THERMODYNAMICALLY EFFICIENT DISTILLATION:

ETHYLENE RECOVERY

D. B. MANLEY
Department of Chemical Engineering, University of Missouri - Rolla
Rolla, Missouri 65409, USA

Keywords: Thermodynamics, Distillation, Ethylene, Olefins, Separations

Abstract
The problem of recovering ethylene and byproducts from the steam pyrolysis of light hydrocarbons is discussed.
Opportunities for improved efficiency using distributed distillation, recycle coupling, heat pumping, and mixed
refrigeration are presented. Emphasis is placed upon energy efficiency with potential savings in capital costs as applied
to refrigerated processes.

1. Introduction ethylene and propylene products, and ethylene and ethane have
Significant savings in utilities may be achieved by using heat similar boiling points as do propylene and propane. As a result large
integrated distillation in innovative configurations. On a percentage diameter columns with many trays are required, and these
basis, capital savings are somewhat smaller than utility savings; but separations are usually accomplished at the end of the recovery
they are not negligible. The improvements are at the expense of process. The recovered products are produced at ambient
increased complexity, and incur the risk of new technology. temperature and pressures sufficient for downstream processing or
However, conventional equipment may be used, and only the
configurations changed. FIGURE 1
The innovative configurations may be generated by observing MULTIPLE FEED DEMETHANIZER FIRST
thermodynamic inefficiencies in conventional process designs. DISTILLATION COLUMN SEQUENCE
These are typically apparent in relationships between the primary
process variables such as temperature, pressure, and composition. H2
The relationships may be observed through conventional analysis
such as McCabe - Thiele diagrams, composite heating and cooling
curves, and temperature - composition plots. C1 C2=
Because of the multiple products produced in the production of
C2
ethylene by steam pyrolysis of light hydrocarbons and because of the
high pressures and low temperatures required for their recovery, DMR C2S C3=
ethylene manufacture provides several opportunities for economical
process improvements through improved thermodynamic efficiency.
DER C3S
2. Conventional Ethylene Recovery
Table 1 shows the feeds and products normally encountered in
the ethylene recovery process. Both the gas (ethane) and liquid
FEED DPR C3
Table 1
Feeds and Products for Ethylene Recovery
Gas Liq Products C4+
Pyro Pyro H2 CH4 C2H4 C2H6 C3H6 C3H8
Deg C 38.7 40.3 32.2 32.2 32.2 32.2 37.8 37.8 for a pipeline.
BarA 1.4 1.4 34.5 6.2 111.3 6.9 15.6 13.0 Figure 1 shows a conventional ethylene recovery distillation
Mole Percent process (Kniel, et. al., 1980). The feed has been compressed,
H2 32.5 11.5 95.0 9.9 treated, dried, and partially hydrogenated to remove acetylene. Part
CH4 4.8 27.6 5.0 90.0 0.05 of the methane and all of the ethylene and heavier components are
C2H4 31.7 30.8 0.1 99.90 0.5
separated from the hydrogen and remaining methane by
C2H6 24.6 3.7 0.05 99.0 0.05
condensation at low temperature. The liquids are then fractionated
C3H6 0.5 9.6 0.5 99.90 0.5
C3H8 0.1 0.2 0.05 99.0 under pressure into products in demethanizer (DMR), deethanizer
C4+ 0.8 11.2 0.5 (DER), depropanizer (DPR), C2 splitter (C2S), and C3 splitter (C3S)
H20 5.0 5.5 distillation columns.
NBP C -253 -162 -104 -89 -48 -42
3. Thermomechanically Integrated Distillation
(naphtha) feeds contain about 31% ethylene, but the light and heavy As discussed above the C2 and C3 splitter columns are large
byproducts differ considerably. The pyrolysis reactions are favored and expensive, and accurate thermodynamic properties are necessary
by low pressure. However, because of the low boiling points of the for their economical design. Figure 2 shows the relative volatility of
products, high pressures and low temperatures must be used for their propylene to propane on isotherms as functions of liquid phase
separation by distillation. High purity is required for both the composition. The logarithm of relative volatility is plotted because

Page 1 of 6
 Figure 2
Propylene Propane Relative Volatility
Logarithm of Relative Volatility
0.30 -20 F
10 F
0.20
70 F 40 F
100 F
130 F
0.10
0.00
0 0.2 0.4
Mole Fraction Propylene in Liquid
it is closely related to the number of stages and the reflux required for
the separation. At the high propylene end the relative volatilities are
small, and they don’t change much with temperature. This implies
that reducing the column pressure, which also reduces the
temperature, will not reduce the column size significantly. However,
at the high propane end the relative volatilities are larger, and they
may be increased significantly by reducing the column pressure. The
same phenomenon occurs in the case of ethylene and ethane because
of the similar olefin / paraffin interaction between the molecules.
The analysis points toward using dual pressure columns for C2
and C3 splitting with the stripping sections at a lower pressures than
the rectifying sections. Normally, this would require an extra
compressor which would be too expensive and unreliable. However,
refrigeration or heat pumping, both of which require compression,
must be used for C2 splitting anyway; and heat pumping may be
used for C3 splitting. Consequently, there is an opportunity to
combine the compression functions using “thermomechanical
integration” (Greene et. al., 1994; Manley and Haddad, 1995) as
shown in figure 3.
The rectifying section in figure 3 is conventional. However, a
few stages below the feed a heat pumped interreboiler is used to
partially condense the overhead while simultaneously compressing
the vapors from the low pressure stripping section below. A
similarly heat pumped reboiler is used to condense additional
overhead vapors. Because the relative volatility of olefin to paraffin
is much larger in the low pressure stripping section, significantly less
boilup is required, and more heat may be used in the interreboiler
0.6 0.8 1
than in a conventional, single pressure, column. The effect is
enhanced because the olefin / paraffin ratios in the feeds generated
by pyrolysis are high by design to increase conversion. For a liquid
overhead product a small amount of addition refrigeration may be
necessary to remove the energy required to drive the compressor.
Figure 4 summarizes the advantages of the more thermodynamically
efficient process.
Figure 4
Advantages of Thermomechanically Integrated Distillation
C Less compressor power than conventionally heat pumped
process
C Smaller and lower pressure stripping section
C Combined condenser / (inter)reboiler
C Essentially independent of external refrigeration system.

FIGURE 3 4. Distributed Distillation of Ethylene

THERMOMECHANICALLY INTEGRATED Another inefficiency inherent in conventional ethylene recovery
OLEFIN / PARAFFIN SPLITTER may be observed in figure 1 by keeping track of the phase changes
necessary to process the major (ethylene) component. Ethylene
OLEFIN enters the recovery process as a gas, is condensed in the
demethanizer feed system, is revaporized in the deethanizer, and is
finally recondensed again as a liquid product from the C2 splitter.
A total of three complete phase changes must be accomplished for
all the ethylene. A similar analysis for other products yields similar
conclusions. Propylene, for example, is condensed in the
demethanizer feed system, revaporized in the depropanizer, and
recondensed again as a liquid product from the C3 splitter. Are all
these phase changes really necessary?
REFRIG
Figure 5 shows an “ethylene distributor” column (Conroy et.
FEED al., 1996) which separates methane from ethane in the presence of
hydrogen while distributing ethylene between the overhead and
bottoms products. A preliminary separation of the C3 and heavier
components is not shown in the figure. The ethylene distributer
column overhead is processed in a downstream demethanizer
column, and the ethylene distributor bottoms is processed in a
downstream C2 splitter column. In a properly designed process
approximately one half of the ethylene in the feed will be distributed
through the demethanizer and about one half will be distributed
through the C2 splitter. However, the half which passes through the
demethanizer must be condensed only once since ethylene product
is produced in the demethanizer bottoms. Consequently, the total
number of phase changes necessary to produce the ethylene product
is reduced, and the thermodynamic efficiency of the process is
improved.
PARAFFIN

Page 2 of 6
 FIGURE 5 FIGURE 7
DISTRIBUTED DISTILLATION OF ETHYLENE DISTRIBUTED DISTILLATION OF ETHYLENE
WITH RECYCLE COUPLING
HYDROGEN
METHANE
HYDROGEN
HYDROGEN METHANE
METHANE
HYDROGEN
ETHYLENE
DEMETHANIZER METHANE
ETHYLENE
DEMETHANIZER
HYDROGEN
METHANE ETHYLENE
ETHYLENE HYDROGEN
ETHYLENE DISTRIBUTOR
ETHANE METHANE ETHYLENE
ETHYLENE
ETHYLENE DISTRIBUTOR
ETHANE
C2 SPLITTER
ETHYLENE
ETHANE C2 SPLITTER
ETHYLENE
ETHANE
ETHANE

5. Recycle Coupling ETHANE

Figure 6 shows the liquid composition profile for the ethylene
distributor column in figure 5. The feed at about -66oF is separated FIGURE 8
into ethane free methane and ethylene on the top stage at about -70oF ETHYLENE DISTRIBUTOR WITH RECYCLE COUPLING
and into methane free ethane and ethylene on the bottom stage at 100
about -29oF. However, because of the presence of hydrogen, the
condenser must cool the overhead to about -103oF in order to LIQUID PHASE MOLE 80 ETHYLENE
generate the required reflux. This condensing process “remixes” FRACTION
methane and ethylene, which have been more completely separated 60
at the entrance to the condenser; and they must then be “reseparated”
in the downstream demethanizer column. A similar phenomenon 40
occurs to a lesser extent in the reboiler at about -28oF where ethane
20 ETHANE
and ethylene are “remixed” and must then be “reseparated” in the
downstream C2 splitter column. METHANE
0
-110 -100 -90 -80 -70 -60 -50 -40 -30 -20
FIGURE 6 STAGE TEMPERATURE, DEG F
ETHYLENE DISTRIBUTOR WITHOUT RECYCLE COUPLING
100 reduced.
ETHYLENE In figure 7 the ethylene distributor condenser and reboiler from
LIQUID PHASE MOLE

80 the figure 5 process have been replaced by an intercondenser on the

demethanizer and an interreboiler on the C2 splitter respectively. This
FRACTION

60 allows the same utilities to be used in both cases. However, because

40
ETHANE
20
METHANE
0 Figure 9 shows how thermomechanical integration, ethylene
-110 -100 -90 -80 -70 -60 -50 -40 -30
STAGE TEMPERATURE, DEG F
The mixing and separating occurring in the condenser and
reboiler of the ethylene distributor column may be eliminated by
using “recycle coupling” (Manley, 1996) as shown in figure 7. In
this case, the ethylene distributor column is refluxed using a liquid
sidedraw taken from the feed stage of the downstream demethanizer,
and the ethylene distributor column is reboiled using a vapor
sidedraw taken from the feed stage of the downstream C2 splitter column.
Figure 8 shows the effect of recycle coupling on the
composition profile in the ethylene distributor column. Remixing is
eliminated and consequently the separations required in the
downstream demethanizer and C2 splitter columns are significantly
of the improved thermodynamic efficiency when recycle coupling is
used, the reflux and reboil flows in the demethanizer and C2 splitter
are smaller in the case with recycle coupling. An added advantage of
the figure 7 process is the elimination of the demethanizer reboiler by
using overhead vapor from the C2 splitter to provide reboil vapor.
-20
distribution, and recycle coupling may be used in a
thermodynamically efficient process for the recovery of ethylene from
pyrolyzed ethane. The compressed, treated, dried, and hydrogenated
gases are cooled, and the C3 and heavier components are removed in
a deethanizer (DER) column. The deethanizer overhead feeds the
downstream ethylene distributor column (C2D), and reflux for the
deethanizer is provided through recycle coupling with the ethylene
distributor. An interreboiler and intercondenser are used on the
deethanizer and ethylene distributor respectively to provide optimum
integration with the utility systems. For the same reason, a
dephlegmator is used as the demethanizer (DMR) rectifying section.
Reboil for the deethanizer is provided through recycle coupling with

Page 3 of 6
the C2 splitter (C2S), and the C2 splitter is thermomechanically FIGURE 11
integrated with a bottoms heat pump. Finally, the demethanizer is PURE COMPONENT, MULTISTAGE,
reboiled using overhead vapor from the C2 splitter. The process CASCADED REFRIGERATION PROCESS
shown in figure 9 requires less capital and utilities than the
PROPYLENE
conventional process shown in figure 1 because it is more
REFRIGERATION
thermodynamically efficient.
CW
105 DEG F
FIGURE 9 229 PSIA
ETHYLENE RECOVERY FROM
50 DEG F
PYROLYZED ETHANE
123 PSIA
H2
C1
15 DEG F
63 PSIA

DMR
-15 DEG F
35 PSIA ETHYLENE
REFRIGERATION
C2= -35 DEG F
C2D
-40 DEG F 242 PSIA
20 PSIA
-70 DEG F
FEED DER C2S 122 PSIA

-110 DEG F
C3+ 52 PSIA

C2 -150 DEG F
16 PSIA
6. Mixed Refrigerant
The thermodynamic efficiency of the recovery process in figure
9 may be further improved by using mixed refrigerants because the -40oF. Propylene is used to absorb energy from the ethylene cycle and
cooling curves resulting from the recycle coupling, intercondensing, to provide refrigeration from about -40oF to +50oF. The energy
dephlegmation, and thermomechanical integration are less flat than absorbed by the propylene is rejected to cooling water at about 100oF.
When the refrigeration process of figure 11 is used to provide cooling
FIGURE 10 for a process with the cooling curve shown in figure 10, the resulting
PROCESS COMPOSITE COOLING CURVE composite cooling and heating curves shown in figure 12 result.
ETHYLENE CONDENSATION PROCESS In figure 12 the condensation of the ethylene and propylene
refrigerants is shown by the plateaus at -35oF and +105oF in the
80 cooling curve respectively. The vaporizing refrigerants are shown by
the seven plateaus below +90oF in the heating curve. The heating
TEMPERATURE, DEG F

40 curve for the cooling water is shown between +90oF and +100oF. The
sloping cooling curve from about +165oF to about +105oF represents
0
the desuperheating of the compressed propylene vapors. A similar
desuperheating curve for the ethylene refrigerant is combined with the
-40
ethylene condensation curve from about +54oF to about -35oF. The
combined processes require about 220 MMBtu/Hr of heat exchange.
-80
Several of the thermodynamic inefficiencies associated with
-120 using cascaded propylene / ethylene refrigeration for condensing
ethylene are summarized in table 2. Because the ethylene
-160 condensation curve is sloping and the refrigerant vaporization curves
0 10 20 30 40 50 60 70 are flat there is necessarily a nonuniform temperature driving force in
DUTY, MMBTU/HR the heat exchangers, and the minimum average temperature driving
force is limited to about half the temperature difference in
for a conventional process. Figure 10 shows the cooling curve for a refrigeration levels. A closer approach in the heat exchangers would
typical ethylene condensation process which may be used as a basis increase heat exchanger cost slightly, but would decrease compressor
for comparing refrigeration processes. and operating costs more than enough to compensate.
A conventional pure component, multistage, cascaded Similarly, the relatively flat condensation curve for the
refrigeration process is shown in figure 11. Pure ethylene refrigerant propylene refrigerant mismatches with the sloping heating curve for
is used as a refrigerant between about -70oF and -150oF, and the the cooling water. This limits the cooling water temperature rise
absorbed energy is rejected to pure propylene refrigerant at about

Page 4 of 6
unless the propylene condensing pressure is raised with
commensurately increased compression costs.
FIGURE 12
COMPOSITE HEATING AND COOLING CURVES
CONVENTIONAL REFRIGERATION PROCESS
150
110
70
TEMPERATURE, DEG F
30
-10
-50
-90
-130
-170
0 40 80 120 160
DUTY, MMBTU/HR
Although it is not apparent in the figures, partial flash
vaporization of the refrigerants through the refrigeration valves
contributes to compression costs since the vapors must then be
recompressed and recondensed without providing any process
cooling.
Finally, there is a limited selection of pure component
refrigerants so their properties cannot be optimized for an arbitrary
process application. Propylene is used for the high temperature cycle
in the conventional refrigeration process because it can be condensed
at 100oF and can be practically vaporized as low as -54oF. An even
lower vaporization temperature would be advantageous since less
heat transfer would be necessary in the cascade interexchanger
between the high and low temperature cycles. However, ethane, the
next lower boiling pure component becomes supercritical at 90oF and
cannot be condensed with cooling water.
TABLE 2
THERMODYNAMIC INEFFICIENCIES
ASSOCIATED WITH CONVENTIONAL REFRIGERATION
MISMATCH OF PROCESS COOLING AND REFRIGERANT HEATING
CURVES
MISMATCH OF REFRIGERANT COOLING AND WATER HEATING
CURVES
IRREVERSIBLE FLASHING THROUGH VALVES
LIMITED SELECTION OF REFRIGERANT PROPERTIES
Figure 13 shows a seven level cascaded mixed refrigeration
process (Manley, 1997a,b) suitable for providing cooling for a process
with the cooling curve shown in figure 10. The high temperature
cycle mixed refrigerant comprised of ethylene, ethane, propylene, and
FIGURE 13
MULTILEVEL, CASCADED, MIXED REFRIGERANT PROCESS
110 PSIA 402 PSIA
-147 DEG F
-123 DEG F
A -100 DEG F
21
PSIA
-55 DEG F
57
PSIA
-12 DEG F
122
PSIA
29 DEG F
218
PSIA
A
200 64 DEG F
338
CW 100 DEG F
PSIA
CW 539 PSIA
525
343 MLBS/HR
PSIA
propane is completely condensed at 100oF and 525 psia using cooling
water. To avoid excessive flashing in the 59oF level refrigeration
valve the condensed refrigerant is subcooled simultaneously with the
process fluid in a multistream heat exchanger using 59oF level
refrigerant as a heat sink. The 59oF level mixed refrigerant pressure
of about 338 psia is chosen so that the 59oF level refrigerant stream
is about 5oF colder than the subcooled stream, and so that the
completely vaporized 59oF level refrigerant is heated to the cooling
water temperature of about 90oF. The composition of the mixed
refrigerant is chosen so that the refrigerant condenser pressure is a
practical maximum of about 525 psia, and so that the heating curve
for the mixed refrigerant is approximately linear or slightly convex.
The completely vaporized 59oF level mixed refrigerant is mixed with
desuperheated compressed refrigerant from the lower levels, and is
compressed to the water cooled condenser pressure.
The 59oF level refrigeration loop described above is essentially
a conventional single loop mixed refrigeration process operating from
59oF to 90oF and providing refrigeration to cool the precss stream
from about 100oF to about 64oF. However, the 59oF level also
provides refrigerant subcooling for the lower levels and provides fifth
stage compression for the combined refrigerants from the lower
levels.
Four lower temperature loops at 24oF, -17oF, -60oF, and -105oF
are also shown of the high temperature cycle in figure 13. Each of
these loops is similar to the 59oF loop, and the entire, five stage, cycle
provides refrigeration continuously to -105oF with a single mixed
Page 5 of 6
 approaches require greater heat exchange area. The power reductions
FIGURE 14
COMPOSITE HEATING AND COOLING CURVES
will contribute directly to operating and capital cost reductions, and
MULTILEVEL MIXED REFRIGERANT PROCESS the reduced volumetric flows will contribute significantly to capital
cost reductions. The increased heat exchange and the smaller
140 temperature approaches will greatly increase the heat exchange area
for the mixed refrigerant process, and the higher compressor
100 discharge pressures will add somewhat to the equipment costs. The
optimal overall process will depend upon an economic balance of
these factors. However, the multilevel mixed refrigerant process has
60
the advantage because of its higher thermodynamic efficiency.
TEMPERATURE, DEG F

20
-20
-60
-100
-140
-180
0 40 80 120 160
DUTY, MMBTU/HR
refrigerant.
A single loop low temperature mixed refrigerant cycle starting
with a pressure of about 408 psia and a condensing temperature of
about -100oF, which is the lowest process temperature achieved in the
high temperature cycle, is used to further cool the process in two
steps to -123oF and then to -147oF while simultaneously subcooling
the mixed refrigerant. The evaporated refrigerant is then compressed
to the condenser pressure and is sequentially cooled and totally
condensed by the high temperature cycle.
Figure 14 shows the composite cooling and heating curves
when the mixed refrigeration process of figure 13 is used to provide
cooling for a process with the cooling curve shown in figure 10. The
close temperature approaches are apparent, and the cooling water is
heated to about 120oF. About 240 MMBtu/Hr of total heat exchange
is required. Because of the subcooling of the mixed refrigerant, this
is about 20 MMBtu/Hr more than in the conventional process shown
in figure 12. The weighted average temperature driving force in the
figure 14 process is less than one half that in the figure 12 process.
Table 3 gives a comparison of several important design and cost
considerations for the conventional cascaded propylene / ethylene
(CONV) and the proposed cascaded multilevel mixed refrigerant
(MLMR) processes. The multilevel mixed refrigerant process
achieves large improvements in compressor power, compressor
suction volumetric flow, cooling water usage, and cooling water
pumping power. However, because of the subcooling some
additional heat exchange is required, and the reduced temperature
TABLE 3
COMPARISON OF REFRIGERATION PARAMETERS
7. Discussion
Several opportunities for the improvement of the thermodynamic
efficiency of processes designed for the recovery of ethylene and
byproducts from pyrolyzed hydrocarbons have been described. As a
result the energy efficiency and resulting utilities costs of the process
are significantly improved. However, each of these improvements
adds additional complexity to the process with associated implications
for process control and installation costs.
The process control questions may be addressed through
appropriate hold-up volumes placed strategically in the process and
through appropriate computer control systems.. The installation costs
may be mitigated through modularization of several pieces of
200 240
equipment into a single unit. However, these subjects are beyond the
scope of the present discussion. The combined effect is a more
economical and reliable operating unit with significantly lower capital
and operating costs.
References
Conroy, B. P., Haddad, H. and Manley, D. B., “Ethylene Recovery
Using Distributed Distillation and Mixed Refrigerants”,
Presented at the AIChE Spring National Meeting, New Orleans,
February 26 (1996).
Greene, D. G., Haddad, H. and Manley, D. B., “Thermomechanically
Integrated Distillation of Ethylene from Ethane”, Proceedings of
the 6th Ethylene Producers Conference, American Institute of
Chemical Engineers, New York (1994).
Kniel, L., Winter, O. and Stork, K., Ethylene, Keystone to the
Petrochemical Industry, Marcel Dekker, New York (1980).
Manley, D. B. and D. G. Greene, “Thermodynamically Integrated
Distillation of Close-Boiling Light Hydrocarbons”, U. S. Patent
No. 5,435,436, July 25 (1995).
Manley, D. B., “Process Designs for Ethylene Recovery”, 5th World
Congress of Chemical Engineering, American Institute of
Chemical Engineers, Volume 4, pages 317-322, July 14-18
(1996).
Manley, D. B., “Multilevel Mixed Refrigeration for Ethylene
Recovery”, Proceedings of the 9th Ethylene Producers
Conference, American Institute of Chemical Engineers, New
York (1997a).
Manley, D. B., “Mixed Refrigerants in Ethylene Recovery”, U. S.
Patent No. 5,626,034, May 6 (1997b).

CONV MLMR RATIO

COMPRESSOR POWER HP 16,990 14,409 85%
COMPRESSOR SUCTION ACFM 76,614 35,836 47%
HEAT EXCHANGE MMBTU/HR 219.75 240.00 109%
AVG. TEMP. DIFF. DEG F 11.9 5.5 47%
COOLING WATER MLB/HR 11,130 3,492 31%
PUMP POWER HP 867 275 31%

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