GTC Lidong Training

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
NC7/Benzene
Techtiv-100
tm
2.44
Sulfolane 2.00
N-methyl Pyrolidone 1.95
N-formyl Morpholine 1.89
Glycol blends 1.35
None 0.57
Solvent power, solvent selectivity, ability to handle
wide-boiling feedstock

Solvent blends offer better performance and high
process flexibility

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
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 non-
aromatics, the relative volatility of the non-
aromatic 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-100
tm
, which makes it
possible to achieve excellent process
performance.

The general flow scheme of the GT- BTX
SM

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

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.

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.
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.

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.

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.
Basic Operating Scheme

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

EDC / SRC Columns

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
Solvent Circulation

Aromatics Recovery Fundamentals
Multi-ring aromatics

Mono-aromatics

Olefins/ Naphthenes

Paraffins
C
5
C
6

C
7

C
8

C
9
Solvent Selectivity toward
Petrochemical
Hydrocarbons
Relative Effect of Polar
Solvents on Hydrocarbon
Species
5 6 7 8 9
Carbon Number
K
-
V
a
l
u
e

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.
Solvent Circulation

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 Solvent temperature
4. Water Content in solvent
5. Aromatic content in solvent
6. Feed temperature
7. Reflux Ratio
8. Hydrocarbon content in lean solvent

Aromatic recovery, feed composition,
and solvent/feed ratio (S/F) are closely
related.

1.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

1.Solvent Rate and Feed Composition
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.

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.

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.

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.
3. EDC Solvent 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 (bottoms
temperature) to maintain extract quality.

In general:
3. Raising temperature increases the
temperature of the raffinate and
increases utility requirements slightly.
It is important to control the Lean Solvent
feed temperature to within +/- 1-2 degC to
ensure stable operation of the EDC

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.

4. 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 175
o
C, to increase the aromatic
purity.
Benzene recovery versus water content
in lean solvent is shown in graph no.
18.
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.

5. 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.

5. Aromatic content in Solvent
Benzene recovery doesnt change
rapidly with a change in feed
temperature.

6. Feed Temperature
6. Feed Temperature
Benzene Recovery vs. Feed Temperature
95.00
96.00
97.00
98.00
99.00
100.00
67 77 87 97 107 117 127 137 147
Feed Temperature,
o
C
B
e
n
z
e
n
e

R
e
c
o
v
e
r
y
,

w
t
%
Reflux R/(R+D)=0.15
Reflux R/(R+D)=0.25
Reflux R/(R+D)=0.35
EDC BTM Temperature = Constant; S/F Ratio = 2.2 @ 105 C
7. 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.
7. Reflux Ratio
Benzene Recovery vs. Reflux Ratio
95.0
96.0
97.0
98.0
99.0
100.0
0.15 0.20 0.25 0.30 0.35 0.40 0.45
Reflux, R/(R+D)
B
z
.

R
e
c
o
v
e
r
y
,

w
t
%
Solvent Temp 95 C
Solvent Temp 105C
Solvent Temp 110C
EDC BTM = Const; S/F Ratio = Const
Design
8. 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.
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.
If the feed includes heavier components
such as 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
Factors affecting Aromatic Purity

The factors affecting aromatic purity at a
given feed rate are:
1. Solvent flowrate
2. EDC / SRC Pressure
3. Water content in Solvent
4. ED Column Feed Temperature
5. ED Column Bottom Temperature
6. Lean Solvent Temperature
7. Reflux Ratio
1. Solvent Flowrate
The selective solvent used in the GT-BTX
process alters unequally the volatility of
the aromatics and non-aromatics, such
that non-aromatics are relatively more
volatile.
An increase in the amount of solvent
increases the activity coefficients of non-
aromatics more than those of aromatics
and thus improves the separation.
2. EDC/SRC Pressure
The EDC pressure must be controlled to
permit condensing the overhead vapors
with the water cooler, and reboiling of the
bottom using the available heat.
Design EDC O/H pressure is 1.2 kg/cm2
Higher pressures may result in temperature
limitations at the bottom of column
In general, as the EDC pressure is
increased, the aromatic recovery may
increase slightly, the aromatic purity
decreases slightly, and the utility costs
increase slightly.
2. EDC/SRC Pressure
The SRC pressure is mainly determined by the
requirements to have a lower bottom
temperature, while effectively stripping the
aromatic hydrocarbon.
Design conditions are:
O/H pressure -0.4 kg/cm2
Bottom Temperature 175 degC
3. Water content in Solvent

In general, water in the solvent
directionally improves the extract quality,
but is detrimental to the aromatic
recovery in the EDC.
A small amount of water can be added to
the base of the EDC to help in rejecting
the non-aromatic from the extract.
4. ED Column Feed temperature
the benzene purity is not greatly affected
up to design feed temperature, but then
sharply decrease the benzene purity with
increase in feed temperature there after.
4. ED Column Feed Temperature
Impurities in
EDC Bottoms Stream vs. Feed Temperature
1
100
10,000
67 77 87 97 107 117 127 137 147
Feed Temperature,
o
C
I
m
p
u
r
i
t
i
e
s

i
n

E
D
C

b
o
t
t
o
m
s

s
t
r
e
a
m
,

w
p
p
m
Reflux R/(R+D)=0.15
Reflux R/(R+D)=0.25
Reflux R/(R+D)=0.35
EDC BTM Temperature = Constant; S/F Ratio = 2.2 (by vol) @ 105 C
5. ED Column bottom Temperature

The benzene purity increases with higher
than design EDC bottom temperature up
to certain range. Typically the benzene
purity increases with higher bottom
temperature at the cost of higher aromatic
content in the raffinate.

The effect of lean solvent temperature on
benzene purity at constant S/F ratio,
reflux ratio and various EDC bottom
temperature is shown in graph no. 10.
Higher solvent temperature at fixed EDC
bottom temperature increases the
benzene purity.
Impurities in the Extract vs EDC Bottom Temperature
@ various Solvent Temperatures
1
10
100
1,000
10,000
100,000
150 155 160 165 170
EDC Bottom Temperature,
o
C
I
m
p
u
t
i
r
y

i
n

E
x
t
r
a
c
t
,

w
p
p
m
Solvent Temp = 95 C
Solvent Temp=105C
Solvent Temp=110C
S/F Ratio = Constant; Reflux R/(R+D)=0.25
7. Reflux Ratio

Effect of various reflux ratios for different
solvent feed temperatures on benzene
purity is shown in graph no. 14.
At constant reflux ratio, increase in
solvent temperature helps in aromatic
purity.
7. Reflux Ratio
Impurities in EDC Bottoms vs. Reflux Ratio
1
10
100
1,000
10,000
0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55
Reflux (R/(R+D))
I
m
p
u
r
i
t
i
e
s

i
n

E
D
C

b
o
t
t
o
m
s
,

w
p
p
m
Solvent Temp. 95 C
Solvent Temp. 105 C
Solvent Temp. 110 C
EDC BTM Temp.= Const; S/F Ratio =
Const.
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 106ME-101 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 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

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.

Water Circulation

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

Factors affecting solvent
losses and solvent quality
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.

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

a) Degradation
In practice at temperatures up to
200
o
C, 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.

a) Degradation
Although the Solvent degradation is
minimal up to 200
o
C in an inert
atmosphere, the SRC bottom
temperature should not exceed 180
o
C
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.

a) 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.

a) Degradation
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.

b) 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).

b) 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.

b) 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.

b) 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.

b) 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.

b) 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.

b) Neutralization
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.

c) 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.

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

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.

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.

Wash water can be recirculated around
the EDC overhead receiver, through a
static mixer in order to enhance the
water-hydrocarbons contact. Fresh
makeup water mixed with SRC ovhd
vapors as necessary and thus makeup
water added to the system.
The tendency of solvent losses with the
ratio of H2O / HC is shown in graph no. 9.
Solvent Content in the Raffinate vs. H20/HC mole ratio
0
1
2
3
4
5
6
7
8
9
10
0.12 0.24 0.36 0.48 0.60 0.72 0.84 0.96 1.08 1.20
H2O/HC mole Ratio
(@ EDC Ovhd. Receiver)
Solvent Content in
Raffiante, wppm
10 wppm of solvent in Mixer feed
25 wppm of solvent
50 wppm of solvent
100 wppm of solvent
Solvent Temp. & S/F : Constant; Reflux rate : const
d) Solvent Losses in the Extract

The primary control parameter for solvent
losses in the SRC overhead is the column
reflux. The top tray vapor from the
solvent recovery column contains pure
aromatic, water, (that originated as steam
in the base of the column), and potential
traces of solvent.
This mixture is condensed and separated
into an aqueous phase and a hydrocarbon
phase.

Part of the hydrocarbon phase is
withdrawn as extract, and part is returned
to the top of the column as reflux to
reduce the amount of solvent in the
overhead. As in the EDC, the small
amount of solvent which does go
overhead will distribute between aqueous
and hydrocarbon phases. Any solvent in
the extract will be lost in the fractionation,
while any solvent in the aqueous phase
will be recovered in the system.
The solvent content of the overhead can
never be reduced to zero, so the optimum
loss must be based on economic
considerations.
The higher the reflux/extract ratio, the
lower the loss and the higher the utility
consumption.
A second possibility for solvent losses in
extract product is caused by entrainment
from the flashing feed. The SRC column has
been designed to minimize entrainment, but
it is possible to further reduce this tendency
by -Increasing SRC column pressure
Decreasing SRC bottom temperature
Lowering EDC Bottom temperature
Decreasing stripping steam rate
Decreasing solvent to feed ratio
subject to other conditions.
SUMMARY
Major changes Solvent/Feed ratio
Trim changes
EDC bottoms temperature
Reflux
Maintain clean solvent
SRC bottoms temperature
Stripping steam
Recycle to feed tank either BOTH raffinate
and extract, or NONE

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Aromatics Recovery

Refinery and petrochemical plant process

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