known in the
liquid phase, the composition of the liquid and the vapor are fixed. It is on the basis of this
equilibrium curve that the McCabe-Thiele method was developed for the rapid determination of
the number of theoretical plates required for a given separation.

With a ternary system the conditions of equilibrium are more complex, for at constant pressure
the mole fraction of two of the components in the liquid phase must be given before the
composition of the vapor in equilibrium can be determined even for an ideal system. This mole
fraction yA in the vapor depend not only on the xA in the liquid but also on the relative proportions
of the other two components.

To obtain the equilibrium relationships for a multi component mixture experimentally requires a
considerable quantity of data, and one of the two methods of simplification is usually adopted.
For many systems particularly those consisting of chemical similar substances, the relative
volatilities of the components remain constant over a wide range of temperature and
composition.

In multi component mixtures one component may be more volatile than the average in one part
of the column and less volatile than the average in another part, which leads to complex
concentration profile.

Light and Heavy key components:

In the fraction of multi component mixtures, frequently the essential requirement is the
separation between two components. Such components are called the Key Components and by
concentration attention on these, it is possible to simplify he handling of complex mixtures.

Suppose a four component mixtures A-B-C-D in which A is the most volatile and D is the least
volatile, is to be separated as shown in the table,
Separation of Multicomponent Mixture

Feed Top Product Bottom Product

A A

B B B

C C C

D D

Then B is the lightest component appearing in the bottoms and is termed the light key
component and C is the heaviest component appearing in the distillate and is called the heavy
key component. The main purpose of the fraction is the separation of B from C.

Plate Column:
Distillation may be carried out in plate columns in which each plate constitute a single stage.

The number of theoretical stages required to effect a required separation and the corresponding
rates for the liquid and vapor phases.

To translate these quantities into an actual design the following factors must be considered:

 The type of tray of plate

 The vapor velocity which is a major factor in determining the diameter of column
 The plate spacing, which is a major factor in fixing the height of the column where the
number of stages is known.

Types of tray:

The minimum requirement of a tray is that it should provide intimate mixing between the liquid
and vapor streams, it should be suitable for handling he desired rates of vapor and liquid without
excessive entrainment of flooding, it should be stable in operation and it should be reasonable
easy to erect and maintain.

The liquid reflux flows across each tray and enters the down comer via a weir, the height of which
largely determines the amount of liquid on the tray. The down comer extends beneath the liquid
surface on the tray below thus forming a vapor seal. The vapor flows upwards through risers into
caps or through simple perforations in the tray.
There are basically three conventional types of trays

 Bubble cap tray

 Sieve tray
 Valve tray

Types of Flow:

The arrangements of the liquid flow over the tray depend largely on the ratio of liquid vapor flow.

 Cross flow
 Reverse flow
 Double pass

Selection of Sieve or Perforated Trays:

The major factors to be considered when comparing the performance of trays are cost, capacity,
operating range, efficiency and pressure drop.

Sieve trays have been chosen because of their following advantages.

 Their simpler and cheaper construction has led to there increasing use.
 The turn down ratio is lowest in sieve trays.
 Sieve trays have lower capacity ( the diameter of column required for the given flow
rate) than the other two.
 Sieve trays give the lowest pressure drop.
 Sieve trays have average tray spacing.
 Sieve trays have moderate entrainment.
 There are least troublesome of maintenance, fouling tendency and effect of corrosion
in sieve trays.
 The vapor passes vertically through the holes into the liquid on the tray.
 The vapor velocity through the perforations must not be less than a certain minimum
value in order to prevent the weeping of the liquid stream down through the holes.
 At other extreme, a very high vapor velocity will lead to excessive entrainment and
loss of tray efficiency.
 It also is possible to increase the flexibility of a sieve tray for occasional low through
put operation by maintaining a high vapor boil up and increasing the reflux ratio.
 This may be economically desirable when the low throughput occurs for a small
fraction of the operating time.
 Flexibility can be increased by the use of blanking plates to reduce the hole area.
  This is particularly useful for initial operation when it is proposed to increase the plant
capacity ager a few years.
 There is no evidence to suggest that blanked-off plates have inferior performance to
unblanked plates of similar hole areas.

Plate Hydraulic Design:

The basic requirements of a plate contacting stage are that it should:

 Provide good vapor liquid contact.

 Provide sufficient liquid hold up for good mass transfer and hence high
efficiency.
 Have sufficient area and spacing to keep the entrainment and pressure drop
within the acceptable limits.
 Have sufficient down comer area for the liquid to flow freely from plate to plate.

Design Steps for Sieve Tray Tower:

Following are the design steps for a column having sieve trays.

1. Calculate theoretical number of plates in the column.

2. Estimate the overall column efficiency and calculate the actual number of
plates.
3. Calculate or estimate the system properties.
4. Select the tray spacing.
5. Choose turn down ratio.
6. Find maximum vapor velocity at the top and bottom of the column and
calculate the operating velocity as 80% of the maximum allowable velocity.
From operating velocity find out the diameters of column at the top and
bottom.
7. Select the liquid flow arrangement.
8. Find out down comer back up, it should be less than half of the tray spacing.
9. Check weeping velocity.
10. Estimate fractional entrainment, it should be well below 0.1.
11. Select the suitable material of construction.
12. For the optimum conditions calculate the thickness of the shell.
Column Shell and Trays:

 The tower may be made of any number of materials depending upon the
corrosion conditions expected.
 Glass, glass-lined metal, impervious carbon, plastics even wood but most
frequently metals are used.
 For metal towers, the shells are usually cylindrical for cost reasons.
 Manholes should be provided to give access to individual trays for cleaning,
maintenance and installation.
 Adequate foundation must be provided.
 Supporting beams are used to stiffen the trays must be fastened securely to
prevent movement caused by gas surges.
 To allow for thermal expansion and to facilitate installation, slotted bolt
holes should be provided in the supporting rings.
 There should be adequate clearance between the tray and shell wall.

Heavy Key = Aniline

Light Key = Cyclohexylamine

Stages Using Fenske’s Equation

 x  x 
ln lk   hk 
  hk  D  lk B
x x
N min
 
ln  lk / hk av

• Nmin = 8

Calculation of Minimum Reflux

  H fs  H f
q


q = 1.6
  i x fi
• 1 q 
i  

• Θ = 1.75

  i xd i 
Rmin  1   
 i   

• Rmin = 1.03

• R = 1.5 (Rmin)

• R = 1.55

Ideal Number of Equilibrium Stages

N  N min   R  Rmin 0.566 

 0.751    
N 1   R  1  

• N = 14

Actual Number of Stages

Overall efficiency of the column is given by :

  
E  0.17  0.616Log    f L 
 W 

E = 64%

Actual Number of Plates = Equilibrium Number of Stages

Efficiency

Equilibrium Number of Stages = 14

0.64

Actual Number of Stages = 22

Ratio of Number of Plates above and below the feed plate

ND  B      LK W 
2

log 0.206log  HK    
NB  D   LK  F   HK D  

ND / N B = 1.4

ND=9

NB=12

Where ND is the number of plates in the rectifying section and NB is the number of plates in
the stripping section.

Tray Spacing = 0.4 m

Evaluation of Physical Properties at the Bottom and Top of the column

Liquid Lm 32.8 kg mol 0.83kg mol

Flow Rate

Vapour Vm 1.36 kg mol 1.34kg mol

Flow Rate

Vapour ρv 7.9 kg/m3 11.2kg/m3

Density

Liquid ρl 1029 kg/m3 871.4kg/m3

Density

Surface σ 24.54 dyne/cm 21.29dyne/cm

Tension

Molar Mr 93.89kg/kgmol 99.13kg/kgmol

Weight

Souders Csb 0.1m/s 0.02m/s

and
Brown
Factor at
Flooding
Conditions

Bottom Diameter Calculation

Flooding Velocity can be calculated as from the equation below:

0.5
    L  V 
0.23

VNF  Csb    
 20   V 
 Vnf = 1.2 m/s

Operating Velocity = Vn = 0.8 Vnf

Vn = 0.96 m/s

Vm M r
An 
V Vn 3600

An= 0.56 m2 where An is the net column area

Assuming that the down comer covers 85% of column cress sectional area

Ac = An / 0.85

Ac = 0.66 m2

4 Ac
D


D = 0.91 m

Top Diameter Calculation

Flooding Velocity is given by :

0.5
    L  V 
0.23

VNF  Csb    
 20   V 

Vnf= 0.08 m/s

Operating Velocity = Vn = 0.8 Vnf

Vn = 0.064 m/s

An= Vm Mr / v Vn × 3600
 An= 0.05 m2

Ac = An / 0.85

Ac = 0.06 m2

4 Ac
D


D = 0.3 m

Column Height

Tray Spacing=0.4m

Top Section:

For a column of diameter 0.9m,

A = 1m

M = 0.5m
Feed Section Height :

Di = 0.9m

E = 0.1m

Feed inlet Nozzle = Df = 0.02m

D = Df + 300

D = 0.3m

F= ( 0.13 × Di ) + D

F = 0.4m

H = 0.6m

TS = 0.6m

Total Height of Feed Section = 1.74m

Bottom Section Height:

V = ( Π / 4 ) D2 H

H = V / 0.65

ρ= 1029 kg/m3

mv = 2949 kg/hr

V = 0.048 m3

H = 0.08 m

TL – LLL = 1 P

TL – LLL = 0.08m

LLL – HLL = 2P

LLL- HLL = 0.16 m

Total Height at the bottom = 1001mm

Total Height of the Column = Number of Trays ×Tray Spacing + Total Height at top + Feed
Section Height + Bottom Section Height

Total Column Height =12m

Plate Design

Column Diameter = Dc = 0.91 m

Column Area = Ac = 0.65 m2

Down comer Area = Ad =12% of Ac

Ad = 0.078 m2

Net Area = An = Ac–Ad = 0.572 m2

Active Area = Aa = Ac–2Ad = 0.494 m2

Hole Area = Ah = 0.0009 m2

Weir Length from graph 11.31 = Iw = 0.7

Weir Height = hw = 0.02m

Hole dia = 0.005m

Plate Thickness = 0.005m

Maximum Liquid Rate can be given as follows:

Lm  M r
L\ w 
3600

Lw =0.86 kg/sec

Minimum Liquid Rate = L\w = Turn Down × Max. Liquid Rate

L\w = 0.6 kg/sec

Weir Liquid Crest is given by

2
 L\  3
how  750 w 
 L Iw 

how= 6.6 mm liquid

hw + how = 26.6 mm liquid

Vm M r
Min. Vapour Rate =
v  3600

Min. Vapour Rate = 0.0045 m/s

ActualMin.VapourRate=(0.7×Min.VaporRate)/Ah

Actual Min. Vapour Rate =0.4 m/s

Minimum Vapour velocity through the holes can be given as

K 2  0.9(25.4  d h )
U h\min  1
2

Where

dh is hole diameter

K2 =19 from fig. 11.30

Ùh,min = 0.2 m/s

So Actual min. Vapour rate is greater than the min. vapour rate so weeping won’t take place.

Down Comer Liquid Backup

hap =hw - 10

hap =10mm

Area under apron= Aap =Iw × hap

As Ad > Aap

So we be using Ad for calculating hdc

2
 L 
hdc  166 wd 
  L Am 

hdc= 19.81 mm ,which is the head loss in down comer head loss due to resistance at its end

Backup in down comer = hb = hw+how+ht+hdc

hb = 0.12 < ½ of plate spacing + weir height. So plate spacing is acceptable

Perforated Area :
Iw / Dc = 0.76

θc = 990

Angle subtended by the edge of the plate = 180 – 99 = 810

Mean length of perforated area = [(0.79 - 50×10-3 ) / Π ] × 81 / 180

Mean length of perforated area = 1.05 m

Area of unperforated edge strips = 50×10 -3 ×1.05 = 0.053 m2

Mean length of calming zone = weir length + area of unperforated strips

Mean length of calming zone = 0.75 m

Area of Calming zones = 2(0.65 × 50×10-3 ) = 0.065 m2

Total area of perforations = A p = Aa - 0.053- 0.065

Ap = 0.38m2

Area of one hole = 1.964 ×10-5 m2

.

Number of holes = 500 holes

Aspen HYSYS Simulation of Distillation Column:
Comparative Analysis:
Parameter Aspen Calculation Manual Calculation

No.of Actual Stages 21 22

Tray Height 0.6096m 0.4m

Total Reflux 1.5 1.4

Dia of Column 0.87m 0.91m

References:
1.W.LowenBach, J.Schliesinger, J.King, “Nitrobenzene and Aniline Manufacturing”,Virginia,2001

2.Pasek Joseph,Petrisko Miroslav,” A method for the catalytic reduction of nitrobenzene to

aniline in the liquid phase”,2012

3. James G. Speight,” Chemical and Process Design Handbook”

4.Binay K.Dutta,”Principles of Mass Transfer and Separation Processes”

5.J.M.Smith, H.C.Van Ness, “Introduction to Chemical Engineering Thermodynamics”.