ACKNOWLEDGEMENT

I have completed my six weeks Training at IOCL Panipat successfully in

PX-PTA Plant (Petrochemical Division). It was a great learning experience
although it’s not possible to cover all the aspects of refining processes. By
the way I am satisfied that I have a fair Idea about functioning of units and
process involved.
I would like to thanks Mr. L.D Batra ( Manger,T & D) for his gentle
concern. I would also like to thank Mr. P.K Das , Mr. Manish Tewari
Mr Sujeet, Mr Neeraj Singhal and all those who contributed to make this
training successful.

-AMIT KUMR SINGH

(Vocational Trainee at IOCl Panipat)
 INDIAN OIL PETROCHEMICAL PROJECT

PX ( Para- Xylene ):
Product of Heart Cut Naptha having boiling point
138.4 DegC

Process Involved:
1Destillation
2Absorption
3Desulphurization
4Reforming
5PX-Separation(Adsorption)
6Isomerisation
7Trans-alkylation
8Disproportion
9Solvent Extraction
10Fractionation etc.

PTA- Two steps from PX

1.Catalytic Oxidation of PX to make CTA (Crude Terepthallic Acid)
2.Purification of CTA to PTA
 Hydrogenation
 Crystallization
 Solvent Recovery
 Centrifuging
 Drying
 Conveying etc

Licensors
PX Units -----UOP Design
PTA Units-----DuPont Design
PX PACKAGE UNITS:

1NHT
2CCRU
3SULPHOLANE
4BTF
5TATORAY
6XFU
7PAREX
8ISOMAR

PTA PACKAGE UNITS:

1OXIDATION PLANT
2PURIFICATION PLANT

USES: PX IS USED TO FORM:

1DMT
2PTA
3PET

PTA IS USED TO MAKE:

1PSF(Polyester Staple Fiber)
2PFY(Polyester Filamone Yarn)
3Polyester Resins

BENZENE IS USED IN FOLLOWING:

1Caprolactum(Nylon)
2LAB(Detergent)
3Phenol
4Styrene
5Nitro Benzene
6Chlorobenzene
7Solvent Pesticides
UNIT CAPACITY MAX. Pr(Kg/cm2) PURPOSE
& Temp.(Deg C)

NHTU 50,0000 40 345 Naptha Treatment

CCRU 50,0000 6 545 Catalytic Reforming

enrich aromatic
precursors
XFU 452700 20 285 Separate C6,C7
from C8+ streams to
generate mixed
Xylenes
BTF 308500 High Purity
115500 Benzene 7
Toluene(secondary
feed to PX
production)
ISOMAR 1654600 23 429 Re-establishing
equilibrium mixture
of isomers in Parex
unit Raffinate to
increase yield of
PX.
PAREX 2017300 Recover PX from
mixed Xylenes
TATORAY 349600 35 500 Disproportion &
Transalkylation of
Toluene along with
C9 aromatics to
maximize PX.
PTA Plant 5530000 85 350 PTA by catalytic
oxidation
 NAPTHA
HYDROTREATE
R
INTRODUCTION
Naptha Hydrotreating process is a catalytic refining process employing a
slect catalyst and a hydrogen rich gas stream to decompose organic
sulphur ,oxygen and nitrogen compounds contained in hydrocarbon
fractions.
Additionaly removes organo-metallic compounds and saturated olefinic
compounds.

AIM-To remove Platforming poisons from naptha .

CATALYST-Alumina base impregnated with compounds of cobalts ,nickel

and molybedenum in oxidized state.

PROCESS PRINCIPLES
Six basic types of reactions occurs in NHT.
1.Organic Sulphar to sulphide
C-C-C-C-SH + H2 = C-C-C-C + H2S
Operating Range-(315-340oc)
At High Temprature
C-C-C=C + H2S= C-CS-C-C(mercaptan)
A specified level of sulphar is required to optimize slectivity and stability
of catalyst.

2.Nitrogen Compounds to Ammonia

Ammonium Chloride formed casues product to slop.Denitrification is
favoured more by pressure than temperature so design pressure for unit is
crucial.

3.Organic Oxygen to water

By hydrogenation of Carban-Hydroxyl Bond.
Any Oxygenator in the product will quantatively to water in the
Platforming unit.Units normally not designed for oxygen removal may find
difficulty to get adequate product quality.

4.Olefins saturation
Hydrogenation of olefins necessary to prevent fouling or coke deposits in
downstream units.Reactions are exothermic in nature ,these should be
handle with care.
Straight Naptha- Low Olefins
Cracked Naptha-High Olefins.

5.Chloride to Halide conversion

Halide removal is much less at operating conditions mainly nitrogen &
sulphar removal governed.
Periodic checks of sample required for chlorine content as HIGH
CHLORIDE CONTENT CAUSES CORROSION TO DOWNSTREAM OF
THE REACTOR.

6.Metal Removal
Mainly arsenic, iron, magnesium,phosporus, lead removal.These reactions
are temperature dependent .

REACTIONS RATE OF RX RELATIVE HEAT OF RX

Desulpharification 100 1
Olefin Saturation 80 5
Denitification 20 0.1

PROCESS FLOW SCHEME

Naphta Hydrotreating Unit mainly divided in three sections-

1.REACTOR SECTION WITH RECYCLE GAS
Naphta feed pas through combined feed exchanger to heat up feed then it
will pass through the charge heater to reach desired reaction
temperature.Feed goes to reactor added with hydrogen gas and reaction
will take place in reactor.

2.STRIPPING SECTION
Stripper Section will strip off hydrogen sulphide,water, light hydrocarbons
and dissolved hydrogen.

3.SPLITTER SECTION
Stripper bottoms may contain C5 and minus compounds and it will be
necessary to fractionate the hydrotreated before sending to platforminf
feed. Splitter will split stream in two parts-
Less than C5 in overhead(light naptha)
Above C5 in Bottoms (as heavy naptha)

ALTERNATE USES OF NHT

1.Stabilizing naptha from storage using stripper section
- Removing light ends

2.Stripping Sweet Naptha

Operate stripper section at total reflux thus removing all water .
 CCR-
PLATFORMER
INTRODUCTION
As name suggest this unit employed of continuous catalyst generation one
of the greatest achievement in Refining Technology processes.
CCRU produces high octane reformats or aromatics raw material for further
processing downstream.
1By products are Hydrogen and LPG
2Accomplished in Hydrogen atmosphere at elevated temperature and
pressure across a Platinum containing catalyst .

FEED SPECIFICATIONS
Completely Hydrogenated ,product specifications-
Total Sulphar <0.5 wt ppm
Total Nitrogen <0.5 wt ppm
Total Chloride <0.5wt ppm
Total Water <5 mole ppm in recycle gas
Olefins,metals halides and oxygen negligible.
Feed mainly constitute of three components—
1. Paraffins
2. Nathenes
3. Aromatics

PLATFORMING REACTIONS

Dehydrogenation of Napthenes
The dehydrogenation reaction is easy to promote and produces aromatic
hydrocarbans in addition to hydrogen as byproducts.

C6H11-R = C6H5-R + 3H2

Isomerisation of Napthenes and Paraffins

The isomerisation involves ring ARRANGEMENT AND PROBABILITY
FOR RING OPENING TO FORM A PARAFFIN is quite high .Therefore
reaction of alkylcyclpentens to cyclopentanes is not 100% slective.The
reaction dependent on process conditions involving carbonium as
intermediate.

C5H9-R ----> C6H11-R

Dehydrocyclization of Paraffins
This is most difficult platforming reaction.Conversion of Paraffins to
Napthenes.It becomes easier as the molecular weight of Paraffins
increases.

R-C-C-C-C ---> C5H9-R’/C6H11-R’’ + H2

Hydrocracking
Feed Acid function requires for dehydrocyclization also promote
hydrocracking.The reaction consumes Hydrogen and results in lower
reformate yield.

R-C-C-C-C +H2 = RH + C-C-C-H

Demethylation
These generally occurs in very serve conditions .It can be attenuation by
action of catalyst metal function by addition of sulphur or a second
metal.

R-C-C-C + H2 = R-C-C-C-H +CH4

Dealkylation of Aromatics
Same as demethylation , different in removal of fragment from the ring.
If alkyl side is bulky than leads to cracking.

C6H5-R + H2 = C6H5-R’ + R’’

REACTION CATALYST TEMPERATURE PRESSURE
Napthenes Metallic High Low
Dehydrogenation
Napthenes Acidic Low -
Isomerisation
Paraffin Acidic Low -
Isomerisation
Paraffin Acid/Metal High Low
Dehydrocyclization
Hydrocracking Acidic High High
Demethylation Metallic High High
Aromatic Acid/Metal High High
Dealkylation

Heat of Reaction:

HEAT OF REACTION DEL H(k cal/mol H2)

Paraffin-----> Napthenes 10.5(endothermic)
Napthenes---> Aromatic 16.9(exothermic)
Hydrocracking -13.5

Catalyst Chemistry
The Platforming Catalyst should have proper balance between the metallic
and acid function.This is important to minimize the hydrocracking while
maximize the dehydrogenation and dehydrocyclization reaction. This
balance is maintained by proper balance H2O/Cl control. In the vapor phase
the HCl and H2O are in equilibirium with the hydroxyl groups and
chloride groups on the surface.Too much water on the vapor phase will
force chlorides from the surface leading to an under chloride catalyst.
While too much chloride in vapor phase has the reverse effect. Therfore
Proper control of water/ chlorides is crucial in maintaining an active acid
site.

CATALYST
REGENARATOR
INTRODUCTION
For any Catalyzed reaction or operation it’s necessary to have a optimally
working catalyst as deactivation of catalyst will lead to decline in
production as well as purity of the product.

In platformer catalyst regeneration is must because reforming catalyst is

different from traditional catalyst in which SOR and EOR temp play a vital
role. In platformer catalyst should have a proper balance between the Acid
and metal function. As due to coke deposition on the catalyst surface active
surface area of the catalyst decreases and consumption or disbalance of
chlorine concentration in the catalyst acid site weaken the fuctioning of the
catalyst decline in the Dehydrogenation as well Dehydrocyclization reaction.
SO IN PLATFORMER REGENRATION OF CATALYST IS MUST.

Regeneration also necessary to avoid :

1.Increase in Recator Pressure Drop
2.Exchanger Fouling

Catalyst Chemistry
Base- Alumina
Acid Sites-Chloride
Metal Sites- Platinum

Each step must be done well for optimal catalyst performance and catalyst
life.

REGENRATION
Regenration involves the following steps—
1.Coke Burning
2.Oxychlorination
3.Drying
4.Reduction
COKE BURNING
Coke + O2------> Co2 + H2O + Heat
O2 concentration is controlled limit Heat
1Hydrothermal damage to Catalyst Base
2Agglomeration of platinum

OXYCHLORINATION
PERC + O2--------> 2Cl2 + 2H2
HCl + O2-----------> Cl2 + H2O
Base-OH + HCl-----> Base-Cl + H2O
Metal + O2-(Cl2)-------> oxidized/ dispersed metal
Cl2 is necessary to redisperse agglomerated Pt.

DRYING
Base-H2O + Dry gas-----> Base + gas + H2O
Advantages
1Improves Catalyst reduction
2Limit moisture Carry over to Reactor Section.

REDUCTION
Oxidised Metal + H2------> Reduced Metal + H2O

Propertly Balanced Operation

Increasing Oxygen Supply------> Coke Burning in Regeneration Zone
Increasing Coke Supply----------> Cokes Breaks through into Chlorination
Zone

Desired Coke Oxygen Balance

1Moderate Burning Temperature
2Catalyst properly preserved
3Maximum Catalyst Life
SULPHOLANE
UNIT
INTRODUCTION
Liquid-liquid extraction from the reformate stream with solvent followed by
extractive distillation process is the most effective means of purifying
aromatics from reformate stream.
Repulsion of one hydrocarbon relative to other measure the ability of
solvent to discriminate between them and thus achieve separation.The
relative repulsion is called slectivity of the solvent.

Shell Sulpholane unit uses sulpholane as a solvent to recover benzene

,toluene , xylene and C9 aromatics of high purity from an aromatic rich
deheptanised strem. The extraction take place by counter current contact of
hydrocarbans with sulpholane solvent in liquid phase.

SHELL PROCESS
The process employs a raindeck extractor for extracting aromatics and a
jet deck controller for washing the aromatic lean raffinate product to
recover solvent,a water stripping column is provided to remove traces of
dissolved non aromatics from the solvent- rich wash water.
The non aromatics hydrocarbans remaining in the rich solvent are
removed in the s stripper column and recycled to extractor . a recovery
column is used to recover the solvent from the aromatic product (extract).
Un desired material , including degradation products from the
decomposition of solvent are removed in the solvent regenerator section
.The aromatic extract is the clay treated to remove olefins and is
fractionated in the benzene and the toluene columns.

Solvent regeneration
The sulpholane solvent undergoes minor oxidative degradation . A small
slip stream of circulating solvent is directed to the solvent regenerator for
removal of oxidized solvent , polymers and salt formed by neutralization
with MEA. The regenerator operates under vacuum and run intermittently
in conjuction with recovery column. The heavy components (regenerator
bottoms ) are rejected to drums.

OPERATING CONDITIONS

Raindeck Extractor

Pressure Kg/cm2 9.8

Temperature Deg C 88
Solvent Flow Kg/hr 79334
Raffinate Water Wash Column
Pressure Kg/cm2 2.8
Temperature Deg C 131
Raffinate Flow Kg/hr 3291
Stripper

Pressure Kg/cm2 0.7

Top Temperature Deg C 124
Bottom Temperature Deg C 174
Recovery Column
Pressure Kg/cm2 -0.6
Top Temperature Deg C 72
Bottom Temperature Deg C 173

Solvent Conditioning

Degradation Mechanism
Sulpholane undergoes oxidation degradation to acid at temperature
above 200 deg C. The oxygen attacks the sulpholane to form acid which
is followed by ring opening and sulphur dioxide abstraction(release). The
SO2 reversibly reacts with unsaturated aldehydes to from very strong
corrosive acids . The thermostable acidic polymers are weaks acids
partly soluble in sulpholane and at high concentrations appear as solids.

Neutralization
The acidic compounds formed by degradation of sulpholane these are
to be neutralized by injecting MEA. PH is maintained in the range of
5.5~6.0. The salts formed by neutralization with MEA decompose at high
temperature .

Clay treating of Extract

Clay treating is done to remove olefins as in particular di-olefins (from
reformer) being polar are partly extracted along with aromatics. So its
necessary to treat the extract from sulpholane extraction.

Thiophenes and mercaptans are broken down to H2S which will

concentrate in the benzene product.
LHSV Normally kept 1
Clay Life 5000~7000 MT of aromatics /ton of clay.

Clay Disposal
When the bed is exhausted the removal of aromatics is easily effected by
flashing followed by stream stripping .The after it can be dumped in a
truck and used for landfill.
PAREX UNIT
INTRODUCTION
Para-Xylene is the intermediate product used in the manufacture
terepthalic acid(PTA) and di-methyl tere-phalate(DMT). The reformate
from CCR is extracted for aromatics.
The paraxylene is slectively adsorbed on fixed bed Zeolite crystals
(adsorbant) from the mixed xylenes, the adsorbed para xylene is then
displaced from the adsorbent bed by using a desorbent. The desorbent
and para Xylene are separated by fractionation to get para Xylene.

PAREX is just one of the family of UOP SORBEX processes that effect
separations by means of simulated counter current adsorption.
PX is produced by separating it from a mixture of C8 aromatics isomers
and non aromatic hydrocarbans. It can be achieved by crystallization or by
adsorption.Crystallization is commonly proven, but it requires
refrigeration and recover about 60% of para Xylene per pass. The Parex
Proces recovers >96% PX per pass while consuming less utilities.

The by products of the Parex process are are the C8 or aromatics rejected
as raffinate.Toulene is also rejected as another by product and is routed to
TATORAY for trans alkylation to benzene and xylene.
Para-Xylene forms the feed stock for manufacture of Terephthallic acid by
oxidation process.

C6H4-(CH3)2 + 2O2---------> C6H4-(COOH)2 + H2O

Para-Xylene is also used for the production of dimethyl terephthalate

(DMT), another raw material in production of polyester fibers and
plastic.
C6H4-(CH3)2 + CH3-OH -------> CH3-COO-C6H4-COO-CH3

ADSORBENT
The adsorbent consists of X-Type Zeolite ,an aluminosillicate held
together by a clay binder . The particle size of the adsorbent ranges from
20 to 60 mesh.
Alumina rich sieves have very high affinity to water and other polar
molecules. Silica are essentially hydrophobic and adsorb n- paraffins in
preference to water.
All hydrocarbans in the feed can enter the selective pores of the adsorbent
But paraxylenes is passed through the adsorbent more slowly than the other
feed components.

DESORBENT
The desorbent is a liquid of different boiling from the feed components
which is capable of displacing feed components from the adsorbent.Two
types of adsorbents are used—
Heavy Adsorbent
Light Adsorbent
The light desorbent utilizes toluene desorbent and ADS-4 adsorbent .This
is slected when cost of fuel is low & for once through operation.
Hy desorbent has lower operating cost.It has design advantages when
intergrated with isomerisation loop or non extracted feed stocks containing
relatively high level of non aromatics .The heavy desorbent system utilizes
D-1000 desorbent whose main component is para diethyl benzene)p-DEB)
and adsorbent ADS-27

FEEDSTOCK
Several types of feed stock can be separated in PAREX unit. These includes
extracted C8 aromatics , unextracted C8 aromatics from reformate
heartcut,Deheptanized C8 isomerate & Pyrolysis gasoline.

PROCESS PRINCIPLES
Equilibrium: No net change occurring in the process
Ki= K(Phase A)/K(Phase B)

Enrichment Factor: The relationship between the concentration of a

component I two different phases.
Yi,j=Ki/Kj
As the Enrichement factor becomes larger the separation between the two
components becomes easier.

ADSORBENT SYSTEM
In a system where the actual circulation of solid adsorbent ,the adsorbent
moves continuously in a close d past the fixed circuit past the fixed points
where the fed and desorbent are added and extract and raffinate are
withdrawn.
The same effect can be achieved by keeping the adsorbent bed stationary
and periodically moving the points which the liquid stream are added and
withdrawn from the chamber,this will simulate the motion.

ZONE-I: Section Between the Feed and Raffinate points

Primary function is to Adsorp ParaXylene.

ZONE-II:Section between the Extract and Feed points.

Primary function of ZONE II is to remove extract from the pores of the
adsorbent.

ZONE-III: Section between the Desorbent and the Extract point.

Primary function of this ZONE is to desorb A from the Pores.

ZONE-IV: Section between the Raffinate and the Desorbent

This act like buffer ,its purpose is to keep component B to avoid
contamination.

LINE FLUSH
The line between the rotary valve and the bed is employed successively in
carrying feed to bed and carrying extract from it. To avoid extract
contamination with feed components it is necessary to flush the line
Similarly if the line for extract is subsequently use for desorbent line flush
and secondary flush are used.

XYLENE
FRACTIONATOR
INTRODUCTION
The Xylene Fractionator unit fractionates three streams into four product
streams .The Separation is achieved by three Columns ,a reformate splitter
column, a xylene column, and a Hy aromatics column.

Feed Streams
1Reformate from CCR unit
2Toulene column bottoms from BT fractionation unit
3Recycle xylene stream from Isomerization unit.

Product Streams
1C7 cut
2C8 Parex feed cut
3C9 aromatics for Tatoray
4C10 Heavy aromatic cut

The C7 material is sent to sulpholane unit for aromatic extraction and

separation of aromatics by extractive distillation. The reformate splitter
bottom material is clay treated to remove olefins and then sent to xylene
column, The C8 aromatics product is taken overhead from the xylene
column to Parex. The C9+ Hy aromatics from the bottoms of the xylene
column is sent to Hy aromatics column. The C9 material is routed to
Tatoray for undergoing dis-proportionate trans alkylation reactions.

The special feature of the xylene fractionation unit is the high pressure
Xylene column Design. By this design we can use the column overhead
vapours as heating media to reboil the extract and the raffinate columns in
the Parex unit.

PROCESS DISCRIPTION
Feed to the Xylene Fractionation is a combination of Debutanizer bottoms
from CCR, Toluene column Bottoms and clay treated recycle xylenes from
the Isomar deheptanizer bottoms.
The overheads from the xylene column are condensed in the reboiler of
reformate splitter ,Parex Raffinate reboiler and Parex extract column
reboiler.The Xylene column bottoms are use to reboil the Parex extract
column, Isomar deheptanizer column,Parex desorbent re-run column,Heavy
aromatics column as well as clay treater feed.

ISOMAR UNIT
INTRODUCTION
Isomerisation is a catalytic isomerisation process to efficiently convert a
mixture of C8 aromatics to a near equilibrium mixture of PX and OX. It
employs a dual function noble metal catalyst which operates in a pressure
and temperature range that favours p-x and o-x from meta –xylene (m-x) and
ethyl benzene and to crack many of saturates from the fresh feed.

FEED
The feed to isomar unit is the rafinate from the Parex unit.The raffinate is
p-x and o-x depleted. The fee dis combined with Hydrogen rich recycle gas ,
vaporized and sent to the fixed bed radial flow reactor. The effluent is
condensed so that the hydrogen rich recycle gas can be seprated from the
liquid. The liquid is sent o fractionator to remove light material from the
products . The Bottoms is sent to clay treater and subsequently the xylene
splitter column in xylene fractionation unit.

General Discription
The isomar unit consists of a reactor section and a fractionation section
where C7 material is removed . The deheptanizer net bottoms stream is
clay treated and sent to xylene fractionation unit . The raffinate stream
from the Parex unit is recycled back to the Isomar unit where C8 aromatics
are efficiently isomerised to desired p-X and o-X products.

PROCESS PRINCIPLES

Xylene Isomerisation Reactions

The acidity of the Isomar catalyst is much stronger than reforming catalyst,
as this is required for isomerisation.Xylene equilibrium is a function of
temperature .
At 400 Deg C Equilibrium concentration are:
24 % each of o-X & p-X
The balance being m-X,
Ethylbenzene equilibrium concentration is 8% of C8 aromatics.

Ethyl Benzene Conversion

Ethyl benzene reacts at high severities and the products would be
mostly benzene and Heavy aromatics..Conversion becomes more
difficult approach to equilibrium..Products will be result of dealkylation
rather than isomerisation.
Basically Isomerisation occurs via collapse to a five member
ring(Trimethyl cyclopentane and expansion back to six member ring with
the methyl group moved to different location on the aromatic ring.

The presence of Napthenes (mainly C8) makes conversion possible by

rapid hydrogenation the aromatic system so that it will be additive to the
Isomerisation path.

The desired isomerisation required a catalyst having both

metal(platinum) and strong acid function.
In the course of the reaction some C8 aromatic ring loss by trans
alkylation, dealkylation and cracking , these are unavoidable.

Isomar Catalyst
The I-20 catalyst is a bifunctional extrudate catalyst containg both acid
sites(zeolite) and metal sites (Platinum).The acid function is quite stable
so no halogen injection is required. The metal function provided by
platinum is affected by coke build up to acertain extent. As a result
gradual decline in EB conversion is experienced and regeneration of
catalyst is necessary.

OPERATING CONDITIONS
CFE SOR EOR

Inlet temp deg C 104 104

Outlet temp deg C 385
Furnace
Outlet temp deg C 372 417
Reactor
Feed Flow Kg/Hr 204409 204409
Outlet temp deg C 375 420
Pressure Kg/cm2 8.1 16.5

BENZENE-
TOULENE
FRACTIONATOR
INTRODUCTION
There are three separate streams entering the BT Fractionation unit
1Overhead from sulpholane recovery column
2Overhead material from Parex finishing column
3Bottoms material of Tatoray stripper.
The streams are fractionated to produce pure benzene and toluene. The
bottom Xylene Rich stream is routed to Xylene Fractionation column for
recovery of C8 stream.

PROCESS DISCRIPTION
The overhed material from the sulpholane recovery column is collected in
the clay treater charge tank. From the Charge tank the material is pumped
and preheated by charge heater and olefins are removed by using clay
treater.Feed mixed with Parex unit overhead material from the finishing
column. The combined stream then enters to the benzene column which
separate pure benzene product stream from the water , toluene and heavier
aromatics. NOW bottoms are sent to toluene column where toluene
separated. Net column bottoms is pumped to Xylene fractionation unit.
TATORAY UNIT
INTRODUCTION
The Tatoray process is a catalytic process for transalkylation and
disproportionation of aromatics. That is a C7(toluene) and C9 aromatics are
converted to benzene (C6) and mixed xylenes and C10 aromatics.
Thus Tatoray unit increses the production of benzene and C8 aromatics
from toluene and C9 fraction.Toulene from the BT fractionation and C9
aromatics from the Xylene column are fed to Tatoray reactor where
reaction take place in presence of Hydrogen.

The reaction products are stripped of lighter material and sent back to the
BT fractionator for separation of Benzene and toluene recycle and C8+
aromatic stream which is charged to the Xylene stripper for further
processing and separation of the C9 aromatics recycle.

PROCESS PRINCIPLES

Chemistry:
The basic Chemical reaction is the transalkylation of methyl group in
methyl substituted aromatic compounds so as to obtain more desirable
species from les desirables one. Typically a mixture of toluene and heavy
methyl benzene is converted to benzene and C8 aromatics .
The feed also contain ethyl, propyl and butyl substituted aromatic
compounds and saturates. The deactivation of the catalyst is due to
Saturtates ,bicyclis and hetromolecules normally crack to lighter
components on account of higher severity associated with their
hydrocarcking.The optimum conversion taking into account fed stocks
,product values and utility costs is the fed having about 40% of the mixed
feed (C9) and 43-47% for toluene fee d(C7).
Reaction
Methyl group:
Toluene + H2-----> Benzene + mixed Xylenes + C9 + C10
Toluene + C9 + H2------> Mixed Xylenes +C9 +C10

Ethyl Group:
Ethyl benzene + H2-------> Benzene + Ethane
Ethyl benzene + H2------->Toluene + Methane
Ethyl benzene + H2------->mixed Xylenes

PROCESS DISCRIPTION
The fresh feed from the Tatoray unit comes from the overheads of the
Toluene column in the BT fractionation unit and the overheads of the
Heavy aromatics column in the Xylene fractionation unit routed to Feed
surge drum. Feed from the feed surge drum is pumped and is first combined
with the Hydrogen rich recycle gas in the combined feed exchanger where
it is preheated and vaporized with the Reactor effluent upto reaction
temperature Which then fed to reactor where reaction takes place. Reactor
effluent is then condensed to ambient temperature and then separated in a
separator.
 PTA
(PURIFIED
TEREPTHALIC
ACID)
INTRODUCTION
PTA is a white crystalline Compound, in powder form having a Median
Particle size (MPS) in 90-120 Microns. This is primarily used for polyester,
PET & Films manufacture
Terepthallic acids is produced by liquor phase oxidation of Para-Xylene
Oxidation Process is a series Reaction in the following four steps.

Step 1: CH3-C6H4-CH3 + O2 = CHO-C6H4-CH3 + H2O

Para-Xylene(PX) Methyl Benzaldehyde

Step 2: CH3-C6H4-CH3 + ½ O2 = COOH-C6H4-CH3

Methyl Bezaldehyde Para- Toluic Acid

Step 3: COOH-C6H4-CH3 + O2 = COOH-C6H4-CHO + H2O

Para- Toluic Acid 4-CBA (Carboxy Benzaldehyde

Step 4: COOH-C6H4-CHO + ½ O2 = Cooh-C6H4-COOH

4-CBA (Carboxy Benzaldehyde Terepthallic Acid

Overall Reaction is as follows:

CH3-C6H4-CH3 (PX) + 3O2 = COOH-C6H4-COOH(TA) + 2H2O

PTA plant is divided in two sections –

1Oxidation
2Purification
Primary Reaction of TA formation take place in oxidation plant .
 However oxidation product is called CTA( Crude Terephallic Acid), as it
contains about 2000-3000 ppm of 4-CBA and some coloured
impurities.

Purification Plant reduces 4-CBA to less than 25 ppm in finished

product .This is done by Hydrogenation reaction af 4-cba TO P-Toluic
Acid which can be removed with relative ease.

COOH-C6H4-CHO + H2 = COOH-C6H4-CH3 + H2O

4-CBA (Carboxy Benzaldehyde Para- Toluic Acid

OXIDATION SECTION

PAC(Process Air Compressor ) & Reactions

Oxidation Reaction takes place in a cster (continuous Stirred Tank
Reactors ).There are two parallel Reactors in which pX is reacted with air.
Reaction take place at 15 Bar G and 200 Deg Celsius.
Air supplied at 18 Bar G and 160 Deg C by Compression of Atmosphere air
in 5 stage Centrifugal Compressor(called PAC). PAC is driven by motor ,
Steam turbine and Hot gas expander. PX along with Rotary Filter Mother
Liquor( mainly acitic Acid and catalyst) is pumped to the Reactors through
Static Mixer. Acetic acid keeps solid TA produced in suspension as slurry
for ease of transfer of material.

Catalyst is a combination of Cobalt acetate,Maganese Acetate , HBr

(Hydrobromic acid

Reaction slurry is depressurized in a series of three agitated Crystallizers

operating at 11 Bar G & 185 Deg C/ 3 Bar G & 155 Deg C/-0.5 Bar G &
95 Deg c. Reaction is Highly exothermic. Vaporized Acetic Acid and PX
are condensed in a series of Heat Exchangers in Reactor overheads.First
majority of PX and acetic Acid are condenses because of higher Boiling
Point 6 of Acetic Acid and these streams are returned back to Reactors as
Reflux. Next water rich streams named Water Draw Off are condensed
.Since water is a reaction product it has to be remove removed from the
system. Water Draw off and Crystallizers Flash vapors are sent to
Dehydration (DH) Column for Water separation from the acetic acid.
Heat of Exotherm is removed by first generating LP stream, then ELP
stream then heating up to PAC turbine Condensate /DM water going to
DEAERATOR and finally against cooling water LP and ELP stream are
sent to the PAC steam turbine for power recovery .

Gases after cooling goes to the HP (HIGH Pressure ) Absorber for removal
of organics by scrubbing with first acetic acid and then by water.
Online analyzers are mounted in reactor off gas for indicating O2,CO2,CO
volume percentage.
This helps in quality control.

Filtration and Drying

Slurry from 3rd crystallizers is filtered in rotary vacuum filters.
Cake is collected above filter clothes and then Conveyed by screws in to a
Rotary Steam Tube Driers .Drying obtained by indirect contact .Steam
passes through tubes.Acid vapors are carried along with Gas circulated by
Blowers.

Acid vapors are removed in a scrubber and then inerts are vented out to
atmospheric absorber for final scrubbing before letting them to
Atmosphere.CTA product is conveyed to CTA fee d Hooper by conveying
gas .
Rotary Filter separated Liquid is called mother liquor is sucked in through
Filter cloth by Vacuum pumps. Mother Liquor is rich in catalyst and hence
majority of it is recycled out.15-20% of mother Liquor is purge out for
removal of Reaction impurities

Expansive Cobalt is recovered from purged mother Liquor by

addition of Oxalic Acid , which forms Cobalt Oxalate and then
separated by using a high speed centrifuges. Purged Mother Liquor
devoid of cobalt is sent to Solvent recovery section.

Solvent Recovery
Purge Mother Liquor is concentrated in a series of forced Circulation and a
thin Film Evaporator to remote maximum possible acetic acid by
vaporization using LP steam & HP steam. Vapors from evaporator goes to
DH column. Cake is diluted with water and then burned in thermal
oxidizer which is a down fired furnace.This breaks down to CO/CO2.
DH column is an azeotropic Column using n-PA (Normal propyl Acetate )
as Entrainer n-PA bring down the boiling point and hence reduced load on
reboiler and condenser. DH Column bottom Product is called DH solvent
(5-7% water) and it used as solvent for scrubbing.

PURIFICATION SECTION
In this section Hydrogenation of 25-30% CTA is done at high pressure and
Temperature(75-85 Bar G and 282-285 Deg C) Temperature is required to
keep CTA in solution for the Reaction and Pressure is required to avoid
boiling and provide Partial Pressure for Hydrogenation.

First slurry is made in water in Agitated Feed Slurry Drum. Then Slurry is
Pumped to high pressure by Sundyne pumps. Heating is done in
Preheaters using process streams and then finally by Fired Heater using
Therminol as Heat Transfer Media.

Hydrogen is compressed from 19 Bar G to 85-90 Bar G in Reciprocating H2

Compressors. Hydrogenation take place on a 0.5 % Palladium
Catalyst(Charcoal Base)
Reactor is having fixed bed of 20 tons of catalyst and Heated CTA solution
is sprayed through distributor over the Catalyst and then H2 reacts inside
the Reactor.

Reacted material is depressurized in aseries Five Agitated Crystallizers to

38 Bar G/22 bar G /14 Bar G/7.5 Bar G / 4 Bar G. First Three Crystallizers
flash steam utilized for slurry preheating.
Fifth Crystallizers Slurry is pumped in pressure centrifuges operating at 4
Bar G. High Pressure is required to maintain p-Toluic acid in solution.

Pressure Centrifuge Liquor is the main plant effluent

After cooling the effluent TA and p-TA are recovered and recycled back to
oxidation, filtrate to ETP.

Pressure Centrifuge cake is reslurried with fresh DM water. Atmospheric

centrifuge cake is dried in Rotary Steam Tube Drier.
Dried product is stored in Batch Tanks and after Laboratory analysis sent to
Marketing Silos.