Aromatics Recovery

Refinery and petrochemical plant process

for recovery of benzene, toluene, and
mixed xylenes
Conventional method: liquid-liquid
extraction using sulfolane or glycols
Leading-edge technology: extractive
distillation using selective solvent blends

Comparison of Technologies
Liquid-liquid extraction:

Reliable, wide reference base in industry

High capital cost, feed flexibility issues, limited

potential for improvements

Extractive distillation:

Modern technology, low-cost, easy to operate

Solvents used until recently, have limitations

Solvent Effectiveness

Solvent power, solvent selectivity, ability to handle

wide-boiling feedstock

Solvent blends offer better performance and high

process flexibility
Solvent

NC7/Benzene
tm

Techtiv-100
Sulfolane
N-methyl Pyrolidone
N-formyl Morpholine
Glycol blends
None

2.44
2.00
1.95
1.89
1.35
0.57

EDC/SRC General Flowscheme

Design Features

Specialized mass transfer equipment for

extractive distillation and solvent recovery
columns

Heat integration

Extraction block - feed and extract pre-heat,

EDC mid-reboiler using lean solvent

Flexibility in adjusting solvent circulation rates for

varying feed quality

Introduction to IPCL

The Benzene Plant will be revamped by

converting the existing sulfolane liquid-liquid
extraction unit to GT-BTX extractive distillation
process.

In this way the production capacity will be

increased to 90 KTA aromatics. The expansion of
the existing plant capacity of 40 KTA benzene
production to 90 KTA benzene and toluene
production is proposed to be implemented in
two phases, i.e., Phase I and Phase II.

Introduction to IPCL

Phase I revamp will allow IPCL to expand the

capacity from the present 40 KTA to 60 KTA
benzene production, while in Phase II expansion
the combined production of benzene and toluene
shall be 90 KTA.

Extractive Distillation

The working principle of ED is the alteration of

the relative volatility of components in the
presence of a highly selective solvent.

In a mixture containing aromatics and nonaromatics, the relative volatility of the nonaromatic components is enhanced over that of
aromatic components in the presence of a
solvent.

Extractive Distillation

This enhancement allows the non-aromatics to

be distilled overhead in a conventional
distillation column, while the aromatics are
recovered in the column bottoms.

The solvent used in the GT-BTX process is the

proprietary blend, Techtiv-100tm, which makes it
possible
to
achieve
excellent
process
performance.

Extractive Distillation

The general flow scheme of the GT- BTXSM

process is very simple and consists of two major
towers: an extractive distillation column (EDC)
and a solvent recovery column (SRC).

Extractive Distillation

Extractive Distillation

Hydrocarbon feed is preheated with hot

circulating solvent and fed at mid-point into the
EDC.

Lean solvent is fed at an upper point and

selectively extracts the aromatics into the tower
bottoms, in a vapor/liquid distillation operation.

The non-aromatic hydrocarbons exit the top of

the column and pass through a condenser.

A portion of the overhead stream is returned to

the top of the column as reflux. This washes
back any entrained solvent.

Extractive Distillation

Rich solvent from the bottom of the EDC is

routed to the SRC, where the aromatics are
stripped overhead.

Stripping steam is used to facilitate the stripping

of the hydrocarbons.

The SRC is operated under vacuum to reduce

the boiling point at the base of the column. Lean
solvent from the bottom of the SRC is passed
through a series of heat exchangers, for heat
recovery, before returning to the EDC.

Extractive Distillation

Aromatics overhead product from the SRC is

condensed and withdrawn as product.

Water from the overhead of the EDC and SRC is

collected and vaporized with hot solvent, and
used as stripping medium.

A solvent regenerator is used to continuously

process a small portion of the circulating lean
solvent.

Extractive Distillation

The regenerator distills the solvent away from

heavy decomposition products, which are
purged on a periodic basis from the regenerator
bottoms.

Since the basic separation in the GT-BTX

process is achieved by distillation, the operation
of the unit is very simple and intuitive.

Control of the main process parameters can be

achieved in a manner very similar to that for a
regular distillation column.

PFD Review

Basic Operating Scheme

The aromatic / non-aromatic separation
in the Extractive Distillation Column
can be divided into the following two
steps:
1. Aromatic recovery from raffinate
(non-aromatics) in the top section of
the column
2. Stripping the non-aromatic
hydrocarbons from the rich solvent in
the bottom section of the column

Basic Operating Scheme

Since virtually pure extract is to be
produced, the most important
performance parameter is the efficient
stripping of the non-aromatic from the
rich solvent.
In the ED process, in the presence of
solvent, the heaviest non-aromatics
must be more volatile than the lightest
aromatics.

EDC / SRC Columns

The differences from liquid extraction are:
a. Recovery and purification of aromatic
occur in the same column
b. Higher selectivity
c. Direct control of the material balance by
reboiler duty and draw-off rate.
d. Independent control and adjustment of
the hydrocarbon and solvent rate

Solvent Circulation
The required solvent rate is based on:
a) Achieving the desired aromatic recovery.
More solvent will tend to absorb the
aromatic more readily.
Sufficient solvent should be used to alter
the volatility such that benzene remains
less volatile than the raffinate stream

Aromatics Recovery Fundamentals

Solvent Selectivity toward
Petrochemical
Hydrocarbons

Multi-ring aromatics
Mono-aromatics

K-Value

C5
C6
C7
C8
C9

Relative Effect of Polar

Solvents on Hydrocarbon
Species

Na
Pa
ph
raf
the
fi
ne
s/ O n s
lef
ins

Aromatic
s

Olefins/ Naphthenes
Paraffins

Carbon Number

Solvent Circulation

Solvent Circulation
b) Maintaining adequate selectivity between
aromatic and non-aromatic at the bottom
of the EDC.
The solvent displays better selectivity at
lower hydrocarbon content at the bottom
of EDC relatively compared to solvent
content.

Solvent Circulation

Solvent Circulation
This means that the higher the aromatic
content in the feedstock is, then higher
solvent / feed ratio is required to maintain
the adequate selectivity.

Factors affecting Aromatic recovery

The factors affecting recovery of aromatic

at a given feed rate are:
1. Solvent rate and feed composition
2. ED Column feed location
3. ED Column bottom temperature
4. Water Content in solvent
5. Aromatic content in solvent
6. Feed temperature
7. Reflux Ratio
8. Hydrocarbon content in lean solvent

Solvent Rate and Feed Composition

Aromatic recovery, feed composition,

and solvent/feed ratio (S/F) are closely
related.
When the aromatic content of the feed
increases, more aromatics dissolve in
the solvent and the raffinate flow
becomes less.

Solvent Rate and Feed Composition

The flow rate of solvent phase relative to

hydrocarbon phase (at constant S/F)
thus increases near the top of the EDC,
resulting in a lower aromatic
concentration in the raffinate.
The percentage loss of feed aromatic to
the raffinate declines due to this lower
concentration and to the lesser amount
of raffinate.

Solvent Rate and Feed Composition

In general, as the aromatic content in

the feed increases under a given solvent
to feed ratio, the relative volatility
between the solvent and the raffinate
phases will be reduced because more
aromatics dissolve in the solvent.
This requires a higher solvent to feed
ratio to maintain product purity and
aromatics recovery

Factors affecting Aromatic recovery

Water Circulation
The EDC overhead water stream contains
some non-aromatic hydrocarbons, which
are not desired in the solvent recovery
column where could affect the aromatic
extract quality.
Therefore, this stream needs to be
processed in the water stripper by
stripping out all hydrocarbon traces.

Water Circulation
Raffinate product at the top of the EDC
could contain some solvent that must be
recovered usually by contact with
water.
Additional fresh water can be brought to
the static mixer 23-ME-341 to help
facilitate the removal of the solvent.
The solvent will separate into the water
phase and will be recycled to the water
stripper.

Water Circulation
The water stripper is installed at the
top of the steam generator; a small
amount of steam is purged out at the
top of the stripper together with the
stripped non-aromatic hydrocarbon
and is sent back to the EDC
condenser.

Water Circulation
In general, very small quantity of the
total water in circulation needs to be
stripped overhead to assure that,
when the remainder is vaporized and
utilized as stripping steam in the SRC,
no non-aromatic components will
contaminate the extract.

Water Circulation
The water is used as stripping steam
injected into the bottom of the solvent
recovery column, and it helps strip
aromatics more easily from solvent by
reducing hydrocarbon partial pressure
at the SRC bottom.
The more stripping steam is injected
the fewer hydrocarbons in the lean
solvent loop remains.

Water Circulation
Typically, the stripping steam ratio will
be 1.0 to 3.0 wt% on solvent flow rate.
Heavier feed and lower solvent to feed
ratio will require more stripping steam.

Factors affecting solvent

losses and solvent quality
The factors which can affect solvent
losses and solvent quality are as
follows:
a. Degradation
b. Neutralization
c. Solvent losses in the raffinate
d. Solvent losses in the extract

Degradation
During use, the solvent usually turns
acidic, though the rate of this process
differs widely according to the
conditions.
The pH number quoted throughout for
solvent is measured after 1:1 dilution
with water.
On this basis, fresh solvent has a pH
of approximately 6.

Degradation
The solvent degrades due two primary
functions:
a. Extreme heat
b. Reaction with free oxygen or
oxygenates

Degradation
In practice at temperatures up to
200oC, there is no acid formation from
solvent in an inert atmosphere.
Therefore, at all temperatures
practically encountered in an
extraction process, acid formation has
to be attributed to attack of oxygen.

Degradation
Although the Solvent degradation is
minimal up to 200 oC in an inert
atmosphere, the SRC bottom
temperature should not exceed 180 oC
to minimize any potential degradation
problem.
There are several intermediates
leading to polymer and acidic polymer
formation, but all are ultimately related
to oxygen exposure.

Degradation
These polymers are only partly
soluble in solvent and when present in
higher concentration, will appear as
solid material that must be removed
by way of the solvent regenerator.
The preferable countermeasure is to
avoid oxygen ingress through the
feed, solvent and water rerun systems
and vacuum leaks around the SRC.

Neutralization
In order to protect the equipment from
corrosion, it is necessary to neutralize
any acidic compound that may be
formed.
Since the intermediate degradation
products are sometimes volatile,
neutralization of the material in the
extractive distillation and recovery
columns is required from the top of the
tower downward, along with
neutralization of the water circulation
system.

Neutralization
MEA is one most effective neutralizing
agent.
Pure solvent in a 1:1 dilution with water
shows a pH of 5.8, while the pH of the
circulating solvent is normally
maintained between 5.5 and 6.0 (in a 1:1
dilution with water).

Neutralization
The MEA dosage can be maintained to
keep the solvent pH in this range. It is
important not to overdose the system
with MEA as MEA could itself be
corrosive.
The pH of the water circulation loop
should also be maintained by MEA
addition, keeping the pH between
approximately 6.5 and 7.5.

Neutralization
The MEA salts formed are not
completely stable and can decompose
at high temperatures (e.g. in the solvent
recovery column).
However, since both the acidic
compounds and MEA are volatile, they
will recombine in the top condensing
area to form neutral salts.
Thus, both phases need to be
considered for any pH control program.

Neutralization
The MEA salts formed are not
completely stable and can decompose
at high temperatures (e.g. in the solvent
recovery column).
However, since both the acidic
compounds and MEA are volatile, they
will recombine in the top condensing
area to form neutral salts.
Thus, both phases need to be
considered for any pH control program.

Neutralization
The major cause of solvent degradation
is the influence of oxygen. If oxygen
ingress could be completely prevented,
regeneration of solvent would probably
be eliminated.
All extraction plant corrosion, fouling,
and the solvent appearance concerns
can in most cases be traced back to
changes in oxygen intake via a feed
system or vacuum leaks.

Neutralization
Process losses of solvent may be to the
raffinate, the extract, or the regenerator
bottoms.
The last is related to the draw off of
decomposition products, the formation
of which is largely controlled by
excluding air from the feed and
preventing air leaks into the plant.

Solvent Losses in the Raffinate

The GT-BTX unit has been designed to
have very little solvent going to the
overhead of the EDC.
The solvent has a low volatility and
therefore goes to the tower bottoms.
However, there may be a small quantity
of solvent entrained into the overhead
vapors.

Solvent Losses in the Raffinate

Thus, the solvent losses to the raffinate
can be controlled as follows:
1. Avoidance of solvent in the overhead
by using hydrocarbon reflux and
temperature adjustments.
Directionally, a higher reflux rate and
lower solvent temperature will reduce
solvent in the raffinate.

Solvent Losses in the Raffinate

Graph no. 3 shows the solvent losses
in the raffinate at a constant EDC bottom
temperature with constant S/F ratio with
various feed temperatures.

Solvent Losses in the Raffinate

Solvent Losses in the Raffinate

Graph no. 11 shows the solvent losses
at various solvent temperatures with
various reflux ratios (R/(R+D)).

Solvent Losses in the Raffinate

Solvent Losses in the Raffinate

The larger the reflux ratio is, the less
solvent losses become.
The solvent losses tend to decrease as
the lean solvent temperature decreases.
The solvent losses due to higher solvent
temperature can be compensated for by
properly increased reflux.

Solvent Losses in the Raffinate

2. Phase separation of the solvent into
the water phase in the overhead
accumulator system.
The distribution of solvent into water is
approximately 100 times greater than
into non-aromatic hydrocarbons.

ED Column feed location

With a fixed number of total stages, the

feed point can be adjusted to vary the
number of stages above and below the
hydrocarbon feed in actual operation in
order to meet certain extract purity or
aromatic recovery targets.
Simply stated, the stages above the feed
function to extract aromatic from the
hydrocarbon phase and those below the
feed to strip the non-aromatic from the
rich solvent.

ED Column feed location

In general, aromatics losses increase

when there are fewer stages above the
hydrocarbon feed point, while the
extract purity will increase by having
more stages below the hydrocarbon
feed point.
More trays below the feed tray are
required for high aromatic feed whereas
more trays above the feed tray are
required for low aromatic feed.

ED Column feed location

The selectivity ( product purity) is more

critical than solvency (product recovery)
for high aromatic content in feed, and it
is reverse for low aromatic content in
feed.
As a result, high aromatic feed requires
more trays below the feed tray and
fewer trays above the feed tray than low
aromatic feed.

EDC Bottom Temperature

The temperature of the solvent entering

the EDC is an important factor in
controlling the aromatic recovery.
The solvent temperature also dictates
the column temperature profile because
the solvent is the greatest bulk flow rate.

EDC Bottom Temperature

In general:
1. Raising the solvent temperature will
improve the recovery of aromatic,
through the effect of a higher solvency
and reduced viscosity, which improves
mass transfer.
2. Raising the temperature slightly
lowers the solvent selectivity, which
may require a higher heat input to
maintain extract quality.

EDC Bottom Temperature

In general:
3. Raising temperature increases the
temperature of the raffinate and
increases utility requirements slightly.
4. Benzene recovery versus the EDC
bottom temperature at various reflux
ratios, various solvent temperatures and
various S/F is shown in graph no. 5, 13
& 16.

Water Content in Solvent

The water content of the solvent is

primarily established by the temperature
and pressure at the bottom of the
solvent recovery column.
Typical water content in the solvent is
0.6-0.8wt%.
Water decreases the solubility of
hydrocarbons in the solvent and
therefore decreases aromatic recovery,
but directionally improves the extract
quality from EDC.

Water Content in Solvent

A small amount of water can be added

to the base of the EDC, if necessary to
keep the EDC bottom temperature lower
than 175oC, to increase the aromatic
purity.
Benzene recovery versus water content
in lean solvent is shown in graph no.
18.

Water Content in Solvent

Aromatic content in Solvent

Aromatics that are not completely

stripped in the SRC and remain in the
solvent lead to greater aromatic losses
in the EDC than would be experienced
with an aromatic-free solvent.
The aromatic content of the solvent is
depending by the temperature in the
base of the solvent recovery column
and by the quality of the stripping
steam.

Aromatic content in Solvent

At higher aromatic content or higher

molecular weight extract, more stripping
steam or a higher bottom temperature
will be required to maintain the aromatic
below a few tenths of a percent in the
solvent.

Feed Temperature
Benzene recovery doesnt change
rapidly with a change in feed
temperature.

Reflux Ratio

The effect of reflux ratio on benzene

recovery at various solvent temperature
shown in graph no. 12.
At solvent design temperature, the higher
reflux ratio decreases the benzene
recovery.

Reflux Ratio

Hydrocarbon content in Lean Solvent

Excessively high hydrocarbon in lean

solvent will affect aromatics recovery
more than product purity. If the lean
solvent includes too high a hydrocarbon,
the hydrocarbon can be lost to the
raffinate at the EDC as a aromatics
reentry loss to raffinate from the lean
solvent. In this case, concentration of
other aromatics heavier than benzene can
be higher than that of benzene in the
raffinate product.

Hydrocarbon content in Lean Solvent

A typical hydrocarbon content in lean

solvent is less than 1.0 wt%.
However, Hydrocarbon in lean solvent has
little effect on product recovery and purity
even if the hydrocarbon content in the lean
solvent is as high as 5 wt%.
The hydrocarbon content in lean solvent is
controlled by stripping steam, which is
typically 1.2 % -1.8 wt% on lean solvent
flow rate for BTX feed.

Hydrocarbon content in Lean Solvent

If the feed includes heavier components

such heavy aromatics, it will require higher
stripping steam ratio than 2 3 wt%. In
addition to the stripping steam rate, the
followings can help reduce the hydrocarbon
in the lean solvent.
Decreasing SRC column pressure
Increasing SRC bottom temperature ( not
higher than 180 oC )
Increasing EDC Bottom temperature
Increasing Solvent to feed ratio

Feed Temperature

Feed Temperature