Chemical Engineering Research and Design 186 (2022) 672–684

Available online at www.sciencedirect.com

Chemical Engineering Research and Design

journal homepage: www.elsevier.com/locate/cherd

Applying a new configuration for thermal

integration of ethane cracking and CLC processes
]]
]]]]]]
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to enhance the ethylene and hydrogen

productions
⁎
Sepide Zandhaghighi a, Davood Iranshahi a, , Mahdi Shakeri a,
Esmaeel Bagherpour-Ardakani b
a
Department of Chemical Engineering, Amirkabir University of Technology (Tehran Polytechnic), No. 424, Hafez
Avenue, Tehran 15914, Iran
b
School of Mechanical Engineering, College of Engineering, University of Tehran, 1439955961 Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: In this study, a new method for applying the chemical looping combustion (CLC) process
Received 29 May 2022 instead of the furnace to provide the required heat for the ethane thermal cracking reactor
Received in revised form 24 July 2022 has been suggested. It has been proposed that the new configuration of the ethane
Accepted 2 August 2022 thermal cracking process be performed in the three separate series reactors. The structure
Available online 5 August 2022 of these new integrated reactors consists of three concentric cylinders. In the internal
cylinder with a small diameter, the thermal cracking process is performed, while in the
Keywords: middle and external sides of new reactors, the oxidation and reduction processes of
Ethane thermal cracking process oxygen carriers are executed, respectively. The essential thermal energy for the en­
Chemical looping combustion dothermic ethane thermal cracking process is provided by the exothermic oxidation re­
process action in the air reactor. Furnace removal prevents nitrogen oxide emission, and a
Ethylene and hydrogen production significant amount of carbon dioxide is recovered in the CLC process. According to the
yields results of this new configuration, the ethylene and hydrogen production yields rise by
Integrated rectors about 12% and 15%, respectively, compared to the conventional ethane cracking reactor.
Oxidation and reduction of oxygen Finally, the effects of design parameters such as inlet feed temperatures of the air, fuel
carrier and cracking reactors, as well as the mass flow rates of ethane and oxygen carrier on the
performance of ethane thermal cracking have been investigated.
© 2022 Institution of Chemical Engineers. Published by Elsevier Ltd. All rights reserved.

the most significant processes in the petrochemical industry

1. Introduction
(Choudhary and Mulla, 2001). Thermal cracking involves
breaking heavy hydrocarbons and converting them into light
The low-cost ethylene is an essential raw material, with the
olefins (Froment et al., 1976). Ethane is easily found in nature,
largest production volume among petrochemical products.
so breaking ethane in the thermal cracking process is a
Thus, improving the ethylene synthesis process has a high
proper choice for providing ethylene and other relevant
economic value for the petrochemical industry (Bigdelou
substances such as hydrogen (Deng et al., 2009).
et al., 2020; Li et al., 2016). The principal method for the
The kinetics of the thermal cracking of ethane has most
commercial production of ethylene and other olefins such as
frequently been described by a radical mechanism. A mole­
propylene is the thermal cracking reaction, which is one of
cular reaction scheme for thermal cracking of ethane and
propane mixture has been investigated by Sundaram and
⁎
Froment (Sundaram and Froment, 1977). Estimation techni­
Corresponding authors.
ques and a multi-response approach and minimizing a
E-mail addresses: iranshahi@aut.ac.ir (D. Iranshahi).
https://doi.org/10.1016/j.cherd.2022.08.004
0263-8762/© 2022 Institution of Chemical Engineers. Published by Elsevier Ltd. All rights reserved.
 Chemical Engineering Research and Design 186 (2022) 672–684 673

Nomenclature i number of reaction

j number of component
Ac cross-section of the reactor (m2 ) s solid
b stoichiometric ratio t total
C gas concentration (mol /m3 )
CP specific heat capacity ( J / mol. K )
dP particle diameter(m)
dt reactor diameter of thermal cracking (m) weighted sum of squares of residuals by means of Mar­
D1 inside diameter (m) quardt’s nonlinear regression routine were used for the rate
D2 outside diameter (m) parameters. Though, the simulation data were in good
DC coke diameter (m) agreement with the experimental results through the esti­
E activation energy ( J mol ) mation techniques used in this research. The statistical
Fj molar flow rate of component j (mol /s) thermodynamics for obtaining standard entropies and the
Fr friction factor transition state theory for estimating frequency factors have
total molar flow rate (mol /s) been applied by Willems and Froment (Willems and
G total mass flow rate (kg (m2 . s)) Froment, 1988), so these reaction rate parameters are used
h convection heat transfer coefficient (W (m2 . K )) for a large group of similar reactions and thus, the number of
k rate constant of reaction i (1/s or 1/mol . s) unknown parameters is significantly reduced.
Kc equilibrium constant Modeling and simulation of the thermal cracking reactor
kc thermal conductivity of coke (W /m/K) are essential to predict the performance of this process (Van
kt thermal conductivity of the gas phase (W /m. K ) Goethem et al., 2008; Plehiers et al., 1990). The homogeneous
kw thermal conductivity of the inner wall of the one-dimensional mathematical model has been employed by
reactor (W /m. K ) Masoumi et al. to investigate the static and dynamic per­
L length of reactor (m) formance of a thermal cracking pilot plant (Masoumi et al.,
m mass (kg) 2006). To reduce ethane consumption in the process of
M. W molecular weight (kg / kmol ) thermal cracking of ethane, Feli et al. (Feli et al., 2017) sug­
n reaction order gested increasing the ratio of hydrogen to hydrocarbon and
Nu Nusselt number adding some propylene as an additional supplement. Based
P pressure (Pa) on the results obtained in this modeling, adding propylene to
Q heat transfer rate ( J s) the input will increase the efficiency of propylene produc­
ri rate of reaction i (mol /m3 . s) tion, decrease the concentration of ethylene, and increase
rg grain radius (m) the reaction time.
rs rate of oxidation and reduction reac­ Process intensification (PI) involves the concept of ap­
tions (1/s) plying synergy between different parts of a system or con­
R universal gas constant ( J / mol. K ) necting several systems to reduce the energy consumption
Rb radius of the tube bend (m) and the production costs, also boost production efficiency in
Re reynolds number various fields including energy and mass transfers
t time (s) (Ovchinnikova et al., 2019; Patil and Baral, 2021; Jiang and
tc coke thickness (m) Agrawal, 2019). The application of membranes for separation
T temperature (K ) (Tanco et al., 2020; Drioli et al., 2011; Zhang et al., 2020;
Tf furnace temperature (K ) Shakeri et al., 2019) and the combination of reactions (Wang
Tw tube wall temperature (K ) et al., 2017; Shakeri et al., 2020; Abu-Hamdeh and Salilih,
u velocity (m /s) 2021; Shakeri et al., 2019) can be mentioned as examples of
U overall heat transfer coefficients (W (m2 . K )) this method to improve the processes. The heterogeneous
Us oxygen carrier mass flow rate (kg / s) model for the interpretation of the indirection combination
Xs oxygen carrier conversion of ethanol combustion with ethanol steam reforming process
z axial reactor coordinate (m) in a micro-reactor has been developed by Bruschi et al.
(Bruschi et al., 2016). Another study was performed on a
Greek letters thermally double coupled reactor by Thirabunjongcharoen
m molar density of the oxygen carrier (mol /m3 ) et al. (Thirabunjongcharoen et al., 2020) in which the aqu­
parameter of tube bend eous phase glycerol reforming combined with methanol
angle of tube bend synthesis process. Ebrahimian et al.(Ebrahimian et al., 2019)
b bed porosity examined the integration of propane ammoxidation and
stoichiometric coefficient naphtha endothermic reforming to improve the production
H heat of reaction ( J / mol) of aromatics and hydrogen as well as acrylonitrile (the raw
time for complete solid conversion (s) material of many polymers). In this study, in addition to in­
µ viscosity (kg / m. s) creasing the aromatic output by 10%, they also managed to
σ Boltzmann constant (W /m2 /K4 ) save energy consumption due to the coupling process and
heat-absorbing and heat-generating process. Applying the
Subscripts
membrane reactors for the combination of endothermic and
1 tubes
exothermic reactions is another method of PI concept in
2 air reactor
which both energy and components are transferred si­
3 fuel reactor
multaneously (Patel and Sunol, 2007; Mirvakili et al., 2012).
g gas
The use of a membrane as one of the essential PI tools in a
674 Chemical Engineering Research and Design 186 (2022) 672–684
Fig. 1 – (a) Representation of the chemical-looping combustion system containing air and fuel reactors and (b) a general
scheme of the conventional ethane thermal cracking process.
thermal couple reactor has been used by Hamedi et al.
(Hamedi et al., 2017) In this proposed system, a Pd/Ag
membrane was used in an integrated system of the trans­
alkylation process and dehydrogenation of methylcyclo­
hexane to increase the production of xylenes and pure
hydrogen. This new configuration ultimately increased the
production of xylene. In a quasi-homogeneous reactor, Abo-
Ghander et al.(Abo-Ghander et al., 2008) investigated the
thermal coupling of two processes of ethylbenzene to styrene
and catalytic hydrogenation of nitrobenzene to aniline in the
presence of a membrane. After reviewing the simulation
results and comparing them with the results of a conven­
tional industrial process, it showed an increase in the pro­
duction efficiency of styrene and aniline.
Fossil fuel applications reached their peak simultaneously
with the industrial revolution and the presence of fossil fuel
in human life became so colorful, but the negative effects of
fossil fuel on the environment have forced researchers to
consider solutions for their disadvantages (Lu et al., 2021).
Researchers have spent years looking for ways to prevent the
productions of CO2 and nitrogen oxides (NOx) as the most
harmful gases for human health (In-na et al., 2020; Sher et al.,
2020; Chi et al., 2020; Won et al., 2020; Ohenoja et al., 2020).
Chemical looping combustion reactors are one of the most
important proposed methods with two separate reactors to
prevent the interaction of air nitrogen molecules and fuel,
and thus, inhibiting the production of NOx. As shown in
Fig. 1(a), the CLC reactor separates the oxygen from the air by
the oxidation reaction by applying a metal oxide called the
oxygen carrier in the first reactor (air reactor) and transfers it
to the second part (fuel reactor). After the reduction reaction
in the fuel reactor, the oxygen carrier leaves this reactor as
metal and returns to the air reactor to perform the oxidation
reaction. As the most prominent feature of the CLC reactor,
the gases from burning fuel are the mixture of the carbon
dioxide and the water vapor, which the carbon dioxide gas is
easily recovered by condensing the steam (Bhui and
Vairakannu, 2019; Wang et al., 2020; Osman et al., 2020;
Hammache et al., 2020; Murri et al., 2020; Imanieh et al., 2016;
Wang et al., 2019). Other chemical looping reactors are sui­
table for solid fuels such as coal because solid fuel typically
burns at a low rate. Using different types of chemical looping
reactors increases the oxidation rate. One type of these re­
actors is known as iG-CLC reactors. In iG-CLC reactors, one of
the fuel reactor's outputs, carbon or hydrogen, re-enters the
fuel reactor. It causes solid fuel gasification and prevents the
reaction of solid fuel and oxygen carriers, thus increasing the
reactivity of solid fuel. In this type of reactor, a system for air
separation is no longer needed, and a mixture of carbon di­
oxide and water enters the fuel reactor, where carbon di­
oxide performs the gasification process of solid fuel. One of
 Chemical Engineering Research and Design 186 (2022) 672–684 675

these types of reactor problems is the combustion reaction's
slow rate (Czakiert et al., 2022).
Another problem is escaping some char particles to the air
reactor along with the oxygen carrier. This was solved by
introducing another type of chemical looping reactor, che­
mical looping oxygen uncoupling (CLOU). In this type of
chemical loop reactor, the release of oxygen in the fuel re­
actor happens differently than in the iG-CLC reactor. CLOU
reactors use oxygen carriers such as copper, which can re­
lease oxygen at high temperatures, so direct oxidation of
solid fuel is done. Eliminating the gasification stage accel­
erates the combustion reaction of solid fuel (Abuelgasim
et al., 2021).
In this research, it has been proposed that instead of
furnace, the CLC reactor would be used to provide the re­
quired heat for the ethane thermal cracking process. The
thermal coupling simulation results of these two processes
are compared with the conventional thermal cracking pro­
cess. The effects of design parameters including the inlet
feed temperatures of all three coupled reactors and inlet
ethane molar flow rate of the cracking reactor on the process
performance and the production efficiency have been in­
vestigated.
2. Process description
2.1. Thermal cracking of ethane
converted into three tubes with different lengths. According
to Fig. 2(b), each integrated reactor is made of three con­
centric cylinders in which the exothermic oxidation reaction
of nickel is performed in the middle side (air reactor) and
provides the required thermal energy to exert both en­
dothermic reactions of ethane cracking in the inner side and
reduction process in the outer side of this novel integrated
reactor. Ethane feed should be diluted before entering the
cracking side for the reasons mentioned earlier. Using carbon
dioxide produced from the reduction process instead of
steam increases the efficiency of the cracking reactions. As
this mixture moves in series through the inner tubes,
cracking reactions are occurred and finally, the desired pro­
ducts such as ethylene are achieved. Due to the low con­
version of ethane from the outlet of the first reactor, it is
proposed that the cracking tubes be in series. While the fuel
and air reactor feeds enter the suggested integrated reactors
in parallel. Information about the operating conditions and
the other parameters of all three fuel, air and thermal
cracking reactors are given in Table 1.
3. Kinetic model
3.1. Ethane thermal cracking process
In this work, the following molecular kinetic model for ex­
planation of ethane thermal cracking process has been used
by Sundaram and Froment (Sundaram and Froment, 1977):

The ethane thermal cracking process is the most important C2 H6 C2 H4 + H2 (1)

method for ethylene production as one of the essential ma­
2C2 H6 C3 H8 + CH4 (2)
terials applied in the petrochemical industry (Tarafder et al.,
2005). According to Fig. 1(b), the thermal cracking unit con­ C3 H8 C3 H6 + H2 (3)
sists of numerous parts including a furnace (radiation and
convection sections), transfer line exchanger, compressors, C3 H8 C2 H4 + CH4 (4)
and separators. In the upper part of the furnace, the inlet
C3 H6 C2 H2 + CH4 (5)
feedstock is preheated by the convection mechanism, then a
certain amount of steam is injected into the feedstock to C2 H2 + C2 H4 C4 H6 (6)
increase the feed temperature and reduce the pressure drop.
This mixture is ready for thermal cracking when it reaches 2C2 H6 C2 H4 + 2CH4 (7)
the proper temperature in the radiation section, so ethane is
converted to a combination of aromatics and olefins. Then C2 H6 + C2 H4 C3 H6 + CH4 (8)
they are immediately entered into the transfer line ex­ The rate equations of above reactions are as follows:
changer and are cooled to prevent undesired reactions.
2
Quenching time is a significant factor in determining the FC2H6 Pt FC2H 4 FH2 Pt
r1 = k1 (9)
quality of the final product. Finally, to complete the cracking Ft RT kc1 Ft 2 RT
process and achieve the desired products, the cracked ma­
terials go to the compressors and separators. Temperature FC2H6 Pt
control is a very important principle in this process in which r2 = k2 (10)
Ft RT
case precise thermocouples are used. The lower tempera­
tures do not cause cracking reactions, and the higher tem­
peratures cause the hot spots on the furnace and the coke FC3H8 Pt
r3 = k3 (11)
production. The temperature of the cracking reaction is be­ Ft RT
tween 750 and 900 °C (Thermal/catalytic, 2015).
FC3H8 Pt
r4 = k4 (12)
2.2. Integrated reactor for combination of ethane thermal Ft RT
cracking with CLC process
2
FC3H6 Pt FC2H2 FCH 4 Pt
r5 = k5 (13)
The schematic of the proposed configuration has been pre­ Ft RT kc5 Ft2 RT
sented in Fig. 2(a). The conventional ethane thermal cracking
reactor has been replaced by the novel configuration con­ 2
FC2H2 FC2H 4 Pt
taining three integrated series reactors. The conventional r6 = k6 (14)
Ft 2 RT
thermal cracking reactor, which is more than 90 m long, is
676 Chemical Engineering Research and Design 186 (2022) 672–684

Fig. 2 – (a) The schematic of the suggested configuration for combination of the thermal cracking process with the CLC
process and (b) the detailed schematic of an integrated reactor.

solid core that has not yet reacted with the gas. As gas passes
FC2H6 Pt through the ash toward the surface of the solid core, the solid
r7 = k7 (15)
Ft RT is constantly reduced in volume and eventually turns to ash.
In the non-catalytic systems, the density ratio of the ash to
FC2H6 FC2H 4 Pt 2 the solid can predict reaction conversion over time (Liu et al.,
r8 = k8 (16) 2014; Hossain and de Lasa, 2008; Wesenauer et al., 2020).
Ft 2 RT
The material selected as the oxygen carrier should have
The rate and equilibrium constants, as well as the heat of the special properties such as high melting point, high avail­
reactions presented in this kinetic model, are given in Table 2. ability, low price, sufficient capacity to carry oxygen, pro­
viding suitable rate for oxidation and reduction, stability
3.2. Chemical looping combustion process under oxidation-reduction reactions, and providing the
thermodynamic conditions for complete combustion of the
The shrinking core model is one of the simplest and most gases fuels (De Diego et al., 2004; Arjmand et al., 2014; Yang
practical kinetic models for oxygen carrier reduction-oxida­ et al., 2015). Zylka et al. (2019) studied a system for simula­
tion reactions as the two main reactions in the chemical tion of copper-based oxygen carriers in the CLC reactor. They
looping combustion reactors based on the porosity and the used the combination of copper, ilmenite and fly ash as an
size of oxygen carrier particles in the solid-gas systems oxygen carrier, which succeeded in increasing the reaction
(Amiri et al., 2015). The ash is the product of the reaction rate and oxygen carrier capacity by using the combination of
between the gases and solid that covers the area around the iG-CLC and CLOU methods.
 Chemical Engineering Research and Design 186 (2022) 672–684 677

Table 1 – Specific properties and operating conditions of the integrated reactors.

Parameter 1st reactor 2nd reactor 3rd reactor

Inner, middle and outer diameters (m) 0.108, 2.70, 4.47 0.108, 2.37, 3.98 0.108, 2.23, 3.81
Length (m) 25 32 38
Specific properties and operating conditions for the ethane thermal cracking process (Koyama and Dranoff, 1992).
Parameter Numerical value Unit
Steam to hydrocarbon mass ratio 0.4 –
Mass flow rate of ethane feed 2265 kg/h
Inlet temperature 680 °C
Inlet pressure 1.356 atm abs
Specific properties and operating conditions for the chemical looping combustion (Air reactor).
Parameter Numerical value Unit
Air mass flow rate for each bed 4700 kg/h
Mass flow rate of Ni for each bed 756 kg/h
Inlet temperature 1200 °C
Inlet pressure 1700 kPa
Bed porosity 0.52 –
Specific properties and operating conditions for the chemical looping combustion (Fuel reactor).
Parameter Numerical value Unit
Methane mass flow rate for each bed 86.5, 144.3, 52.0 kg/h
Mass flow rate of NiO for each bed 756 kg/h
Inlet temperature 1200 °C
Inlet pressure 1000 kPa
Bed porosity 0.52 –

kJ
Table 2 – Rate constants and heat of reactions for the CH4 + 4NiO 4Ni + CO2 + 2H2 O = 156.5 (18)
mol
ethane thermal cracking.
E
The rate of oxidation and reduction reactions have been
ki =k0 exp( RTi ) k0 (s 1
or mol 1s 1 ) E ( J /mol )10 5 H (kJ /mol )
given as below (Dueso et al., 2012):
k1 4.651013 2.73 136.33 dXs 3 2
rs = = (1 Xs ) 3 (19)
k2 3.851011 2.73 -11.56 dt
k3 5.891010 2.15 124.91
m rg
k4 4.691010 2.12 82.67 = (20)
bi k Cn
k5 6.81108 1.54 133.45
k6 1.03109 1.73 -171.47 E
k = k0 e RT (21)
k7 6.371023 5.30 71.10
k8 7.081010 2.53 -22.98 The following correlations are applied to calculate the
kc,1 8.49105 136.5 conversions of oxygen carrier in both air and fuel reactors,
kc,2 3.81105 147.2 respectively:
mNiO
Xs, AR = (22)
mNiO + mNi
Idziak et al. (2020) investigated various materials such as
iron, nickel, cobalt, and copper to compare their properties as Xs, FR = 1 Xs, AR (23)
oxygen carriers. In this study, it was found that nickel oxide Table 3 presents the properties of the oxygen carrier, as
is faster than other oxygen carriers and it is considered as a well as the kinetic parameters of oxidation and reduction
strong oxygen carrier. Although iron and its compounds are reactions, occurred in air and fuel sides of integrated re­
compatible with nature, they do not show the appropriate actors.
rate and resistance in oxidation and reduction reactions.
Copper has many concerns for the environment. Despite its 4. Mathematical modeling
high reactivity, it cannot be a suitable oxygen carrier. On the
other hand, manganese causes problems in the system due The component, energy and momentum balances have been
to its magnetism. separately used for the conventional and the integrated re­
Among the various metals found in nature, nickel, man­ actors to obtain the performance of each system and predict
ganese, copper, and iron have the most mentioned proper­ the effects of design parameters on their behaviors. Due to
ties to volunteer for oxygen transfer between air and fuel the axial movement of the currents through both types of
reactors (De Diego et al., 2004; Arjmand et al., 2014; Cabello reactors, the one-dimensional and homogenous mathema­
et al., 2014). The nickel has been used as the appropriate tical model has been derived in the present study. Besides,
oxygen carrier in the chemical looping combustion process The following assumptions are used to simplify the gov­
in this work. Hence, the following reactions are carried out in erning equations:
the air and fuel reactors, respectively (Lyngfelt et al., 2001):
1. steady-state conditions are implemented for both con­
kJ
O2 + 2Ni 2NiO = 479.4 (17) ventional and integrated reactors.
mol
678 Chemical Engineering Research and Design 186 (2022) 672–684

Where R1 R5 are the heat transfer resistances associated

Table 3 – Kinetic parameters for the oxidation and
with convection of process gas stream, conduction of coke
reduction of the NiO18-Al2O3 oxygen-carriers (Dueso
et al., 2012). layer, conduction of tube wall thickness, convection of fur­
nace medium and radiation between furnace and tube wall,
reaction n k0 (mol1 n. m3n 2 / s) E (kj /mol )
respectively.
oxidation 0.7 0.84 22 To calculate the pressure drop in the conventional
reduction 0.2 0.20 5 cracking reactor, the following equation has been applied:
Properties of NiO18-Al2O3 oxygen-carriers.
parameter value unit dPt,1 G2 du
= Fr +G (33)
NiO content 18 wt% dz dz
Particle porosity 0.43 –
Particle density 2.5 g/cm3 In Eq. (33), Fr is the fraction coefficient and is estimated for
Specific surface area 7 m2/g the straight parts (Fr, s) and bends (Fr, b) as follows:

Re 0.2
Fr, s = 0.092 (34)
D1
2. The air and fuel reactors are assumed to be moving beds
that the non-catalytic solid-gas reactions occurred Re 0.2
Fr, b = 0.092 + (35)
in them. D1 Rb
3. The energy loss from the outer wall of the integrated re­
where
actors is insignificant.
4. The streams through each side of the reactors are con­ D1
sidered as ideal gases. = 0.7 1 + 0.51 + 0.19 (36)
90° Rb
5. The mass and heat axial dispersions aren’t considered
inside the thermally coupled reactors. In the above correlation, and Rb are the angle and radius
of tube bend, respectively. Equations (37) and (38) present the
The mass and energy balance equations in ethane pyr­ mass and energy balances in the air reactor:
olysis reactor are derived as follows:
dFi,2 b,2
dFi,1 8 = Ac,2 (1 b,2 ) rsi,2 (37)
D12 dz M. Ws,2
= ij rij (24)
dz 4 j=1

g g dT2
(Ftot ,2 Cp,2 + Us,2 Cp, s,2 )
dT dz
Fi,1 Cp, i,1 1
i dz b,2
8
= Ac,2 (1 b,2 ) rs2 ( Hf ,2 ) ( D1 ) (38)
D12 M. Ws,2
= (1 )Q D1 + rj ( H) + ( D1 ) (25)
4 j= 1 U1 2 (T2 T1 ) ( D2 ) U2 3 (T2 T3 )
U1 2 (T2 T1 )
As well as, the governing equations in the fuel side of
In the equation (25), is a constant coefficient that it is integrated reactors have been derived as follows:
considered to be zero for the conventional ethane cracking dFi,3 b,3
process and 1 for the modeling of the integrated reactor. Also = Ac,3 (1 b,3 ) rsi,3 (39)
dz M. Ws,3
Q is the heat flux transferred from the furnace to the ethane
cracking reactor and is empirically calculated by the corre­
dT3 b,3
lation below:
g
(Ftot Cg + Us,3 Cp, s,3)
,3 p,3
= Ac,3 (1 b,3 ) rs3
dz M. Ws,3
(40)
d2 ( Hf ,3 ) + ( D2 ) U2 3 (T2 T3 )
Q = U t ( Tf T) (26)
4
U1 2 and U2 3 are the overall heat transfer coefficients
U is overall heat transfer coefficient which:
between different sides of the proposed reactors and are
1 estimated as follows (Smith et al., 2001):
U= (27)
Rt
D
1 1 A1 ln( D2 ) A 1
Rt is total heat transfer resistance: = + 1
+ 1 (41)
U1 2 h1 2 Lkw,1 2 A2 h2
Ac
R1 = (28)
(D1 Dc ) zhi D
1 1 A2 ln( D3 ) A 1
= + 2
+ 2 (42)
U2 h2 2 Lkw,2 3 A3 h3
Acln ( D1
D1 2tc ) (29)
3

R2 = h1, the convection heat transfer coefficient in the cracking

2 kc z
side of novel reactors is calculated by the equation below
Acln ( ) D2
D1
(30)
(Holman, 2002):
R3 = 0.83 0.42
2 kw z hD g ug D µCp
Nu = = 0.015 (43)
kt µ kt
Ac
R4 = (31)
D2 zh0 Subsequently, h2 and h3 are the convection heat transfer
coefficients in air and fuel reactors, respectively and are es­
Ac timated by following empirical correlation (Wen and
R5 = (32)
f( . F) (Tf + Tw )(T2f + T2w ) zD Ding, 2006):
 Chemical Engineering Research and Design 186 (2022) 672–684 679

Table 4 – Comparison between simulation results and industrial information for the ethane thermal cracking process.
Simulation results

Plant (Koyama and Dranoff, 1992) Conventional reactor (coil) Integrated reactor

Yield (wt%)
Ethylene 47.926 46.232 51.761
Hydrogen 3.793 3.678 4.228
Methane 3.209 3.858 5.274
Propylene 0.653 0.721 0.738
Ethane conversion (%) 60.810 59.790 69.480
Temperature (0C) 849.200 802.900 815.900

0.365
kt g u g dp
h=4 (44)
dp µ

To solve the above ordinary differential equations, the

numerical method of Runge-Kutta has been applied in
MATLAB software.

5. Results and discussions

5.1. Model validation

Table 4 gives information about the modeling results of the

conventional and integrated reactors of the ethane pyrolysis
process, such as temperature and output yield of some im­
portant process components, as well as industrial data.
Firstly, the industrial ethane cracking reactor (coil) has been
simulated through equations (24−44). According to Table 4,
obtained results from the simulation are in good agreement
with the industrial data. Therefore, the governing equations
can be used for modeling the proposed novel system to
predict the behavior of the integrated reactor and to in­
vestigate the effects of design parameters on its perfor­
mance.

5.2. Results

Fig. 3(a) presents the profiles of ethane and ethylene molar

flow rates as the main components of the ethane thermal
Fig. 3 – (a) The molar flow rates of the ethane and ethylene
cracking process in both conventional and integrated re­
and (b) the molar flow rates of propylene and hydrogen for
actors. The molar flow rate of ethane reduces due to breaking
ethane thermal cracking process in both conventional and
its carbon-carbon bonds during the thermal cracking reac­
integrated configurations.
tions in both types of reactors, but this reduction is more
pronounced in the integrated reactors. With the coupling of
the thermal cracking reactor and the chemical looping
combustion process in the proposed system, the exothermic
oxidation reaction that occurs in the air reactor is used to
supply the required heat for the cracking process. This in­
direct combination causes more heat transfer flux from the
air reactor toward the thermal cracking reactor compared to
the furnace in the conventional system. Consequently, en­
larged heat flux to the cracking pipes increases the conver­
sion rate of ethane to ethylene and further reduces the molar
flow rate of ethane. In addition, new integrated reactors use
CO2 produced in the fuel reactor instead of water steam to
dilute the inlet feed of the cracking reactor, which speeds up
the pyrolysis of carbon-carbon bonds inside the cracking
tubes. The final amount of ethane in the conventional
thermal cracking reactor is about 8.4 mol/s, while this
reaches around 6.3 mol/s in the proposed new reactors with a
decrease of about 24%. The intensity of the ethane reduction Fig. 4 – Temperature profile and ethane conversion in both
rate in the last coupled reactor is more than in the previous conventional and integrated reactors.
680 Chemical Engineering Research and Design 186 (2022) 672–684

two reactors. Because the length of the third reactor is more

than the other two reactors, the residence time of the stream
through it is more than the others. As well as, the tempera­
ture inside the third reactor is higher than the temperature of
the first two reactors (Fig. 4). This figure also shows the
profile of ethylene molar flow as the main product of the
ethane pyrolysis process. Increasing the cracking rate of
carbon-carbon bonds in ethane feed improves the rate of
ethylene production. The production yield of ethylene in the
conventional reactor is around 47.9%, while in the integrated
reactors is about 51.8%.
Fig. 3(b) illustrates the changes of the hydrogen and pro­
pylene molar flow rates as by-products of the ethane pyr­
olysis process for both conventional and integrated reactors.
According to the mentioned kinetic model to describe the
ethane thermal cracking process (equations 1–8), propylene
is produced in the third and eighth reactions and is con­
sumed in the fifth reaction. In both conventional and in­
tegrated reactors, the molar flow rate of propylene increases,
because the production rate of propylene during the cracking
process is higher than its consumption rate. As can be seen
in this figure, at the beginning of the process, due to the low
input heat flux to the integrated and conventional cracking
reactors and consequently, the low cracking reactor tem­
perature, the rate of ethane conversion and propylene pro­
duction is low. In the suggested integrated reactors, the
higher rate of nickel oxidation reaction causes a higher heat
transfer toward the cracking tubes compared to the furnace
in the conventional cracking process. Accordingly, propylene
Fig. 5 – (a) The molar flow rates of the oxygen and NiO in
production in all parts of coupled reactors is higher than the
conventional ones. The difference in the molar flow rate of the air reactor (middle side) and (b) the molar flow rates of
propylene produced between two novel and conventional methane, CO2 and steam in the fuel reactor (outer side).
systems increases during the process until it reaches the
maximum value (around 0.02 mol/s) at the dimensionless because of the higher heat fluxes of the furnace. The output
length of x = 0.87. After this point, due to the excessive rise of ethane conversion in the conventional coil is about 59%.
the cracking environment temperature, the rate of propylene Supplying of required thermal energy for the ethane pyr­
consumption (reaction (5)) overcomes its production rate olysis process in the suggested reactors is the responsibility
(reactions (3) and (8)) and therefore, the propylene molar flow of the CLC process, especially the air reactor. This fact is
rate falls slightly. The propylene molar flow rate at the shown in Fig. 2. Due to the highly exothermic nature of the
output of the third integrated reactor is about 25% higher nickel oxidation reaction in the air reactor, this process is a
than the amount produced at the conventional system. suitable heat source for the thermal ethane cracking process.
Fig. 3(b) also demonstrates the molar flow rate of hydrogen as Furthermore, since the nickel oxidation reaction generates a
one of the most important products of the ethane thermal high amount of thermal energy, it can provide the heat re­
cracking versus the length of conventional and coupled re­ quired for the reduction reaction in the fuel reactor (outer
actors. As previously mentioned, due to the heat flux trans­ side) (Dueso et al., 2012; Dueso et al., 2012; Luis et al., 2008).
ferred to the ethane cracking tubes at the beginning of the For this reason, it has been suggested that the nickel oxida­
process (x = 0.06), the molar flow rate of hydrogen production tion reaction should be performed in the intermediate
is negligible in both conventional and integrating systems. channel of integrated reactors to supply the thermal energy
The hydrogen production profile in the proposed configura­ required for both cracking and reduction reactions that take
tion has a completely upward trend and the molar flow rate place in the inner and outer sides of the proposed reactors,
of hydrogen produced in the output of the third integrated respectively. The heat flux transferred to the cracking tubes
reactor is reached about 13.3 mol/s, which is about 15% more by the air reactor in the proposed configuration is higher
than its molar flow rate in a conventional reactor. than the heat flux applied by the furnace in a conventional
The ethane thermal cracking temperature changes, as reactor. As well as, the addition of carbon dioxide instead of
well as its conversion profile in both types of integrated and steam to the ethane feed increases the cracking reactor
conventional reactors have been illustrated in Fig. 4. As the temperature and improves the conversion of ethane to
thermal cracking process is highly endothermic, it requires ethylene. Therefore, the temperature of cracking pipes in all
thermal energy to perform. Therefore, the furnace is applied three coupled reactors is higher than the conventional re­
to provide the heat required for the cracking process actor temperature. Consequently, the ethane conversion in
(Fig. 1(b)). The convection section of the furnace is used to the proposed system is higher than the conventional system.
preheat the ethane feed (ethane and steam) and the radia­ The final ethane conversion from the last coupled reactor is
tion part is applied to perform the pyrolysis reactions. In the about 69%.
conventional system, the increase in reactor temperature at Fig. 5(a) presents the molar flow rate of oxygen versus the
the initial lengths of the coil is greater than the final lengths, length of the middle sides of the integrated reactors. As the
 Chemical Engineering Research and Design 186 (2022) 672–684 681

oxidation process takes place in the air reactor, nickel is

converted to nickel oxide by capturing oxygen molecules,
and as expected, the amount of nickel oxide increases along
with the integrated reactors. As can be seen in Fig. 5(a),
oxygen carrier and air (oxygen) enter into each integrated
reactor as fresh feeds. Since at the beginning of the oxidation
reaction, oxygen as the main reactant of the oxidation pro­
cess has a high concentration, the rate of nickel conversion is
approximately high. For this reason, the increase in the slope
of the oxygen molar flow rate at the inlet of each integrated
reactor is steeper than other lengths. As the oxidation reac­
tion progresses, two factors will slow down the nickel oxide
production rate. Firstly, the concentration of oxygen de­
creases along the coupled reactors during the reaction. The
second reason is that by passing hot currents inside the air
reactor, heat is continuously transferring from the air reactor
to the internal and external sides. The elimination of heat
flux from the air reactor reduces the temperature of the air
reactor and consequently, the rate of the oxidation reaction
is greatly decreased. The average molar flow rate of NiO
produced at the output of each integrated reactor is ap­
proximately 2.25 mol/s. As shown in this figure, it is sug­
gested that the amount of molar flow of inlet excess air in all
three coupled reactors are equal and contain around
9.45 mol/s of oxygen. Fig. 5(b) illustrates the trend of changes
in the methane molar flow rate as a reactant of the reduction
reaction, as well as, the molar flow rates of its products such Fig. 6 – (a) The temperature profiles and (b) the conversion
as H2O and CO2 along the length of the outer parts of com­ of oxygen carrier in both air and fuel reactors of CLC
bined reactors. The molar flow rate of methane reduces process.
during the reduction reaction in the reactor. Due to the high
speed of the reduction reaction at the beginning of the pro­ endothermic reaction and also the feed temperature of the
cess, the slope of the methane profiles is significantly high fuel reactor is the same as the feed temperature of the air
and after that, it decreases in other lengths of fuel reactors. reactor and therefore, no heat enters from the middle side to
Methane enters the fuel sides of the suggested reactors as the outer part at the beginning of the reduction, the tem­
the excess reactant. Methane is inexpensive and available, so perature of this process falls in all three coupled reactors.
it is used more than the required amount at the inlet fuel After that, with increasing the air reactor temperature and
reactor to provide adequate feed flow rate as well as high thus increasing the driving force of heat transfer, the amount
values of heat transfer coefficient at the exterior of these of input energy from the intermediate side to the fuel side
reactors. According to Fig. 5(a), the molar ratio of the steam increases and prevails over the energy consumption rate in
to carbon dioxide in all three coupled reactors is the same the fuel reactor. For this reason, the temperature in the fuel
and equal to 2. The produced CO2 is separated from H2O by reactor increases until it reaches the maximum value. The
condensation of steam and is added to the inlet of the maximum temperatures in the fuel sides of the integrated
cracking tubes. reactors are about 1632, 1585 and 1562 K, respectively.
Fig. 6(a) illustrates the temperature profiles of oxidation Hereafter, by reducing the temperature difference between
and reduction processes in the intermediate and external air and fuel reactors, the thermal energy consumed in the
channels of all three integrated reactors, respectively. Al­ external channel of the integrated reactors becomes more
though the heat transfers from both walls of middle in­ than the input thermal energy, and thus the temperature of
tegrated reactors to the internal (cracking process tubes) and this part reduces. The heat consumption rate decreases in
the external (reduction reaction) channels, the temperature the fuel reactor at the final lengths and in contrast, the inlet
of the intermediate channel (air reactor) in all three coupled heat rate to this side of novel reactors increases. In the
reactors rises at the beginning of the process. Because the second and third integrated reactors, the temperature of the
significant thermal energy is generated in the air reactor due fuel reactor is even slightly higher than the temperature of
to the highly exothermic nickel oxidation reaction and this the air reactor and causes heat to transfer from the external
thermal energy released overcomes the thermal energy re­ channels to the internal channels. Fig. 6(b) shows the con­
moved from the air reactor. As the oxidation reaction pro­ versions of oxygen carriers in air and fuel channels versus
ceeds, the rate of this reaction and consequently, the heat the lengths of three integrated reactors. As shown in the
generation rate decreases so that the amount of output en­ figure, the rate of oxidation-reduction reactions in both re­
ergy from the air reactor exceeds the amount of energy actors is significantly high at the beginning of the CLC pro­
generated through it at one point and thus, the temperature cess, so the nickel and nickel oxide conversion profiles have
decreases in all three coupled reactors. As a result, the initially steeper slopes. Because the temperature of the air
maximum temperatures in the three air reactors are about reactor in all parts of the integrated reactors is higher than
1657, 1607 and 1589 K, respectively. Fig. 6(a) also presents the the fuel reactor temperature (Fig. 6(a)), the rate of oxygen
temperature profile of the reduction process along with the carrier conversion in the middle channel is always higher
integrated reactors. Since the nickel oxide reduction is an than the external channel. As a result, the oxidation reaction
682 Chemical Engineering Research and Design 186 (2022) 672–684
Fig. 7 – The conversion of ethane in different feed
temperatures and different mass flow rates of ethane feed.
is performed completely in all three coupled reactors.
Oxygen carrier conversions in fuel reactors are approxi­
mately 96.9%, 98.2% and 97.6%, respectively.
The effects of two design parameters of temperature and
mass flow rate of input ethane feed to the first coupled re­
actor on the ethane conversion in the proposed configuration
have been demonstrated in Fig. 7. Increasing the tempera­
ture of ethane feed at the inlet of the first reactor leads to an
increase in the rate of cracking reactions in the internal
tubes. Thus, the ethane conversion enhances by raising its
temperature. As can be seen in this figure, by enhancing the
ethane feed temperature from 900 K to 1100 K at a constant
mass flow rate of 2250 kg/h, the conversion of this reactant
improves by about 25%. As well as, the effect of changing the
mass flow rate of ethane feed on the performance of the
suggested system is investigated in this figure. Reducing the
mass flow rate of ethane feed in the cracking pipes leads to a
decrease in heat transfer coefficient in this part (h1) and thus,
reduces the heat transfer from the air reactor to it. In con­
trast, as the ethane mass flow rate reduces in the cracking
reactor, the residence time of the currents in the inner tubes
increases, so leading to further breakdown of the carbon-
carbon bonds. The effect of increasing the residence time of
currents is higher than the effect of decreasing the heat
transfer coefficient. Therefore, reducing the input of the
ethane mass flow rate increases its conversion during the
thermal cracking process. For example, at 950 K of cracking
feed, the conversion of ethane increases from 68% to 75% by
decreasing the mass of ethane from 2300 kg/h to 2100 kg/h.
Fig. 8 demonstrates the changes in final ethane conver­
sion at different temperatures of air and fuel feeds in the new
integrated configuration. Higher temperatures of the air re­
actor feed (oxygen gas) lead to higher rates of thermal energy
generated by the oxidation reaction in this reactor. Because
as the inlet temperature of oxygen feed increases, the oxi­
dation rate of nickel to nickel oxide improves in all three
coupled reactors. Furthermore, increasing the inlet tem­
perature of the middle side of the integrated reactors causes
an increase in the temperature difference between the air
and the cracking reactors. Hence, the driving force of heat
transfer increases between these sides. Subsequently, the
rate of thermal cracking reactions improves, which leads to
an increase in the ethane conversion. In this study, the inlet
temperature of the middle channels has been changed from
1350 K to 1550 K. The effect of the feed temperature of fuel
reactor (methane) on the performance of integrated reactors
Fig. 8 – The conversion of ethane in different feed
temperatures of air and fuel reactors.
has also been investigated in Fig. 8. Increasing the feed
temperature of the fuel reactor diminishes the temperature
difference between oxidation and reduction processes.
Therefore, the heat flux transferred reduces from the middle
channel to the external channel. This leads to an increase in
the temperature through the middle channel and thus, the
heat flux increases from this part of the integrated reactors
to the cracking pipes. Consequently, raising the temperature
of the methane feed entering the fuel reactor increases the
ethane conversion and improves the ethylene production
rate. According to the results, the effect of fuel reactor feed
temperature on the performance of the thermal cracking
process is much less than the effect of air reactor feed tem­
perature on this process. For example, at 1350 K of air reactor
feed, by changing the fuel reactor feed temperature from
1350 K to 1550 K, the conversion of ethane increases by about
5%. While, at 1350 K of the methane feed, as the temperature
of the oxygen feed increases by 200 0C, the ethane conversion
increases by about 29%.
6. Conclusion
In this work, the combining of the ethane thermal cracking
reactor with the CLC process has been investigated. It is
suggested that the chemical looping combustion process as
an alternative to the furnace be performed in the novel in­
tegrated reactors to provide the heat required for the ethane
thermal cracking process. Other advantages of coupling the
thermal cracking process with CLC are saving of equipment
and maintenance costs, as well as reducing the emission of
environmental pollutants. The homogenous mathematical
model has been derived in the axial direction for predicting
the performance of the new integrated reactors. The simu­
lation results have been compared with the industrial data of
a conventional cracking coil. According to the results, there is
good agreement between the results of this modeling and
industrial data. Furthermore, the ethylene production yield
has been increased by about 12% by this novel configuration.
Using CO2 produced in the reduction process instead of
steam in the new proposed reactors increases the ethane
conversion and also, large amounts of CO2 are prevented
from entering the atmosphere. The effects of some design
parameters on the thermal cracking of ethane have also been
investigated. According to the achieved results, reducing the
mass flow rate of ethane enhances the ethane conversion in
the cracking reactors. Also, the positive effect of the inlet
 Chemical Engineering Research and Design 186 (2022) 672–684 683

feed temperature of the air reactor on the cracking ethane an impregnated NiO-based oxygen-carrier for chemical-
conversion has been demonstrated. In addition, it is found looping combustion (CLC). Appl. Catal. B: Environ. 126,
186–199.
that an increase in ethane feed temperature increases its
Dueso, C., Ortiz, M., Abad, A., García-Labiano, F., Luis, F., Gayán,
conversion and thus improves the production yield of
P., Adánez, J., 2012. Reduction and oxidation kinetics of nickel-
ethylene. based oxygen-carriers for chemical-looping combustion and
chemical-looping reforming. Chem. Eng. J. 188, 142–154.
Declaration of Competing Interest Ebrahimian, S., Iranshahi, D., Bahmanpour, A.M., 2019. A novel
reactor concept for thermal integration of naphtha reforming
with propane ammoxidation. Chem. Eng. Process. -Process.
The authors declare that they have no known competing fi­
Intensif. 146, 107659.
nancial interests or personal relationships that could have
Feli, Z., Darvishi, A., Bakhtyari, A., Rahimpour, M.R., Raeissi, S.,
appeared to influence the work reported in this paper. 2017. Investigation of propane addition to the feed stream of a
commercial ethane thermal cracker as supplementary feed­
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