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305726 Simulation and Modeling of a Radial Flow Pseudo-Isothermal

Methanol Reactor for a More Efficient Exploitation of the Synthesis Gas

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 Article

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Steady-State Simulation of a Novel Annular Multitubular Reactor for

Enhanced Methanol Production
Abdulaziz Alarifi,* Ali Elkamel, and Eric Croiset
University of Waterloo Waterloo, Ontario, Canada N2L 3G1

ABSTRACT: In this study, a one-dimensional heterogeneous model with intraparticle diffusion limitation has been developed
for methanol synthesis from syngas. The synthesis gas produced from the reformer is compressed at a pressure of 60−100 bar
and then heated up to 200−250 °C in order to prepare it for the methanol production reaction. Syngas reacts on a copper oxide/
zinc oxide/alumina catalyst. The annular multitubular (AMT) reactor proposed in this article has a design capability to efficiently
remove the heat generated by the exothermic reaction in methanol synthesis and improve methanol production by at least 3%
more than the conventional converter. In addition, the converter is operated under mild conditions, especially at the end of the
tube, which makes the catalyst lasts for a longer period. This leads to process intensification and allows for the use of a compact
distillation step. In addition, this new design has the advantage of preheating the feed gas in the reaction by having the inner
tubes replace the feed gas preheater. Methanol production and temperature profile are the most important characteristics of
methanol synthesis reactor. The predicted methanol concentration and temperature profile indicate that an increase in
temperature is accompanied with a reduction in the methanol equilibrium concentration and hence limiting the profitability in
the industrial plant. The use of an AMT reactor is shown to be able to overcome this limitation. The novelty lies in a process
modification which employs an inner tube that is disposed in the reactor and then the catalyst is charged into a circular space
surrounded by the reaction tube on one side and inner tube on the other side. Simulation studies show that this design allows the
temperature to increase gradually and, hence, delays the equilibrium to be reached to the end of the reactor. In other words, more
methanol is produced and less byproducts.

■ INTRODUCTION
The demand for methanol has been growing at an average
annual rate of 10% since 2010, and this increase is expected to
potentially continue until the end of this decade. Methanol is
mainly used as a raw material for formaldehyde production,
accounting for almost 27% of the world’s consumption. The
use of methanol as direct fuel is the second-largest market, with
almost 11%, then acetic acid comes as the third-largest
methanol end use. China is the largest consumer, with almost
41% of universal consumption.1 Recently, there has been a
movement toward employing methanol to replace hydrogen as
a fuel for the future, since it is easy to store and can be readily
used in the current infrastructure of fuel stations; this is not the
case with hydrogen.2 As a result, many organizations have
redirected their research focus; for instance, the U.S Depart-
ment of Energy decided to stop funding hydrogen gas
production and storage research from 2010 onward.3 Methanol
can be easily transformed to dimethyl ether (DME) or directly
to olefins, which makes it potentially in more demand.4
Methanol technologies are licensed by numerous companies
such as Davy process Technology (DPT) and Johnson Matthey
Catalyst (JM), Lurgi, Mitsubishi Gas Chemical (MGC), and
Haldor Topsoe. Methanol technologies consist of two major
stages.5 The first stage is the generation of synthesis gas
(carbon monoxide and hydrogen from reforming natural gas
(methane) or other heavy hydrocarbon feedstock such as crude
oil, naphtha, or coal. Synthesis gas from reforming or gasifying
processes is characterized by a stoichiometric number, SN=(H2
− CO2)/(CO + CO2). The second stage is the production of
methanol from the synthesis gas. The current low-pressure
processes operating at 50−100 bar in the vapor phase is widely
used to produce methanol from synthesis gas. The flow
diagram is illustrated in Figure 1, where the converter is either a
tubular heat exchanger (Lurgi), a double-tube heat exchanger
(Mitsubishi) superconverter, or a multiple stage adiabatic
quenching reactor (Casale methanol) and is normally used for
plants requiring no steam in the synthesis unit, However, it is a
low-cost reactor. The superconverter was developed and is
owned by MGC and Mitsubishi Heavy Industrial (MHI); it
consists of a simple converter with a double tubular heat
exchanger, where the catalyst is packed in the shell side,
between the inner tube and outer tube, as shown in Figure 2.
As reflected in the potential demand for methanol, many new
plants have been built across the world, especially in the Middle
East. In the first quarter of 2008, a new mega methanol plant
(Ar-Razi No. 5) began on stream, with an annual capacity of 1.7
million tons. This plant is located in Jubail, Saudi Arabia and is
owned by SABIC and a Japanese consortium led by Mitsubishi.
Moreover, in 2012, the Qatar Fuel Additives Company awarded
a contract to MHI to build a new methanol plant with a
capacity of 1 million tons per year. MGC and MHI owned and
patented a new methanol process including the additional
humidifiers coming after the distillations, which result in a
lesser amount of wasted water released to the environment
while reducing the amount of water fed into the boiler.6 In
Special Issue: NASCRE 3
Received: March 1, 2013
Revised: September 19, 2013
Accepted: September 19, 2013
Published: September 19, 2013

© 2013 American Chemical Society 15387 dx.doi.org/10.1021/ie4006589 | Ind. Eng. Chem. Res. 2013, 52, 15387−15393
Industrial & Engineering Chemistry Research
Figure 1. Process flow diagram of methanol synthesis.
Figure 2. Schematic configuration of (a) a conventional tubular reactor and (b) a double tube reactor.
addition, they improved the performance of the converter by
inventing a superconverter, which is basically a simple tubular
heat exchanger where the catalyst is filled in the annular side,
between inner and outer tubes.
This configuration provides a methanol process in which the
distillation system is reduced in size by efficiently removing the
heat generated by the reactions and inhibits the byproducts.
■ MODEL DEVELOPMENT
Reaction Kinetics. Many researchers have studied the
kinetics of methanol synthesis. Three main reactions may
possibly occur, namely, (i) the hydrogenation of carbon
monoxide to methanol (eq 1), (ii) the hydrogenation of
carbon dioxide to methanol (eq 2), and (iii) the reverse water-
gas shift reaction (eq 3).
CO + 2H 2 ⇌ CH3OH
CO2 + 3H 2 ⇌ CH3OH + H 2O
CO2 + H 2 ⇌ CO + H 2O
Article
Early kinetic models were derived for the ZnO/Cr2O3 catalyst
of high-pressure processes, which has been now almost
completely abandoned in favor of low-pressure technology.7,8
Leonov et al.9 were the first to model methanol synthesis
kinetics over a Cu/ZnO/Al2O3 catalyst. Their model again
assumed CO to be the source of carbon in methanol and did
not account for the influence of CO2 in the feed. Klier et al.10
considered other components as sources of carbon but assumed
that CO is the most important source of carbon in methanol.
Later, McNeil et al.11 expanded on the mechanism of the direct
hydrogenation of CO2 and the possible role of ZnO as a
hydrogen reservoir. Despite the much larger number of
parameters in the resulting model, the latter authors did not
manage to show a significantly better agreement between the
experimental and the simulated results than that already
obtained by Klier et al.10 Villa et al.12 realized that a thorough
(1)
modeling of the methanol synthesis system should also involve
a description of the water-gas shift reaction. Graaf et al.13−15
(2) considered both the hydrogenation of CO and CO2 as well as
the water-gas shift reaction. Parallel to these developments,
(3) Russian groups led by Rozovskii and Temkin16 developed
15388 dx.doi.org/10.1021/ie4006589 | Ind. Eng. Chem. Res. 2013, 52, 15387−15393
Industrial & Engineering Chemistry Research Article

several kinetic models for the Cu/ZnO/Al2O3 catalysts. Since 1 dFi

neither of these groups ever succeeded in producing methanol − + Acavkgi(Fi ,s − Fi ) v = 0; i = 1 , ..., nc
L dx (8)
from a dry mixture of CO and hydrogen, the models are all
based on the direct hydrogenation of CO2 to methanol, while a dT2 4U1
majority also account for the occurrence of the water-gas shift ugρg Cpg − avhf (Ts − T2) − (T1 − T2)
dx d t1
reaction. The present view is that methanol is formed from
CO2 over a copper-containing catalyst. This is confirmed by C- 4U2
− (T2 − Tw ) = 0
14 labeling17,18 and in situ measurements.19 The kinetic model d t2 (9)
proposed by Vanden Bussche and Froment20 for the
conversion of syngas over Cu/ZnO/Al2O3 catalyst accurately where Fi is the flow rate of component i and T2 is the
predicts the kinetic behavior reported from other authors temperature inside the shell side. The solid-phase equations are
outside the experimental window and kinetic equations expressed by
describe the influence of inlet temperature, pressure, and feed kgi(Fi − Fis) Nrxn
composition in a physically acceptable way. In this work, we + ρb ∑ vj , iηjrj = 0
have adopted the Vanden Bussche and Froment kinetic model. v j=1 (10)
The main rate expressions are as follows:
Nrxn
⎛ 1 pH2O pCH3OH ⎞ avhf (T2 − Ts) + ρb ∑ ηjrj( −ΔHr , j) = 0
k1pCO pH ⎜1 − ⎟
2 2⎝ K eq 1 pH 3 pCO ⎠ j=1 (11)
2 2
rCH3OH =
⎛ p ⎞ 3
The inner tube is disposed in the reaction tube to preheat the
⎜1 + K ad 1 pH2O + K ad 2 pH + K ad 3pH O ⎟ reactants while they flow upward to the top of the reactor. The
⎝ H2 2 2 ⎠ (4)
tube side (feed reactants gas flow) energy balance is
⎛ pH O pCO ⎞
dT1 4U1
k 2pCO ⎜1 − Keq 2 p 2 p ⎟ ugρg Cpg + (T1 − T2) = 0
2⎝ H2 CO2 ⎠
rRWGS = dx d t1 (12)
⎛ p ⎞
⎜1 + K ad 1 pH2O + K ad 2 pH + K ad 3pH O ⎟ where T1 is the temperature of the reactants when they flow
⎝ H2 2 2 ⎠ (5) through the tube. The Ergun equation,
Equilibrium relation:
dP G ⎛ 1 − ϕ ⎞⎡⎢ 150(1 − ϕ)μ ⎤
⎥
3066 =− ⎜ ⎟ + 1.75G
log10(Keq 1) = − 10.592 dx ρgcd p ⎝ ϕ3 ⎠⎢⎣ dp ⎥⎦ (13)
T (6)
2073 has been used to predict the pressure drop along the shell side
log10(Keq 2) = − + 2.029 of the reactor, with the following boundary conditions:
T (7)
The reaction rate and adsorption constants are of the Arrhenius Fi(0) = Fi,0 T2(0) = T2,0
form, with constants as given below in Table 1.
T1(1) = T1,0 P(0) = P0
Table 1. Rate and Adsorption Parameters Dusty-Gas Model for Diffusion Limitation in Porous
Catalyst. The following sets of differential equations are the
ki = Ai exp ( RTB )
i
A B mass balances of each component along the pellet radius:
k1 1.07 −36696
Dei ⎛ d2pi dpi ⎞ Nrxn
11.22 × 1010
k2 94765
⎜ s + 2 s ⎟ + ρ ∑ vijajrj = 0
2⎜
kad 1 3453.38 10−5R gTR
s p ⎝ dξ
2
ξ dξ ⎟⎠ s
j=1 (14)
kad 2 0.499 17197
kad 3 6.62 × 10−11 124199 where ξ = r/rp and the boundary conditions are as follows:

Heterogeneous Model. A one-dimensional heterogeneous dpsi

model with intraparticle diffusion limitation has been developed =0 i = 1 , ...., nc
dξ
for an annular multitubular (AMT) reactor. This model ξ= 0 (15)
accounts for a double tube heat exchanger that is employed
to remove the heat generated by the methanol synthesis dpsi
exothermic reactions. −Dei = kgi (psi |ξ = 1 − pbulk
i
) i = 1 , ...., nc
dξ
This new synthesis reactor is a simple double-tube type ξ=1 (16)
vertical exchanger. The catalyst is packed in the annular space
and the boiler water circulates in the shell side (see Figure 2b). Hence, the effectiveness factor can be calculated using the
The feed gas flows first into the inner tube from the bottom following formula:
toward the top and is preheated by heat generated in the 1
catalyst bed then is collected in the top of the reactor and flows 3 ∫ rjξ 2 dξ
0
ηj =
into the catalyst bed. The catalyst bed is cooled by the boiling r js (17)
water circulating in the shell side and the feed gas preheated in
the inner tube. The mass and energy balances for the fluid The diffusion and heat-transfer correlations are listed in Table
phase are 2.
15389 dx.doi.org/10.1021/ie4006589 | Ind. Eng. Chem. Res. 2013, 52, 15387−15393
Industrial & Engineering Chemistry Research Article

Table 2. Diffusion and heat transfer parameters

parameter source mathematical expression
effective and Knudsen diffusion coefficients ref 21
εs ⎛ 1 1 ⎞
−1
Dei = ⎜
τ ⎝ Dmi + ⎟
Dki ⎠

1/2
2 R gT
Dki = R pore 3
4
( )
π Mwi

multicomponent molecular diffusion coefficient ref 22

j
n j ≠ i ys
Dmi = ∑ j =c, i i ,j
Db

binary diffusion coefficient refs 23−25

0.143T1.75
D bi , j =
PsWm0.5(Vi1/3 + Vj1/3)2
2
Wmi, j = 1 1
+
Mwi Mw j

mass-transfer coefficient ref 26

kgi = 1.17 × 103Re−0.42(Sc i)−0.67 ug
μ
Sc i = i
ρg Dm × 10−4
2R pug
Re = μ

overall heat-transfer coefficients ref 27

1 1 dt Bi + 3
Uw
= hw
+ 6λer Bi + 4
Nusselt number refs 28 and 29
h w d pv
Nuw =
λf
8βs
= + Nuw Re > 50
dt / d pv

8βs λrs d pv ⎛ βf ⎞
= + 2Bis ⎜1 + ⎟ Re < 50
dt / d pv λ f dt ⎝ λrs /λf ⎠

Biot number ref 30

Bi−1 = Bif −1 + Bis−1
⎛ d ⎞ Perf
Bif = Nu fw⎜ 2dt ⎟ RePr
⎝ pv ⎠ ( )
⎛d ⎞2
Bis = 0.48 + 0.192⎜ d t − 1⎟
⎝ pv ⎠

Computational Techniques. The differential and non- Table 3. Design and Catalyst Specifications of a 10 t/d Pilot
linear algebraic equations of the reactor model (eqs 8−13) Plant Constructed in MGC’s Niigata Plant
were numerically solved by Matlab Gear’s method stiff solver parameter value
ode15s. This solver uses the backward differentiation formulas
catalyst tube length length 20 m
(BDFs) simultaneously, using fsolve for the set of nonlinear
outer tube diameter 85 mm o.d., 75 mm i.d.
solid phase equations. Emden’s equations generated by the inner tube diameter 19 mm o.d., 17 mm i.d.
dusty-gas model were solved by Matlab boundary value number of catalyst tubes 6
problem solver bvp4c by identifying the singular terms 2/ξ in tubes material carbon −0.5%Mo
the program. shell material carbon steel

■
capacity 10 t/d
RESULTS AND DISCUSSIONS pressure range 45−110 kg/cm2
catalyst type Zn/CuO/Al2O3
Model validation was carried out by comparing the model ρs) 1214 kg m−3
results with the process data provided by a new 10 t/d pilot- dp 6.53 × 10−3 m
plant reactor constructed in MGC’s Niigata Plant.31 The design λs 0.004 W m−1 K−1
and catalyst specifications have been summarized in Table 3. av 626.98 m2 m−3
The pilot plant used for this study has six catalyst tubes εs/τ 0.123
arranged circumferentially in the reactor, each with a length of
20 m, for the purpose of imposing severe conditions and
15390 dx.doi.org/10.1021/ie4006589 | Ind. Eng. Chem. Res. 2013, 52, 15387−15393
Industrial & Engineering Chemistry Research Article

Figure 3. Temperature profile and methanol mole percentage versus

pilot plant operation for the double tube reactor. Figure 4. Comparison of methanol (MeOH), as a percentage, and
temperature profile along the reactor length between the new reactor
Table 4. Experimental and Simulation Results of a Pilot and the conventional reactor (pressure P = 98 bar and space velocity
Plant Using a New Methanol Synthesis Reactor SV = 6000 h−1).
outlet
parameter inlet observed calculated
composition (%)
CH3OH 0.39 10.32 10.51
CO2 5.78 5.39 5.25
CO 8.93 2.37 1.97
H2O 0.09 1.64 1.25
H2 72.06 65.01 64.48
N2 0.69 0.83 1.34
CH4 12.06 14.44 15.2
space velocity (h−1) 6260
cooling temperature (°C) 250
temperature (°C) 150 215.5 217.14
pressure (bar) 62.3 55 56.14

Table 5. Inlet Compositions and Operating Conditions

parameter Gas A Gas B Figure 5. Effect of gas composition on gas temperature profile and
composition (%) methanol concentration (P = 98 bar and SV = 6000 h−1).
CH3OH 0 0
CO2 8 5
CO 9 8 outlet. The observed reactor performance agrees well with the
H2O 0 0 model results as presented in Table 4.
H2 65 80 A comparison study was performed in order to assess the
N2 5 1 performance of the new reactor versus the conventional tubular
CH4 13 6 reactor. The latter reactor is comprised of a tube (packed with
space velocity (h−1) 3000−6000 catalyst) that is externally cooled by boiler water and a nearly
cooling temperature (°C) 250 isothermal temperature profile is formed in the catalyst bed and
feed temperature (°C) 150 aims at recovering the heat of the synthesis reaction in the form
pressure (bar) 59−98 of high-pressure steam to the maximum possible extent. The
tube equivalent diameter of a conventional reactor was
calculated to give a similar cross-sectional area of the new
predicting the behavior of a comparable longitudinal size used reactor; both reactors have an identical amount of catalyst and
in the commercial plant. have similar operating conditions. This comparison was
Methanol production and temperature profile are the most conducted under the conditions presented in Table 5.
important characteristics of methanol synthesis reactor. The Figure 4 shows the temperature profiles of a conventional
predicted result of methanol concentration and temperature reactor and a double tube reactor; both are identical before
profile with the corresponding observed data are shown in reaching the peak temperature and then the conventional
Figure 3. reactor temperature gradually decreases to reach the cooling
The gas temperature peaks at the point of one meter near the temperature bottom line whereas the new reactor still
catalyst tube inlet and then decreases while flowing toward the undergoes a decreasing temperature profile toward the outlet.
15391 dx.doi.org/10.1021/ie4006589 | Ind. Eng. Chem. Res. 2013, 52, 15387−15393
Industrial & Engineering Chemistry Research
Figure 6. Effect of pressure on temperature profiles and methanol
concentration along the reactor length.
This latter temperature profile is very favorable, in terms of
reaction rate, and encourages the production of methanol.
The methanol mole fraction profile increases gradually and
reaches 11.36% and 11.92% for the double tube exchanger and
the conventional converter, respectively. Hence, the production
of methanol is improved by ∼3%, compared to the conven-
tional converter, while at the same time the converter is
operated under mild conditions, especially at the end of the
tube, which makes the catalyst lasts longer. Furthermore, a one-
dimensional analysis was carried out for two different cases of
feed gas compositions. The first case is a typical syngas
composition produced via the combination of steam reforming
and partial oxidation for natural gas reformer (gas A), and the
other case is a syngas produced via steam reforming of natural
gas (gas B) .
For different gas compositions, the case of rich hydrogen
content (gas B) shows a sharper temperature peak at inlet stage
of the catalyst tube than the lower hydrogen content gas (gas
A), as shown in Figure 5. The methanol concentration profiles
are almost identical, except that gas A is higher than gas B at the
outlet, since it has more carbon oxides and its SN ratio is closer
to the optimal value.
Figure 6 shows the model results of different synthesis
pressures ranging from 59 bar up to 98 bar. Higher synthesis
pressures lead to an increase of reaction rate but the removal of
15392
Article
Figure 7. Effect of space velocity (SV) on the temperature profiles and
methanol concentration along the reactor length.
reaction heat becomes more difficult. Based on Le Chatelier’s
Principle, the production of methanol can be improved by
increasing the synthesis pressure, and this is consistent with the
current results.
The simulations for different space velocities of feed gas are
presented in Figure 7. Since the heat-transfer coefficients
between particles and gas film within the catalyst tube depend
upon the space velocity, a lower space velocity leads to lower
heat-transfer rate and then the temperature in the tube outlet
becomes higher. As a result, the methanol concentration in the
tube outlet also becomes higher. However, an extremely low
space velocity results in thermal damage of the catalyst,
especially at the inlet of the catalyst tubes and near the peak
point.
■
CONCLUSION
The new proposed reactor design in this article has a capability
to efficiently remove the heat generated by the exothermic
reaction in methanol synthesis, and its temperature profile is
very favorable, in terms of reaction rate and an increase in the
production of methanol rate. The methanol mole fraction
profile increases gradually and reaches 10.36% and 10.92% for
the double tube exchanger and the conventional converter,
dx.doi.org/10.1021/ie4006589 | Ind. Eng. Chem. Res. 2013, 52, 15387−15393
 Industrial & Engineering Chemistry Research Article

respectively. Hence, the production of methanol is improved by
3%, compared to the conventional converter, while, at the same
time, its operation is under mild conditions, especially at the
end of the tube. This makes the catalyst lasts longer. This leads
to process intensification and allows for the use of a compact
distillation step. In addition, this new design has the advantage
of preheating the feed gas in the reaction, and the inner tubes
will replace the feed gas preheater.
(8) Bakemeier, H.; Danner, G. A. Methanol Technology and
Economics. Chemical Engineering Progress Symposium Series, No.
98, Vol. 66; American Institute of Chemical Engineers: New York,
1970; p 98.
(9) Leonov, V. E.; Karabaev, M. M.; Tsybina, E. N.; Petrishcheva, G.
S. Kinet. Catal. 1973, 14, 970−975.
(10) Klier, K.; Chatikavanij, V.; Herman, R. G.; Simmons, G. W.
Catalytic Synthesis of Methanol from CO/H2 IV. The Effects of
Carbon Dioxide. J. Catal. 1982, 74, 343−360.

■ AUTHOR INFORMATION
Corresponding Author
(11) Mcneil, M. A.; Schack, C. J.; Rinker, R. G. Methanol Synthesis
from Hydrogen, Carbon Monoxide and Carbon Dioxide over a CuO/
ZnO/Al2O3 Catalyst. Appl. Catal. 1989, 50, 265−285.
(12) Villa, P.; Forzatti, P.; Ferraris, G.; Garone, G.; Pasquon, I. The
*Tel.: 519-888-4567, ext. 37157. E-mail: aalarifi@uwaterloo.ca. synthesis of alcohols from carbon dioxide and hydrogen. 1. The
Notes kinetics of the methanol synthesis. Ind. Eng. Chem. Process. Des. Dev.
The authors declare no competing financial interest. 1985, 24, 12−19.

■
(13) Graaf, G. H.; Scholtens, H.; Stamhuis, E. J.; Beenackers, A. A.
Intra-particle Diffusion Limitations in Low-Pressure Methanol Syn-
NOMENCLATURE thesis. Chem. Eng. Sci. 1990, 45, 773−783.
L = tube length, m (14) Graaf, G. H.; Sijtsema, P. J.; Stamhuis, E. J.; Joosten, G. E.
Fi = molar flow rate of component i in the fluid phase per Chemical Equilibria in Methanol Synthesis. Chem. Eng. Sci. 1986, 41,
tube, mol/s 2883−2890.
x = dimensionless length of tube (15) Graaf, G. H.; Stamhuis, E. J.; Beenackers, A. A. Kinetics of Low
Ac = cross-sectional area, m2 Pressure Methanol Synthesis. Chem. Eng. Sci. 1988, 43, 3185−3195.
(16) Malinovskaya, O. A.; Rozovskii, A.Ya.; Zolotarskii, I. A.; Lender,
av = specific surface are of catalyst pellet, m2 m−3 Yu.V.; Matros, Yu. Sh.; Lin, G. I.; Dubovich, G. V.; Popova, N. A.;
kgi = mass-transfer coefficient for component i, m/s Savostina, N. V. Synthesis of Methanol on Cu-Based Catalyst: Kinetic
Fis = molar flow rate of component i in the solid phase per Model. React. Kinet. Catal. Lett. 1987, 34, 87−92.
tube, mol/s (17) Chinchen, G. C.; Denny, P. J.; Parker, D. G.; Spencer, M. S.;
nc = number of components Waugh, K. C.; Whan, D. A. Mechanism of methanol synthesis from
ρb = density of catalytic bed, kg/m3 CO2/CO/H2 mixtures over copper/zinc oxide/alumina catalysts
Nrxn = number of reactions Use of C-14-labeled reactants. Appl. Catal. 1987, 30, 330.
vj,i = stoichiometric coefficient of component i in reaction j (18) Chinchen, G. C.; Denny, P. J.; Jennings, J. R.; Spencer, M. S.;
ηj = effectiveness factor Waugh, K. C. Synthesis of Methanol part 1. Catalysts and kinetics.
rj = rate of reaction j, mol kg−1 s−1 Appl. Catal. 1988, 30, 333−338.
(19) Muhler, M.; Tornquist, E.; Nielsen, L. P.; Clausen, B. S.;
ug = gas velocity, m/s Topsøe, H. On the role of adsorbed atomic oxygen and CO2 in
ρg = molar density of gas, mol/m3 copper-based methanol synthesis catalysts. Catal. Lett. 1994, 25, 1−2.
Cp,g = heat capacity of gas mixture, kJ kmol−1 K−1 (20) Vanden Bussche, K. M.; Froment, G. F. A Steady-State Kinetic
T1 = temperature in tube 1, K Model for Methanol Synthesis and the Water Gas Shift Reaction on a
U1 = overall heat-transfer coefficient for tube 1 Commercial Cu/ZnO/Al2O3 Catalyst. J. Catal. 1996, 161, 1−10.
dt1 = tube diameter of tube 1, m (21) Froment, G. F.; Bishchoff, B.Chemical Reactor Analysis and
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■
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