Working with an extractive distillation

n the mid-60s, Krupp Uhde developed the
Morphylane process (extractive distillation
process) originally for the recovery of high-
purity benzene from hydro-refned coke oven
benzole, the reason being that the existing liquid-
liquid methods of extraction were unable to
process coke oven benzole due to its high aromat-
ics content. The liquid-liquid extraction techniques
exploit the different solubilities of aromatics and
non-aromatics in a polar solvent (Figure 1).
Two liquid phases are formed: the aromatics,
which tend towards the solvent phase, usually
the heavy phase, due to their higher polarity and
Gerd Emmrich, Helmut Gehrke and Uwe Ranke Krupp Uhde GmbH
thus higher solubility, and the light phase, which
consists mainly of non-aromatics.
The extraction process essentially consists of
four process units:
• Extractor, where the feedstock is brought into
contact with the solvent
• Extractive stripper, where the non-aromatics
which have also been dissolved are stripped off
• Solvent stripper, where the aromatics are sepa-
rated from the solvent
• Raffnate washer for the recovery of the solvent
residue which has been dissolved in the
raffnate. PTQ Q3 2001 1
A cost comparison between progressive extractive distillation of aromatics
versus a more conventional technology
Figure 1 Morphylex liquid-liquid extraction
It is obviously a very long-winded process.
However, if the aromatics content of the feed
material is too high, formation of two phases
does not take place as the aromatics act as a
solubility agent for non-aromatics. As a result,
extractive separation of the aromatics and non-
aromatics is not possible because the entire feed
material dissolves in the solvent.
Polar solvents, as commonly used for this
purpose, also demonstrate another exceptional
physical property in addition to the solubility
differences of aromatics and non-aromatics.
Their polarity can infuence hydrocarbon vapour
pressures. They lower vapour pressures of all
hydrocarbons contained in the solution, albeit to
2 PTQ Q3 2001
different degrees. What does this mean, exactly?
The molecular structure of N-formylmorpho-
line is shown in Figure 2, the solvent used in
Krupp Uhde’s proprietary Morphylex and
Morphylane processes. The different molecular
groups on both sides of the molecule have an
electrical effect, making the molecule act like a
small dipole.
The electrical effect acts on the double bond of
the hydrocarbons. A loose bond is formed imped-
ing the mobility of the molecules concerned. The
more double bonds a molecule has, the greater
its movement is impeded and the more diffcult
for it to be converted from a liquid to a vapour
state in the presence of such solvents.
How signifcant are these vapour
pressure changes?
Example: the frst temperature
column in Table 1 shows the boiling
points of the pure components such as
benzene (80°C), methyl-cyclohexane
(MCH) (101°C) and n-heptane (98°C).
If these components are now mixed
with NFM to a ratio of 15 mol% hydro-
carbons:85 mol% NFM, the resulting
mixtures have boiling points of 135°C
for benzene, approximately 110°C for
MCH and 103°C for n-heptane. The
reduction of the vapour pressure is
Figure 2 Characteristics of N-formylmorpholine (NFM)
Components NFM Boiling points
15 mol% 85 mol% Pure comp °C Mix °C
2,2-dimethylpentane 79.19 83.43
2,4-dimethylpentane 80.49 84.74
2,2,3-trimethylbutane 80.88 85.21
N-heptane 98.43 103.15
Cyclohexane 80.72 87.39
Methylcyclohexane 100.93 109.55
Benzene 80.09 134/70
Initial boiling points of NFMl HCs
Table 1
2 PTQ Q3 2001
dramatic in the case of benzene, while in the
case of n-heptane, it is only minimal.
The most important point, however, is that in
the pure component mixture benzene is the low
boiler, while in the mixture containing the
solvent, it is the high boiler. This is the principle
of extractive distillation where, at frst, a close-
boiling distillation cut is produced; this is then
mixed with a polar solvent to increase boiling
differences between components, thus increasing
the relative volatility of the non-aromatics.
Azeotropes are also destroyed. The principle
arrangement of extractive distillation is very
simple (Figure 3).
The extractive distillation column shown in
Figure 3 consists of three sections: Stripping
section, rectifying section and solvent recovery
The feed material, in this case the benzene
fraction, is added between the stripping and the
rectifying section; the solvent NFM is introduced
above the rectifying section. The vapourised
benzene is removed in the enrichment zone by
the infuence of NFM. Some light non-aromatics
are also dissolved and stripped off in the strip-
ping section.
Solvent vapours also fow to the top of the
column together with non-aromatics, according
to their partial pressure. These solvent traces are PTQ Q3 2001 3
washed back into the column in the solvent
recovery section by non-aromatics refux. The
solvent-benzene mixture which accumulates in
the bottom of the ED column is transported to
the stripper column, which operates under a
slight vacuum. Here the benzene is separated
from the solvent.
The NFM in the benzene vapours is washed
back by the refux to less than 1ppm. The
condensed benzene meets all product specifca-
tions. The solvent, which contains a minimal
benzene content, is fed back to the extractive
distillation column from the bottom of the strip-
ping column after intensive heat exchange.
In principle, this is a conventional two-column
distillation system in which the low-boiling
component is taken overhead in the frst column,
the medium boiling component leaves as over-
head in the second column and the high-boiling
component accumulates in the bottom of the
second column. The only difference is that the
high-boiling component is recycled back to the
frst column as extraction solvent. Separation of
a three-component mixture (ABC) into individ-
ual components A, B and C, by distillation in
direct sequence is shown in Figure 4a. The three
components can also be separated using a main
column and a side column. Depending on the
boiling conditions of component B, either a side
Figure 3 Morphylane extractive distillation
stripper or a side rectifer can be used. These are
both thermally coupled columns as the two
columns are connected with each other at the
reboiler or condenser side.
These side columns can also be incorporated
in one column by dividing the column into
sections. If the two aforementioned methods are
combined, a fully thermally coupled column is
obtained. If the side column is then incorporated
in the main column, the result is the divided-wall
column (Figure 4b).
What is the thermodynamic advantage of the
thermally coupled column over the conventional
two-column system?
If one considers the concentration profle of an
extractive distillation process in a two-column
system, where mol fractions of benzene are plot-
ted against the number of theoretical stages, it
can be shown that the benzene concentration
drops off again before entering the second
column. This is called back-mixing. Therefore,
additional energy must be expended in column 2
in order to reverse this back-mixing.
However, if one considers the concentration
profle of a thermally coupled single-column
extractive distillation process, it can be seen that
the benzene with the highest concentration
occurs in the separated section. How, then, can
this principle of thermally coupled columns be
applied to extractive distillation (Figure 5)?
A main column with a side rectifer can be
used as an example of extractive distillation. If
the composition in the bottom of the extractive
distillation column is taken into consideration, it
can be seen that it must be similar to that on the
stripper column feed tray. Therefore, the draw to
the side rectifer must be positioned at such a
location that the packing below the draw in the
main column corresponds to that of the stripper
column, such that this bottom packing, combined
with the side rectifer, corresponds to the strip-
per column (packings V and IV), while the
column section above the side draw constitutes
the extractive distillation column (packings I, II
and III).
A single-column extractive distillation confgu-
ration of this type is shown in Figure 6. Feed
material, the benzene or benzene/toluene frac-
tion, is added above packing III on the feed side.
Packing II, above
which the solvent is
added, is located
above the feed entry
point. Packing I,
which plays the role
of removing solvent
traces from the non-
aromatic vapours by
means of refux, is
arranged at the
column head. Solvent
traces are also
removed on the
product side of the
baffe plate through
aromatics refux onto
packing IV, in this
4 PTQ Q3 2001
Figure 4a Direct sequence
Figure 4b Thermally coupled columns
case, however, from the pure aromatics.
Below the baffe plate there is a chimney tray,
which directs the entire liquid through a reboiler
heated with hot, stripped solvent. Packing V, in
which the aromatics are stripped from the
solvent to a residual content of 0.1–0.2 per cent,
by means of a bottoms reboiler, is located below
the chimney tray.
Column operation
Aromatics are removed from the vaporised feed
material by the solvent in packing II until a
residual content of 0.5–1 per cent is reached.
However, some of the non-aromatics are also
dissolved. These are stripped off by aromatic
vapours in packing III. The solvent traces, which
fow to the column head with the non-aromatics
(proportionate to the vapour pressure of the
solvent) are washed back with the non-aromatics
The solvent traces are removed from the
aromatics vapours in packing IV, again by refux.
It is, however, packing V, where the aromatics
are stripped off from the solvent, that is of
crucial importance. Extractive distillation can
only be effective if the aromatics content is dras-
tically reduced to ~0.1 per cent. Intensive PTQ Q3 2001 5 4 PTQ Q3 2001
Figure 5 Thermally coupled columns
Figure 6 Thermally coupled extractive distillation
aromatics-stripping is crucial for the aromatics
The wall forms two separate chambers. The
vapours which enter both sides have the same
composition and their non-aromatics content
must conform with the product quality for pure
aromatics. The purity of the aromatics is regu-
lated in packing III, the yield is regulated in
packings II and V and the solvent is retained in
packings I and IV.
Overall column control is the most critical
factor in the process.
In order to ensure that the aromatics stripping
in the bottom of the column is intensive enough,
the column operates under a vacuum. Special
signifcance is attached to the pressure regula-
tion since it also regulates purity and yield. If,
for example, the temperature in the upper
section of packing IV rises, this is a sign that the
percentage of solvent vapours is increasing. If
the pressure in the aromatics refux drum is now
raised, fewer vapours fow to the condenser while
the refux rate remains constant.
As a result, solvent is washed back to the lower
packing section by the increased refux ratio. If,
for example, the temperature in packing II rises,
this is a sign that the benzene front in the pack-
ing is rising, which in turn results in an increased
benzene loss. Such a column confguration was
frst demonstrated in an Aspen Plus steady state
It was found that the system was surprisingly
quick to converge, it demonstrated the required
values for product purity and yield and attained
the expected reduction in energy consumption.
The only thing still to do was to test the process
and, in particular, the control concept in a pilot
For this, a pilot plant equipped with a DCS
system at the laboratory/pilot plant test centre
in Ennigerloh, Germany, was assembled to
demonstrate comprehensively the mode of oper-
ation. The aim of the experiments was both to
confrm the simulation calculations and also to
demonstrate the controllability of the column as
needed in commercial scale applications.
Simulation calculations for the recovery of
pure benzene from reformate or fully hydrogen-
ated pyrolysis gasoline reveal energy savings of
16 and 20 per cent, respectively, in the new tech-
nology application (Figure 7).
The catalytic reformate gives a lower energy
saving as the percentage of non-aromatics in the
feed to the extractive distillation process is
higher than in the pyrolysis gasoline cut. This
produces a higher percentage of overhead prod-
6 PTQ Q3 2001
Figure 7 Comparison of concepts
6 PTQ Q3 2001
uct (raffnate). As the quantity of heat required
for vaporising the raffnate is the same for
conventional ED and progressive ED, the energy
saving is correspondingly lower if there is a high
percentage of non-aromatics in the feed fraction.
To confrm the simulation results, a pilot-scale
column with an internal diameter of 72mm was
installed. Its dimensions were based on those of
the columns and other equipment (eg reboiler,
feed plates) which already have been used at
Krupp Uhde facilities for the development of the
Morphylex and Morphylane technologies. A typi-
cal arrangement of the column details is
illustrated in Figure 8.
Number 022 in detail drawing A shows the
cover plate welded to the aromatics discharge
side above the wall and the vapour draw for the
aromatics. Detail drawing B shows an intermedi-
ate fange with a feeder on the left-hand side of
the wall and an aromatics refux feeder on the
right-hand side of the wall. The design is based
largely on the conventional divided-wall columns
installed at Krupp Uhde facilities some time ago.
Special semicircular structured packings were
manufactured for the vertical wall section of the
column. The structural geometry corresponds to
that of commercial packings. The semicircular
elements were installed at a 90 degree tray angle
in order to achieve good liquid distribution
across the column section. Resistance thermom-
eters were installed directly in the structured
packings at close intervals to each other to allow
the temperature profles to be measured as accu-
rately as possible.
To compensate for heat losses of the column,
each individual column element is insulated and
equipped with electric tracers. The tracers are
set in accordance with the temperature level for
each experimental run. As a rule, heat balances
of approximately 105 and 110 per cent of the
theoretically required heat quantity are achieved
at the test facility. In order to achieve steady-
state conditions and thus guarantee stable
operation with sustainable results, the column
was operated continuously in a number of runs,
each lasting fve days at least. The total mass and
heat balances were recorded at hourly intervals
and balances for each component were also
listed separately.
Figure 9 shows the temperature profle
recorded on the ED side and stripper side
sections of the column for one test phase
compared with the simulated temperature
profle. The correlation between the two profles
is extremely good, especially in the divided wall
section of the column. This clearly demonstrates PTQ Q3 2001 7
Figure 8 Realisation
that Krupp Uhde’s existing simulation model can
also be applied to the new process equipment.
Figure 10 illustrates the results of two evalu-
ated test phases with a C6 cut of pyrolysis
gasoline and reformate respectively. The respec-
tive values obtained in the pilot plant for the
benzene content in the raffnate, the content of
non-aromatics in the benzene and the heat duty
are compared with the corresponding simulation
The heat duties for the pilot plant column were
only around 5 per cent higher than calculated for
the same product purities. This confrms the
substantial energy
savings of progres-
sive extractive
distillation (with
only one column)
over conventional
extractive distilla-
tion (with two
columns), arrived at
in the simulation
Two additional
facts which favour
the use of the
progressive extrac-
tive distillation were
observed in the pilot
plant operations. Surprisingly a very simple star-
tup behaviour and a very robust and stable mode
of operation could be noticed.
Economic viability
In order to ascertain how the concept of progres-
sive ED compares with the conventional
technology the required investment costs were
calculated. This was done on the basis of a
completed project for conventional benzene ED
to allow a direct comparison between the two
methods. The progressive ED was designed for
the same general parameters. The fndings of the
8 PTQ Q3 2001
Figure 9 Temperature profiles
Figure 10 Comparison of simulation and pilot plant test runs
pilot tests were also taken into account.
The cost of the designed process vessels and
machinery was then calculated using up-to-date
databases for material prices. A substantial part
of the equipment is no different from the conven-
tional technology and could therefore be adopted
directly from the completed project.
Bulk materials and construction costs were
calculated using a common factor calculation
method and verifed and adjusted on the basis of
the completed project. Engineering costs were
calculated in the usual way for such projects and
then also verifed on the basis of completed
The fnal cost estimate made in this way
revealed a cost advantage of approximately 20
per cent for progressive ED, which was lower
than expected. This is partly due to the lower
condensation temperature at the ED head which
is caused by the vacuum operation and which
thus requires more condensing surface. However,
the economic advantage of progressive ED
becomes clearer when the energy consumption
and utilities consumption are also considered.
If the different temperature levels for the inte-
gration of external energy are taken into account,
a cost saving in steam consumption of approxi-
mately 20 per cent can be assumed in the case of
progressive ED. Cooling water costs are also
reduced by approximately 10 per cent. The elec-
tric energy requirement remains unchanged.
For an aromatics plant which recovers approx-
imately 40t/h of high purity benzene from 50t/h
of a pyrolysis gasoline cut, an operating cost
saving of at least DM1 million per annum can be
expected (approximately DM3 per tonne of
benzene produced). If the investment cost
savings for a plant of this size are then spread
over six years through allocation to the benzene
quantity produced, this refects an additional
saving of approximately DM2 per tonne.
This may be an insignifcant amount with
current benzene prices of approximately DM800.
However, if the already highly developed state-
of-the-art in aromatics extraction is taken into
account, this may prove to be the decisive factor
in favour of the more modern alternative. Also,
the high oil prices at the time of writing are an
indication of the fact that energy is not expected
to become cheaper in the future.
This article is based on a paper presented at the European
Refining Technology Conference, Rome, 13-15 November 2000.
Gerd Emmrich is research and development manager in Krupp
Uhde’s Oil and Gas Division. He graduated as a chemical engineer
from Rheinisch Westfaelische Technische Hochschule, Aachen,
and is involved in the development of various refining processes
in the field of refineries and petrochemicals.
Helmut Gehrke is head of Krupp Uhde´s laboratory/pilot plant at
Ennigerloh, Germany. He holds an MSc and a PhD in chemistry
from the University of Essen and his main fields of activities are
thermal separation processes and GC analytics.
Uwe Ranke is head of the process department at Oil & Gas of
Krupp Uhde. During his professional career he has been working
in the fields of hydrocarbon processing and gasification for 15
years. He holds a PhD from the University of Bochum. PTQ Q3 2001 9 8 PTQ Q3 2001

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