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This work investigates the impact of catalyst structuring into particles or monoliths on methanol production from
only CO2 and H2 at a large scale. Methanol synthesis in multi-tubular reactors is evaluated using packed-bed and
monolithic reactors by modeling heat and mass transfer in each reactor. The obtained simulation results show that,
at low gas hourly space velocity (GHSV = 10,000 h1 ), the performances of both reactor technologies are similar. In this
case, the packed-bed reactor technology is the most appropriate technology due to its simplicity of installation and
operation. At high GHSV (25,000 h1 ), the packed-bed reactor technology is limited by a considerable pressure drop
that causes an important loss in productivity due to thermodynamic equilibrium, whereas the monolithic reactors
exhibit negligible pressure drop and achieve far better performances.
2014 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Keywords: Methanol synthesis; Monolith; Packed bed; Reactor modeling; Carbon dioxide; Hydrogen
1.
Introduction
CO + 2H2 CH3 OH
(A)
CO2 + H2 CO + H2 O
(B)
(C)
Abreviations: CPA, cubic-plus-association; DME, dimethyl ether; GHSV, gas hourly space velocity, h1 ; PC-SAFT, perturbed-chain
statistical associating uid theory; SRK, SoaveRedlichKwong; WHSV, weight hourly space velocity, h1 .
List of symbols
Hr
asf
C
Cp
d
dh
Dax
dt
Dm,i
D
e
et
f
F
h
k
kd
K
Kp
Lt
l
M
Nt
P
Q
R
rj
udh
Redh =
S
Sc = D
Sh =
T
u
u
U
v
V
Vp
x
z
Z
Kdp
D
Reynolds number
surface, m2
Schmidt number
Sherwood number
temperature, K
uid velocity, m s1
uid supercial velocity, m s1
global heat-transfer coefcient, W m2 K1
molar volume, m3 mol1
reactor volume, m3
volume of a single catalyst particle, m3
depth in the solid phase, m
axial position, m
compressibilty factor
Greek letters
volume ratio
2599
Subscripts
ax
axial
A, B, C reaction
cata
catalyst
eff
effective
i
chemical species number
j
reaction number
m
mixture
p
particle
t
tube
w
internal wall of the tube
Superscripts
ce
center of the solid
f
uid
int
internal
s
solid
su
surface of the solid
2.
Modeling of reactors
To perform a reliable comparison of both technologies, in conjunction with a parametric study, a detailed model of the
system rst must be developed.
2.1.
Description of technologies
2600
rCH3 OH,C =
kC KCO2 1
3/2
fCO2 fH
2
fCH3 OH fH2 O
3/2
(fH Kp,C )
(4)
1/2
2.2.
Thermodynamics
Based on the data presented in Table 1, thermodynamic computations have been carried out in order to understand the
evolution of chemical equilibria of methanol synthesis with
pressure ranging between 30 and 90 bar, and temperature
between 120 and 320 C. The considered gas mixture is composed of CO2 (24 mol%), H2 (72 mol%), and N2 (4 mol%).
Methanol synthesis from CO2 and H2 is favored at high
pressure and low temperature while the rates of reactions
become larger as the operating temperature increases. Thus,
there should be an optimal temperature for which the production of methanol is maximal.
The SoaveRedlichKwong equation of state (SRK) is used
to estimate the compressibility factor Z for the gas mixture at
high pressure and temperature (Skrzypek et al., 1995), and it
is found close to unity (Eq. (1)). Thus, the use of the ideal gas
law is a good approximation to represent the thermodynamic
behavior of the uid.
Pv = ZRT RT
2.3.
(1)
Kinetics
3/2
2
fCH3 OH
(2)
1/2
(fH Kp,A )
2
rH2 O,B = kB KCO2 1 fCO2 fH2
fH2 O fCO
Kp,B
(3)
Log10 (Kp )
5139
T 12.621
2073
+ 2.029
T
3066
T 10.592
(bar2 )
()
(bar2 )
1/2
2.4.
2.5.
Mass-transfer modeling
The mass balance in the gas phase leads to Eq. (5) that considers mass convection with a mean velocity u, axial dispersion
of species i with a coefcient Dax,i , mass transfer between the
owing gas and the catalyst as a function of the interphase
2601
Table 2 Parameters of the kinetic model used in simulations (Graaf et al., 1990).
Parameter
Expression
kA
kB
kC
KCO
KCO2
KH2 O /
(7.05 1.39) 10
KH2
exp +
(uCi )
Unit
(4.89 0.29) 10 exp 113,000300
RT
(9.64 7.3) 1011 exp 152,9001800
RT
(1.09 0.07) 105 exp 87,500300
RT
(2.16 0.44) 105 exp + 46,800800
RT
(6.37 2.88) 107 exp + 61,700800
RT
84,0001400
9
Dax,i
2 Ci
z2
kd,i asf
(Ci Csu
)
i
(5)
At the reactor inlet (z = 0), molar ows of species are considered constant and equal to those upstream the inlet. That
leads to the boundary condition described by Eq. (6).
f
(6)
(uCi )
z
|z=Lt = 0
(7)
Csu
i
x
|x=R
(8)
Mass transfer inside the catalyst is governed by pure diffusion. The diffusion and reaction equation at a depth x in the
solid is given by Eq. (9).
(Deff,i Sx i )dx +
i,j rj s dV s = 0
x
x
s
(9)
RT
per mass unit of solid, s the density of the solid, and dVs the
elementary solid volume between depths x and x + dx.
At a depth x = 0 in the catalyst, the mass ow by molecular
diffusion is set equal to zero. This assumption leads to the
boundary condition represented by Eq. (10).
Deff,i
Csi
x
|x=0 = 0
(10)
kd,i dp
= 2 + 1.8
Dm,i
p
f ud
1/2
f Dm,i
1/3
(11)
kd,i dh
ud2h
= 2.696 1 + 0.139
Dm,i
Dm,i Lt
0.81
(12)
2602
2.6.
Heat-transfer modeling
The tubes are all considered similar and possess the same
global heat-transfer coefcient U. The reactors are cooled by
pressurized boiling water at a constant temperature on the
shell side. Therefore, tubes external wall temperature Tw is
considered constant along the axial direction z. Heat balance
over the Nt cooled tubes leads to Eq. (13).
Nt dint
t U(T Tw ) =
z
f
uCi Cp,i T
+Q
(13)
Q=
1
Vp
Vp
( Hr,j )rj s dV s
(18)
dint
t
2.7.
1 f u 2
(1 ) u
dP
+ 1.75 3
= 150
3
2
dz
dp
dp
(19)
e
(15)
The Blasius correlation is used to estimate the Fanning friction factor F for turbulent ow (2.1 103 < Redh < 104 ) in the
monolithic reactor:
F=
where Vp is the volume of a single catalyst particle, Hr,j is
the heat of reaction j, and dint
is the internal diameter of the
t
tubes.
The temperature at the reactor inlet (z = 0) is assumed constant and that at the outlet (z = L) is assumed equal to the
temperature just after the reactor. These assumptions are
included in the integration of the heat balance equations
through the following boundary conditions:
(20)
0.0791
(21)
Re0.25
d
h
The 2D model can be made equivalent to a onedimensional pseudo-homogeneous model that does not
consider mass transfer limitations. The one-dimensional
model results will be used as a reference to evaluate masstransfer limitations in the reactors.
3.
Geometric comparison of both reactor
technologies
(16)
and
T(z)
|z=Lt = 0
z
dint
t + 2et
(14)
T(z)|z=0 = T0
2
Nt (dint
t )
(l + 2e + 2d)
dint
1
1
= + t ln
U
h
2t
The left side of Eq. (13) represents the amount of heat transferred per unit of reactor length from the tubes to the shell,
while the right side of this equation describes heat transport
by convection through the reactor open cross-section , and
the power per unit of length Q generated by the reactions. The
expressions of Q for the packed-bed reactor and the monolithic reactor are given by Eqs. (14) and (15), respectively:
Q=
(17)
For the same mass of catalyst, a comparison of the two considered reactor technologies is performed in order to identify the
impact of catalyst structuring on the volume of each reactor
and its interfacial area. This comparison is general and independent of the considered operating conditions and reactions
since it only considers geometrical aspects. The catalyst volume in the packed-bed reactor and in the monolithic reactor
are given by Eqs. (22) and (23), respectively.
Vpacked bed =
Vmonolith =
Mcata 1
cata 1
Mcata (l + 2e + 2d)
cata
4e(l + e)
(22)
2
(23)
The catalyst density cata is the same for both reactors since
the catalyst internal structure is supposed not to change with
catalyst structuring into particles or coating layers.
For ratios dp /dt lower than 0.15, the external porosity of the
packed-bed reactor ranges between 0.4 and 0.417. Thus, the
external porosity of the packed-bed can be assumed constant
and equal to 0.41. In other words, for a given mass of catalyst,
the gas volume in the packed-bed reactor can be considered
constant for ratios dp /dt lower than 0.15 and the impact of
the porosity change near the tube walls can be neglected. The
2603
1
0.8
0.6
0.4
0.9
1
1.1
1.2
1.3
1.5
1.8
2.2
0.2
1
2
3
4
Channel hydraulic diameter l (mm)
0 270
260
265
267
1
0
263
4
Axial position (m)
261
4.
Vmonolith
(l + 2e + 2d)
=
=
(1 )
Vpackedbed
4e(l + e)
4l
(l + 2e + 2d)
(25)
400
0.8
500
0.6
0.4
0.2
600
800
1000
1200
1
2
3
4
Channel hydraulic diameter l (mm)
(24)
4.1.
Heat transfer
2604
External
Internal
6
Particle diameter (mm)
Internal + external
(K)
max
Packedbed reactor
Tmax (K)
0
10
Internal + external
5
External
Monolithic reactor
Internal
0
240
250
260
270
280
290
77
80
85
88
93
95
97
300
(26)
kd,i Cex,i ( Hr )
=
hf
12
(28)
(27)
4.2.
10
6
8
1
WHSV (h )
Mass-transfer study
Mass-transfer limitations become negligible as the parameter gets close to unity. It should be noted that the geometric
parameters used for mass-transfer study lead to a pressure
drop lower than 3 bar in the packed-bed reactor and a pressure
drop of 0.02 bar in the monolithic reactor. The tube diameter
is set equal to 2 cm in order to satisfy the 2D model hypothesis related to the absence of radial thermal gradients in the
tubes. Results of the mass-transfer study in the packed-bed
reactor and the monolithic reactor are reported in Figs. 7 and 8,
respectively.
For the packed-bed reactor, internal mass-transfer limitations become signicant for particle diameter greater than
2 mm. Regarding the monolithic reactor, the internal masstransfer limitations appear for thicker coating layers.
The catalyst efciency is quite similar in both reactors
for almost all congurations. Nevertheless, the differences
that appear in catalyst efciency are related to the difference between the interfacial area in the reactors. In fact, for a
channel hydraulic diameter equal to 2 mm and a coating thickness of 1.5 mm, the interfacial area of the monolithic reactor
is around 270 m2 /m3 while that of the packed-bed reactor
2 65
Coating thickness (mm)
90
75
1.5
80
85
89
92
95
97
0.5
99
6
8
WHSV (h1)
10
12
2605
Tube
Particle
Monolith
Range
dt
Lt
dp
[1; 2] cm
[0.5; 8] m
[1; 3] mm
l
e
d
[1; 2] mm
[0.1; 0.6] mm
[0; 0.5] mm
Constraints
Max(Tw T) < 10 K
Min P
Global efciency of the
catalyst > 90%
Min P
Small reactor
5.
Methanol production
Range
[240; 260] C
[250; 270] C
80 bar
[24; 72; 4] mol%
[2; 10] h1
Parameter
Value
Unit
dt
Lt
dp
l
e
d
T0
Tw
P0
[CO2 ; H2 ; N2 ]
WHSV
2
[0.5; 8]
[1.3; 3]
1.5
[0.1; 0.6]
0.25
250
260
80
[24; 72; 4]
4 and 10
cm
m
mm
mm
mm
mm
C
bar
mol%
h1
5.1.
4 h1
Fig. 9 shows the results of simulations for the packed-bed reactor. Methanol production is represented as a function of tube
length ranging from 0.5 to 8 m for different particle diameter.
The productivity is large for short tubes and large diameters of
particles and it decreases slightly as the tubes become longer
and as the particles become smaller. The obtained results for
the packed-bed reactor can be explained by the pressure drop
that is reported in Fig. 10. In fact, the pressure drop moves
the thermodynamic equilibria towards a lower production of
methanol.
5.2.
4 h1
Parameter
540
Case A1
Particle diameter (mm)
530
520
3
2.5
2
510
1.5
1.3
500
2606
Case A1
0.5
2.5
1
2
3
4
1.5
3
4
5
6
Tube length (m)
0.1
538
0.2
536
0.3
534
0.4
1000
3
2.5
2
800
1.5
1.3
600
4
6
Tube length (m)
0.5
532
0.6
530
3
4
5
6
Tube length (m)
3000
2000
1000
15000
5000
0.6
4
5
6
Tube length (m)
5.4.
Case B2: monolithic reactor with WHSV equal to
10 h1
Simulations have been carried out for the monolithic reactor and show that an enhanced production of methanol can
be achieved. Fig. 15 describes the evolution of methanol production with the geometric parameters of monoliths. The
production of methanol in the monolithic reactor remains
Packedbed reactor
Monolithic reactor
10000
5.3.
Case B1: packed-bed reactor with WHSV equal to
10 h1
Tubes number
Case A2
540
Case B1
542
1200
Case B1
2.5
3
5
8
12
15
20
30
40
1.5
1
3
4
5
6
Tube length (m)
1110
Case B2
Coating thickness (mm)
0.5
1100
1090
0.4
0.3
0.6
0.2
1080
1070
0.1
3
4
5
6
Tube length (m)
6.
1102
1099
1095
0.4
0.3
0.6
0.2
0.5
0.1
6000
4000
1091
1088
1084
8000
2000
more investments and operating costs through energy consumption and compressors.
The monolithic reactor may raise the issue of the cost of
the catalyst manufacturing and regeneration. If the rate of the
catalyst deactivation is high, and the regeneration requires
the extraction and treatment of monoliths out of the reactor,
the operating cost will rise and make the monolithic reactor
less appropriate from an economic point of view. The use of
extruded monoliths made of the catalytic phase will cost less
than using a supported catalytic phase (Boger et al., 2004). The
choice between the considered reactor technologies should be
completed by an accurate economic study in order to evaluate
the viability of the chosen reactor technology. More aspects
such as the reactor fabrication cost, the catalyst structuring
and regeneration feasibility should be evaluated more precisely.
7.
Conclusion
Acknowledgments
Tube number
A maximum tube length should be considered in order to minimize their number in the shell. For example, if a tube length
of 8 m is considered, the number of tubes is around 500 for the
packed-bed reactor and around 700 for the monolithic reactor (for e = 3 mm). The high number of tubes in the monolithic
reactor makes their fabrication more expensive than that of
the packed-bed reactor. Fig. 16 shows that this issue of fabrication does not appear for the monoliths extruded from the
catalytic phase and the number of tubes is slightly lower than
that for the packed-bed reactor.
For tubes longer than 6 m, the mass of methanol produced
in the monolithic reactor is at least 10% higher than that
obtained using the packed-bed reactor at a WHSV of 10 h1 .
Moreover, high pressure drop in packed-bed reactor is not suitable from the standpoint of process viability since it induces
2607
0.1
0.6
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