AASCIT Journal of Energy

2017; 4(3): 12-18

http://www.aascit.org/journal/energy
ISSN: 2381-1315 (Print); ISSN: 2381-1323 (Online)

Conceptual Study of Fixed-Bed

Tri-Reforming Reactor Based on a
Dynamic Model to More Careful
Examination of Synthesis Gas
Production
Mahmoud Bemani1, 2, Iman Ahmadi Kakavandi2,
Ehsan Javadi Shokroo2, 3, Mehdi Farniaei2, Mehdi Baghbani2
1
Department of Chemical Engineering, Islamic Azad University Science and Research Branch,
Shiraz, Iran
2
Department of Research and Development, Fateh Danesh Sourena Part Shimi-Fapkco
Keywords Engineering Group, Shiraz, Iran
Tri-Reformer Reactor, 3
Chemical Engineering Department, Selinus University of Sciences and Literature, Bologna, Italy
Synthesis Gas,
Modeling, Email address
Dynamic Model ehsan.javadi@hotmail.com (E. J. Shokroo)

Citation
Mahmoud Bemani, Iman Ahmadi Kakavandi, Ehsan Javadi Shokroo, Mehdi Farniaei, Mehdi
Baghbani. Conceptual Study of Fixed-Bed Tri-Reforming Reactor Based on a Dynamic Model to
Received: July 18, 2017
More Careful Examination of Synthesis Gas Production. AASCIT Journal of Energy.
Accepted: November 19, 2017
Vol. 4, No. 3, 2017, pp. 12-18.
Published: December 18, 2017
Abstract
The tri-reformer reactors play an important role in methanol production units, enhancing
efficiency of synthesis gas preparation required to produce methanol. In the present
work, using energy and mass balances and by exerting an appropriate kinetic model, a
proper dynamic and homogeneous model was proposed. The obtained equations were
solved by means of MATLAB® software. In certain circumstances, changes of various
parameters versus length of the rector and time were examined. Eventually, effects of the
major parameters, including inlet temperature and ratio of inlet material (CO2/CH4,
O2/CH4 and steam/CH4), using the proposed model were studied. The results showed that
increase of oxygen to methane ratio and steam to methane ratio, and also decrease of the
temperature led to enhance hydrogen amount in product.

1. Introduction
In recent years, the technologies of hydrogen production have attracted many interests
because of the main role of hydrogen in various applications, including purification of
oil, methanol, diethyl ether, ammonia and aniline [1].
Methanol is one of the most important alcohols having many applications, especially,
in public fields. The alcohol has also been applied in industrial as solvent, fuel and initial
material in production process of chemical material including formaldehyde, methyl
halides, methyl amines and acetic acid [1].
Little percent of methanol has been attained by using distillation and wood fermentation
methods. Direct oxidation of hydrocarbons also led to a little production of hydrogen. The
most important method to produce methanol is involved to utilize the synthesis gas. In
other word, the mentioned method leads to produce the majority methanol in all world. The
synthesis gas is a combination of CO and H2, which it produces from reaction of natural
gas or other hydrocarbons with air and oxygen or steam [2].
13 Mahmoud Bemani et al.: Conceptual Study of Fixed-Bed Tri-Reforming Reactor Based on a Dynamic Model to
More Careful Examination of Synthesis Gas Production
Three major catalytic reactions occur to convert natural
gas to synthesis gas:
1- Steam methane reforming (SMR):
°
CH 4 + H 2O ↔ CO + 3H 2 ∆H 298 = 206.3kJ / mol (1)
2- Carbon dioxide reforming (CDR) or dry methane
reforming
CH 4 + CO2 ↔ 2CO + 2 H 2 ∆H 298 = 247.3kJ / mol (2)
3- Partial oxidation of methane (POM)
CH 4 + 1 2 O2 ↔ CO + 2 H 2 ∆H 298 = −35.6kJ / mol (3)
Recently, Song [3] reported a new method named tri-
reforming methan (TRM) to produce synthesis gas. In the
process, CO2 reforming was carried out by steam and partial
oxidation of methane in a reactor. During the reactions, O2 and
H2O make decrease of deposition of carbon on the catalyst,
and the H2 to CO ratio in TRM should be controlled to achieve
an optimum of the ratio. Accordingly, process TRM is a
combination of endothermic and exothermic reforming. In the
new method, to produce synthesis gas, a fixed-bed tri-reformer
reactor is used instead of CAR and CSR. The heat produced
from POM process is applied in the reforming process.
Therefore, the energy will be saved [4]. It should be noted that
in process TRM the obtained CO2 from wasted gases can be
exploited as Co-Reactant to produce synthesis gas, which has a
wide applications in industrial including methanol production
and dimethyl ether production. It is predicted that the
respective process can be used to convert low quality natural
gas to valuable synthesis gas [5].
Lee et al. studied TRM using CO2 to produce the synthesis
gas needed dimethyl ether production [6]. The results,
obtained using TRM by utilizing Ni/Ce-ZrO2 and Ni/ZrO2
catalysts and Haldor Topsoe R67-7H, showed that the
catalysts caused to considerably decrease deposition of coke
on the floor and walls of the reactor. Maciel et al. [7] studied
the kinetic of TRM process to produce the synthesis gas.
Conversion of natural gas in a fixed-bed reactor containing
catalyst Ni/ -Al2O3 was examined. The kinetic was
examined at temperature ranging from 923 to 1123 K and
atmospheric pressure condition. The results showed that at
temperatures beyond 1000 K and in conversion percents for
methane and carbon dioxide equal to 97/35 and 46/75,
respectively, the production percents for carbon monoxide
and hydrogen were attained up to 4/99 and 37/35,
respectively.
Arab et al. [4] studied optimization of the fixed-bed tri-
reformer reactor in stable condition. The reactor is very often
replaced to the conventional steam reformer and the heat
automatic reformer, and the reactor makes the big furnaces
remove from the steam reforming process. In the process a
heterogeneous mathematical model was used to simulate the
reactor and key operational parameters such as inlet
temperature and O2 to CH4 ratio were analyzed. The obtained
results showed that the methane conversion was high and
hydrogen to carbon dioxide ratio was in a suitable range that
it can be used as feed of methane unit.
Rahim pour et al. [8] proposed the production of synthesis
gas in a tri-reformer rector to use in producing methanol in a
stable condition. They suggested a fixed-bed membrane
reactor instead of methane steam reformer. The process was
simulated by hysys software. They deduced that by using the
process the oxygen consumption was considerably saved.
Syngas, a mixture of carbon monoxide and hydrogen,
plays a very important role in chemical industries and can be
converted to bulk chemicals like methanol, dimethyl ether,
aldehydes, hydrogen, and ammonia [9-14].
2. Reaction Scheme and Kinetics
In the present work, it supposes that the follow reactions
will be occurred in the tri-reformer reactor:
°
CH 4 + H 2O ↔ CO + 3H 2 ∆H 298
= 206.3kJ / mol (4)
CH 4 + 2 H 2O ↔ CO2 + 4 H 2 ∆H 298 = 164.9kJ / mol (5)
CO + H 2 O ↔ CO2 + H 2 ∆H 298 = −41.1kJ / mol (6)
CH 4 + 2O2 ↔ CO2 + 2 H 2O ∆H 298 = −802.7kJ / mol (7)
First reaction is steam reforming methane (SRM) and third
reaction is water-gas shift reaction (WGSR).
2.1. Assumptions
In the model, the follow assumptions were applied:
1- The gas phase is ideal.
2- The flow is one dimension and plug.
3- The axial diffusion of mass and heat are negligible.
4- Porosity of the bed is constant in radial and axial direct.
5- The process is homogeneous. Therefore, mass and
energy balance in single phase, gas phase, is performed.
6- Waste of heat is negligible.
7- The temperature of wall changes axially along the
reactor.
8- The inlet pressure of reactor is constant.
2.2. Modeling
The general mass balance equation in a dimension is as
follows:
∂ci ∂c ∂2c
+ u z i = D 2i + Ri (8)
∂t ∂z ∂z
In the above equation, ci is the concentration of component
i, uz is the gas phase velocity along direction z, D is the
diffusion coefficient and Ri is the reaction.
∂ 2 ci
The term D is eliminated with attention to the
∂z 2
assumption 3. Whereas the reaction is catalytic:
 AASCIT Journal of Energy 2017; 4(3): 12-18 14

ci = ε ct yi (9) temperature.
By replacing equation (15) to equation (13), the following
Where, ct is the total concentration, ε is the bed porosity equation will be attained:
and yi is the mass fraction of component i. The total
∂T π Di
N
concentration is constant. With attention to the assumption 4, ∂T F
ε ct c pg = − t c pg + U w (Tw − T ) + ρ B a η ri (−∆H fi ) (16)
∑
the bed porosity is constant. Thus, the terms ε and ct will be ∂t Aa ∂z Aa i =1
gotten out from the differential operation. With replacement
of equations (10) and (11), the final equation (12) for mass To obtain the total mass transfer coefficient, equation (17)
balance will be obtained: was used:

Ft 1 1 A ln( Do / Di )
ε ct u z = (10) = + i (17)
Aa U w hi 2π LK w

Where, Ft is the total flow in each reactor and Aa is the hi cp µ 0.458 ρ ud p −0.407
( )2/3 = ( ) (18)
cross section are of each reactor. c p ρµ k εB µ
To compute the reaction kinetic, by considering that the
reaction is catalytic, it can be say: Where, hi is the heat transfer coefficient between the fluid
Ri = η ri ρ Bα phase and the reactor wall, µ is the gas phase viscosity, k is
(11)
the conductivity in gas phase and dp is the droplet diameter.
In the above reaction, ri is the reaction kinetic of The boundary and initial conditions is as follow:
component i, η is the effect factor, ρB is the catalyst bed z = 0 → yi = yi 0 & T = T0
density and α is the catalyst activity.
t = 0 → yi = yiss & T = T ss
∂yi F ∂y
ε ct = − t i + η ri ρ B a (12)
∂t Aa ∂z The condition t=0 signifies the steady state. It means that
equations (17) and (18) will be solved by equaling to zero:
Equation (13) is expressed for the energy balance in one
Ft ∂yi
dimension: − + η ri ρ B a = 0 (19)
Aa ∂z
∂T ∂T ∂ 2T Q
+ uz =α 2 + (13)
∂T π Di
N
∂t ∂z ∂z ct c pg −
Ft
+ U w (Tw − T ) + ρ B a η ri ( −∆H fi ) = 0 (20)
Aa
c pg
∂z Aa i =1
∑
Where, T is temperature, α is the thermal diffusion
coefficient, cpg is the special heat in constant pressure and Q Where, i is number of species.
is the reaction heat. The respective kinetics are as follow:
As can be seen in the assumption 3, the thermal diffusion
rCH 4 = −η1 R1 − η2 R2 − η4 R4 (21)
∂ 2T
is disregarded. Therefore, term α will be eliminated.
∂z 2 rO2 = −2η4 R4 (22)
Since the system is catalytic, hence the expression should be
multiplied by ε. The reaction heat can obtain by equation
(14): rCO2 = η2 R2 + η3 R3 + η4 R4 (23)

N rH 2O = −η1 R1 − 2η2 R2 − η3 R3 + 2η4 R4 (24)

Q = ρB a ∑η r (−∆H
i fi ) (14)
i =1
rH 2 = 3η1 R1 + 4η2 R2 + η3 R3 (25)
In the above equation, ∆Hfi is the formation heat of
component i. rCO = η1 R1 − η3 R3 (26)
Furthermore, the heat also wastes among the reactor wall.
Therefore, the follow term is added to the main equation: In the equations we have:

π Di η1 = 0.07,η 2 = 0.06,η3 = 0.7,η 4 = 0.05

U w (Tw − T ) (15)
Aa
k1 pH3 2 pCO 1
R1 = ( pCH 4 pH 2O − )× (27)
Where, Di is the internal radius of the reactor, Uw is the pH2.52 KI ϕ2
total coefficient of mass transfer between the pipe wall and
the reaction region in the reformer and Tw is the wall
15 Mahmoud Bemani et al.: Conceptual Study of Fixed-Bed Tri-Reforming Reactor Based on a Dynamic Model to
More Careful Examination of Synthesis Gas Production

k2 pH4 2 pCO2 1 p H 2O
R2 = ( pCH 4 pH2 2O − )× (28) ϕ = 1 + K CO pCO + K H 2 p H 2 + K CH 4 pCH 4 + K H 2O (31)
pH3.52 K II ϕ2 pH 2

In table 1, the equilibrium constants and arrhenius kinetic

k3 p H 2 pCO2 1
R3 = ( pCO p H 2O − )× 2 (29) parameters are listed. Van't Hoff adsorption parameters are
pH 2 K III ϕ tabulated in table 2. The reactor characteristics are shown in
table 3.
k4a pCH 4 pO2 k4b pCH 4 pO2
R4 = + (30)
(1 + KCH 4 pCH 4 + K OC2
C
pO2 ) (1 + K CH 4 pCH 4 + K OC2
C
pO2 )

Table 1. Equilibrium constants and arrhenius kinetic parameters of the reactions [4].
Reaction, j Equilibrium constant, Kj koj (mol/(kgcat s)) Ej (J/mol)
−26830
1 K I = exp( + 30.114) 1.17×1015 bar0.5 240100
Ts
2 K II = K I .K III 2.83×1014 bar0.5 243900
4400
3 K III = exp( − 4.036) 5.43×105 bar-1 67130
Ts
5 -2
4 --- 8.11×10 bar 86000
−E j
k j = koj × exp( )
RT

catalyst. In this work it was assumed that the commercial

Table 2. Van't Hoff parameters for adsorption. catalyst (CuO/ZnO/Al2O3) was used. Accordingly, TR is
Koi (bar-1)
∆Hi KoiC ∆HiC equal to 513 K, Ed is equal to 91270 J/mol and Kd is up to
(J/mol) (bar-1) (J/mol) 0.00439 h-1.
CH4 6.65×10-4 -38280 The Euler method was used to solve the equations at
CO 8.23×10-5 -70650
version 7.8.0.347 (R2009a) Matlab software. Euler is a first
H2 6.12×10-9 -82900
order computational method. It means that the error
H2O 1.77×105 bar 88680
associated with each step depends on the square amount of
CH4 (combustion) 1.26×10-1 -27300
O2 (combustion) 1.26×10-7 -92800
the respective step, and the total error related to each step is
dependent on the amount of the respective step. Also, the
−∆H
Ki = Koi × exp( ) method is applicable for the stable problems. Therefore, the
RT
method is usually used as a basis for the more complicated
−∆H iC
K iC = koiC × exp( ) methods. Euler method is an explicit way that it uses the
RT
marching procedure to solve the equations. To solve in each
Table 3. The reactor characteristics. time interval, the method uses the past time interval. In this
method, the spatial derivative is performed as backward and
Parameter Quantity the time derivative is carried out as forward. The final
Pressure (bar) 40 formula is as follow:
Total flow rate of the feed (kmol/h) 9129.6
Number of pipes 184 uin +1 = (1 − υ )uin + υ uin−1 (33)
Internal diameter (mm) 124
The heated height (m) 2
C ∆t
Total volume of the catalyst (m3) 29.7 υ= (34)
Temperature (˚C) 790 ∆x
Particle diameter (mm) 16
External diameter of the pipe (mm) 130
Equation (35) will be attained using the present
expressions:
As time goes on, the catalyst will be deactivated in the reactor.
u (i, j + 1, k ) = (1 −ν )u (i, j , k ) + ν u (i − 1, j , k ) + F (k ) (35)
Therefore, in the present work the below expression will be used
to formulate the diminishing activity of the catalyst.
3. Results and Discussion
da −E 1 1
= − K d exp( d ( − ))a 5 (32)
dt R T TR 3.1. Examination of Changes Against the
Reactor Length and Time
Where, TR signifies the reference temperature, Ed is the
By solving the equations, three dimensional graphs were
activation energy and Kd is the deactivation constant of the
 AASCIT Journal of Energy 2017; 4(3): 12-18
attained, which showed in figure 1. These graphs are related
to mole fraction of hydrogen, carbon monoxide, carbon
dioxide, water, methane and oxygen and also gas phase
temperature, respectively. As can be seen in figure 1a,
hydrogen mole fraction along the reactor was increased and
the increase was less by passing time, which can be attributed
to diminishing activity of the catalyst.
Figure b1 shows that carbon monoxide was increased
along the reactor and the increase was less by passing time.
As can be seen in figure 1c, carbon dioxide amount was
firstly increased and then decreased. As time goes on, the more
increase and the less decrease can be seen in outset of the
reactor, and finally the carbon dioxide amount will be further.
Figure 1a. Changes of H2 against the reactor length and time.
Figure 1b. Changes of CO against the reactor length and time.
Figure 1c. Changes of CO2 against the reactor length and time.
16
3.2. Examination of Changes Versus the
Reactor Length and Final Time
In figure 2, hydrogen produced versus O2/CH4 ratio and in
various inlet temperatures were exhibited. As can be seen in
the graph, increase of inlet temperature led to increase of
hydrogen production. In other hand, increase of O2/CH4 ratio
caused to increase of hydrogen production too. Also, it can be
included when O2/CH4 ratio is around unit, the inlet
temperature doesn’t considerably affect on the hydrogen
production.
Figure 2. Effect of temperature on the hydrogen production.
Figure 3 shows H2/CO ratio versus O2/CH4 ratio in various
temperatures. Both Increase of temperature and of O2/CH4
ratio led to decrease of H2/CO ratio. It can also be deduced
when O2/CH4 ratio is about unit the temperature isn’t
effective.
Figure 3. Effect of temperature on the H2/CO ratio.
Figure 4 shows effect of steam/methane ratio on the
hydrogen production. With increase of the ratio, the hydrogen
production will also be increased. This increase is due to
consuming steam in the three reactions. It should be noted
17 Mahmoud Bemani et al.: Conceptual Study of Fixed-Bed Tri-Reforming Reactor Based on a Dynamic Model to
More Careful Examination of Synthesis Gas Production
that in high ratio of steam to methane, there is no significant
difference in the hydrogen production.
Figure 4. Effect of steam to methane ratio on the hydrogen production.
In figure 5, effect of steam to methane ratio on the
hydrogen to carbon monoxide ratio was shown. As can be
seen in figure 5 when steam to methane ratio was increased
the hydrogen to carbon monoxide ratio was also increased. In
other hand, increase of oxygen to methane ratio led to
decrease of hydrogen to carbon monoxide ratio. It is worthy
to say when oxygen to methane ratio is around unit the
change of steam to methane ratio doesn’t significantly affect
on the hydrogen to carbon monoxide ratio.
Figure 5. Effect of H2O/CH4 ratio on the H2/CO ratio.
Figure 6 exhibits the effect of oxygen to methane ratio in
various ratios of carbon dioxide to methane ratio. With
decrease of carbon dioxide to methane ratio the WGSR will
be gone to right side, based on Le Chatelier's principle. Thus,
the hydrogen production will be increased.
Figure 6. Effect of CO2/CH4 on the hydrogen production.
Figure 7 shows the changes of H2/CO against CO2/CH4 in
various amounts of O2/CH4. As can be seen in figure 7 the
changes have a minimum point that with increase of amount
of CO2/CH4 the point will go to less amount of O2/CH4.
Figure 7. Effect of CO2/CH4 on the hydrogen to carbon monoxide ratio.
4. Conclusion
The tri-reformer reactors play an important role in the
units associated with production of methanol. The reactors
enhance the efficiency of the synthesis gas production
required to produce methanol. In this work, the mass and
energy balances were examined and an appropriate kinetic
and model for the reactors in homogeneous and dynamic
condition was proposed.
By using the proposed model, the effects of key
parameters including inlet temperature and ratio of initial
material versus length of the reactor and time were studied.
The follow results were obtained using the modeling:
1- Increase of oxygen to methane ratio led to increase of
hydrogen production.
2- Increase of temperature led to decrease of hydrogen to
carbon monoxide ratio.
 AASCIT Journal of Energy 2017; 4(3): 12-18 18

3- The hydrogen to carbon monoxide ratio was decreased
by increasing oxygen to methane ratio.
4- Decrease of carbon dioxide to methane ratio led to
increase hydrogen production.
5- There is a minimum point in Changes of hydrogen to
carbon monoxide ratio versus changes of carbon dioxide to
methane ratio. When carbon dioxide to methane ratio was
increased, the minimum point was gone to decrease the
oxygen to methane ratio.

Nomenclature
overall heat transfer coefficient between tube wall and
Aa cross section area of reactor, m2 Uw
reaction side streams in steam reformer, Wm-2 K-1
mole fraction of component i in the fluid phase, mol
cpg specific heat of the gas at constant pressure, J mol-1 yi
mol-1
dp particle diameter, m Z axial coordinate, m
Di inside diameter of steam reformer, m
Ed the deactivation energy
Ft total flow rate per each reaction side, mol s-1
∆Hfi formation heat of component i, Wm-2 K-1
heat transfer coefficient between fluid phase and
hi
reactor wall, Wm-2 K-1
Kd deactivation constant of the catalyst Greek letters
reaction rate constant for the first rate equation, mol
Ki α activity of catalyst (where a = 1 for fresh catalyst)
kg-1 s-1
K conductivity of gas phase (W m-1 K-1) ρB density of catalyst bed, kg m-3
Q Heat due to the reaction, W ε void fraction of catalytic bed
reaction rate of component i (for exothermic
ri reaction: mol kg-1 s-1; for endothermic reaction: mol µ viscosity of fluid-phase (kg m-1 s-1)
m-3 s-1)
Ri
first rate of reaction for steam reforming of CH4, η effectiveness factor
mol kg-1 s-1
Tw wall temperature of steam reformer, K
TR signifies the reference temperature

[7] Leonardo J. L. Maciel • Aleksa´ndros E. A´. M. de Souza,

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