10448 Ind. Eng. Chem. Res.

2009, 48, 10448–10455

Modeling of the Kinetics for Methanol Synthesis using Cu/ZnO/Al2O3/ZrO2

Catalyst: Influence of Carbon Dioxide during Hydrogenation
Hye-Won Lim,† Myung-June Park,*,† Suk-Hwan Kang,‡,§ Ho-Jeong Chae,‡ Jong Wook Bae,‡ and
Ki-Won Jun*,‡
Department of Chemical Engineering, Ajou UniVersity, Suwon 443-749, Korea, and Petroleum Displacement
Technology Research Center, Korea Research Institute of Chemical Technology, Daejeon 305-600, Korea

A kinetic model for methanol (MeOH) synthesis over Cu/ZnO/Al2O3/ZrO2 catalyst has been developed and selected
to evaluate the effect of carbon dioxide on the reaction rates due to its high activity and stability. Detailed kinetic
mechanism, on the basis of different sites on Cu for the adsorption of carbon monoxide and carbon dioxide, is
applied, and the water-gas shift (WGS) reaction is included in order to provide the relationship between the
hydrogenations of carbon monoxide and carbon dioxide. Parameter estimation results show that, among 48 reaction
rates from different combinations of rate determining steps (RDSs) in each reaction, the surface reaction of a
methoxy species, the hydrogenation of a formate intermediate HCO2, and the formation of a formate intermediate
are the RDS for CO and CO2 hydrogenations and the WGS reaction, respectively. It is shown that the CO2
hydrogenation rate is much lower than the CO hydrogenation rate, and this affects the methanol production rate.
However, carbon dioxide decreases the WGS reaction rate, which prevents methanol from converting to dimethyl
ether, a byproduct. In such a way, a small fraction of carbon dioxide accelerates the production of methanol indirectly
within a limited range, showing a threshold value of the CO2 fraction for the maximum methanol synthesis.

1. Introduction dual site mechanism for the dissociative adsorption of the

hydrogen molecule on ZnO while carbon monoxide is adsorbed
Owing to high octane number, methanol (MeOH) is consid-
on the site of monovalent copper. Similarly, the kinetics for
ered as an excellent alternative energy resource. The high octane
the synthesis of methanol from carbon dioxide by a Cu-based
number ensures good antiknock performance, in addition to high
catalyst has been reported more than two decades ago.6,7
volatility, denser fuel-air charge, and excellent lean burn
According to the reports, the kinetic mechanism for the methanol
properties.1 Methanol is an excellent fuel in its own right, and
synthesis may involve both CO and CO2. Klier and co-workers8
it can also be blended with gasoline, although it has half the
assumed the adsorption of reactants, and they evaluated the
volumetric energy density relative to gasoline or diesel.2 It was
effect of carbon dioxide on the catalytic synthesis of methanol
also found that methanol can be conveniently converted into
over the copper-zinc oxide catalysts. They also proposed
ethylene or propylene in the MTO (methanol-to-olefins) process,
several mechanisms: (1) H2, CO, and CO2 were assumed to
and in turn, these olefins can be used to produce hydrocarbon
adsorb on the catalyst competitively (single site mechanism),
fuels and their products.3 In addition, recycling excess carbon
(2) CO and CO2 were assumed to adsorb on the catalyst
dioxide from industrial gases and the atmosphere, by chemical
competitively while hydrogen adsorbs on the different site from
reduction of CO2 with hydrogen to produce MeOH, will mitigate
CO and CO2 (dual site mechanism), (3) the adsorption site for
a major manmade cause of global warming.2 For this reason, a
CO and H2 are different and CO2 competes for both the CO
lot of research work is ongoing for its mass production and the
sites and the hydrogen sites. For more detailed elementary steps,
design of commercial processes. As a catalyst for methanol
it was shown that carbon monoxide is adsorbed in the form of
synthesis, Cu, Zn, Cr, and Pd are mostly used to prevent the
a carbonyl species, and a formate species is a usual intermediate
production of hydrocarbons and maximize the selectivity as well
for methanol synthesis and water gas shift reaction.9 There are
as the yield. Among these, Cu/ZnO catalyst is well-known for
many reports introducing the adsorption of CO and CO2 on two
high activity and selectivity for methanol synthesis reaction.
different sites.8,10,11 However, since their work ignores the
Support such as Al2O3 can further increase the activity and
water-gas shift (WGS) reaction, the relationship between CO
selectivity. Furthermore, the promoter such as Zr is known to
and CO2 (e.g., synergetic effect of CO2) on the methanol
enhance the copper dispersion and catalytic activity on methanol
synthesis reaction rate is not clearly understood.
synthesis catalysts, and its increased dispersion is due to the
As shown by Klier and co-workers,8 the copper is reduced
geometric effect of promoter on the ZrO2-CuO interaction
or oxidized by the adsorption of CO and CO2, respectively, and
originated from oxygen vacancies of ZrO2.4
this phenomenon suggests different adsorption sites for CO and
Although many kinetic mechanisms have been suggested for
CO2. It is worth noting that the published reports present
the synthesis of methanol and water, the exact mechanism is
conflicting viewpoints on the identity of the active sites on Cu-
not clearly discussed. Herman and co-workers5 proposed the
containing catalysts for the methanol synthesis. Most of them
* To whom all correspondence should be addressed. Tel.: +82-31- have considered CO hydrogenation to be the most significant
219-2383. Fax: +82-31-219-1612. E-mail: mjpark@ajou.ac.kr (M.-J.P.). reaction for methanol production. A possible reason for the
Tel.: +82-42-860-7671. Fax: +82-42-860-7388. E-mail: kwjun@ seemingly contradictory results in the literature is that CO2
krict.re.kr (K.-W. Jun). hydrogenation also occurs to some extent under a certain
†
Ajou University.
‡
Korea Research Institute of Chemical Technology. reaction condition. Perhaps, two different sites are necessary
§
Current address: Plant Engineering Center, Institute for Advances for methanol synthesis, and if that is the case, the apparent
Engineering (IAE), Suwon 443-749, Korea. disagreement over the identity of the active site might be solved.
10.1021/ie901081f CCC: $40.75  2009 American Chemical Society
Published on Web 09/16/2009

Figure 1. Schematic diagram of the lab-scale reactor.
Therefore, the kinetics of methanol synthesis by CO and CO2
hydrogenation is taken into account in the present study.
A kinetic mechanism where CO and CO2 are assumed to
adsorb on different sites of Cu is suggested for the development
of hydrogenation reaction rates, while hydrogen is supposed to
be adsorbed on the site of ZnO. In addition, the WGS reaction12
is considered which may relate CO hydrogenation to CO2
hydrogenation. Since there are several elementary steps for each
overall reaction, various combinations of rate determining steps
(RDSs) are developed, and then, the parameters are estimated
using experimental data to find the best fit model to evaluate
the detailed mechanism for methanol synthesis. It should be
noted that the mechanism for the production of dimethyl ether
(DME) is also included in the reaction set, since the experimental
data in the present study suggest the augmentation of additional
reactions other than the three main reactions. These details are
explained in the section 3.
2. Experimental Section
2.1. Catalyst Preparation and Characterization. The cata-
lysts were synthesized by the coprecipitation method using an
aqueous solution containing copper acetate, zinc acetate,
aluminum nitrate, and zirconium oxide nitrate of required
quantities (with the weight ratio of CuO/ZnO/Al2O3/ZrO2 )
61.5/31.5/3.3/3.7). The precipitant, Na2CO3, was dissolved in
deionized water and two separate solutions of precipitant and
metal precursors were simultaneously mixed with a controlled
feeding rate of around 10 mL/min at 343 K. The final pH of
the solution was maintained at around 7. The precipitate was
further aged for 3 h at 343 K and then washed with deionized
water of 2 L. The dried power was calcined at 573 K for 5 h.
Furthermore, catalytic activity on the well-known Cu/ZnO/Al2O3
methanol synthesis catalyst with composition of CuO/ZnO/Al2O3
) 61.5/31.5/7.0 was compared, and finally, Cu/ZnO/Al2O3/ZrO2
catalyst was selected due to its high activity and stability instead
of Cu/ZnO/Al2O3 catalyst. The BET surface area and average
pore size of Cu/ZnO/Al2O3 and Cu/ZnO/Al2O3/ZrO2 catalysts
were determined by N2-physisorption method using a Mi-
cromeritics ASAP2400 apparatus at liquid-N2 temperature
(-196 °C). The powder X-ray diffraction (XRD) patterns were
obtained with a Rigaku diffractometer using Cu KR radiation
Ind. Eng. Chem. Res., Vol. 48, No. 23, 2009 10449
to elucidate the particle size of CuO (before reaction) and
metallic Cu (after reaction) with their crystalline phases.
2.2. Activity Test. Catalytic activity tests were carried out
in an isothermal tubular fixed bed reactor (10.2 mm I.D.) with
a catalyst weight of 1.0 g. The schematic diagram of the lab-
scale reactor system is shown in Figure 1. Prior to the reaction,
the catalyst was reduced for 4 h at 523 K using 5% H2 balanced
with nitrogen. After reduction, the synthesis gas (H2/CO ) 2)
was fed into the reactor. The reaction conditions included the
composition change in feed gas (CO, CO2, and H2), T )
503-553 K, P ) 5.0 MPa and space velocity (SV) )
2000-6000 mL/gcat · h. The above range of reaction variables
were appropriately selected to show a significant variation of
catalytic activity under different reaction conditions. The
catalytic activity at steady state after 15 h on stream without
showing significant catalyst deactivation was selected to conduct
further reaction kinetics and reactor modeling. The products
were analyzed with an online gas chromatograph (Donam model
DS 6200) using thermal conductivity detector (TCD) to analyze
Ar, CO, and CO2 with a carbosphere packed column and flame
ionized detector (FID) for hydrocarbons such as DME and
MeOH and hydrocarbons with a GS-Q capillary column.
2.3. Characteristics of Cu/ZnO/Al2O3/ZrO2 Catalyst
and Its Catalytic Performance. To select an appropriate
catalyst for reaction kinetics and reactor modeling, a catalytic
activity test on two different methanol synthesis catalysts, Cu/
ZnO/Al2O3 and Cu/ZnO/Al2O3/ZrO2, was carried out under the
following reaction conditions: T ) 523 K, P ) 5.0 MPa, and
SV ) 4000 mL/gcat · h. The CO conversion and MeOH selectiv-
ity on Cu/ZnO/Al2O3/ZrO2 catalyst are higher than those of Cu/
ZnO/Al2O3 catalyst as shown in Table 1. The high catalytic
performance is mainly attributed to the presence of smaller
metallic copper particles and higher surface area around 121.9
m2/g with the help of Zr promoter during the preparation step.
The presence of small particle size around 9.8 nm on Cu/
ZnO/Al2O3/ZrO2 catalyst compared to that of 11.7 nm on Cu/
ZnO/Al2O3 catalyst reveals a high metallic surface area of
copper, resulting in high catalytic performance such as CO
conversion around 35.8% and MeOH selectivity around 94.1%.
Therefore, Cu/ZnO/Al2O3/ZrO2 catalyst was finally selected to
carry out further reaction kinetics and reactor modeling in the
present manuscript.
10450 Ind. Eng. Chem. Res., Vol. 48, No. 23, 2009

Table 1. Catalytic Performance and Physicochemical Properties of Cu/ZnO/Al2O3 and Cu/ZnO/Al2O3/ZrO2 Catalysta
surface area average pore particle size particle size CO conversion selectivity [mol %]
catalyst [m2/g]b size [nm]b of CuOc of Cuc [mol %] (MeOH/DME/HCd)
Cu/ZnO/Al2O3 106.9 27.9 11.6 11.7 26.8 93.5/2.7/3.8
Cu/ZnO/Al2O3/ZrO2 121.9 16.1 10.4 9.8 35.8 94.1/1.9/4.0
a
The catalytic activity measurement was performed under the following reaction conditions: T ) 523 K, P ) 5.0 MPa, and SV ) 4000 mL/gcat · h.
b
BET surface area and average pore size of the calcined catalysts were determined by N2-physisorption. c The particle size of copper oxide (before
reaction) and metallic copper (after reaction) was calculated from the values of full width at half-maximum (fwhm) of XRD diffraction peaks at 2θ )
35.5 and 43.3 respectively with the help of Sherrer’s equation. d The byproducts of hydrocarbons (HC) mainly include C1-C4.

3. Reaction Kinetics and Reactor Modeling Table 2. Elementary Reactions for Cu/ZnO/Al2O3/ZrO2 Catalyzed
Methanol Synthesis
3.1. Reaction Rates. Methanol synthesis reaction is com-
posed of three main reactions: (1) the hydrogenation of carbon H2 + 2s2 a 2H · s2
monoxide, (2) hydrogenation of carbon dioxide, (3) water-gas CO + s1 a CO · s1
shift reaction. In addition to these three main reactions, a side adsorption CO2 + s3 a CO2 · s3
reaction for the synthesis of dimethyl ether (DME) from H2O + s2 a H2O · s2
methanol is considered in this study.
CO + 2H2 a CH3OH (1) surface reaction elementary steps
(A) CO
CO2 + H2 a CO + H2O (2) hydrogenation Step 1: CO · s1 + H · s2 a HCO · s1 + s2
reaction13 Step 2: HCO · s1 + H · s2 a H2CO · s1 + s2
H2CO · s1 + H · s2 a H3CO · s1 + s2
CO2 + 3H2 a CH3OH + H2O (3) Step 3:
Step 4: H3CO · s1 + H · s2 a CH3OH + s1 + s2
2CH3OH a CH3OCH3 + H2O (4)
(B) water-gas
shift Step 1: CO2 · s3 + H · s2 a HCO2 · s3 + s2
Reaction 4 is included in this study, because the experimental reaction12,16 Step 2: HCO2 · s3 + H · s2 a CO · s3 + H2O · s2
results for CO2 conversion shows negative values under some
conditions. In the case that reaction 4 is excluded, CO2 is (C) CO2
generated by the WGS reaction (the reverse reaction of 2) whose hydrogenation Step 1: CO2 · s3 + H · s2 a HCO2 · s3 + s2
rate is dependent on the amount of H2O produced by the CO2 reaction14,15 Step 2: HCO2 · s3 + H · s2 a H2CO2 · s3 + s2
hydrogenation (reaction 3). As a result, the amount of CO2 Step 3: H2CO2 · s3 + H · s2 a H3CO2 · s3 + s2
generation cannot be larger than the amount consumed in Step 4: H3CO2 · s3 + H · s2 a H2CO · s3 + H2O · s2
reaction 3, corresponding to non-negative values of conversion. Step 5: H2CO · s3 + H · s2 a H3CO · s3 + s2
Step 6: H3CO · s3 + H · s2 a CH3OH + s3 + s2
Therefore, the additional reaction for the production of water
is required to explain the experimental observation. The
methanol selectivity data also shows values lower than 90%,
which supports the production of a product other than MeOH (C), respectively, are determined by fitting the experimental data
(data not shown). available in the literature.19 Figure 2 shows the comparison
The elementary reactions for the hydrogenation of CO and between experimental data and calculated values.
CO2, and the reverse water-gas shift (RWGS) reaction are listed
in Table 2. It is worth noting that there are two different sites 9.8438 × 104
ln KPA ) - 29.07 (5)
(s1 and s3) for the adsorption of CO and CO2, respectively.5 RT
The symbol “s1” represents Cu1+ while Cu0 is denoted by the
symbol “s3”. -4.3939 × 104
ln KPB ) + 5.639 (6)
For CO hydrogenation, the most strongly supported mecha- RT
nism consists of successive additions of adsorbed hydrogen
atoms to an adsorbed carbon monoxide molecule13 while the KPC ) KPA × KPB (7)
synthesis of methanol from carbon dioxide occurs via a formate
species (HCO2) adsorbed on copper.14,15 There is general where R represents the gas constant in Joules per mole kelvin.
agreement that hydrogen and water adsorb on Zn sites.16 Since The equilibrium constant for DME production is available in
the adsorption of H2 is rapid,10,17 it is assumed that the the literature.20
concentrations of ZnO sites and adsorbed hydrogen on ZnO
sites remain constant during synthesis.
The reaction is assumed to be reversible since the concentra- KDME ) 0.106 exp ( 2.1858 × 104
RT ) (8)
tion of MeOH is high, and the Langmuir-Hinshelwood model
is applied for the reaction rates. The assumption of rapid 3.2. Reactor Model. To consider the effect of external mass
equilibrium is applied to the adsorption steps, and the reaction transfer, the speed of agitation is varied in a batch reactor (the
rates are developed when each step is assumed to be a rate gas flow rate in a fixed-bed reactor). Since the size of the catalyst
determining step (cf. Table 3). Therefore, 48 combinations of particle is very small and both the flow rate and pressure are
reaction rates are obtained for methanol synthesis. For the relatively high, no external mass transfer resistance is assumed.21
production of DME, the reaction rate available in the literature18 The occurrence of any internal pore diffusion limitation is
is used. determined on the basis of the Weisz-Prater criterion, where
Equilibrium constants, KPA, KPB, and KPC for CO hydrogena- the dimensionless Weisz-Prater parameter (CWP) is calculated
tion (A), reverse WGS reaction (B), and CO2 hydrogenation as follows:
 Ind. Eng. Chem. Res., Vol. 48, No. 23, 2009 10451

-rA,obsFcRc2 resulting in a concentration gradient from the catalyst surface

CWP ) (9) to its pores.22,23
DeffCA
The effective diffusivity for multicomponents mixture is
calculated using the following equation:24
where -rA,obs is the rate of the reaction in moles per kilogram
of catalyst per second and Fc is the catalyst density in
kilograms per cubic meter. The symbols Rc, Deff, and CA N
Cj
represent the effective radius of the catalyst (the ratio of Deff )
1
DKe i
+ ∑D e
(10)
catalyst pellet volume to the surface area of catalyst) in j)1 i,jCt
j*i
meters, the effective diffusivity in squared meters per second,
and the limiting reactant concentration in the mixture in moles
per cubic centimeter, respectively. If the CWP is much greater where Knudsen diffusion coefficient (DeKi)24 and binary diffusion coefficient
than one, a strong resistance to internal pore diffusion exists, e 25
(Di,j) are calculated as follows:

Table 3. Reaction Rates for Methanol Synthesis Reaction and DME Production
reaction RDS rate equations

kAKCOKH20.5(PCOPH22 - PCH3OH /KPA)/PH21.5

CO hydrogenation A1 rA )
(1 + KCOPCO)(1 + KH20.5PH20.5 + KH2OPH2O)

kAKCOKH2KCH,CO(PCOPH22 - PCH3OH /KPA)/PH2

A2 rA )
(1 + KCOPCO)(1 + KH20.5PH20.5 + KH2OPH2O)

kAKCOKH21.5KCH,CO(PCOPH22 - PCH3OH /KPA)/PH20.5

A3 rA )
(1 + KCOPCO)(1 + KH20.5PH20.5 + KH2OPH2O)

kAKCOKH22KCH,CO(PCOPH22 - PCH3OH /KPA)

A4 rA )
(1 + KCOPCO)(1 + KH20.5PH20.5 + KH2OPH2O)

kBKCO2KH20.5(PCO2PH2 - PCOPH2O /KPB)/PH20.5

WGS reaction B1 rB )
(1 + KCOPCO)(1 + KH20.5PH20.5 + KH2OPH2O)(1 + KCO2PCO2)

kBKCO2KH2KCH,WGS(PCO2PH2 - PCOPH2O /KPB)

B2 rB )
(1 + KCOPCO)(1 + KH20.5PH20.5 + KH2OPH2O)(1 + KCO2PCO2)

kCKCO2KH20.5(PCO2PH23 - PCH3OHPH2O /KPC)/PH22.5

CO2 hydrogenation C1 rC )
(1 + KH20.5PH20.5 + KH2OPH2O)(1 + KCO2PCO2)

kCKCO2KH2KCH,CO2(PCO2PH23 - PCH3OHPH2O /KPC)/PH22

C2 rC )
(1 + KH20.5PH20.5 + KH2OPH2O)(1 + KCO2PCO2)

kCKCO2KH21.5KCH,CO2(PCO2PH23 - PCH3OHPH2O /KPC)/PH21.5

C3 rC )
(1 + KH20.5PH20.5 + KH2OPH2O)(1 + KCO2PCO2)

kCKCO2KH22KCH,CO2(PCO2PH23 - PCH3OHPH2O /KPC)/PH21

C4 rC )
(1 + KH20.5PH20.5 + KH2OPH2O)(1 + KCO2PCO2)

kCKCO2KH22.5KCH,CO2(PCO2PH23 - PCH3OHPH2O /KPC)/PH20.5

C5 rC )
(1 + KH20.5PH20.5 + KH2OPH2O)(1 + KCO2PCO2)

kCKCO2KH23KCH,CO2(PCO2PH23 - PCH3OHPH2O /KPC)

C6 rC )
(1 + KH20.5PH20.5 + KH2OPH2O)(1 + KCO2PCO2)

kDMEKCH3OH2(CCH3OH2 - ((CH2OCDME)/KP,DME))
DME production18 rDME )
(1 + 2√KCH3OHCCH3OH + KH2OCH2O)4
10452 Ind. Eng. Chem. Res., Vol. 48, No. 23, 2009

4 8RT Table 4. Physical Properties and Reactor Specifications
DKe i ) rpore (11) parameter value unit
3 πMi
bulk gas
kg/m3
10-4T1.75(Mi-1)1/2
0.498
density (Fg)
Dei,j ) (12) bulk pellet 700-900 kg/m3
Patm( ∑V i
1/3
+ ∑V j
1/3 2
) density (FB)
catalyst weight 0.001 kg
tube diameter (D) 0.0127 (1/2 in) m
The values of diffusion volume (V) are available in the heat of reaction CO hydrogenation -98438
literature.25 Since the values of CWP for all experimental (Hrxn) CO2 hydrogenation -54931 kJ/mol
conditions are calculated lower than 0.01, it is assumed that RWGS 43466
there exists no internal diffusion limitation.
Since no mass transfer resistance is assumed and the L-to-D where XCO and XCO2 represent the CO conversion and CO2
ratio of a lab-scale fixed-bed reactor used in the experiments is conversion, respectively. Subscripts “calc” and “exp” mean the
very large, a pseudohomogeneous plug flow model is used to calculated and experimental values, respectively, and wi is a
simulate the reactor as follows: weighting factor.
When the temperature dependence of kinetic parameters is
Mass balance considered, the strong correlation between pre-exponential factor
R N and the activation energy leads to a highly nonlinear problem,
dci
-us
dz
+ FB ∑
Ri,j ) 0 (13) and thus, the following form is used in the estimation procedure
j)1 to reduce the temperature dependency:

Energy balance

usCp
dFgT
) FB
NR

∑
(-∆Hi)jRj +
4U
(T - T) (14)
[ ( )]
kl(T) ) kl,0 exp -
El 1
R T
-
1
T0
(17)

dz Dt W

j)1
Boundary conditions
at z ) 0, ci ) ci,0 ; T ) Tin
Here, us, FB, Fg, Rj, and Ri,j represent the linear velocity, bulk
and gas densities, reaction rate and stoichiometric coefficient,
respectively, and other symbols are defined in the Nomenclature.
Heat capacity (Cp), calculated using the values of each
component (Cp,i) as a function of temperature, and reaction
enthalpy for the reaction j (∆µHj) are assumed to be constant.
The values of Cp,i and ∆µHj are available in a process simulator
(UniSim Design Suite, Honeywell Inc.). Other physical proper-
ties and reactor specifications are listed in Table 4.
3.3. Parameter Estimation. To estimate kinetic parameters,
conversions of CO and CO2 are taken into account, and thus,
the following objective function is defined:
[ ( )]
-∆Hi 1 1
Ki(T) ) Ki,0 exp - (18)
R T T0
(15)
The constants at the reference temperature, activation ener-
gies, and enthalpies are scaled in the form of yscaled ) yactual/
yscaling-factor in order to reduce the statistical correlation and to
prevent the ill-conditioning problems resulting from the differ-
ences of the orders of magnitude between parameters.
The objective function, eq 16, is minimized using the
lsqcurVefit subroutine in Matlab (The MathWorks, Inc.) where
the Levenberg-Marquardt method is applied, and the numerical
integration of eqs 13 and 14, which is required during each
iterative step in the nonlinear regression, is performed by the
ordinary differential equation (ODE) solver, ode23s imple-
mented in Matlab.

{(
4. Results and Discusssion
Fobj )
1
2 ∑ w1
XCO,calc - XCO,exp 2
XCO,exp
+ ) Since each experimental condition produces 2 data points (i.e.,
CO conversion and CO2 conversion) and the number of

(
XCO2,calc - XCO2,exp
)}
2 experimental condition is 28, a total of 56 points are used in
w2 (16) the nonlinear data-fitting procedure. Detailed experimental
XCO2,exp
conditions are listed in Table 5.
The estimation results for 48 sets of RDS combinations are
summarized in Table 6. According to the parametric sensitivity
analysis, only 6 (when the B1 is applied) or 7 (RDS for the
WGS is assumed to be B2) influences the reaction rates
significantly, and thus, these parameters are estimated while the
other parameters are based on the values from the literature.11,12
The weighting factors are specified as 1 and 1.2 for CO and
CO2 conversion, respectively, by trial and error to improve the
estimation performance for CO2 conversion. The total average
error is defined as ∑i|(yexp,i - ycalc,i)/yexp,i|(100/N) is calculated
for the results of CO and CO2 conversions separately. Since
one of the aims of parameters estimation is to find the reaction
mechanism which best describes the kinetics of the system over
the wide range of conditions, the standard deviation of the
individual error of each experimental run around the total
Figure 2. Comparison of equilibrium reaction constants between experi- average error (STD) is also calculated as STD ) [(individ error
mental data and calculated values. - t avg error)2/(N - 1)]1/2.
 Ind. Eng. Chem. Res., Vol. 48, No. 23, 2009 10453
Table 5. Experimental Conditions Table 7. Estimated Parameters for the RDS Combination of 412
(Model No. 38)
feed composition [mol %]
estimated valuesa
number temperature [K] SV [mL/g · h] CO CO2 H2
1
2
3
523 4000 2
2
2
1
4
2
7
16
10
kA ) 1.16 × 10-9 exp - [ 7.01 × 103 1
R T(-
1
523 )]
4 2 0 4

[ )]
5 2 0.5 5.5
2.70 × 102 1 1
6
7
2
2
1
1
5
8
kB ) 2.82 × 10-5 exp -
R T(-
523
8 2 0.5 3.5
9 2 1.5 6.5
10
11
2
2
0.5
1.5
6.5
9.5
kC ) 1.15 × 10-6 exp - [ 1.19 × 102 1
R T(-
1
523 )]
12 0 1 3
13 2000 2 1 7
14
15
16
503
6000
4000
2
2
2
1
1
0.5
7
7
5.5
kDME ) 2.51 × 1011 exp - [ 6.45 × 105 1
R T
- (1
523 )]
17 2 1.5 8.5

[ )]
18 2 1 5
9.93 × 103 1 1
19
20 2000
2
2
1
1
8
7
KCO ) 4.96 × 10-8 exp
R T(-
523
21 6000 2 1 7
22 553 4000 2 1 7
23
24
2
2
0.5
1.5
5.5
8.5
KCH3OH ) 1.41 × 10-3 exp [ 6.05 × 103 1
R T(-
1
523 )]
25 2 1 5
26 2 1 8
27 2000 2 1 7 a
R is 8.314 J/mol · K, and T is in kelvin.
28 6000 2 1 7
rate determining steps for CO and CO2 hydrogenation are A4
In order to guarantee the balanced estimation between CO (surface reaction of a methoxy species H3CO · s1 and H · s2)9 and
and CO2 conversion, the selection criteria has been applied to C2 (hydrogenation of a formate intermediate HCO2),14 respec-
the error and standard deviation of each conversion; the tively. In addition, model no. 23 is a little bit worse for the
combination is selected if the values of the errors and the STD’s prediction of CO2 conversion since it cannot predict the negative
of CO and CO2 conversion are lower than 17%, 60%, 10%, CO2 conversion which is observed in the experimental data
and 30%, respectively. In Table 6, the selected RDS combina- under some conditions. Therefore, it is assumed that these
tions are highlighted with bold text, among which only two experimental results are also effective for the case of different
combinations have three bold cells: RDS combinations of 225 adsorption sites for CO and CO2 in the present study, and thus,
(A2-B2-C5, model no. 23) and 412 (A4-B1-C2, model no. 38). model no. 38 is selected for the best fit model and the values
Although the estimation result for the combination of 225 of estimated parameters are listed in Table 7.
(model no. 23) is as good as that for the model no. 38 (the It is worth noting that the formation of a formate intermediate
combination of 412), there is experimental evidence that the (B1 in Table 2) is determined as the RDS for the WGS reaction,

Table 6. Total Average Errors and Standard Deviations from the Estimation Results
error STD error STD
no. RDS CO CO2 CO CO2 no. RDS CO CO2 CO CO2
1 111 22.47 61.21 11.55 49.59 25 311 18.95 103.44 9.89 89.86
2 112 82.25 74.06 38.87 70.48 26 312 19.35 59.76 9.95 43.98
3 113 80.20 68.72 35.63 39.87 27 313 18.54 62.76 11.93 46.71
4 114 77.05 289.20 35.73 260.85 28 314 19.37 61.24 9.96 42.30
5 115 78.48 273.21 36.92 257.49 29 315 19.35 59.67 9.95 44.09
6 116 80.61 281.18 38.71 369.79 30 316 18.70 59.20 12.01 43.20
7 121 82.02 72.81 37.46 60.73 31 321 42.06 66.53 23.98 46.00
8 122 83.66 91.68 38.08 28.63 32 322 14.65 62.61 10.34 44.68
9 123 83.64 92.42 38.04 26.03 33 323 42.08 92.01 24.35 20.29
10 124 83.02 91.17 37.69 22.01 34 324 38.00 93.79 23.57 20.29
11 125 42.54 91.89 29.73 21.29 35 325 56.70 92.64 27.41 21.68
12 126 83.26 92.63 37.62 24.59 36 326 55.60 93.65 27.24 21.26
13 211 71.97 111.83 16.77 100.82 37 411 15.68 77.31 12.93 71.88
14 212 74.52 63.86 16.65 49.28 38 412 16.72 58.98 9.27 46.26
15 213 80.06 68.18 35.53 40.99 39 413 51.71 60.70 15.84 45.19
16 214 15.02 59.48 10.92 41.64 40 414 51.76 61.03 15.83 44.05
17 215 74.52 63.71 16.64 48.89 41 415 16.03 64.25 10.03 50.94
18 216 18.84 58.67 10.72 43.61 42 416 51.72 60.67 15.84 45.07
19 221 16.68 65.08 11.07 47.49 43 421 14.57 64.34 11.67 46.23
20 222 15.33 59.40 10.33 40.75 44 422 13.47 72.73 8.63 31.34
21 223 18.21 61.84 10.41 46.05 45 423 15.44 60.27 9.11 41.40
22 224 17.06 58.99 10.08 39.91 46 424 14.20 85.13 10.85 21.69
23 225 15.41 59.43 9.50 43.52 47 425 12.73 59.59 10.35 40.64
24 226 14.65 62.87 11.11 38.10 48 426 13.03 59.31 11.71 40.75
10454 Ind. Eng. Chem. Res., Vol. 48, No. 23, 2009
Figure 3. Comparison of (a) CO and (b) CO2 conversions between
experimental and simulation data using model no. 38.
Figure 4. Effect of the CO2 fraction on (a) the concentrations of MeOH
and DME; (b) MeOH selectivity; cumulative reaction rates of (c) CO
hydrogenations and DME production, (d) CO2 hydrogenations, (e) reverse
water-gas shift reaction, and (f) CO and CO2 conversions at the exit of
the reactor.
and this result is also reported by Peppley and co-workers in
their modeling study.26 However, Graaf and co-workers12
assumed that B2 is the RDS for their kinetic study.
Figure 3 shows the comparison of CO and CO2 conversions
between experimental and simulation data. It is observed that
the CO conversions are in good agreement, while the CO2
conversion shows deviation from the experimental data, prob-
ably resulting from the unknown mechanism.
One of the interesting features for the MeOH synthesis by
both CO and CO2 is that the production rate is rapidly increased
when even a small fraction of CO2 is included in the feed. This
feature is reported in several literature works,8,27,28 but there is
no clear kinetics-based explanation of how the CO2 fraction
influences the methanol synthesis reaction rates. In order to
explain this phenomenon, the reaction rates for each hydrogena-
tion reaction and WGS reaction are examined with a variety of
CO2 fractions in the feed. Figure 4a clearly shows the increase
of MeOH concentration at the exit of the reactor when the CO2
fraction is increased from 0, and the concentration of methanol
is decreased after CO2 fraction gets higher than the threshold
value. This feature is contributed to the decrease of DME
production with the increasing CO2 fraction. As shown in Figure
4e, when the CO2 fraction is very low or zero, the WGS reaction
(corresponding to the negative values of RWGS reaction) rate
is high or highest which results in the consumption of water.
As a result, the DME production rate is high. As the CO2
fraction increases, the WGS reaction rate is decreased and, in
turn, the increase of water prohibits the DME production rate
by the increase in the reverse reaction, leading to the increase
of MeOH concentration. However, since the CO hydrogenation
reaction rate decreases much faster than the WGS reaction with
the increasing CO2 fraction (cf. Figure 4c), the MeOH concen-
tration decreases after a threshold value of CO2 fraction.
Consequently, it is summarized that the existence of CO2
increases the production of methanol to some extent, via the
decrease in WGS reaction, but the effect is limited to the small
fraction of CO2. Between 0 and about 0.25 CO2 fraction, the
MeOH concentration is higher than the case for no CO2, and
the maximum MeOH concentration is accomplished when the
fraction is about 10%. It is worth noting that this value is based
on the kinetics only. If other factors such as transport resistance
in the reactor and a deactivation mechanism are considered, the
optimal value in the sense of process operation might be slightly
different from our value.29
Although the DME production affects the concentration of
MeOH, methanol selectivity is very high (close to one), which
means that the DME production is not dominant in the whole
reactions. Figure 4d shows that the contribution of CO2
hydrogenation is very low, and thus, one can infer that the CO2
gives rise to the synergetic effect on methanol production not
directly from the CO2 hydrogenation but indirectly through the
WGS reaction. The low reaction rate for CO2 hydrogenation is
also observed in Figure 4f, where the CO2 conversion shows
highly negative values due to the high WGS reaction rate (CO2
generation) and the low CO2 hydrogenation rate (CO2 consump-
tion). It is reported that the high concentration of CO2 diminishes
the methanol synthesis reaction rate,8 and this result supports
the low CO2 hydrogenation rate.
It is worth noting that, since the relationship between CO
and CO2 hydrogenation reactions may depend on the number
of s1 and s3 sites, the different amount of ZrO2 which is known
to affect the number of Cu0 and Cu1+ sites may change the
degree of the relationship. Therefore, it might be necessary to
find a different set of kinetic parameters with respect to the
amount of ZrO2 used in the catalyst preparation.
5. Conclusions
A mechanism for the adsorption of CO and CO2 on the
different site of Cu-based catalyst for methanol synthesis has
been suggested and total of 48 reaction rates have been
developed on the basis of different combinations of RDS for
CO and CO2 hydrogenations and WGS reaction. Kinetic
parameters estimation shows that the combination of the surface
reaction of a methoxy species, the hydrogenation of a formate
intermediate HCO2, and the formation of a formate intermediate
for CO and CO2 hydrogenations and WGS reaction, respectively,
is the best fit model, and the results are supported by
experimental evidence in the literature. Further analysis has
implied that the existence of CO2 in the reactants increases the
methanol concentration at the exit of the reactor in a synergetic
manner, that is, a small fraction of CO2 prevents the conversion
of MeOH to DME indirectly, via the WGS reaction. Although
there are several reports discussing the effect of CO2 on the
MeOH synthesis reaction rates, it is the first time that the kinetic
mechanism for the relationship between CO and CO2 hydro-
genation reactions is suggested. In conclusion, the kinetic model
proposed in this study clearly proves the effect of carbon dioxide
on the methanol synthesis and it is expected that the optimal
 Ind. Eng. Chem. Res., Vol. 48, No. 23, 2009 10455
fraction can be calculated using the developed model in Literature Cited
industrial processes.
(1) Chen, Z.; Yao, M.; Zhen, Z.; Zhang, Q. Energy Fuels 2009, 23,
2719–2730.
(2) Olah, G. A. Angew. Chem., Int. Ed. 2005, 44, 2636–2639.
Acknowledgment (3) Olah, G. A.; Doggweiler, H.; Felberg, J. D.; Frohlich, S.; Gridinia,
M. J.; Karpeles, R.; Keumi, T.; Inaba, S.; Ip, W. M.; Lammertsma, K.;
The authors would like to acknowledge the financial support Salem, G.; Tabor, D. C. J. Am. Chem. Soc. 1984, 106, 2143–2149.
of Ajou University (Contract No. 20071030) and the Ministry (4) Toyir, J.; de la Piscina, P. R.; Fierro, J. L. G.; Homs, N. Appl. Catal.,
of Knowledge Economy of Republic of Korea (2007-E-1D25- B 2001, 34, 255–266.
P-02-0-00). (5) Herman, R. G.; Klier, K.; Simmons, G. W.; Finn, B. P.; Bulko, J. B.
J. Catal. 1979, 56, 407–429.
(6) Chinchen, G. C.; Denny, P. S.; Parger, D. G.; Spenser, M. S.; Whan,
Nomenclature D. A. Appl. Catal. 1987a, 30, 333–338.
(7) Denise, B.; Sneeden, R. P. A. J. Mol. Catal. 1982, 17, 359–366.
CA ) concentration [mol /cm3] (8) Klier, K.; Chatikavanij, V.; Herman, R. G.; Simmons, G. W. J. Catal.
Cp ) heat capacity [kJ/kg · K] 1982, 74, 343–360.
CWP ) Weisz-Prater parameter (9) Edwards, J. F.; Schrader, G. L. J. Phys. Chem. 1984, 88, 5624–
5627.
D ) tube diameter [m] (10) McNeil, M. A.; Schack, C. J.; Rinker, R. G. Appl. Catal. 1989, 50,
Deff ) effective diffusivity [m2/s] 265–285.
e
Di,j ) binary diffusion coefficient for component i and j [cm2/s] (11) Coteron, A.; Hayhurst, A. N. Chem. Eng. Sci. 1994, 49, 209–221.
DKi ) Knudsen diffusion coefficient [cm2/s]
e (12) Graaf, G. H.; Stamhuis, E. J.; Beenackers, A. A. C. M. Chem. Eng.
Sci. 1988, 43, 3185–3195.
El ) activation energy [J/gmol · K] (13) Chinchen, G. C.; Hay, C. M.; Vandervell, H. D.; Waugh, K. C. J.
Fobj ) objective function Catal. 1987b, 103, 79–86.
Hj ) reaction enthalpy [kJ/mol] (14) Tagawa, T.; Plerzier, G.; Amenomiya, Y. Appl. Catal. 1985, 18,
kl,0 ) forward reaction rate constant (l ) A, B, C, DME), [gmol/ 285–293.
gcat · s] (15) Bowker, M.; Hadden, R. A.; Houghton, H.; Hyland, J. N. K.;
Waugh, C. J. Catal. 1988, 109, 263–273.
Ki ) species adsorption equilibrium constants (16) Dennison, P. R.; Packer, K. J.; Spencer, M. S. J. Chem. Soc.
KP,I ) reaction equilibrium constants Faraday Trans. I 1989, 85, 3537–3560.
Mi ) molecular weight [g/gmol] (17) Kung, H. H. Catal. ReV. Sci. Eng. 1980, 22, 235–259.
N ) total number of data points (18) Ng, K. L.; Chadwick, D.; Toseland, B. A. Chem. Eng. Sci. 1999,
54, 3587–3592.
Pi ) pressure [Pa] (19) Graaf, G. H.; Sijtsema, P. J. J. M.; Stamhuis, E. J.; Joosten, G. E. H.
R ) gas constant (R ) 8.314) [J/gmol · K] Chem. Eng. Sci. 1986, 41, 2883–2890.
rl ) reaction rate [mol/kgcat · s] (20) Mizsey, P.; Newson, E.; Truong, T.; Hottinger, P. Appl. Catal. A:
rA,obs ) observed rate [mol/kgcat · s] Gen. 2001, 213, 233–237.
Rc ) catalyst radius [m] (21) Chae, H. J.; Choo, S. T.; Choi, H.; Nam, I. S. Ind. Eng. Chem.
Res. 2000, 39, 1159–1170.
Rj ) reaction rate [mol/kgcat · s] (22) Fogler, H. S. Elements of Chemical Reaction Engineering; Prentice-
rpore ) mean pore radius [m] Hall: New Jersey, 1999.
STD ) standard deviation (23) Akpan, E.; Sun, Y.; Kumar, P.; Ibrahim, H.; Aboudheir, A.; Idem,
T ) temperature [K] R. Chem. Eng. Sci. 2007, 62, 4012–4024.
(24) Lommerts, B. J.; Graaf, G. H.; Beenackers, A. A. C. M. Chem.
Tw ) wall temperature [K] Eng. Sci. 2000, 55, 5589–5598.
us ) linear velocity [m/s] (25) Fuller, E. N.; Schettler, P. D.; Gidding, J. C. Ind. Eng. Chem. 1966,
Vi ) diffusion volume [cm3/mol] 58, 19–27.
w ) weighting factor (26) Peppley, B. A.; Amohlett, J. C.; Kearns, L. M.; Mann, R. F. Appl.
X ) conversion Catal. A: Gen. 1999, 179, 21–29.
(27) Monnier, J. R.; Apai, G.; Hanrahan, M. J. J. Catal. 1984, 88, 523–
Greek Letters 525.
(28) Vanden Bussche, K. M.; Froment, G. F. J. Catal. 1996, 161, 1–
Fc ) catalyst density [kg/m3] 10.
FB ) bulk densities [kg/m3] (29) Zahedi, G.; Elkamel, A.; Lohi, A. Energy Fuels 2007, 21, 2977–
Fg ) gas densities [kg/m3] 2983.
Ri,j ) stoichiometric coefficient
ReceiVed for reView July 6, 2009
Subscripts ReVised manuscript receiVed August 26, 2009
Accepted August 27, 2009
calc ) calculated value
exp ) experimental data IE901081F