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Optimal Design of Ethane Pyrolysis Reactor

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International Journal of Science and Advanced Technology (ISSN 2221-8386) Volume 2 No 9 September 2012
http://www.ijsat.com

Optimal Design of Ethane Pyrolysis Reactor

Hesham G. Ibrahim*, Abdulmajed R. Alagta Abdulfatah M. Emhamed

Al-Mergheb University, Faculty of Engineering, Chemical Surman High Institute, Mechanical Eng. Dep.,
and Petroleum Engineering Department, Sports Boulevard, Surman City, Libya
Omer Ben Abdul Aziz street, Khoms City, Libya
*e-mail: [email protected]

Abstract—Olefins production is one of the largest because the thermal cracking of ethane is
petrochemical sectors and is the building blocks in thermodynamically limited. However, the increase in
manufacturing of petrochemicals. Ethylene (C2H6) is cracking temperature adversely affects the ethylene
produced commercially by thermal cracking (pyrolysis) of selectivity and coking formation because of undesirable
ethane, ethane-propane mixture or naphtha with/without
secondary pyrolysis. Accordingly, many other techniques
steam. Pyrolysis is a gas-phase reaction at very high
temperature of saturated hydrocarbons ranging from ethane are under investigation to improve ethylene production
to heavy gas oils usually produces ethylene. This gas phase using oxidative or non-oxidative catalytic systems [2, 4-
reaction takes place in metal alloy tubes within a fired 9], for instance the catalytic ceramic membrane system
furnace. Dehydrogenation processes of ethane are expected with a selective hydrogen permeability [10, 11]. However
to be more important because ethane is an abundant in spite of these numerous studies, the most economically
component in natural gas that makes it as an alternative viable process in industrial is still the thermal cracking of
resource of traditional petroleum. This study focused on saturated hydrocarbons with or without steam.
mathematical modeling of the ethane pyrolysis reactor, the
developed model is based on overall mass balance, an
This process is highly endothermic, energy-intensive
empirical rate, heat balance and forces for the main
hydrocarbon decomposition reaction of (C2H6). Then, the and also involves extensive coke formation. The large
results are analyzed for fixed reactor capacity with various amount of coke deposited on the inner walls of the tubular
tube diameters by calculation of design parameters for a cracking reactor causes a serious problem, the reduction in
given conversion. The differential equation solutions are the rate of heat transfer from reactor walls, and as
obtained by numerical methods and the results are consequence a higher wall temperature (up to 1375 K) is
compared with experimental data. The model results are in a required to achieve the desirable ethane conversion, this
good agreement with the experimental and literature model. lead to an increase in the energy demanded also reduces
Finally, simulation and optimization results indicate that the the life of the reactor tubes. Furthermore a periodically
6-in. tubular reactor is preferable due to the availability of
process shutdown is required for removing the formed
high heat-transfer surface area per unit volume of the
reactor (=26.22 m2/m3), less time of reaction ( = 4.69 sec)
coke. Moreover, the ethane conversion achieved is less
and acceptable pressure drop (P= 0.75 psia) which is the than about 70%, thus requiring a large recycle of the
main factor in design of the pipes; whereas the P decreases unconverted ethane. However in order to overcome and
by 90% compared with 4-in tube. solve the mentioned problems and reach the desired
conversion rate the temperature distribution through the
Keywords-Pyrolysis; Tubular reactor; optimization; reactor under a different conditions must be known, also
ethane decomposition; Euler's method the residence time of the mixture inside the reactor must
be maintained as short as possible to prevent of coke
formation.
I. INTRODUCTION
Ethylene, which is a cornerstone in the petrochemical The pyrolysis of ethane to ethylene is carried out in
industry, is produced commercially by thermal cracking long coils which are heated in fired furnaces. The process
of ethane, ethane-propane mixture or naphtha with a gas is cracked at temperatures up to 1140 K. it is known
presence of steam or without it [1,2]. Thermal cracking, that a short improved olefin selectivity [12]. However, the
namely pyrolysis, of saturated hydrocarbons ranging from lower residence time requires more intensive heat transfer
ethane to heavy gas oils usually produces ethylene. It is to the process gas and increased furnace firing. Therefore,
worth to note that the dehydrogenation processes of the throughput and efficient of the cracking process is
ethane are expected to play an important role in the future limited by the heat transfer through the coil. Because the
production of ethylene since ethane is an abundant alkane pyrolysis is a complicated chemical reaction and
component in natural gas which is an alternative resource has the following specific features: it is accompanied by
to traditional petroleum [3]. secondary and tertiary reactions; it is very endothermic;
coke deposits reduce the pipe diameter, thereby raising the
In the conventional dehydrogenation process, it is pressure drop and lowering the conversion of the raw
necessary to maintain a high temperature (9701170 K) material; pyrolysis increases the volume of reaction
for a significant conversion and a high reaction rat
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International Journal of Science and Advanced Technology (ISSN 2221-8386) Volume 2 No 9 September 2012
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mixture, raising the linear velocity of the gas; recycling of products (=0.0), (--).
the unreacted raw material affects the dynamics xmax Maximum mole fraction of ethane converted
(stationary) of the process, making it necessary to take to products, (--).
into account the interaction between the raw material and yA Mole fraction of ethane, (--)
the products. These facts complicate optimal design of Z Length measured from reactor inlet, (m).
alkane pyrolysis and prompt designers to develop special-  Heat-transfer surface area per unit volume of
purpose procedures. So, the main objective of this work is the reactor, (m2/m3)
modeling and simulation of the ethane pyrolysis by Heat of formation, (kJl/kgmol).
considering only the main hydrocarbon decomposition Heat of pyrolysis reaction, (kJ/kgmol).
reaction for (C2H6). This procedure includes the following P Pressure drop through reactor, (psia).
steps:
Greek symbols
- Development of a mathematical model based on σ Expansion factor for light hydrocarbon
equations of mass, and heat balance and pressures cracking, It's value 0.92 for ethane of the
drop equation. conversion range (0.0 - 0.65), [14].
- Analysis, in terms of this model of ethane pyrolysis at  Residence time, (sec).
a fixed reactor capacity and varied tube diameter and ρ Density of the mixture at any point in the
calculation of design parameters for a given reactor, ( )
conversion. Solution of these differential equations ( )

done by numerical methods. µ Viscosity of ethane at inlet condition,

- Reactor optimization based on the obtained results (=2.4×10-5 kg/m.sec)
from second step.
II. MATHEMATICAL MODELING OF PROCESS
NOMENCLATURE
A Cross-sectional area of tube, (m2). A. Basics of Process
CA Concentration of ethane, (kgmol/m3). Pyrolysis of ethane is represented essentially by the
Cpi Specific heat capacity of component i, irreversible first order chemical reaction in the temperature
(kJ/kgmol.K). range 900 to 1200 K:
D Pipe inside diameter, (m).
(1)
f Fanning friction factor
G Mass flux (= ), (kg/m2.sec) A pure ethane is fed at known inlet temperature and
h Step size change, (--) pressure to a steel tube contained in an ethane pyrolysis
L Length of the tube (reactor), (m) furnace. Heat is supplied by the furnace to the reactor. A
K Reaction rate constant, (sec-1). thermodynamic properties for this reaction such as
Mwt Molecular weight of ethane, (kg/kgmol). standard heat of formations ( ), temperature-
no Inlet molar feed rate of ethane, (kgmol/sec). dependent specific heat capacities (Cp); and all kinetic
Molar flow rate of ethylene at any point, data are temperature dependent (rate constant for Eqn. (1)
(kgmol/sec). and physical constants for components are shown in
Molar flow rate of ethane at any point, Table.1).
(kgmol/sec).
Molar flow rate of hydrogen at any point,
(kgmol/sec).
P Total pressure at any point, (kPa).
Po Inlet total pressure, (kPa).
Q Heat input from furnace, (kJ/sec.m(of reactor
length)). Table.1 Physical properties and data for ethane pyrolysis reaction
R Specific reaction rate, (kgmol of Cp
Comp.
ethane/m3.sec) (kJ/kgmol) (kJ/kgmol.K)
R Universal gas constant, C2H6 -83820 14.1504 + 7.549×10-2T – 1.799×10-5 T2
(8.314 kPa.m3/kgmol.K)
Re Reynolds number, ( ), (--). C2H4 52510 11.839 + 1.19167×10-1T – 3.6515×10-5 T2
T Absolute temperature, (K). H2 0.00 27.012 + 3.5085×10-3T + 6.9×104 /T
To Inlet temperature, (K). Reaction rate constant -
Tout Outlet temperature, (K) (sec-1): k=4.717×1014
U Superficial velocity, (m/sec). Atomic Weights: C=12, H=1
V Volume of reactor, (m3).
Gas constant (R): 8.314 kPa.m3/kgmol.K
X Mole fraction of ethane converted to
products, (--).
xo Inlet mole fraction of ethane converted to

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International Journal of Science and Advanced Technology (ISSN 2221-8386) Volume 2 No 9 September 2012
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B. Material Balance For a given tube ID., inlet reactor pressure, and inlet
The molar flow rates of three constituents according to ethane flow rate, the first term of the right hand side of
chemical reaction referring by Eqn. (1) are: Eqn.(8) is constant; the second term is a function of
temperature.

Constituent Inlet molar Outlet molar flow rate at C. Energy Balance

flow rate conversion x
The energy balance over the differential volume
C2H6 no no(1-x) element dV must account for heat liberated due to reaction;
C2H4 0 nox heat introduced from the furnace through the tube wall,
and sensible heat effects (because of temperature change)
H2 0 nox in the flowing gas stream. For a change dx in conversion
Total nTo=no nT=no+nox in the differential element, the heat liberated by the
reaction is ( ). The energy introduced into the
differential element through the tube wall is . The
Thus, the total number of moles flowing at any point in corresponding gain in enthalpy of the flowing gases is
the tubular reactor is; given by;
nt=no+nox (2) ( )
and the corresponding mole fraction of ethane is; ( ( ) ( ))
( - )⁄( ) (3) (9)
The problem is now approached by establishing steady
Where, dT is the temperature change across the
state material and thermal balance over a differential
element dz of reactor length, as shown in Fig.(1). differential element. Energy balance is;
Assuming that plug flow in the tube of reactor. Basis is ( )
moles of ethane.
[( ) ( )] (10)

Then the change in temperature as a function of length

is described by the first order ordinary differential
equation;
( )
Figure 1. Differential element of tubular reactor.
(11)
( ) ( )
The material balance for ethane over the differential
volume element is: The heat capacity relationships from Table.1 can be
introduced directly into the denominator of Eqn.(11).
Flowing In + From reaction = Flowing Out
(4) The heat of reaction may be calculated as following;
Rearranging Eqn. (4);
∫ ( )
( )
(5) (12)

But for the given first order irreversible reaction, rate, r is; The heat of reaction at 298 K can be calculated from
the heats of formation of Table.1 as 52510 + 83820 =
(6) 136330 kJ/kgmol.K. Introducing the heat capacity
At the low pressure (not exceeds 5 bar) of the reacting relationships of Table.1 into Eqn. (12), and integrating;
gas mixture (system), the ideal gas law holds, [13]; so that yields the heat of reaction at any temperature T (K).
Eqn. (6) becomes;

( ) (7) [ ( ) ( )
From Eqns. (5&7) and Table.1; the conversion x as a
function of reactor length z is described by the solution of ( ) ]
the first order ordinary differential equation; ( )

( ) (13)

( ) (8)
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International Journal of Science and Advanced Technology (ISSN 2221-8386) Volume 2 No 9 September 2012
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D. Pressure Drop
For flow in pipes, the pressure drop along the length of
the pipe is given by Fogler [15];

(14)

Whereas; f is given by Eqn.(15), [16];

(15)

III. ALGORITHM
Eqns. (8, 11 & 14) are three coupled nonlinear first-
order ordinary differential equations which must be solved
simultaneously. The length z is the independent variable,
while x, T and P are the dependent (solution) variables.
The initial conditions are:
( ) ( ) (no conversion at inlet)
( ) ( ) (inlet feed temperature)
( ) ( ) (inlet feed pressure) Figure 2. Algorithm of the program.

1
Converaion Fraction of C2H6/Production

Three differential equations can be solved in parallel

using Euler's method of the following equation[17]; 0.9

( ) ( ( )) (16) 0.8

Whereas; ( ) = initial value of the function y at xo. 0.7

Let step size be denoted by , then Eqn.(16) becomes; 0.6

0.5
( ) (17) Expermintal data, Hawboldt [18]
0.4 Model Data (This Work)
Model Data, Hawboldt [18]
( ) (18) 0.3
0 1000 2000 3000
( ) (19) Reynolds Number
Figure 3. Comparison of models predictions and experimental data and
Here, , and are respectively, the conversion, literature model
temperature and pressure at .At the beginning of (Operating conditions: Feed rate (5-14 SLPM), Inlet temperature= 1123
K, Inlet pressure=308 kPa, ID=0.005m, Length= 3m, Heating supplied=
the step. The values of , and have (5.75-8.2 kJ/ .sec.m2 (of inside tube area), Length increment=0.1).
already been calculated. The values of ⁄ , ⁄
and ⁄ can be computed from (8, 11 and 14), then ,
and can be computed from Eqns.(17, 18 and 19) The advantage of using ethane as a feedstock is a high
respectively. The process is repeated for subsequent steps ultimate ethylene yield combined with a minimum of co-
until xi exceeds some desired upper limit , products. A conversion of 60-65% on a single pass basis
. The program contains provision for printing is considered optimum [19]. So, the program has been
values for , , and at specific intervals in . rerun to reach 65% as maximum conversion of ethane
using the following parameters (A pure ethane is fed to
the reactor at rate of 0.3 kg/sec and 900 K, heat is supplied
by the furnace to the tube at a rate of 20 kJ/ m2.sec (of
IV. RESULTS AND DISCUSSION
inside tube area) and total pressure of inlet stream is 406
The validity of the presented models and program is
kPa) with several different values for the length
tested and evaluated using temperatures and flow rates
increment, z. All calculations have been made using
given by Hawboldt [18], the obtained results compared
single precision arithmetic (note the influence of round-
with the experimental data and model predictions obtained
off error in the tabulated values for z in the results for the
by Hawboldt [18]. The model results are in a good
first data set). The total reactor length, conversion,
agreement with the experimental and literature model,
temperature and the pressure at the reactor outlet
that reveals to the validity of this model as illustrated in
corresponding to known percent conversion value of
Fig.(3)
ethane, determined by linear interpolation on the
computed results, are shown in Table.2.

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International Journal of Science and Advanced Technology (ISSN 2221-8386) Volume 2 No 9 September 2012
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Table.2 Reactor length, outlet pressure and temperature for 65% Table.3 Reactor length, outlet pressure and temperature for 65%
conversion of ethane conversion of ethane for varies inner diameters (length increment = 0.1
m)
z L xoutlet Toutlet Poutlet ID L Toutlet Poutlet
(m) (m) (--) (K) (kPa)
(in.) (m) (m) (K) (kPa)
0.1 133.2989 0.65 1062.582 349.5418
0.5 133.5 0.6515 1062.698 349.4852 4.026 0.102255 133.2989 1062.582 349.5418
1 134 0.654337 1062.978 349.2666 6.0065 0.152558 89.29921 1049.579 400.8548
5 135 0.661 1063.589 349.304 7.981 0.202708 67 1040.581 405.0216
10 140 0.68258 1065.669 347.5115 10.02 0.254496 53.499 1033.478 405.7403
15.2 152 0.69622 1074.909 343.1283 12.09 0.307071 44.399 1027.813 405.9126
13.25 0.336534 40.49995 1025.011 405.9491
15.25 0.387331 35.20004 1020.797 405.977
Results are almost identical for the length increments 17.25 0.438129 31.1 1017.079 405.9905
of 0.1 m to 1.0 m, suggesting that the truncation errors are 19.25 0.488926 27.80007 1013.674 405.9917
small and the results accurate. There is very little 21.25 0.539724 25.20006 1010.807 405.9987
conversion of ethane in the first 15 m of tube length; the 23.25 0.590521 23.10005 1008.359 406
gas temperature is rising (because of heat input from the
furnace through the tube wall) but the reaction velocity Analysis at varied tube diameter and 65% conversion
constant is quite small, and only a small amount of of the raw material demonstrated that this conversion is
decomposition takes place. Once the temperature is high attained approximately to the same outlet pressure,
enough, the rate of reaction becomes significant. The roughly changes of temperatures for dimensions (7.981 –
temperature rises only very slowly thereafter; the heat 23.25 in) with different reactor length, also (4.026 and
introduced from the furnace is roughly balanced the heat 6.0065 in) dimensions gave good results.
of reaction for the endothermic (energy-consuming)
pyrolysis reaction. Euler's method produces rather Basic process parameters for these reactors are listed
accurate results for substantial length increments, because in Table.4. All tube diameters are acceptable from the
the derivatives of eqns. (8, 11 and 14) are small and standpoint of the outlet pressure (less than 10 psia [20])
virtually constant over a substantial portion of the reactor and temperature. Although the 4-in. tube needs to be
length. longer than the other tubes for the desired conversion to
be achieved, its walls would have smaller volume and
Significant errors begin to show up in the results for a accordingly, weight and tube itself would be less
length increment of 5 m. Notice the curious oscillation of expensive. Furthermore, the 4-in. reactor would have a
temperature and pressure down the length of the reactor; much larger heat-transfer surface per unit volume, this
this behavior would be quite unreasonable from physical fact must be taken into account when designing a
and chemical considerations. These oscillations occur pyrolysis furnace to prevent formation of coke. Moreover,
because the temperature at the beginning of a length owing to the shorter mixture residence time, the former
increment is assumed to hold throughout the entire would suffer less from coke deposition and, therefore, be
increment. When the temperature is rather low, the rate of in services for a longer time [21]. However the main
reaction will be low, and heat from the furnace will be disadvantage of 4-in reactor is the presence of high
absorbed primarily as sensible heat, raising the pressure drop comparing to the other diameters.
temperature at the beginning of the next segment. This
higher temperature will lead to a high reaction rate and to Generally data reveals that, the 6-in. reactor is
the consumption of all of the heat from the furnace (and preferable, due to all results of calculations are made
some of the sensible heat of the reacting gases) by the accepted in which  around 26 m2/m3 and  ≈ 4.7 sec in
decomposition reaction, leading to a lower gas which Olefins are formed by primary reactions and
temperature at the beginning of the next increment. As the therefore require a low residence time [19], also
length increment is made larger, these oscillations become acceptable length reached and P is about 0.7 psia the
more serious. For length increments of 10 and 15 m, the main factor in design of the pipes; whereas the P
results become completely meaningless. So, the low decreases by 90% compared with 4-in tube.
increment gives a best results and high accuracy. By the
same program for other tubes, that have diameter 6, 8 and
10 inches their results are given in Table.3. Results for V. CONCLUSION
ethane pyrolysis process of many tube diameters at the The presented mathematical modelling and simulation
following initial conditions: mass rate= 0.3 kg/sec, of ethane pyrolysis is evaluated and found suitable in
Po=406 kPa and To= 900 K are given in Table (3). determining the reactor specifications. An adequate
reactor dimensions is required to achieve the optimum
conversion of the feed. The main criterion for the reactor
design depend on the selection of the proper dimensions
that provide the lowest value of pressure drop and
residence time to prevent any explosion and coking of
hydrocarbons throughout a reactor respectively.

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 International Journal of Science and Advanced Technology (ISSN 2221-8386) Volume 2 No 9 September 2012
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Table.4 Basic parameters of the ethane pyrolysis for different diameters for tested tubes
I.D. L V u Tout P  
(m) (m3) (m/sec) (K) (psia) (sec) (m2/m3)
(in.) (m)
4.026 0.102255 133.2989 1.09413 49.16394 1062.582 8.192848 2.711314 39.11773
6.0065 0.152558 89.29921 1.631493 19.0219 1049.579 0.746638 4.694547 26.2196
7.981 0.202708 67 2.161146 10.57129 1040.581 0.141979 6.337921 19.73287
10.02 0.254496 53.499 2.720043 6.64775 1033.478 0.037686 8.047685 15.71737
12.09 0.307071 44.399 3.286401 4.541573 1027.813 0.012683 9.776128 13.0263
13.25 0.336534 40.49995 3.60065 3.769989 1025.011 0.007386 10.74272 11.88589
15.25 0.387331 35.20004 4.145506 2.834353 1020.797 0.003338 12.41907 10.32708
17.25 0.438129 31.1 4.686335 2.206458 1017.079 0.001379 14.09499 9.129739
19.25 0.488926 27.80007 5.216774 1.764091 1013.674 0.001204 15.75886 8.181195
21.25 0.539724 25.20006 5.762543 1.443821 1010.807 0.000189 17.45373 7.4112
23.25 0.590521 23.10005 6.323442 1.204472 1008.359 0 19.17857 6.773677

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