Professional Documents
Culture Documents
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 results showed that the methane conversion was high and
gas to synthesis gas: hydrogen to carbon dioxide ratio was in a suitable range that
1- Steam methane reforming (SMR): it can be used as feed of methane unit.
Rahim pour et al. [8] proposed the production of synthesis
°
CH 4 + H 2O ↔ CO + 3H 2 ∆H 298 = 206.3kJ / mol (1) gas in a tri-reformer rector to use in producing methanol in a
stable condition. They suggested a fixed-bed membrane
2- Carbon dioxide reforming (CDR) or dry methane reactor instead of methane steam reformer. The process was
reforming simulated by hysys software. They deduced that by using the
process the oxygen consumption was considerably saved.
CH 4 + CO2 ↔ 2CO + 2 H 2 ∆H 298 = 247.3kJ / mol (2)
Syngas, a mixture of carbon monoxide and hydrogen,
3- Partial oxidation of methane (POM) plays a very important role in chemical industries and can be
converted to bulk chemicals like methanol, dimethyl ether,
CH 4 + 1 2 O2 ↔ CO + 2 H 2 ∆H 298 = −35.6kJ / mol (3) aldehydes, hydrogen, and ammonia [9-14].
Recently, Song [3] reported a new method named tri- 2. Reaction Scheme and Kinetics
reforming methan (TRM) to produce synthesis gas. In the
process, CO2 reforming was carried out by steam and partial In the present work, it supposes that the follow reactions
oxidation of methane in a reactor. During the reactions, O2 and will be occurred in the tri-reformer reactor:
H2O make decrease of deposition of carbon on the catalyst,
°
CH 4 + H 2O ↔ CO + 3H 2 ∆H 298
and the H2 to CO ratio in TRM should be controlled to achieve = 206.3kJ / mol (4)
an optimum of the ratio. Accordingly, process TRM is a
combination of endothermic and exothermic reforming. In the CH 4 + 2 H 2O ↔ CO2 + 4 H 2 ∆H 298 = 164.9kJ / mol (5)
new method, to produce synthesis gas, a fixed-bed tri-reformer
reactor is used instead of CAR and CSR. The heat produced CO + H 2 O ↔ CO2 + H 2 ∆H 298 = −41.1kJ / mol (6)
from POM process is applied in the reforming process.
Therefore, the energy will be saved [4]. It should be noted that CH 4 + 2O2 ↔ CO2 + 2 H 2O ∆H 298 = −802.7kJ / mol (7)
in process TRM the obtained CO2 from wasted gases can be
First reaction is steam reforming methane (SRM) and third
exploited as Co-Reactant to produce synthesis gas, which has a
reaction is water-gas shift reaction (WGSR).
wide applications in industrial including methanol production
and dimethyl ether production. It is predicted that the 2.1. Assumptions
respective process can be used to convert low quality natural
gas to valuable synthesis gas [5]. In the model, the follow assumptions were applied:
Lee et al. studied TRM using CO2 to produce the synthesis 1- The gas phase is ideal.
gas needed dimethyl ether production [6]. The results, 2- The flow is one dimension and plug.
obtained using TRM by utilizing Ni/Ce-ZrO2 and Ni/ZrO2 3- The axial diffusion of mass and heat are negligible.
catalysts and Haldor Topsoe R67-7H, showed that the 4- Porosity of the bed is constant in radial and axial direct.
catalysts caused to considerably decrease deposition of coke 5- The process is homogeneous. Therefore, mass and
on the floor and walls of the reactor. Maciel et al. [7] studied energy balance in single phase, gas phase, is performed.
the kinetic of TRM process to produce the synthesis gas. 6- Waste of heat is negligible.
Conversion of natural gas in a fixed-bed reactor containing 7- The temperature of wall changes axially along the
catalyst Ni/ -Al2O3 was examined. The kinetic was reactor.
examined at temperature ranging from 923 to 1123 K and 8- The inlet pressure of reactor is constant.
atmospheric pressure condition. The results showed that at
2.2. Modeling
temperatures beyond 1000 K and in conversion percents for
methane and carbon dioxide equal to 97/35 and 46/75, The general mass balance equation in a dimension is as
respectively, the production percents for carbon monoxide follows:
and hydrogen were attained up to 4/99 and 37/35,
respectively. ∂ci ∂c ∂2c
Arab et al. [4] studied optimization of the fixed-bed tri- + u z i = D 2i + Ri (8)
∂t ∂z ∂z
reformer reactor in stable condition. The reactor is very often
replaced to the conventional steam reformer and the heat In the above equation, ci is the concentration of component
automatic reformer, and the reactor makes the big furnaces i, uz is the gas phase velocity along direction z, D is the
remove from the steam reforming process. In the process a diffusion coefficient and Ri is the reaction.
heterogeneous mathematical model was used to simulate the ∂ 2 ci
reactor and key operational parameters such as inlet The term D is eliminated with attention to the
temperature and O2 to CH4 ratio were analyzed. The obtained ∂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)
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
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
attained, which showed in figure 1. These graphs are related 3.2. Examination of Changes Versus the
to mole fraction of hydrogen, carbon monoxide, carbon Reactor Length and Final Time
dioxide, water, methane and oxygen and also gas phase
temperature, respectively. As can be seen in figure 1a, In figure 2, hydrogen produced versus O2/CH4 ratio and in
hydrogen mole fraction along the reactor was increased and various inlet temperatures were exhibited. As can be seen in
the increase was less by passing time, which can be attributed the graph, increase of inlet temperature led to increase of
to diminishing activity of the catalyst. hydrogen production. In other hand, increase of O2/CH4 ratio
Figure b1 shows that carbon monoxide was increased caused to increase of hydrogen production too. Also, it can be
along the reactor and the increase was less by passing time. included when O2/CH4 ratio is around unit, the inlet
As can be seen in figure 1c, carbon dioxide amount was temperature doesn’t considerably affect on the hydrogen
firstly increased and then decreased. As time goes on, the more production.
increase and the less decrease can be seen in outset of the
reactor, and finally the carbon dioxide amount will be further.
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
Figure 5. Effect of H2O/CH4 ratio on the H2/CO ratio. energy balances were examined and an appropriate kinetic
and model for the reactors in homogeneous and dynamic
Figure 6 exhibits the effect of oxygen to methane ratio in condition was proposed.
various ratios of carbon dioxide to methane ratio. With By using the proposed model, the effects of key
decrease of carbon dioxide to methane ratio the WGSR will parameters including inlet temperature and ratio of initial
be gone to right side, based on Le Chatelier's principle. Thus, material versus length of the reactor and time were studied.
the hydrogen production will be increased. 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 carbon monoxide ratio versus changes of carbon dioxide to
by increasing oxygen to methane ratio. methane ratio. When carbon dioxide to methane ratio was
4- Decrease of carbon dioxide to methane ratio led to increased, the minimum point was gone to decrease the
increase hydrogen production. oxygen to methane ratio.
5- There is a minimum point in Changes of hydrogen to
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