Optimization of Propylene—Propane Distillation Process*

S. M. MAUHAR**, B. G. BARJAKTAROVIĆ, and M. N. SOVILJ

Department of Chemical Engineering, Faculty of Technology,

University of Novi Sad, YU-21000 Novi Sad
e-mail: [email protected], [email protected], [email protected]

Received 1 April 2004

Dedicated to the 80th birthday of Professor Elemír Kossaczký

Optimization of distillation process, based on the real operating data taken from the factory, was
carried out using Aspen Plus simulation engine. A need for the optimization came from the fact
that the feed stream quality had been significantly changed recently, together with some of the
process parameters. The right combination of pressure and reflux rate was to be found in order to
minimize the energy consumption in the reboiler and to obtain the required product purity. The
real column efficiency was found and the possibility of column capacity enlargement was tested.

Distillation is an important unit operation in the THEORETICAL

polypropylene production. The biggest polypropylene
producer in Serbia and Montenegro is HIPOL Com- The Soave—Redlich—Kwong equation of state was
pany from Odžaci, which uses the process based on the the chosen thermodynamic property model, since it
Mitsubishi technology [1]. Propylene is polymerized in can be used for hydrocarbon systems that include
two mixed flow reactors in homogeneous phase, using common light gases (CO2 , N2 ) [2]. The form of the
a highly active catalyst. High-purity propylene (99.2 equation of state is
mole %) is needed in a reactor section because even
small amounts of certain components (such as water, RT a(T )
P = − (1)
ethane, ethylene, CO, etc.) could deactivate the cata- vm + c − b (vm + c) (vm + c + b)
lyst.
Raw material is the mixture of propylene, propane, where T is temperature, P pressure, vm denotes molar
methane, ethylene, C-4 fraction, hexane, water, hydro- volume, and
gen, N2 , and some other components from a petro-
chemical plant. Due to a high feed stream purity



a= xi xj aij + a

wi x2w xi (2)
propylene has to be separated from propane and the
i j i
other impurities in the distillation column. After leav-
ing a drying section, the mixture potentially contain- aij = aji ; aij = (ai aj )0.5 (1 − kij ) (3)
ing small amount of water goes to a distillation column kij = aij + bij T ; kij = kji (4)
where it is separated to give high-purity propylene.

The aim of this paper was simulation of the b= xi bi (5)
i
propylene—propane distillation column using Aspen

Plus 11.1 simulation engine provided by Aspen Tech- c= xi ci (6)
nology in order to estimate the influence of the main i
operating parameters on the product composition and
reboiler duty [2, 3]. For this purpose, the process pa- In these equations xi and xj are mole fractions of
rameters were monitored for 14 h and measured every component i and j in the mixture. SRK model has sev-
30 min. The average value of each parameter (flow eral important corrections comparing to the Redlich—
rate, composition, etc.) was compared with the com- Kwong—Soave model, which is based on the same
puter simulation. equation. First of all, a volume translation concept

*Presented at the 31st International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare,
24—28 May 2004.
**The author to whom the correspondence should be addressed.

386 Chem. Pap. 58 (6) 386—390 (2004)

OPTIMIZATION OF PROPYLENE—PROPANE DISTILLATION PROCESS

introduced by Peneloux et al. [4] is used to improve

E-004 Gas
molar liquid volume calculated from the cubic equa-
tion of state. Further, the phase equilibrium calcula-
tions for mixtures containing water are improved by V-003
using the Kabadi—Danner  modification for the mix-
ing rules [5]. The term i a

wi x2w xi is used only when Feed
Reflux
the Kabadi—Danner option is enabled, where
P-002
C-001 C-002
aij = a
wj ; a
wj = (aw aj )0.5 (1 − kwj ) (7)
  0.8 


T
awi = Gi 1 − (8)
Tcw

In these equations w represents water and j hydro- E-003

carbon; kwj is obtained from experimental data; Tcw
is the critical temperature of water; Gi is the sum of
Product
the group contribution of different groups which make Bottom P-001
up a molecule of hydrocarbon. For pure components
parameters ai , bi , and ci are given by the following Fig. 1. Schematic picture of the propylene—propane distilla-
equations tion column.

ai = f (T, Tci , Pci , ωi ) (9)

which corresponds to the stage 156 in the one-column
bi = f (T, Tci , Pci ) (10)
  simulation model (numbered from the top, starting
RTci with the top stage) and the product stream leaves
ci = 0.40768 (0.29441 − zRAi ) (11)
Pci C-002 column at the stage 12 (also numbered from
the top, but starting with the condenser). A reason
Tci , Pci being the critical temperature and pressure, for this nonconventional withdrawal of the distillate
and ωi , zRAi correspond to acentric and compressibil- stream is the fact that there is a high concentration of
ity factor of the pure component i, respectively. some light components at the top of the column, which
could later on poison the catalyst. The column inter-
EXPERIMENTAL nals data [1] as well as the temperature and pressure
ranges measured in the column are given in Table 1.
The propylene—propane distillation column is The feed stream is at 2.3 MPa and 17 ◦C and it is
schematically shown in Fig. 1. Because of the high 100 % liquid.
product purity and the low relative volatility, the num- Table 2 shows the process parameters necessary for
ber of stages required for this separation is very high. the computer simulation. As mentioned before, these
Two towers are installed because a single tower would values are average for the period of 14 h of the column
be too tall (C-001 and C-002), C-001 having 122 stages operation. The flow rates, pressure and temperature
(including reboiler) and C-002 with 121 stages (includ- values were measured in-line and taken directly from
ing condenser). Two pumps are noted as P-001 and the control board of the distillation process, while the
P-002. The reboiler, condenser, and reflux vessel are sample composition of each material stream was ana-
noted as E-003, E-004, V-003, respectively. The feed lyzed using a GC-FID in the laboratory.
stream is inserted in the column C-001 on the stage 85, A computer simulation was applied for the descrip-

Table 1. Column Internals Data and Temperature and Pressure Ranges Measured in the Column

Diameter/m 2.1
Number of stages 241
Tray type Sieve + valve (each fourth plate is with valves), 2 passes, hole diameter 0.039 m, 388 holes per tray
Tray spacing/m 0.45
Weir height/m 0.0545
Downcomers Side Centre
Width at a top/m 0.35 0.28
Width at a bottom/m 0.35 0.28
Clearance/m 0.0445 0.0445
P/MPa 1.595—1.756
t/ ◦C 35.7—49.2

Chem. Pap. 58 (6) 386—390 (2004) 387

 S. M. MAUHAR, B. G. BARJAKTAROVIĆ, M. N. SOVILJ

Table 2. Measured and Simulated Material Stream Composition

F /(kg h−1 ) D/(kg h−1 ) B /(kg h−1 ) G/(kg h−1 )

Stream
component Measured Simulated Measured Simulated Measured Simulated Measured Simulated

Hydrogen 0.13 0.13 – – – – 0.13 0.13

Nitrogen 1.76 1.76 – 0.01 – – 1.76 1.75
Ethane 0.16 0.16 – 0.09 – – 0.16 0.07
Propane 178.73 178.73 37.57 37.87 141.10 140.81 0.06 0.05
Propylene 5304.48 5304.48 5262.43 5262.03 28.16 28.45 13.89 14.01
Butane 2.20 2.20 – – 2.20 2.20 – –
Heptane 8.54 8.54 – – 8.54 8.54 – –
Total 5496 5496 5300 5300 180 180 16 16

tion of the distillation column. RADFRAC unit oper-

0.998
ation model from the Aspen Plus model library was
used [2, 3, 6]. RADFRAC is a rigorous model for sim-
0.996
ulating all types of multistage vapour-liquid fraction-
ation operations. Although RADFRAC assumes equi-
0.994

xD,propylene
librium stages, it is possible to specify Murphree effi-
ciency to match plant performance. Two columns used
in the polypropylene plant are considered as one by 0.992
the simulation program since the column 2 acts as an
extension of the column 1 (the column division into 0.990
two parts comes as a physical restriction of the RAD-
FRAC unit operation model). 0.988
The column efficiency was unknown parameter.
30 40 50 60 70 80 90
For this system propylene was considered as a light key
η /%
component and propane as a heavy key component.
In Design Specs of the Flowsheeting Options menu Fig. 2. The propylene mole fraction in the distillate as a func-
propylene and propane mass fractions in the distillate tion of the column efficiency.
and bottom stream were used as design specifications
while the column efficiency was the manipulating vari-
able. Determined stage efficiency was used for all other 17
0.994
simulation runs.
0.992 16
The reflux rate was the manipulating variable in a
sensitivity analysis performed in order to estimate its 15
0.990
influence on some important process parameters such
as the reboiler duty and the product purity. These 14

Q reb/(GJ h-1)
0.988
x D,propylene

simulations were performed with the aim to investi-

0.986 13
gate the influence of feed flow rate increase on the
propylene production. 0.984 12
A tray rating calculation was performed in order
to estimate how the feed flow rate variation will af- 0.982 11
fect the column hydrodynamics parameters such as
0.980 10
the flooding factor. 30000 34000 38000 42000 46000
R /(kg h -1)
RESULTS AND DISCUSSION
Fig. 3. Influence of the reflux flow rate on the reboiler duty
The column efficiency was varied from 30 % to (◦) and product purity ( ).
100 %. A target value for the propylene (propane)
mass fraction in the distillate stream was 0.9929
(0.00709) and in the bottom stream 0.1564 (0.7839). was run in order to obtain the material streams com-
As a result, the efficiency was found to be 40.75 %, rel- positions. Results of this simulation are also given in
atively low but realistic value, according to [7]. Fig. 2 Table 2 for comparison with the real process data. It is
shows the variation of propylene mole fraction in the worth mentioning that the simulation results fit very
distillate (xD,propylene ) with the column efficiency (η). well the measured data.
With the overall efficiency determined simulation During sensitivity analysis, based on variation of

388 Chem. Pap. 58 (6) 386—390 (2004)

OPTIMIZATION OF PROPYLENE—PROPANE DISTILLATION PROCESS

Table 3. Column Process Parameters Variation with the Feed 1.00

Flow Rate
0.95
F/(kg h−1 ) R/(kg h−1 ) Qreb /(GJ h−1 ) (Qreb /F)/(GJ kg−1 )
0.90
5496 43211 15.43 2.81 0.85
7000 56200 19.98 2.85
0.80

FF
9000 72000 25.73 2.86
0.75
0.70
0.65
the reboiler duty (Qreb ) and the propylene purity
(xD,propylene ) with the reflux flow rate, the indepen- 0.60
dent variable R was varied from 30000 kg h−1 to 46000 0.55
kg h−1 . Fig. 3 summarizes the results of this simula- 0 20 40 60 80 100 120 140 160 180 200 220 240
tion. As expected, variation of the reboiler duty with
NS
the reflux flow rate was linear. It is obvious that the
energy consumption in the reboiler is reduced decreas- Fig. 4. The flooding factor as a function of the plate number
ing the reflux flow rate. On the other hand, this de- for the feed flow rates of 5496 ( ), 7000 (◦), and 9000
crease affects the product purity by reducing it. As it (
) kg h−1 .
is shown in Fig. 3, the minimum reflux flow rate to
obtain the required distillate purity of 99.2 mole %
of propylene is 39600 kg h−1 (η = 0.4075), to which 1.2
corresponds the reboiler energy consumption of 14.15
GJ h−1 . 1.1
In order to investigate the column capacity the dis-
tillate to feed and bottom to feed mass flow ratios were 1.0
kept unchanged (D/F = 0.96, B/F = 0.033) while the
Ki,K1/K2

reflux flow rate was adjusted to give 99.3 mass % of

0.9
propylene in the distillate. The reflux flow rate, re-
boiler duty, and specific heat consumption (heat con-
sumption per ton of feed, Qreb /F ) are presented in 0.8
Table 3 for the feed flow rates of 5496 kg h−1 , 7000
kg h−1 , and 9000 kg h−1 . The simulation results show 0.7
that the specific heat consumption is about the same
for all the feed stream flow rates. Working on long 0.6
terms this could be quite profitable. But before draw- 1.2 1.3 1.4 1.5 1.6 1.7 1.8
ing a general conclusion, real column flexibility should P/MPa
be checked. It means that the tray rating calcula-
Fig. 5. Pressure influence on the propylene—propane phase
tion (with detailed constructive description of a plate) equilibrium at t = 25 ◦C. • K2 (factor for propane),
should be done in order to obtain a value of the flood- ◦ K1 (factor for propylene),
K1 /K2 .
ing factor which should not exceed unity.
The tray rating calculation gives the flooding fac-
tor (defined as a ratio between the actual vapour ve- heating and cooling fluid flow rates and temperatures.
locity and the vapour velocity, at which the flooding A sudden flooding factor decrease between the
point is reached, FF) for a tray in the column as well stage 12 and 13 is a consequence of the distillate
as the maximum flooding factor for the entire col- stream withdrawal from the stage 12, which signifi-
umn. This calculation was tested for the selected feed cantly reduces the liquid flow rate in the column. A
stream flow rates of 5496 kg h−1 , 7000 kg h−1 , and similar situation occurs between the stage 156 and
9000 kg h−1 . The most important input hydraulic pa- 157: the flooding factor increases due to the feed
rameters of a plate column used during the calculation stream input on the stage 156.
are given in Table 1. Fig. 4 shows the flooding factor Another possibility for the operation costs reduc-
as a function of the plate number (NS ). The maximum tion is a pressure reduction in the column. Apart from
flooding factors for the three selected flow rates were the boiling point temperature decrease, the pressure
0.6071, 0.7872, and 1.014, respectively. Theoretically, reduction influences the quantity of propylene in the
the column could be operated even at a feed flow rate vapour phase for propylene—propane mixtures by in-
a bit lower than 9000 kg h−1 . But reaching this point, creasing it. This behaviour is shown in Fig. 5, for the
another restriction should be taken into account: the temperature of 25 ◦C [8]. The propylene—propane rel-
reboiler and condenser heat transfer area as well as the ative volatility (a ratio between the propylene and

Chem. Pap. 58 (6) 386—390 (2004) 389

 S. M. MAUHAR, B. G. BARJAKTAROVIĆ, M. N. SOVILJ

Table 4. Pressure Influence on the Energy Consumption of the Distillation Process

P/MPa ttop / ◦C tbottom / ◦C R/(kg h−1 ) Qreb /(GJ h−1 )

1.595 36.7 50.5 43211 15.43

1.4 31.4 45.4 39200 14.31
1.2 25.3 39.3 35650 13.29

propane K factors) increases with the pressure de- R gas constant in eqns (1) and
crease. (11) J K−1 mol−1
The following analysis should give a path for the R reflux mass flow rate kg h−1
pressure adjustment at the top of the column. If the vm molar volume m3 mol−1
goal is to obtain the distillate with 99.3 mass % of x mole fraction in liquid phase
propylene, then the adjusted reflux flow rates for ob- y mole fraction in vapour phase
taining this purity are given in Table 4 (for the pres- zRA Rackett’s compressibility factor
sures at the top of the column of 1.4 MPa and 1.2
MPa and D/F and B/F unchanged). Also, Table 4 Greek Letters
shows the temperatures at the top and the bottom
of the column, together with the reboiler heat duty. η Murphree efficiency
However, some process limitations, such as the lowest ω acentric factor
cooling water temperature which can be achieved, do
not permit to operate under the pressure at the top of Subscripts
the column lower than 1.2 MPa. On the other hand,
working under the pressure of 1.4 MPa would result bottom bottom of the column
in significant energy saving (14.31 GJ h−1 instead of c critical
15.43 GJ h−1 ). m molar
i, j components
reb reboiler
SYMBOLS top top of the column
w water
a parameter of SRK equation of state J mol−1
B bottom mass flow rate kg h−1 REFERENCES
b parameter of SRK equation of
state m3 mol−1 1. Polypropylene Plant Process Documentation. Mitsubishi
Petrochemical Engineering Co., 1980.
c parameter of SRK equation of
2. Aspen Plus 11.1 Documentation, Unit Operation Mod-
state m3 mol−1 els and Physical Property Methods and Models. Aspen
D distillate mass flow rate kg h−1 Technology Inc., 2001.
F feed mass flow rate kg h−1 3. Seider, W. D., Seader, J. D., and Lewin, D. R., Process
FF flooding factor Design Principles. Wiley, New York, 1999.
G the sum of the group contribution of groups 4. Peneloux, A., Rauzy, E., and Freze, R., Fluid Phase
which make up a molecule of hydrocarbon Equilib. 8, 7 (1982).
G gas mass flow rate kg h−1 5. Kabadi, V. and Danner, R. P., Eng. Chem. Process
g mass fraction Des. Dev. 24, 537 (1985).
K K factor (K = y/x) 6. Smejkal, Q. and Šoóš, M., Chem. Eng. Process. 41, 413
k binary interaction coefficient for SRK equa- (2002).
7. Raschety osnovnykh protsessov i apparatov neftepe-
tion of state
rerabotki. Spravochnik pod redaktsiei E. N. Sudakova.
NS tray number (Calculations of the Principal Processes and Appara-
T thermodynamic temperature K tuses at the Oil Processing. A Handbook Edited by E.
◦
t Celsius temperature C N. Sudakov.) Khimiya, Moscow, 1979.
P pressure MPa 8. McWilliams, M. L. and Charlestone, W. V., Chem.
Q heat duty GJ h−1 Eng. 29, 138 (1973).

390 Chem. Pap. 58 (6) 386—390 (2004)