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Dynamic Simulation of Demethanizer

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Article in Petroleum Technology Quarterly · February 2003

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 PETROCHEMICALS and GAS PROCESSING
Dynamic simulation of a
demethaniser column
An implicit approach-based method for calculating distillation column dynamics
has been used to model time-dependent effects of independent disturbances with
a demethaniser column. Startup and shutdown sequences can be tested in this way
M Sadrameli M Shakeri J Towfighi
Chemical Engineering Department, Modares University
D
ynamic simulation has been
applied to the second 50-tray
demethaniser column at the
Arak olefin plant in Iran, in which
methane, hydrogen and carbon mono-
oxide are separated from the heavier
components of the cracked gas. The
model is based on the implicit
approach, where the time dependent
variations of inventory, temperatures,
liquid and vapour flows and composi-
tions are superimposed at each time step
on the steady-state solution.
The implicit method, rather than the
explicit, is used to solve the non-linear
differential equations resulting from the
heat and mass balances. This is because,
for a relatively large-enough integration
step using the implicit method, the
numerical solution may become unsta-
ble even if the response of the model
equations is dynamically stable.
For these purposes, the implicit
method does not incur the same stabi-
lity limitations as the explicit method.
The results of the computer programs
have been compared with the plant data
and good agreement has been obtained.
Thermal steam cracking of hydrocar-
bons in tubular furnaces produces a
considerable part of the world ethylene
production. Global ethylene demand is
projected to reach 136 million
tons/year by 2010. The Middle East and
East Asia will be the fastest growing
regions. Polyethylene is the driving
force behind ethylene consumption
and this end-use pattern is not expected
to change significantly.
Gas-advantaged countries, such as
those in the Middle East, will have a
considerable competitive advantage due
to low ethane feedstock costs. These
feedstock costs will be the driving force
behind new ethylene production capa-
city in the Middle East. Derivatives
based on low cost ethylene will there-
fore be able to compete effectively in
both East Asian and European markets.
The feedstocks for steam cracking
units range from light paraffinic hydro-
carbon gases to various petroleum frac-
tions and residues. The properties of
these feedstocks are documented in var-
ious publications and technical jour-
nals. The thermal cracking reactions are
principally bond-breaking, and a sub-
stantial amount of energy is needed to
drive the reaction towards olefin pro-
duction. The simplest paraffin and the
most widely used feedstock for produc-
ing ethylene is ethane, such as at the
Arak olefin facility. The cracking of
ethane is highly endothermic, so it is
favoured at higher temperature and
lower pressures. Cracking ethane can be
visualised as a free radical dehydrogena-
tion reaction, where hydrogen is a co-
product.
An ethylene unit can be considered to
consist of two sections. The first is the
hot section, where thermal cracking of
hydrocarbons occurs in tubular reactors
at very high temperatures. Steam is
added to the feedstock to reduce the par-
tial pressure of the hydrocarbons in the
tubular coils.
A free radical mechanism is known to
be involved in the primary decomposi-
tion of saturated hydrocarbons to
olefins, methane and hydrogen. Ethane,
which is one of the dominant feedstocks
for ethylene manufacture, can yield over
85% of the theoretical possible yield of
ethylene, when processed through mod-
ern pyrolysis furnaces. Significant quan-
tities of methane are also produced.
Traces of diolefins, aromatics, heavier
olefins and paraffins are also detected in
the reactor effluent.
The second section is the cold section
where the cracked gas is cooled and sep-
arated into products in the distillation
columns. One of the most important
stages of the separation process is the
demethanisation column, which is dis-
cussed later in this article.
All ethylene or olefins manufacturing
processes incorporate a great number of
unit operations involving catalytic and
non-catalytic reactions, absorption and
adsorption, fractionation (demethanisa-
tion and others), heat exchange and
compression arranged in a complex
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P T Q SPRING 2003
w w w. e p t q . c o m
array to achieve the production of high
purity ethylene and other important
olefins, such as propylene. The typical
plant contains hundreds of important
pieces of equipment. For certain ser-
vices, a single piece of equipment can-
not be economically manufactured with
sufficient capacity and therefore multi-
ple pieces (for example, two
demethanisers) and their supporting
systems must be employed.
Thermal steam cracking olefins plants
employ extreme temperatures ranging
from over 860ºC at the outlet of the
pyrolysis furnaces to –170ºC in the cryo-
genic hydrogen-methane separation sys-
tem. These extreme temperatures call for
the application of a multitude of materi-
als of construction, which could include
molybdenum alloy for the methanator,
which is exposed to high hydrogen par-
tial pressures at elevated pressures.
The complexity of the process and
the large number of different pieces of
equipment require an extensive and
complex automation control system.
The typical plant may contain thou-
sands of measuring points for tempera-
ture, pressure, levels, flows and
compositions. Hundreds of control
loops are also involved.
Systems have been developed that
call for the sharp separation of the C3
and heavier components, from the
pyrolysis gas as the first fractionation
step. Although thermodynamic theory
declares all paths to the pure products
are equivalent, most licensors of ethy-
lene process technology appear to prefer
demethanisation as the first sharp frac-
tionation step, which is why dynamic
simulation of the Arak plant’s second
demethaniser has been performed.
In addition, specialised modular simu-
lation programs are also applied to
determine the mass and energy bal-
ances for the refrigeration cascade and
the steam system, which has been dis-
cussed in previous publications. Other
software-based programs have been
developed to perform the process
design calculations for various types of
 PETROCHEMICALS and GAS PROCESSING
Feed characteristics in column T-302
Stream Number 310 323 324
Stream phase Vapour Liquid Liquid
Temperature, °C –25.6 –62.13 –97.98
Pressure (bar) 31.95 31.65 31.57
Flow rate (kg/hr) 8264 16573 10525
Flow rate (kmole/hr) 356.9 631.2 475.9
Table 1
equipment including the pyrolysis
heaters, fractionating trays and heat
exchangers.
Demethaniser
Cryogenic operations in an olefins plant,
such as the Arak facility, involves the suc-
cessive chilling of the pyrolysis gas in heat
exchange with boiling refrigerant and
with cold process streams that have been
vaporised and/or reheated. The pyrolysis
gas can be sent to a high-pressure
demethaniser, which accomplishes the
removal of methane from the condensate.
Ethylene refrigerant boiling in the reflux
condenser at about atmospheric pressure
controls the dew point temperature of the
overhead product.
The ethylene contained in the over-
head product is usually recovered either
through condensation and recycling to
the main compressor or through con-
densation with refrigeration generated
by a turboexpander. However, only con-
densates are usually sent to the
demethaniser in most cases, where com-
plete separation of methane is achieved
from ethylene and heavier components.
Condensing propylene refrigerant
supplies the necessary heat to the reboil-
er, and vaporising ethylene condenses
reflux and some of the overhead prod-
V2
F1
L1
F2
Figure 1 Complex multifeed distillation column with two feeds
Products characteristics from column T-302
325 Stream Number 310
Liquid Phase Liquid
–125.96 Temperature, °C –5.59
31.51 Pressure (bar) 31.77
4424 Flow rate (kg/hr) 27596
254.88 Flow rate (kmole/hr) 948.2
Table 2
uct. The overhead product therefore
consists mostly of methane with a small
amount of hydrogen, which enters the
tower dissolved in the condensates.
Dynamic simulation is a process engi-
neering design tool that predicts how a
process and its controls respond to vari-
ous upsets as a function of time. It also
can be used to evaluate equipment con-
figurations and control schemes and to
determine a design’s reliability and safe-
ty before capital is committed to a pro-
ject. Dynamic simulation models used
for process design are not based on
transfer functions, as found in many
operator-training simulators, but on
fundamental engineering principles and
actual physical equations governing the
process. It also provides controller-tun-
ing parameters for use during startup. In
many cases, accurate controller settings
can prevent expensive shutdown and
accelerate plant start-up.
A new method for the dynamic simu-
lation of distillation columns can be
used to model time-dependent effects of
independent disturbances for the
demethaniser process. The model is
based on an implicit approach, where
the time dependent variations of inven-
tory, temperatures, liquid and vapour
flows and compositions are superim-
D F-1
FX1 VF1
W1 (liquid)
F
W2 (vapour)
Figure 2 Feed tray inlet and outlet
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323 324 316 320
Vapour Liquid Vapour Liquid
–96.49 –96.49 –94.24 –5.59
31.07 31.07 31.27 31.77
8031 4159 19660 4159
513.1 257.4 1232.8 257.4
posed at each time step on the steady-
state solution.
As previously mentioned, dynamic
simulation was performed on the sec-
ond demethaniser column with 50 trays
in which methane, hydrogen and car-
bon monooxide are separated from the
heavier components of the cracked gas.
The implicit method is used to solve the
non-linear differential equations result-
ing from the heat and mass balances.
Process description
The olefin plant’s 50-tray second
demethaniser column (T-302) has four
feeds. The first feed, which is the top
stream of the first demethaniser col-
umn, is fed to tray 28. Streams 323 from
vessel V-302 enter tray 34, and finally
streams 324 and 325 each are divided
into two streams, which are fed to trays
42, 40, 46 and 48 respectively. The top
products of the demethaniser partial
condenser consist of streams 316, 318
and 319 from which stream 319 is recy-
cled to the tower. Tables 1 and 2, respec-
tively, show the feed and products
characteristics of column T-302.
Steady state simulation
A schematic diagram of a complex dis-
tillation column with two feeds and
 PETROCHEMICALS and GAS PROCESSING

that can prevent convergence in certain

Comparison of simulation results for steady state conditions cases. The stage-to-stage calculation
used in the Lewis Matheson method
Stage PROII Simulation PROII Simulation PROII Simulation proceeds from the top down and from
T, °C T, °C V, kmole/hr V, kmole/hr L, kmole/hr L, kmole/hr the bottom of the column up, and may
1C –48.8 –48.8 189.8 189.8 371.8 371.8 be subject to large truncation-error
2 –31.4 –31.6 681.6 681.6 389.2 384.1 buildup.
4 –25.4 –25.3 706.4 706.7 398.1 399.5 The Thiele-Geddes method avoids
6 –24.7 –24.6 707.7 709.7 396.9 399.6 that difficulty, but numerical instabili-
8 –24.2 –24.0 704.6 708.7 390.2 397.7 ties arise as soon as the stage-to-stage
10 –22.1 –22.0 690.1 704.8 1202.4 1189.6 calculation crosses a feed stage. Then, a
15 –7.5 –7.4 1006.1 966.4 1330.4 1288.6 different term appears in the equations,
20 –7.1 –7.0 1014.1 969.6 1334.1 1289.1 which may result in a serious loss of sig-
25 –6.0 –5.9 1006.8 956.1 1312.9 1258.6 nificant digits, making the Thiele-Ged-
27R –0.1 –0.3 953.4 896.4 320.04 320.04
des method basically unsuited for
multiple-feed columns. Because of all
Table 3 these numerical difficulties, neither of
these methods is commonly implement-
two-side stream is shown in Figure 1,, more than the number of equations, ed in modern computer algorithms.
while Figure 2 represents the inlet and three variables, usually D, L1 and col- Nevertheless, their methodology is still
outlet for the feed tray. The input data umn pressure, P, must therefore be very instructive.
for a distillation column are usually specified. In the first method the condenser and
composed of column pressure, number Numerical techniques have been used reboiler mole fractions were considered
of trays, flow rates, compositions, and for the static simulation of distillation independent, while in the second tech-
properties of input feeds, positions of columns, based on the iterative tech- nique, the temperatures of each stage
entering feeds and products, reflux ratio niques of Lewis and Matheson and were considered independent. In the
and type and flow rate of condenser. Thiele-Geddes that have been used since solution of non-linear differential equa-
The model includes equations for the 1963. tions with iterative techniques, the con-
enthalpy and mass balances and equi- Both the Lewis Matheson and Thiele- vergence is not only dependent on the
librium conditions. Geddes methods have been used long independent variables, but also on the
The number of equations are: before the availability of digital comput- sequence of equation solution. Holland
(N+2)(2c+3) with (N+2)(2c+3)+3 vari- ers. It should be noted that these meth- investigated the sequence of the equa-
ables. Since the number of parameters is ods suffer from numerical difficulties tion solution and suggested that for the

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 PETROCHEMICALS and GAS PROCESSING

Comparison of results with plant data Conditions of demethaniser column T-302

Column, T302 Simulation Simulation Plant data Plant data Feed flow rate at boiling temperature: 100 kgmole/hr
Overhead Bottom Overhead Bottom Number of components: 3
Temperature, °C –93.9 –6.64 –96.0 –5.6 Compositions: 60% C3H8, 20% C4H10, 20% C6H14
Pressure, Bar – 31.5 – 28.8 Feed temperature: –62.13
Flow rate, kg/hr 8075.7 – 8400 – Condenser flow rate (liquid): 50 kmole/hr
Reboiler duty, Condenser vapour in: 150 kmole/hr
MMkCal/hr – 1.68 – 1.32
Theoretical number of trays: 5
Feed tray: 4
Table 4 Condenser and Reboiler types: Total
Reboiler type: Total
convergency, using the Theta method is values, which are caused by Column pressure: 300 Psia
necessary. the type of equation of Unsteady condition (different feed composition):
state, which is used in the C3H8: 10%, C4H10: 40%, C6H14: 50%
Calculation algorithm model and in the PROII
A sum of Tj’s and vapour flow rates, Vj’s simulation package (SRK). Table 5
are assumed as a first guess. The sum of However, with regard to
liquid flow rates can be calculated from temperature distribution and vapour choice for process unit dynamic simula-
the mass balance equations. By assum- and liquid flow rate in the column, tions. Over the years, specialised simula-
ing the first stage guess, the tempera- there is very close agreement (between tion software has been developed and is
tures and flow rates of the next stages the results of the two different simula- extensively marketed by organisations
are calculated. tion packages), which proves the accura- specialising in process automation. In
For the evaluation of the software, the cy of the simulation programme for the theory, these simulation languages
simulation results for the steady-state steady state condition. relieve the engineer of knowing any-
condition have been compared with the The steady state results of the model thing about numerical integration.
PROII process simulation package. The are also compared with some of the Therefore, these packages make it easier
input data are listed as follows: plant data of the Arak olefin plant. They for the plant engineer to set up and
Mass flow rate: 629.8 kgmole/hr are listed in Table 4. The difference solve problems that involve process-
Feed composition: 24.196% CH4, between the experimental data and sim- related delays, non-linear behaviour and
59.523% C2H4, 8.748% C2H6, 6.604% ulation results is due to the dramatic the interaction among different control
C3H6, 9.29% C3H8 change in the feedstock in comparison loops. This is particularly the case with
Temperature: –62.13°C with the design case. heat and mass transfer occurring in a
Number of trays: 50 real distillation or fractionation column
Efficiency: 50% Non-linear behaviour such as demethanisers typically used in
Feed tray: 10 Historically, beginning in the late 1940s, olefins plants.
Condenser type: Partial dynamic simulation of distillation has Here, the demethaniser operation is
Reboiler type: Total been linked to analogue computation. translated into a quantitative mathe-
The results of the simulation are pre- In the last 20 to 30 years, digital com- matical model. Due to the very large
sented in Table 3. As it shows, there are puters, with their increased speed and number of equations needed for the
some discrepancies between the L and V capability, have become the machines of rigorous description of the “system”,

2.1 1.00

1.9

Qr
1.7
Duty, MMkCal/hr

0.98 Methane
1.5
in distillate
Mole fraction

1.3

1.1
0.96
0.9 Qc

0.7

0.5
0.94
1,500 1,550 1,600 1,650 1,700 1,750 1,800 1,850 1,900 1,500 1,550 1,600 1,650 1,700 1,750 1,800 1,850 1,900
Feed flow rate, Kmol/hr Feed flow rate, Kmol/hr

Figure 3 Effect of feed flow rate variation on condenser and Figure 4 Effect of feed flow rate on the purity of the condenser
reboiler duty product

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P T Q SPRING 2003
 PETROCHEMICALS and GAS PROCESSING

the calculations are, of course, made Azad University, during the time this
with the use of a computer that incor- article was being prepared for publication.
porates some integration methodology. He graduated from Sharif University of
Therefore, the simulation (in this case) Technology, Tehran in 1995. His
can mimic the non-linear behaviour of postgraduate and professional areas of
the system. Mathematically, dynamic interest include dynamic simulation and
simulation has used two distinct meth- modelling of refinery and petrochemical
ods of solution: explicit (Euler method) processes.
and implicit. J Towfighi is an associate professor of
Briefly, one of the simplest explicit chemical engineering at Tarbiat Modares
methods (Euler method: where the state University and a graduate of Shiraz
variables are calculated explicitly at each University, Iran. He holds an MSc and PhD
integration step from the values result- in chemical engineering from Leeds
ing from the previous step) numerically University and his research interests
integrates, one-by-one, differential include heat recovery, heat transfer,
equations that characterise distillation modelling and simulation of petrochemical
at each time increment, using values of processes, especially olefin technology. He
the last increment’s variables for the is presently head of the chemical
integration. engineering division in the department
The Euler method is the simplest for and consultant of energy conservation
the solution of ordinary differential projects in oil and energy ministries.
equations because it assumes that the
derivative functions are constant over a
small integration interval. Thus the
changes in liquid flow on a tray are con-
sidered to be independent of liquid-flow
changes on the tray above until the end
of the time interval.
The integration interval, ³T, affects
the accuracy of the numerical integra-
tion of the differential equations and the
computer time required to perform the
computations. This time delay introduces
errors, which are often unacceptable in
the presence of significant disturbances.
For the enthalpy, vapour pressure, and K-
value calculation, thermodynamic corre-
lation of SRK has been used.
For the dynamic condition the feed
composition has been altered to 10%
C3H8, 40% C4H10, 50% C6H14. Some of
the results of the simulation including
flow rate distributions are shown in Fig-
ures 3 and 4. For the evaluation of the
dynamic model the results of the com-
puter program have been compared
with a similar separation column in the
literature data.
The conditions of the column at
steady state are listed in Table 5.

M Sadrameli is an associate professor of

chemical engineering at Tarbiat Modares
University, Tehran. He graduated from
Sharif University of Technology, Tehran,
and holds MSc and PhD degrees in
chemical engineering from Leeds
University, UK. His research interests are
heat recovery, heat transfer, modelling and
simulation of petrochemical processes,
particularly with regard to olefin
technology. He is presently head of the
chemical engineering division in the
department and consultant of energy
conservation projects in oil and energy
ministries. Email: sadramel@modares.ac.ir
M Shakeri was a postgraduate student of
the chemical engineering department,

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