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.
Licensors
PX Units -----UOP Design
PTA Units-----DuPont Design
PX PACKAGE UNITS:
1NHT
2CCRU
3SULPHOLANE
4BTF
5TATORAY
6XFU
7PAREX
8ISOMAR
1OXIDATION PLANT
2PURIFICATION PLANT
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.
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.
6.Metal Removal
Mainly arsenic, iron, magnesium,phosporus, lead removal.These reactions
are temperature dependent .
Desulpharification 100 1
Olefin Saturation 80 5
Denitification 20 0.1
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)
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.
Dehydrocyclization of Paraffins
This is most difficult platforming reaction.Conversion of Paraffins to
Napthenes.It becomes easier as the molecular weight of Paraffins
increases.
Hydrocracking
Feed Acid function requires for dehydrocyclization also promote
hydrocracking.The reaction consumes Hydrogen and results in lower
reformate yield.
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.
Dealkylation of Aromatics
Same as demethylation , different in removal of fragment from the ring.
If alkyl side is bulky than leads to cracking.
Heat of Reaction:
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.
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
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
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 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.
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)
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.
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 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
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
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.
OXIDATION SECTION
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.
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
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.
After cooling the effluent TA and p-TA are recovered and recycled back to
oxidation, filtrate to ETP.