ANILINE PLANT

Technology Supplied by: M/s Dupont of U.S.A.

Basic engineering is done by: M/s Chematur Engg. AB of Sweden
Detailed Engineering is done by: M/s IBI Chematur, Bombay
CAPACITY AT 100% PLANT LOAD: 66.66 MT/DAY
Sr. Raw Materials Design Sp. Cons. per MT of ANILINE
No. Production.
1 CNA 0.720 MT
2 H2 0.080MT
3 Catalyst (Wet) 0.119 Kg

IN BUILT SAFETY FEATURE OF PLANT:

1. The amines are a possible carcinogen thats why special design is done in
plant to protect personnel.
2. The thickener and the spent catalyst filter are totally enclosed
3. Surrounding Hydrogenation reactor, water sprinkler system is available for
handling any emergency caused by hydrogen leakage.
PROCESS DESCRIPTION:

1.1 GENERAL
Most aniline is produced by reduction of nitrobenzene in various liquid and
vapour phase reactions using a variety of catalyst.

1.2 INTRODUCTORY
Du Pont has produced aniline from nitrobenzene by a proprietary catalysed
liquid phase Hydrogenation process since 1960. The first production unit was
situated in New Jersey, But is has now been dismantled. A plant at Beaumont,
Texas, was started up in 1972 and is the sole Du Pont aniline production unit.

1.3 GENERAL PROCESS DESCRIPTION

In Du Ponts proprietary process, aniline and water are produced by the
liquid phase, Catalytic hydrogenation of nitrobenzene with hydrogen.
Nitrobenzene (NB) is fed through two stage of counter-current liquid-liquid
extraction, where it is used to recover dissolved aniline from the water of reaction
produced in the reaction between NB and hydrogen.
 The NB from the extractors, containing small amounts recovered aniline, is
preheated and fed to the bottom of the vertical, stage aniline reactor column for
conversion to aniline. Aniline slurry of a precious metal on carbon catalyst,
recycled water, recycled Aniline, and hydrogen is also fed to the base of the aniline
reactor. Hydrogen dissolves in the liquid mixture and reacts with nitrobenzene to
form aniline and water.

The reactor operates at high-pressure bar g at a temperature which reaches

a peak of about 215-225 C near mid-column. The heat of reaction between
hydrogen and NB vaporizes most of the aniline and water and the crude products
are taken overhead as vapour. A liquid side-stream is drawn from the top tray of
the reactor, passes through a gas-liquid separator, and serves to recycle catalyst to
the bottom of the reactor and to purge By-product tars from the system. The side-
stream is cooled and a portion is passed through a catalyst thickner to remove
soluble tars in a filtrate stream. All of the side-stream, except the thickener
filtrate, is returned to the base of the aniline reactor. The thickener filtrate is
transferred to the purge recovery column feed tank and then to the purge recovery
column.

This column operates under vacuum to recover aniline overhead and

concentrate the tars in the column bottom.

Crude aniline, containing non-reactor NB, water, and excess hydrogen, which
leave the top of The reactor as vapours or gases, are cooled and condensed through
a cooling train. This Cooling train consists of two waste heat boilers, which
generates medium pressure steam, a set of boiler feed water pre-heaters and
finally water-cooled heat exchangers. The final cooling is critical to reduce the
temperature of the stream to <40C to promote gravimetric separation. After
cooling, this stream enters a gas-liquid separator and pressure letdown tank where
the un-reacted hydrogen is separated from the liquid water/aniline mixture. The
un-reacted gases are discharged through a pressure control valve, which controls
the pressure at the top of the aniline reactor, and are returned and used as fuel.

The crude aniline and water are separated in a gravimetric decanter. The
water wet crude aniline is transferred to storage for refining. The water phase,
containing dissolved aniline is drawn off and stored in a coarse water tank for
recycle as a direct coolant to the aniline reactor or for aniline recovery by
extraction.

As mentioned earlier, nitrobenzene and the excess water of reaction, which

has been separated from crude aniline, is fed to the previously discussed liquid-
 liquid extractors. The nitrobenzene extraction reduces the aniline content of the
water to ppm levels. The water is then discharged to waste water treatment
facilities.
The crude aniline, which has been stored for refining, is fed to a dehydration
column, which operates under vacuum, where stripping soluble water from the
aniline dehydrates it. The overhead distillate is recycled to the crude product
decanter for recovery of aniline and gravimetric separation of the water phase.
The dehydrated aniline is preheated and fed to a Schiffs base reactor. This
is a large baffled vessel with steam coils, also operated under vacuum. In this
reactor, minor quantities of low boiling impurities such as cyclohexyl-amine,
cyclohexanone, diphenylamine, and cyclohexylaniline react with aniline, in a dry
environment, to form water and a higher boiling Schiffs base tar. The small
amount of water of reaction, generated in this reactor, is stripped from the mass
by heat from the steam coils, condensed and returned to the top of the
dehydration column.
The dry aniline is pumped from the Schiffs base reactor to the aniline
rectifier column, operated under vacuum, where it is refined to product
specification material.
The higher boiling Schiffs bases tars are purged from the bottom of the
rectifier column and are transferred to the purge recovery column. The thickener
filtrate from the catalyst thickener is sent to the purge recovery column feed tank
from which it is pumped to the purge recovery column. This column, operated
under vacuum, recovers aniline together with water in the column overhead
stream, which is sent back via off-decanter and water tank to aniline extractors
and aniline reactor.
2. ANILINE PLANT
INTRODUCTION
Nitrobenzene is produced by the catalysed liquid phase reduction of
nitrobenzene with Hydrogen in a vertical, tray reactor using a slurryfied precious
metal catalyst.
The synthesis process consists of several steps outlined as follows:
NITROBENZENE FEED SYSTEM
Nitrobenzene is pumped to the aniline area by the NB feed pumps (P0703
A/B). These centrifugal pumps transfer to the second stage extractor (S0901)
where it is used as a solvent to extract aniline from process water. NB is also sent
to the aniline Reactor NB feed tank (T1001) for level control.
PROCESS PARAMETERS

Operating pressure 2 bar a

Operating temperature 40 C

EXTRACTOR FEED TANK

The extractor feed tank (T0907) receives process water from the separation
of crude aniline reactor product. This crude aniline reactor product includes crude
aniline and process water of reaction from the hydrogenation of nitrobenzene. The
excess process water is fed to the first stage extractor (S0905) for the recovery of
aniline values prior to wastewater treatment.
PROCESS PARAMETERS

Operating pressure Atmospheric

Operating temperature 40 C

EXTRACTORS
This system consist of two stages of counter-counter, liquid-liquid extraction
Which utilize static mixers to promote contact between phases. Nitrobenzene
Extracts and recovers the dissolved aniline from the water generated in the Aniline
synthesis reactor. The nitrobenzene, containing recovered aniline,
Discharges from the first stage extractor (S0905) to a reactor NB feed tank (T1001)
and is pumped by high speed centrifugal pumps (P1002 A/B) to the aniline reactor
(R1004) for conversion to aniline. The extracted process water, containing < 100 ppm
(wt) of aniline, is transferred to waste treatment facilities. The extractors are
comprised of two horizontal, cylindrical tanks, each equipped with an internal static
mixer. After the intensive mixing the two forming phases are allowed to separate.
The water phase overflows a baffle near the end of the vessel into a small
component from which it is transferred by a centrifugal pump P0906 (first stage
extractor)/P0904 A/B (second stage extractor). Nitrobenzene, the heavy phase,
discharges through a nozzle in the bottom of the extractor vessel.
Raw process water, containing about 4% (wt) aniline, is mixed with
Nitrobenzene from the second stage extractor (S0901), and fed to the static Mixer in
the first stage extractor (S0905).
The light and heavy phases separate in the extractor vessel. The
Nitrobenzene Phase discharges from the first stage extractor by gravity to the
reactor NB feed tank (T1001). The water phase from the first stage extractor is
transferred and mixed with fresh nitrobenzene as the feed to the second stage
extractor. The light and heavy phases separate in the extractor vessel. The
nitrobenzene phase from the second stage Extractor is pumped (P0902 A/B) to the
static mixture of the first stage extractor. The water phase from the second phase
extractor is pumped to a storage tank (T9410) for Waste treatment. A portion of the
heavy liquid from the each extractor can be recycled back to the static mixture feed
point of that stage to maintain a high liquid velocity through the mixers.

PROCESS PARAMETETRS

Operating pressure Atmospheric

Operating temperature 40 C

REACTOR NB FEED TANK

The reactor NB feed tank (T1001) receives nitrobenzene by gravity flow from
the stage extractor. It serves as a minimum reservoir to prevent cavitations of the
reactor NB feed pumps (P1002 A/B). Level in this tank is controlled by the NB feed to
the extractors and a make-up stream of fresh nitrobenzene from storage through a
separate level control valve.

PROCESS PARAMETERS

Operating pressure Atmospheric

Operating temperature 40 C

NB PREHEATER
Nitrobenzene is preheated with steam in shell and heat exchanger (E1003),
to Promote reaction, and is fed to the bottom of the aniline reactor (R1004).

PROCESS PARAMETERS

Operating pressure 20 bar a

Operating temperature 125 C

ANILINE REACTOR
The aniline reactor is a multi-stage, trayed, vertical column. Nitrobenzene,
recycled process water, catalyst slurry, and aniline, are introduced into the bottom
of the column, below the first tray. Hydrogen is fed to the bottom of the reactor
through a ring pipe distributor. At operating pressure, hydrogen dissolves in the liquid
mixture and reacts with nitrobenzene, in the presence of the catalyst, to form
aniline and water. The reaction is highly exothermic and aniline and water are
vaporized and removed overhead as vapour. The temperature of the reactor is
controlled at a mid-column high temperature of 215-230 C by feeding recycled
process water and aniline. The reactor vapour line is provided with a rupture disc
and relief valve in series to protect from vessel over-pressure.

PROCESS PARAMETERS

Operating pressure 18 bar a

Operating temperature 215 C

DEGASIFIER
Since catalyst particles tend to migrate to the top of the reactor, a liquid
side stream containing aniline, tar, water and catalyst is drawn-off from the top tray
of the reactor through a gas-liquid separator or Degasifier (S1005). The gas is
returned to the vapour space above the top tray and the liquid side stream is
processed through the catalyst recycle system.

PROCESS PARAMETERS

Operating pressure 17,85 bar a

Operating temperature 210 C

SAFETY TANK
The over-pressure protection devices on the reactor vapour line discharge to
a safety tank (T1006), which contains and separates the gas and liquid discharged
from the reactor, should an over-pressure occur. The vent on this tank is equipped
with a Steam sparger to prevent light-off of gases by a lightning storm. This tank is
also used to receive draining from the reactor when it is emptied for inspections and
maintenance. Aniline and catalyst are recovered from the safety tank by filtration.

PROCESS PARAMETERS

Operating pressure Atmospheric

Operating temperature 40 C

REACTOR COOLING
Aniline, water vapour and un-reacted hydrogen in the overheads of the
aniline reactor pass through a cooling train, which cools and condenses these
vapours. This cooling train consists of two kettle type steam boilers product
condensers (E4301/E4302), one shell- and-tube product cooler (E4303), which boiler
feed water, and two water cooled shell- and-tube trim coolers (E4304/E4305).

The product condensers are a kettle type reboiler with process on the tube
side of a U-tube bundle. The shell contains boiler feed water and produces steam at
two different Pressures. The boilers are equipped with two mesh type demisters
(S4301.01/S4302.01)

To prevent entrainment of boiler water in the stream, a blow-down is also

provided to purge solids from the boiler.

The product cooler is a shell-and-tube type heat exchanger with process on

the tube side. Boiler feed water is on the shell side.

The trim coolers are water-cooled, shell and tube type exchangers with process on
the tube side and cooling tower water on the shell. They are designed to cool the
water/aniline/non-condensable stream to a temperature that minimizes entrainment
of liquid in the gas phase during subsequent separation and enhance separation of
the aniline and water phases.

PROCESS PARAMETERS

Operating pressure, E4301 17.6 bar a

Operating temperature, E4301 215 C
Operating pressure, E4302 17.4 bar a
Operating temperature, E4302 194 C
Operating pressure, E4303 17.1 bar a
Operating temperature, E4303 146 C
Operating pressure, E4304 16.1 bar a
Operating temperature, E4304 118 C
Operating pressure, E4305 16.1 bar a
Operating temperature, E4305 55 C

REACTOR LET - DOWN TANK

The cooled reactor product mass, which consists of a gas phase and two
Condensed liquid phases, enters a pressure let-down tank (S43060 which serves to
separate the gas and liquid phases and control reactor pressure. It contains a Mesh
type demister to minimise liquid carry-over with the gas stream. The gas phase,
consisting of un-reacted hydrogen, is sent through the reactor pressure control valve
to flare. The two liquid phases are transferred through a level control valve to the
let - down tank separator (S4307).

PROCESS PARAMETERS

Operating pressure 11.4 bar a

Operating temperature 40 C
LET - DOWN TANK SEPARATOR
The two liquid phases enter a let - down tank separator (S4307), which
separates any remaining dissolved gases from the liquids and vents them to the
safety tank (T1006).

PROCESS PARAMETERS

Operating pressure 1.2 bar a

Operating temperature 40 C

CRUDE DECANTERS
The cooled water and aniline products from the aniline reactor coolers are
directed to one of two vertical, cylindrical decanters here the aniline and water
phases are allowed to separate by gravity. One of these tanks is called the product
decanter (S1101) and the other, the off-spec decanter (S1108). The water phase from
these decanters overflow to the coarse water tank (T1114). The aniline phase from
the product decanter is pumped (P1102A/B) to one of two crude analysis tanks
(T1103/T1104). The aniline phase from the off-spec decanter is pumped (P1109 A/B)
to rework aniline storage tank (T1110)

PROCESS PARAMETERS

Operating pressure Atmospheric

Operating temperature 40 C

COARSE WATER TANK

Water from the product and off-spec decanters overflows into the coarse water tank
(T1114). This tank serves as a reservoir for the cooling water supply to control the aniline
reactor temperature. Any entrained aniline, which collects in the bottom of this tank, is pumped
(P1117 A/B) back to the off-spec decanter. Excess process water is pumped (P1116 A/B) to the
aniline reactor through the aniline extractors before it is transferred to waste treatment facilities.

PROCESS PARAMETERS

Operating pressure Atmospheric

Operating temperature 40 C

CRUDE ANALYSIS TANKS

The aniline phase from the product decanter (S1101) is pumped to one of two Crude
Analysis tanks (T1103/T1104). These tanks are vertical, cylindrical tanks, which serve to
provide hold-up time for analysis of the crude aniline being produced. The crude Aniline is
analysed for nitrobenzene only to ensure good conversion in the reactor. One tank accumulates
crude aniline while the other is either being analysed or is being transferred to the crude aniline
storage tank (T1106) or the rework aniline Storage tank (T1110).

PROCESS PARAMETERS

Operating pressure Atmospheric

Operating temperature 40 C

CATALYST RECOVERY SYSTEM

The liquid side stream from the degasifier (S1005) is cooled through a jacketed pipe,
Trombone cooler (E4501) and enters a mechanically agitated thickener feed tank (T4502). Most
of this stream, which contains aniline, catalyst, tar and some water is recycled to the catalyst
feed tank (T4504) for return to the aniline reactor (R1004).

PROCESS PARAMETERS

Operating pressure, E4501 2 bar a

Operating temperature, E4501 210 C
Operating pressure, T4502 Atmospheric
Operating temperature, T4502 95 C

THICKENER
A portion of the cooled, liquid side stream is processed through a thickener (F4508
A/B). The thickener serves to purge soluble tars from the aniline reactor system by removing a
small stream of filtrate, which contains soluble tars generated in the aniline reactor. The bulk of
the side stream slurry circulated through the thickener is returned to the thickener feed tank
(T4502). The small stream of thickener filtrate is transferred to the purge recovery column feed
tank (T1709) for further processing for aniline recovery and tar disposal.

PROCESS PARAMETERS
Operating pressure 6 bar a
Operating temperature 95 C

CATALYST FILTER
A catalyst filter (F4509) is provided to recover catalyst solids for return to a Catalyst
manufacturer for precious metals recovery whenever the aniline Reactor is emptied, or when
material accumulates in the Safety Tank (T1006).

PROCESS PARAMETERS

Operating pressure 6 bar a

Operating temperature 95 C
CATALYST MIX TANK
The catalyst mix tank (T4506) is a vertical, cylindrical tank equipped with a
mechanical agitator. Aniline catalyst received from the catalyst supplier and slurries with aniline
in this tank. As needed, this fresh catalyst slurry is transferred to the mechanically agitated
reactor catalyst feed tank (T4504).

PROCESS PARAMETERS

Operating pressure Atmospheric

Operating temperature 40 C

CATALYST FEED TANK

The reactor catalyst feed tank (T4504) is a vertical, cylindrical tank with a conical
Bottom head. This vessel is mechanically agitated. Recycled catalyst slurry from the thickener
feed tank (T4502) and fresh catalyst from the catalyst mix tank (T4506), as needed, is
transferred to the reactor catalyst feed tank. Recycled or rework aniline is also added to control
the level in this tank to compensate for the removal of thickener filtrate. The catalyst/aniline
slurry is fed by high - pressure centrifugal pumps (P4505 A/B) to the aniline reactor. An
overflow line to the safety tank (T1006), is provided to collect material which may overflow the
tank during upsets.

PROCESS PARAMETERS

Operating pressure Atmospheric

Operating temperature 85 C

CRUDE ANILINE STORAGE TANK

If the analysis of material in the analysis tanks (T1103/T1104) is less than two (2)
parts Per million by weight of nitrobenzene in the crude aniline, the material is pumped to a
vertical cylindrical crude aniline storage tank (T1106) for further processing.

PROCESS PARAMETERS

Operating pressure Atmospheric

Operating temperature 40 C

REWORK ANILINE STORAGE TANK

If the crude aniline is contaminated with two (2) parts per million by weight or greater
of nitrobenzene, the material is pumped to the rework aniline storage tank (T1110) from which
it is returned to the catalyst feed tank (T4504) and aniline reactor. Frequently, crude product
aniline is transferred to rework storage to provide material make-up for the catalyst feed tank.
PROCESS PARAMETERS

Operating pressure Atmospheric

Operating temperature 40 C

WATER DRAW-OFF TANK

Since water phase is lighter than aniline and may accumulate as a top layer in either
the rework storage or crude aniline storage tanks, a small draw-off tank (T1112) is provided.
Any water that accumulates can be decanted to the draw-off tank and transferred back to the
off-specification decanter.

PROCESS PARAMETERS

Operating pressure Atmospheric

Operating temperature 40 C

DEHYDRATION COLUMN
Crude aniline, which contains about 5.5% (wt) of dissolved water, is pumped (P1107
A/B) From the crude storage tank to the dehydration column (C1201) for water removal. This
Column is equipped with structured packing. Vacuum pumps (B1801/B1802) provide the
necessary sub-atmospheric pressure for the column operation. A steam heated, forced draft
reboiler (calandria) (E1203), and pumps (P1202 A/B) provide the circulated draft, provides
boil-up for the column. An overhead condenser (E1204) condenses and cools the water and
aniline mixture stripped from the crude material. The overheads stream is returned to the
product decanter (S1101) where it is recycled to the process. The dry bottoms stream,
containing < 0.05% (wt) of water, is pumped to the Schiffs base Reactor (R1302) through the
base reactor preheater (E1301).
PROCESS PARAMETERS

Column top pressure 0.10 bar a

Column bottom pressure 0.11 bar a
Column top temperature 73 C
Column bottom temperature 114 C
Bottom stream water content < 0,05% (weight)
Reboiler exit temperature 132 C
Condenser exit pressure 0.09 bar a
Condenser exit temperature 40 C

BASE REACTOR PREHEATER

This heater (E1301) is a shell-and-tube exchanger that heats the dry aniline from the
bottom of the dehydration column to a higher temperature for processing in the Schiffs base
reactor
PROCESS PARAMETERS

Operating pressure 2.2 bar a

Operating temperature 150 C

SCHIFFS BASE REACTOR

Cyclohexanone is a minor, low boiling by-product generated by the aniline reactor. A
steam heated and baffled Schiffs base reactor (R1302) vessel provides residence time to permit
reacting of Cyclohexanone with aniline, in a dry environment, to produce a higher boiling
Schiffs Base and water. The base reactor preheater (E1301) and steam coils in the base reactor
provide sufficient heat to aid in stripping the water of reaction. The reactor is operated at sub-
atmospheric pressure and water of reaction is stripped as Overhead and condensed (E1304) for
return to the dehydration column (C1201).

PROCESS PARAMETERS

Reactor operating pressure 0.33 bar a

Reactor operating temperature 147 C
Condenser exit pressure 0.32 bar a
Condenser exit temperature 40 C

RECTIFIER COLUMN
Dry aniline is pumped from the Schiffs base reactor column (C1501).This column is
A trade column. The column operates at sub-atmospheric pressure by the use of vacuum
pumps(B1801/B1802). It has also a forced draft, steam heated reboiler (calandria) (E1503).
Refined aniline is taken overhead and condensed in a water cooled condenser (E1504) from
which it is pumped (P1507 A/B) to finished product analysis tanks (T1671/T1672).A small
bottom stream is drawn from the rectifier column to remove tars and Schiffs base as high-
boiling impurities. This stream is pumped either to the purge recovery Column (C1701) for
recovery of aniline or directly to the tar heels tank (T9420) for disposal by burning in the
incinerator (H9424).

PROCESS PARAMETERS

Column top pressure 0.10 bar a

Column bottom pressure 0.15 bar a
Column top temperature 111 C
Column bottom temperature 135.5 C
Reboiler exit temperature 155 C
Condenser exit pressure 0.09 bar a
Condenser exit temperature 40 C
PURGE RECOVERY COLUMN FEED TANK
This is a vertical cylindrical tank. Thickener filtrate, containing soluble tars, is
transferred to the purge recovery column feed tank (T1709), from which it is fed to the purge
recovery column (C1701) for recovery of aniline and concentration of tars for disposal.

PROCESS PARAMETERS

Operating pressure Atmospheric

Operating temperature 80 C

PURGE RECOVERY COLUMN

This column (C1701) is a trayed column, which is operated by a steam-heated
Reboiler (E1703) at sub-atmospheric pressure. A water - cooled condenser (E1704) Recovers
the water and aniline from the column overhead for return to the Process as rework material.
The bottoms from this column contain tars, concentrated in a solution with aniline. This tar
solution discharges from the Column and is pumped (P1702) to the tar heels tank (T9420) for
subsequent disposal.

PROCESS PARAMETERS

Column top pressure 0.10 bar a

Column bottom pressure 0.16 bar a
Column top temperature 98 C
Column bottom temperature 140.1C
Reboiler exit temperature 148.6 C
Condenser exit pressure 0.09 bar a
Condenser exit temperature 40 C