Ind. Eng. Chem. Res.

2008, 47, 6547–6554 6547

Dimethyl Ether Synthesis from CO2 Hydrogenation on a

CuO-ZnO-Al2O3-ZrO2/HZSM-5 Bifunctional Catalyst
Xin An, Yi-Zan Zuo, Qiang Zhang, De-zheng Wang, and Jin-Fu Wang*
Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical
Engineering, Tsinghua UniVersity, Beijing, 100084, China

A CuO-ZnO-Al2O3-ZrO2 + HZSM-5 physical mixture bifunctional catalyst with a high activity for dimethy
ether (DME) synthesis was used for CO2 hydrogenation. Various factors that affect catalyst activity, including
the reaction temperature, pressure, and space velocity, were investigated. CO2 conversion reached 0.309, and
DME and methanol yields were 0.212 and 0.059 with a stoichiometric ratio of H2 to CO2 of 3 at 523 K, 5
MPa, and a space velocity of 6000 mL/(g cat · h). Well-studied kinetic models for methanol synthesis and
methanol dehydration, respectively, were used to fit the experimental data and the kinetic parameters in the
rate equations for DME synthesis were obtained by regression. A simulated process for CO2 hydrogenation
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indicated that a higher DME yield can be obtained with CO recycle that will also give a CO-free product.

1. Introduction CO2. With the two catalysts being used together, the subsequent
methanol dehydration on the HZSM-5 catalyst continuously
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Recently, the greenhouse effect has become a threat to the

removes the product of methanol synthesis; thus, the CO2
living environment of mankind. The transformation of CO2 into
conversion can be higher than that determined by the thermo-
useful chemicals, e.g. methanol, dimethyl ether (DME), urea,
dynamics of methanol synthesis. Also, CO2 incorporation in the
salicylate, is an attractive way to protect the global environment
reactant is more feasible than in the synthesis of methanol
since CO2 is an important greenhouse gas.1,2 Among them, DME
because the process can be operated at a lower pressure.
is drawing more and more attention as a clean fuel because of
Research works on processes for DME synthesis have been
the worldwide existence of serious air pollution and limited
directed at discriminating catalysts and getting data on the effect
crude oil reserves.3–7 It has the excellent properties of easier
of the operating conditions. The first step in DME synthesis is
compression ignition combustion, lower NOx and CO emission,
a methanol synthesis reaction, and a CuO-ZnO based catalyst
smokeless combustion, and less engine noise. Engine tests
is commonly used. Various modified catalysts, including
indicate that with minor fuel system modifications, engines can
CuO-ZnO-Al2O3, CuO-ZnO-CrO3, and CuO-ZnO-ZrO2
be operated with a thermal efficiency equivalent to that of
have been developed.12–15 It is believed that the ZnO adsorbs
traditional diesel and emissions below the strict criteria pre-
CO2 and Cu adsorbs H2, and the reaction takes place on the
scribed by the California ULEV standard. However, there are
surface of the Cu catalyst. A catalyst with highly dispersed
also some disadvantages for DME as a fuel. These include the
CuO-ZnO is a key factor for high yield and selectivity.
loss of lubricating ability in car engines and the fact that it gets
CuO-ZnO-Al2O3 catalyst has been commonly used in various
liquefied by high pressure at room temperature. As a household
studies, and many modified CuO-ZnO-Al2O3 based catalysts
fuel, DME possesses better combustion performance than
were reported recently. 14–16 By making use of a phase
liquified petroleum gas (LPG). In addition to its use as fuel,
separation effect of nanoparticles on the catalyst surface,17,18 a
DME is being contemplated as a raw material alternative for
fibrous CuO-ZnO-Al2O3-ZrO2 catalyst that is active for
methanol for producing olefins (methanol to olefins process).
methanol production from CO2 (in place of CO) hydrogenation
DME also can be reformed to hydrogen and is considered an
was reported by our group recently.17 A 5% Zr addition gave a
alternative automobile fuel for fuel cell.8,9 Therefore, DME will
methanol space time yield 80% higher than that from a
be an important clean fuel and an effective way to use coal
commercial catalyst. This fibrous CuO-ZnO-Al2O3-ZrO2 was
resources cleanly in the 21st century.
chosen as one component of the bifunctional catalyst in this
Until now, there are two routes for the production of DME
work. The consequent step in DME synthesis is the selective
from CO2 hydrogenation:5–11 a two-step process (methanol
dehydration of methanol, which is catalyzed by an acidic
synthesis on a metallic catalyst and subsequent dehydration of
catalyst. Various catalysts, such as γ-Al2O3, NaHZSM-5, and
methanol on an acid catalyst) and a single-step process using
HZSM-5, were used in previous studies.6,19–24 In contrast tor
both catalysts in the same reactor to perform the two steps
CO hydrogenation, in CO2 hydrogenation, more water is
simultaneously. The two steps in route 1 have been studied
produced. Since HZSM-5 is not sensitive to the concentration
separately for understanding methanol synthesis and methanol
of water, this was chosen as the other component of the
dehydration (DME synthesis), respectively. The latter step,
bifunctional catalyst. Thus, a physical mixture of CuO-ZnO-
methanol dehydration, is actually also an intermediate step in
Al2O3-ZrO2 and HZSM-5 was the bifunctional catalyst chosen
the transformation of methanol into hydrocarbons. Route 2 has
for the CO2 hydrogenation process in this work.
the merit that it is a one-step process (the two reactions are
In CO2 hydrogenation, there is competition between the
carried out in the same reactor). The main merit of DME
reverse water gas shift reaction and methanol and DME
synthesis in a single step is that it is not subject to the
syntheses reactions.22–28 The water gas shift reaction reaches
thermodynamic limitation that exists for methanol synthesis from
thermodynamic equilibrium fast, while the methanol and DME
* To whom correspondence should be addressed. Tel: +86-10- syntheses reactions are much slower. CO, which is a product
62797490. Fax: +86-10-62772051. E-mail: [email protected]. of the reverse water-gas shift reaction, will be present in the
10.1021/ie800777t CCC: $40.75  2008 American Chemical Society
Published on Web 07/26/2008
6548 Ind. Eng. Chem. Res., Vol. 47, No. 17, 2008

Figure 1. Experimental setup for DME synthesis on the CuO-ZnO-Al2O3-ZrO2 + HZSM-5 physically mixed bifunctional catalyst. 1 - Gas cylinders; 2
- depressed valve; 3 - mass flowmeter; 4 - valve; 5 - reactor; 6 - heater furnace; 7 - fixed temperature chamber; 8 - cold trap; 9 - liquid collection container;
10 - backpressure valve; 11 - flowmeter; 12 - gas chromatograph; 13 - computer.

product due to the fast rate of the water gas shift reaction. From Al2O3-ZrO2 catalyst that was prepared by a coprecipitation
a consideration of carbon source utilization, the CO in the outlet procedure.16,17 Solutions of Cu(NO3)2 · 6H2O, Zn(NO3)2 · 6H2O,
stream should be separated from the DME and methanol and Al(NO3)3 · 6H2O, and ZrOCl2 with a concentration of 0.6 mol/L
recycled back into the reactor. Thus, it should be useful to were mixed in the ratio 6:3:0.5:0.5. The mixture was precipitated
simulate a process with this recycle step, for which it is first using Na2CO3 solution at 353 K and vigorous stirring for 1 h.
necessary to understand the catalytic behavior and establish the After filtration and washing, the catalyst was dried for 12 h at
reaction kinetics. There have been previous reports on the 120 °C and calcined for 4 h at 350 °C. The methanol dehydration
kinetics for DME synthesis from CO2 hydrogenation,6,26–34 but acid catalyst was ZSM-5 with a Si/Al ratio of 38 purchased
with a CuO-ZnO-Al2O3/γ-Al2O3 catalyst. This CuO-ZnO- from the Catalyst Plant of Nankai University. It had been
Al2O3 catalyst is less active compared with the novel fibrous synthesized using tetrapropylammonium (TPA) as the structure
CuO-ZnO-Al2O3-ZrO2 catalyst used here for methanol directing agent. First, 20 g TPABr (Fluka 98%) was dissolved
synthesis, and the γ-Al2O3 catalyst has less activity than the in 20 g deionized water, which was followed by the addition
HZSM-5 used here under the high water concentration situation of 25 g Ludox LS to give solution A. Solution B was prepared
that exists during CO2 hydrogenation. by dissolving 0.25 g Al(OH)3 (Aldrich), 0.11 g NaOH (Merck
In this work, a physical mixture of CuO-ZnO-Al2O3-ZrO2 99.98%), and 0.41 g KOH (Merck). Solution A was then added
fibrous methanol synthesis catalyst and HZSM-5 methanol to solution B and the pH was adjusted to 11 by the dropwise
dehydration catalyst was used as a bifunctional catalyst for CO2 addition of 2 M H2SO4 while stirring for 2 h at room
hydrogenation to DME at various reaction temperatures, pres- temperature. The gel was transferred to a 250 mL Teflon lined
sures, and space velocities. Kinetics data that are specific to it steel autoclave, and the zeolite was crystallized under static
were obtained as a basis for the understanding of the catalytic conditions at 170 °C for 14 days. The solid product obtained
behavior and design of a process of CO2 hydrogenation. The was filtered and washed with deionized water until no Br- could
experimental data were fitted to Graaf et al.’s and Tao et al.’s be detected in the washing water (no precipitation with Ag+).
kinetic models for methanol synthesis and methanol dehydration, The final molar gel composition was 78 SiO2:1.0 Al2O3:2.3 K2O:
respectively. On the basis of the kinetic parameters determined, 0.86 Na2O:47 TPABr:4000 H2O (Si/Al ratio 38). The gel was
process simulations were performed and a simulated CO2
soaked in 0.1 M HNO3 solution for 1 h, and filtrated further.
hydrogenation process that recycles CO was suggested because
After calcined at 600 °C for 4 h, the HZSM-5 methanol
this does not waste CO and the presence of CO in the reactor
dehydration catalyst was obtained. The catalysts were physically
inlet gives an increased space time yield of DME. CO is present
mixed together using a CuO-ZnO-Al2O3-ZrO2 catalyst and
in the reactor outlet because the Cu-based catalyst will give
HZSM-5 ratio of 2.0. The prepared catalyst mixture was ground
CO2 and CO concentrations that are determined by the
into a powder, mixed with quartz particles, and placed in the
water-gas reaction thermodynamics at the reactor outlet.
fixed bed. The quartz particles, with a diameter of 1 mm, were
used to dilute the catalyst concentration in the fixed bed so that
2. Experimental Details
the heat production density was decreased in order to give a
The tested catalyst was a physical mixture containing a more uniform temperature in the reactor. Blank experiments
methanol synthesis catalyst and a methanol dehydration catalyst. were carried out to confirm that the quartz particles were inactive
The methanol synthesis catalyst was a fibrous CuO-ZnO- for CO2 hydrogenation.
 Ind. Eng. Chem. Res., Vol. 47, No. 17, 2008 6549
The catalytic reaction on the CuO-ZnO-Al2O3-ZrO2 + where YDME and YMeOH were the yields of DME and MeOH,
HZSM-5 catalyst was carried out in a fixed bed reactor shown SVCO2 was the space velocity of CO2, and MDME and MMeOH
in Figure 1. The reactor had a diameter of 12 mm and a length were the molar masses of DME and MeOH.
of 500 mm. The catalyst and quartz particles were distributed Data on catalyst stability are given in the Supporting
in the center part (about 100 mm long) of the reactor where the Information. The conversion of CO2 changed from 0.268 to
temperature was uniform, Hydrogen, nitrogen, and carbon 0.255 during 145 h of DME synthesis. In this period, the carbon
dioxide used were of purity above 99.999%. Impurities that can mass balance over the reactor closed to within experimental
be present in industrial gases, such as CO, H2S, COS, were error, that is, there was no obvious carbon deposition on the
probably present in negligible concentrations; thus, the experi- catalyst.
ments here did not provide data about the sulfur resistance of The thermodynamics of DME synthesis and methanol syn-
the catalyst. Before reaction, the catalyst was reduced with a thesis reactions were also studied. The equilibrium constants at
5% H2/95% N2 mixture at atmospheric pressure by raising the different temperatures were calculated using Van Hoff equation,
temperature slowly to the reaction temperature over 10 h. Then, and these were used to calculate the equilibrium conversions
the reduction gas was switched to the reaction gas and the and yields for given initial conditions. The details of the
pressure was raised to the reaction pressure to start the reaction. calculation have been given in the work of An et al.37
The first sample of the effluent was taken 2 h after steady
reaction conditions were established, and then samples were 3. DME Synthesis from CO2 Hydrogenation
taken every 30 min for online analysis of the effluent composi-
tion. The reaction temperature was controlled by furnace heating. For DME synthesis from CO2 and H2, there are four
The structure of the catalysts was studied by scanning electron independent stoichiometric reactions, namely
microscopy (SEM), temperature programmed desorption (TPD), Methanol synthesis from CO2
and N2 adsorption methods. The morphology of the CuO-
ZnO-Al2O3-ZrO2 + HZSM-5 catalyst was characterized by CO2 + 3H2 ) CH3OH + H2O (7)
a JSM 7401F high resolution scanning electron microscope Methanol synthesis from CO
(SEM) operated at 5.0 kV. The BET surface area was obtained
with a high resolution BET equipment described in Wang et CO + 2H2 ) CH3OH (8)
al.35,36 Ammonia temperature programmed desorption (NH3- Water gas shift
TPD) was employed for the measurement of acid amounts of
CO + H2O ) CO2 + H2 (9)
the catalysts. After saturated adsorption of NH3, NH3-TPD was
started at a heating rate of 15 °C/min from 100 to 650 °C. Methanol dehydration
The reactor was connected to an online GC 7890II gas 2CH3OH ) CH3OCH3 + H2O (10)
chromatograph with a thermal conductivity detector (TCD) and
a Porapak T (5 m) column connected in parallel with a TDX- Equations 7–9 comprise methanol synthesis, for which the
01 (3 m) column. The Porapak T column was used for the fibrous CuO-ZnO-Al2O3-ZrO2 catalyst was active. For methanol
separation of DME, MeOH, and H2O. The TDX-01 column was dehydration, shown as eq 10, HZSM-5 was the catalyst. As shown
used for the separation of H2, CO, and CO2. The concentrations in Figure 2a, the mechanical mixed (with a ratio of 2.0) catalyst
of these six gases were analyzed. CO2 conversion, DME yield, contained two kinds of particles. HZSM-5 particles with a regular
MeOH yield, and CO yield were defined as follows: crystal morphology was distributed among the fibers of the
CuO-ZnO-Al2O3-ZrO2 catalyst. The high resolution SEM image
nCO2,in - nCO2,out showed that the CuO-ZnO-Al2O3-ZrO2 (12:6:1:1) catalyst
XCO2 ) (1) particles were fibrous, with an aspect ratio over 25 (Figure 2b).
nCO2,in
The CuO-ZnO-Al2O3-ZrO2 catalyst was fibrous due to Zr
2nDME,out incorporation, which had two effects on the metallic function used
YDME ) (2) for methanol synthesis.17,38 One effect was a phase separation
nCO2,in
effect, to which was attributed the fibrous agglomerate morphology
nCH3OH,out and the slow rate for Cu/Zn sintering. The second effect, to which
YMeOH ) (3) was attributed the high activity of a Cu/Zn/Al/Zr catalyst, was an
nCO2,in effect of ion doping and valence compensation. Zr4+ dissolved in
ZnO crystal caused the formation of positive ion defects on the
nCO,out surface of Cu-ZnO. These defects can adsorb Cu+ and form and
YCO ) (4)
nCO,in stabilize more active sites, Cu0-Cu+-O-Zn2+, on the catalyst
surface. Thus, although the catalyst differed from a conventional
where nDME, nCO, and nCO2 were the molar flow rates of DME, methanol synthesis catalyst in the Zr incorporation, they are
CO, and CO2. In and out denotes inlet and outlet molar flow chemically similar in terms of the active sites. This Cu-based
rates. catalyst had a BET surface area of 70.9 m2/g and existed as regular
The space time yields of DME and MeOH, which gave the one-dimensional nanomaterial agglomerates, some of which were
amounts of DME and MeOH produced per gram catalyst per attached to the surface of the HZSM-5 particles (Figure 2a).
second, were defined and calculated using the following Since water is produced in DME synthesis, HZSM-5, which
relations: is a more hydrothermal stable catalyst than Al2O3, was used in
this work. The HZSM-5 catalyst had a BET surface area of
STYDME ) YDME × SVCO2 × MDME × 0.001 (kg/g)/22.4 (L/mol)/2
450.0 m2/g. The amount of Bronsted sites was measured by
(5) NH3-TPD to be 0.630 mmol/g.
From Figure 2, it can be deduced that the two kinds of catalyst
STYMeOH ) YMeOH × SVCO2 × MMeOH × were mixed at the micrometer scale. The pore size distribution
0.001 (kg/g)/22.4 (L/mol) (6) and activity stability data of the bifunctional catalyst can be
6550 Ind. Eng. Chem. Res., Vol. 47, No. 17, 2008

Figure 3. (a) Relationship between the reaction temperature and CO2

conversion, DME yield, and methanol yield. (b) Comparison of CO2
conversion with the methanol synthesis thermodynamic limit, DME
synthesis thermodynamic limit, and experimental results for DME synthesis.
The space velocity was 6000 mL/(g cat · h), the ratio of H2 to CO2 was 3,
and the pressure was 5 MPa.

water gas shift, and methanol dehydration occurred in the same

reactor. The relationship between the reaction temperature and
CO2 conversion or DME or methanol yield is shown in Figure
3a. The reaction rate increased when the temperature was higher,
and more CO2 was converted into DME and methanol. At 523
Figure 2. (a) SEM image of the CuO-ZnO-Al2O3-ZrO2 + HZSM-5 K, CO2 conversion reached 0.256, and it increased to 0.280 at
physically mixed bifunctional catalyst. Regular HZSM-5 catalyst particles
were distributed among the CuO-ZnO-Al2O3-ZrO2 particles. (b) High 543 K. With the bifunctional catalyst used here, methanol was
resolution image of the fibrous CuO-ZnO-Al2O3-ZrO2 catalyst in part dehydrated on the HZSM-5 catalyst which continuously re-
a. moved the product of methanol synthesis; thus, when the
temperature was higher than 523 K, the CO2 conversion was
found in the Supporting Information. The bifunctional catalyst
higher than that determined by the thermodynamics of methanol
had a BET surface area of 167 cm2/g, pore volume of 0.351
m3/g for pores between 1.7 and 300 nm, and average pore synthesis. The thermodynamics limited conversion in metha-
diameter of 12.1 nm. The pore volume data probably includes nol synthesis is shown in Figure 3b. The DME yield and
a contribution from the mesopores that were present between methanol yield, which are the middle and lower lines in Figure
the fibrous CuO-ZnO-Al2O3-ZrO2 catalyst particles. 3a, showed trends similar with CO2 conversion. DME yield
To evaluate the performance and kinetics of DME synthesis increased from 6.44% at 483 K to 15.8% at 543 K, which is
by CO2 hydrogenation, various factors, including the temper- 146% higher. The methanol yield increased from 1.48% at 483
ature, pressure, and space velocity, considered the main factors K to 5.38% at 543 K, which is 263% higher. As the temperature
for DME synthesis were tested and found to have a large effect was increased, the DME yield increased faster than the methanol
on methanol synthesis. The reaction condition intervals used yield. This was because the activity of the HZSM-5 catalyst
have been chosen to be similar to those used previously in the increased faster with temperature than did the Cu-based catalyst.
literature.39,40 A stoichiometry ratio of CO2 and H2 with 3:1 The process did not reach thermodynamic equilibrium under
was used. The details of the dependence on these factors are these conditions, so it was controlled by the kinetics, and a high
given below. temperature, which would increase the reaction rates, was
3.1. Effect of Reaction Temperature. DME synthesis takes needed for a high conversion of CO2. Previous experiments with
place at temperatures from 483 to 543 K. Methanol synthesis, the Cu-based catalyst used here have shown that it can be
 Ind. Eng. Chem. Res., Vol. 47, No. 17, 2008 6551

Figure 4. Relationship between the reaction pressure and CO2 conversion,

DME yield, and methanol yield. The space velocity was 6000 mL/(g cat · h), Figure 5. Relationship between the space velocity and CO2 conversion,
the ratio of H2 to CO2 was 3, and the temperature was 523 K. DME yield, and methanol yield. The ratio of H2 to CO2 was 3, the
temperature was 523 K, and the pressure was 5 MPa.
deactivated at temperatures above 523 K by sintering. Thus,
523 K was the maximum temperature that could be used. Among the various reported kinetic models for methanol
3.2. Effect of Reaction Pressure. From the thermodynamics, synthesis, Graaf’s model 41,42 gave the best fit with our
a high pressure is beneficial for DME production from CO2. experimental data. Although Graaf’s model was developed using
Experimental CO2 conversion and DME and methanol yields a CuO-ZnO-Al2O3 catalyst, it is probable that there was no
are compared in Figure 4. At 2.0 MPa, the CO2 conversion was significant difference in the reaction mechanism with the
just 0.195. When the pressure was increased to 5.0 MPa, the CuO-ZnO-Al2O3-ZrO2 catalyst used here. The difference
CO2 conversion was increased to 0.255. The yield of methanol between the catalysts was that the catalyst here contained Zr; it
and DME also showed similar trends: methanol yield was 0.025 was noted above that the effect of Zr incorporation was to
and 0.046 at 2.0 and 5.0 MPa, respectively. DME yields were increase the number of active sites, but this did not change the
0.026 and 0.149 at 2.0 and 5.0 MPa, respectively. Since the nature of the active sites. In this work, the form of the kinetic
process was controlled by the kinetics, a high pressure, which expressions used was the same, but the kinetic parameters in
meant that the concentrations were increased, was needed for a these expressions were fitted with our experimental data. In
high conversion of CO2. The figure also indicated that the DME Graaf’s kinetic model, the assumption was made that the rate
yield increased faster than methanol yield, which showed that limiting steps are CO hydrogenation, reversed water-gas shift
the HZSM-5 activity increased more sensitive than the reaction, and CO2 hydrogenation, respectively. The details have
CuO-ZnO-Al2O3-ZrO2 activity with pressure. Too high a been given in the work of Graaf et al.41,42
reaction pressure has a higher requirement for the material of The kinetic rate equations for 7–9 were as follows:
the facility and also poses a safety problem. A pressure no more
than 5.0 MPa is recommended from our tests. k1KCO fCOfH23/2 - fCH3OH/(fH21/2Kf1)
[ ]
3.3. Effect of Space Velocity. The space velocity, which is r1 )
(1 + KCOfCO + KCO fCO )[fH + (KH2O/KH21/2)fH2O
1/2
a parameter that reflects the reactor efficiency, was also tested 2 2 2 ]
with a H2/CO2 ratio of 3 at the pressure of 5.0 MPa. Space (11)
velocities of 1000 to 10000 mL/(g cat · h) were used to test the
k2KCO2(fCO2fH2 - fH2OfCO/Kf2)
catalytic behavior. The results are shown in Figure 5. At the r2 )
space velocity of 1000 mL/(g cat · h), the conversion of CO2 (1 + KCOfCO + KCO fCO )[fH
1/2
+ (KH2O/KH21/2)fH2O ]
2 2 2
was about 0.309. When this was increased to 10000 mL/(g
(12)
cat · h), the conversion of CO2 decreased to 0.203. At a higher
space velocity, the residence time was shorter. The DME yield k3KCO2 fCO2fH23/2 - fCH3OHfH2O/(fH23/2Kf3)
decreased faster than the methanol yield, which showed that r3 )
[ ]
(1 + KCOfCO + KCO fCO )[fH + (KH2O/KH2
1/2 1/2
the reactions on HZSM-5 were more affected than
2 2 2 )fH O]
2
CuO-ZnO-Al2O3-ZrO2 by the space velocity or residence (13)
time. The CuO-ZnO-Al2O3-ZrO2 + HZSM-5 catalyst had
its highest DME and methanol yield at 523 K at a space velocity The second reaction was methanol dehydration. Kinetic
of 1000 mL/(g cat · h) and a pressure of 5 MPa. models for methanol dehydration have shown that the kinetics
can depend on the catalyst. Considering that the same HZSM-5
4. Kinetics for Methanol Synthesis from CO2 catalysts were used in the kinetics developed by Tao et al.,43
Hydrogenation this was the kinetic model adopted for this work. In the Tao
kinetic model for methanol dehydration, the rate limiting step
4.1. Kinetic Modeling. Various kinetic models have been was assumed to be the surface reaction between two adjacent
proposed for this process. From the reported kinetic data, it can methanol molecules. The kinetic rate equation for 10 was as
be deduced that reaction 9 is fast and would be at thermody- follows:
namic equilibrium. Although the studied reaction was CO2
hydrogenation, due to reaction 9 both CO and CO2 coexist in k4(fCH3OH2 - fDMEfH2O/Kf4)
the reactor. From studies on CuO-ZnO-Al2O3 catalyst, it is r4 ) (14)
commonly believed that, due to this, the rate will be increased. 1 + K′H2OfH2O + KCH3OHfCH3OH
6552 Ind. Eng. Chem. Res., Vol. 47, No. 17, 2008

Figure 7. Effect of 3% CO substitution for CO2 on DME synthesis. The

Figure 6. Comparison of the kinetic model results and experimental results space velocity was 6000 mL/(g cat · h), the pressure was 5 MPa, and the
of CO2 conversion and DME and methanol yields. ratio of H2 to CO2 and CO was 3. The yield of methanol and DME increased
with the addition of CO.
Table 1. Regression Parameters for the Kinetic Model (Graaf and
Tao’s Model) on the CuO-ZnO-Al2O3-ZrO2/HZSM-5 Bifunctional 4.2. Simulation of CO Cycle Process with the Kinetic
Catalyst Model. Since the kinetics over the CuO-ZnO-Al2O3-ZrO2
Ki ) Ai exp(Bi/RT) + HZSM-5 catalyst had been quantified, a process for DME
ki ) Ai exp(-Ei/RT) synthesis can be simulated. Above, it was noted that although
parameters Ai Bi or -Ei the studied reaction was CO2 hydrogenation, due to the fast
-11
water gas shift reaction, CO will also be present in the reactor.
KCO 8.3965 × 10 1.1827 × 105 It was of interest to see if the rates were affected if a feed also
KCO2 1.7214 × 10-10 8.1287 × 104
KH2O/KH20.5 4.3676 × 10-12 1.1508 × 105 contained CO. An example was performed with a calculation
KH2O′ 8.3503 3.8867 × 10-5 where 3% of the CO2 was substituted with CO, and the
KCH3OH 9.4630 1.1273 × 10-3 calculation result was shown in Figure 7. The value of 3% was
k1 4.0638 × 10-6 -1.1695 × 104 chosen arbitrarily. It can be seen that both the DME and
k2 9.0421 × 108 -1.1286 × 105
methanol yields increased. With a higher temperature, the
k3 1.5188 × 10-33 -2.6601 × 105
k4 1.8966 × 10-3 4.0841 × 103 increase was more obvious. At 540 K, the yields of DME and
methanol were increased 37% and 6.5%, respectively (Figure
where Kf1, Kf2, Kf3, and Kf4 are the equilibrium constants of the 7). It is probable that CO addition into the reactant feed
four reactions, respectively. They were determined by the decreased the water concentration by the water gas shift reaction,
thermodynamic model proposed by Wang.41 KCO, KCO2, KH2O/ and the reduced water competition for adsorption sites enabled
KH20.5, KH2O′, and KCH3OH are the adsorption equilibrium more CO2 and H2 molecules to absorb and the yield of methanol
constants of CO, CO2, H2O, H2, and CH3OH.44 The regression was increased. Also, DME production is from methanol
analysis was based on the data shown in Figures 3–5. The dehydration, in which overall reaction would be faster with a
expressions, ki ) Ai exp(-Ei/RT), are the rate constants of each lower water concentration.
individual reaction. Experimental data from the fixed bed reactor Since CO is inevitably produced during DME production in
was used to fit the kinetic model, and the fugacity in 11–14 the one-step single reactor, the cofeed CO that would increase
was assumed equal to the partial pressure. Parameter estima- the product yield can be obtained from the reactor effluent by
tion was performed using the Matlab software using a program recycling back into the reactor to accelerate DME production.
based on the Nelder-Mead algorithm. The goodness of the fit Thus, a process with CO recycle was designed as shown in
was checked with the χ2 statistics and consistency tests provided Figure 8. The gases CO, and unreacted H2 and CO2, can be
in the software. The objective function in the parameter separated in the first distiller and recycled to mix with the
estimation was the value of F defined as follows: process feed. DME is obtained at the cooler. Methanol is
M
obtained at the second distillation tower. Although no experi-
F) ∑ [(X CO2,exp - XCO2,cal )2 + (YDME,exp - YDME,cal)2 +
mental data are available yet on the recycling process, the
simulation results indicated that CO addition will increase
j)1
the space time yields of methanol and DME, and are an incentive
(YCO,exp - YCO,cal)2] (15)
to actually perform it. There was no CO in the product in the
where X and Y were conversions. The conversions were simulated results, but this was because this was specified by
calculated by integrating the kinetic rate expressions. The the simulation. From the reaction kinetics and the reactor size,
conversions calculated with the kinetic model are compared with the product composition can be calculated for a fixed (yCO +
the experimental results in Figure 6. The fit was good with an yCO2)/yH2 value, temperature, and pressure. The calculation was
average deviation of about 6%. The optimized kinetic parameters performed by iteration by requiring that the CO amount that
are listed in Table 1. Actually, the number of adjustable exits the reactor be equal to the CO amount that enters the
parameters was large, and thus, although the regressed fit was reactor. The simulated reactor had a size the same as that used
good, this did not prove the kinetic models. In this work, the in the catalyst evaluation, a space velocity of 6000 mL/(g cat · h),
main concern was on reactor modeling, and the reaction ratio of H2 to CO2 and CO of 3, and ratio of CO to CO2 of
conditions of the simulated reactor were not very different from 3:22. From the reactor simulation, the relationship between the
those of the reactor used in the experiments. reaction pressure and temperature can be obtained and this is
 Ind. Eng. Chem. Res., Vol. 47, No. 17, 2008 6553

Figure 8. Proposed CO2 hydrogenation process with CO recycle in the system. The inlet gases of the process were CO2 and H2, and the output gases of the
process were methanol and DME.

and DME were also increased. From the simulation results, CO

recycle is important for increasing the space time yield of DME,
and this is a reason for it in addition to the conventional reason
to avoid the unnecessary loss of a feed material.

5. Conclusion
A CuO-ZnO-Al2O3-ZrO2 + HZSM-5 physical mixture
bifunctional catalyst was used to catalyze CO2 hydrogenation.
High CO2 conversion, DME yield, and methanol yield were
obtained. The kinetic parameters were obtained by regression
from experimental data. A process with CO recycle for CO2
hydrogenation was proposed.

Acknowledgment
The authors gratefully acknowledge the financial support by
Figure 9. Relationship between pressure and temperature for a process with
the Chinese National Science Foundation (Nos. 20576060 and
CO recycle for DME synthesis obtained from process simulation with the 20606021) and by the Specialized Research Fund for the
kinetic model. Doctoral Program of Higher Education (No. 20050003030).

Notation
DME ) dimethyl ether
fj ) fugacity of component j, atm
Kfi ) equilibrium constant for reaction i
Kj ) equilibrium constant for adsorption of component j
LPG ) liquefied petroleum gas
M ) mole mass, g/mol
MeOH ) methanol
n ) molar flow rate, mol/s
P ) pressure, MPa
r ) reaction speed, mol/(g cat · s)
STY ) space time yield, g/(g cat · h)
SV ) space time velocity, ml/(g cat · h)
T ) temperature, °C/K
X ) conversion
Y ) yield
Figure 10. Space time yields of DME and methanol from CO2 hydrogena-
tion with/without CO recycle. With CO recycling, the space time yields of Supporting Information Available: BJH adsorption pore
DME and methanol were much increased. distribution and the stability of DME sythesis on the CuO-ZnO-
shown in Figure 9. When the temperature increased, the Al2O3-ZrO2/HZSM-5 bifunctional catalyst. This material is
operating pressure was also increased. The DME yield and available free of charge via the Internet at http://pubs.acs.org.
methanol yield from the proposed operation is shown in Figure
10. The bottom two lines show the yields obtained without CO Literature Cited
recycle and the upper two lines show the yields with CO recycle. (1) Arakawa, H. Research and development on new synthetic routes
The yields when the CO was recycled in the process were much for basic chemicals by catalytic hydrogenation of CO2. Stud. Surf. Sci. Catal.
higher. At the same time, the space time yields of methanol 1998, 114, 19.
6554 Ind. Eng. Chem. Res., Vol. 47, No. 17, 2008

(2) Liu, X. M.; Lu, G. Q.; Yan, Z. F.; Beltramini, J. Recent advances in (25) Guo, Y.; Wang, Y. W.; Li, H. S.; Li, J. H.; Wang, J. F. Cu-based
catalysts for methanol synthesis via hydrogenation of CO and CO2. Ind. catalyst LP201 for one-step synthesis of dimethyl ether from syngas in three-
Eng. Chem. Res. 2003, 42, 6518. phase process. Chin. J. Catal. 2004, 25, 429.
(3) Keil, F. J. Methanol-to-hydrocarbons: process technology. Micropor. (26) Takeshi, K.; Itaru, H.; Hirotaka, M.; Kozo, M.; Kenji, U.; Taiki,
Mesopor. Mater. 1999, 29, 49. W.; Masahiro, S. Kinetic study of methanol synthesis from carbon dioxide
(4) Suh, H. K.; Park, S. W.; Lee, C. S. Atomization characteristics of and hydrogen. Appl. Organometal. Chem. 2001, 15, 121.
dimethyl ether fuel as an alternative fuel injected through a commonrail (27) Kenji, U.; Kozo, M.; Takeshi, K.; Taiki, W.; Masahiro, S. Methanol
injection system. Energy Fuels 2006, 20, 1471. synthesis from CO2 and H2 in a bench-scale test plant. Appl. Organometal.
(5) Yaripour, F.; Baghaei, F.; Schmidt, I.; Perregaard, J. Synthesis of Chem. 2000, 14, 819.
dimethyl ether from methanol over aluminium phosphate and silica-titania (28) Lee, S. G.; Sardesai, A. Liquid phase methanol and dimethyl ether
catalysts. Catal. Commun. 2005, 6, 542. synthesis from syngas. Top. Catal. 2005, 32, 197.
(6) Aguayo, A. T.; Erena, J.; Mier, D.; Arandes, J. M.; Olazar, M.; (29) Ng, K. L.; Chadwick, D.; Toseland, B. A. Kinetics and modelling
Bilbao, J. Kinetic modeling of dimethyl ether synthesis in a single step on of dimethyl ether synthesis from synthesis gas. Chem. Eng. Sci. 1999, 54,
a CuO-ZnO-Al2O3/gamma-Al2O3 catalyst. Ind. Eng. Chem. Res. 2007, 46, 3587.
5522. (30) Breman, B. B.; Beenackers, A. C. C. M.; Oesterholt, E. A kinetic
(7) Wang, T. F.; Wang, J. F.; Jin, Y. Slurry reactors for gas-to-liquid model for the methanol-higher alcohol synthesis from CO/CO2/H2 over Cu/
processes: a review. Ind. Eng. Chem. Res. 2007, 46, 5824. ZnO-based catalysts including simultaneous formation of methyl esters and
(8) Semelsberger, T. A.; Ott, K. C.; Borup, R. L.; Greene, H. L. hydrocarbons. Chem. Eng. Sci. 1994, 49, 4409.
Generating hydrogen-rich fuel-cell feeds from dimethyl ether (DME) using
(31) Wang, L.; Fang, D.; Huang, X.; Zhang, S.; Qi, Y.; Liu, Z. Influence
Cu/Zn supported on various solid-acid substrates. Appl. Catal. A: Gen. 2006,
of reaction conditions on methanol synthesis and WGS reaction in the
309, 210.
syngas-to-DME process. J. Nat. Gas Chem. 2006, 15, 38.
(9) Nilsson, M.; Pettersson, L. J.; Lindstrom, B. Hydrogen generation
from dimethyl ether for fuel cell auxiliary power units. Energy Fuels 2006, (32) Kim, J. H.; Park, M. J.; Kim, S. J.; Joo, O. S.; Jung, K. D. DME
20, 2164. synthesis from synthesis gas on the a mixed catalysts of Cu/ZnO/Al2O3
(10) Peng, X. D.; Toseland, B. A.; Tijm, P. J. A. Kinetic understanding and ZSM-5. Appl. Catal. A: Gen. 2004, 264, 37.
of the chemical synergy under LPDME (TM) conditions-once-through (33) Li, J. L.; Zhang, X. G.; Inui, T. Improvement in the catalyst activity
applications. Chem. Eng. Sci. 1999, 54, 2787. for direct synthesis of dimethyl ether from synthesis gas through enhancing
(11) Wang, Z.; Diao, J.; Wang, J.; Jin, Y.; Peng, X. D. Study on synergy the dispersion of CuO/ZnO/r-Al2O3 in hybrid catalysts. Appl. Catal. A: Gen.
effect in dimethyl ether synthesis from syngas. Chin. J. Chem. Eng. 2001, 1996, 147, 23.
9, 412. (34) Shishido, T.; Yamamoto, M.; Li, D.; Tian, Y.; Morioka, H.; Honda,
(12) Melian-Cabrera, I.; Granados, M. L.; Terreros, P.; Fierro, J. L. G. M.; Sano, T.; Takehira, K. Water-gas Shift Reaction over Cu/ZnO and Cu/
CO2 hydrogenation over Pd-modified methanol synthesis catalysts. Catal. ZnO/Al2O3 Catalysts Prepared by Homogeneous Precipitation. Appl. Catal.
Today 1998, 45, 251. A: Gen. 2006, 303, 62.
(13) Melian-Cabrera, I.; Granados, M. L.; Fierro, J. L. G. Effect of Pd (35) Wang, D. Z.; Wei, F.; Wang, J. F. Method of measuring adsorption
on Cu-Zn catalysts for the hydrogenation of CO2 to methanol: stabilization of gas by powder material involves measuring pressure difference and
of Cu metal against CO2 oxidation. Catal. Lett. 2002, 79, 165. temperature of reference chamber, supply chamber and sample cell directly
(14) Melian-Cabrera, I.; Granados, M. L.; Fierro, J. L. G. Reverse to calculate gas adsorption. U.S. Patent698,1426-B2, Jan 2006.
topotactic transformation of a Cu-Zn-Al catalyst during wet Pd impregnation: (36) Li, F. X.; Wang, Y.; Wang, D. Z.; Wei, F. Characterization of
Relevance for the performance in methanol synthesis from CO2/H2 mixtures. single-wall carbon nanotubes by N2 adsorption. Carbon 2004, 42, 2375.
J. Catal. 2002, 210, 273. (37) An, X.; Li, J. L.; Wang, J. F. Thermodynamic analysis for direct
(15) Zhang, X. R.; Wang, L. C.; Yao, C. Z.; Cao, Y.; Dai, W. L.; He, synthesis of dimethyl ether from CO and/or CO2 hydrogenation. Nat. Gas
H. Y.; Fan, K. N. A highly efficient Cu/ZnO/Al2O3 catalyst via gel- Chem. Ind. 2007, 32, 5.
coprecipitation of oxalate precursors for low-temperature steam reforming (38) Lin, R. C.; Yang, Y. Q.; Yuan, Y. Z.; Lin, Z. Y.; Li, C.; Yang, H.;
of methanol. Catal. Lett. 2005, 102, 183. Wang, Q.; Zhang, H. B. Promoting effect of ZrO2 to catalytic performance
(16) An, X.; Ren, F.; Li, J. L.; Wang, J. F. A highly active Cu/ZnO/ of copper-based catalyst for methanol synthesis. J. Nat. Gas. Chem. 2001,
Al2O3 nanofiber catalyst for methanol synthesis through CO2 and CO 10, 308.
hydrogenation. Chin. J. Catal. 2005, 26, 729. (39) Jun, K. W.; Shen, W. J.; Lee, K. W. Concurrent production of
(17) An, X.; Li, J. L.; Zuo, Y. Z.; Zhang, Q.; Wang, D. Z.; Wang, J. F. methanol and dimethyl ether from carbon dioxide hydrogenation: Investiga-
A CuO-ZnO-Al2O3-ZrO2 fibrous catalyst that is an improved CO2 hydro- tion of reaction conditions. Bull. Korean Chem. Soc. 1999, 20, 993.
genation to methanol catalyst. Catal. Lett. 2007, 118, 264. (40) Qi, G. X.; Fei, J. H.; Zheng, X. M. DME synthesis from CO/H2
(18) Zhang, Q.; Qian, W. Z.; Wen, Q.; Liu, Y.; Wang, D. Z.; Wei, F. over Cu-Mn/gamma-Al2O3 catalyst. React. Kinet. Catal. Lett. 2001, 73, 245.
The effect of phase separation in Fe/Mg/Al/O catalysts on the synthesis of (41) Graaf, G. H.; Stamhuis, E. J.; Beenackers, A. A. C. M. Kinetics of
DWCNTs from methane. Carbon 2007, 45, 1645. low-pressure methanol synthesis. Chem. Eng. Sci. 1988, 43, 3185.
(19) Erena, J.; Garona, R.; Arandes, J. M.; Aguayo, A. T.; Bilbao, J. (42) Graaf, G. H.; Scholtens, H.; Stamhuis, E. J.; Beenackers, A. A. C. M.
Effect of operating conditions on the synthesis of dimethyl ether over a Intra-particle diffusion limitations in low-pressure methanol synthesis. Chem.
CuO-ZnO-Al2O3/NaHZSM-5 bifunctional catalyst. Catal. Today 2005, 107, Eng. Sci. 1990, 45, 773.
467.
(43) Tao, K. Y.; Gao, F.; Zang, Y. R. Reaction kinetic study of methanol
(20) Aguayo, A. T.; Erena, J.; Sierra, I.; Olazar, M.; Bilbao, J.
dehydration to dimethyl ether. J. Fuel. Chem. Tech. 1993, 4, 387.
Deactivation and regeneration of hybrid catalysts in the single-step synthesis
of dimethyl ether from syngas and CO2. Catal. Today 2005, 106, 265. (44) Wang, C. W.; Ding, B. Q.; Zhu, B. C.; Luo, Z. C. Study on phase
(21) Erena, J.; Garona, R.; Arandes, J. M.; Aguayo, A. T.; Bilbao, J. equilibrium for binary system of gas components, methanol and water in
Direct synthesis of dimethyl ether from (H2+CO) and (H2+CO2) feeds. three-phase methanol synthesis process with liquid paraffin. J. Chem. Eng.
Effect of feed composition. Int. J. Chem. Reactor Eng. 2005, 3, 25. Chin. UniV. 2000, 14, 588.
(22) Wang, Z. L.; Wang, J. F.; Diao, J.; Jin, Y. The synergy effect of (45) Herman, R. G.; Klier, K.; Simmons, G. W.; Finn, B. P.; Bulko,
process coupling for dimethyl ether synthesis in slurry reactors. Chem. Eng. J. B.; Kobylinski, T. P. Catalytic synthesis of methanol from carbon
Technol. 2001, 24, 507. monoxide/hydrogen. I. Phase composition, electronic properties, and
(23) Wang, Z. L.; Diao, J.; Wang, J. F.; Jin, Y.; Peng, X. D. Study on activities of the copper/zinc oxide/M2O3 catalysts. J. Catal. 1979, 56, 407.
synergy effect in dimethyl ether synthesis from syngas. Chin. J. Chem. Eng.
2001, 9, 412. ReceiVed for reView January 6, 2008
(24) Xie, F.; Li, H. S.; Zhao, X. L.; Ren, F.; Wang, D. Z.; Wang, J. F.; Accepted June 6, 2008
Liu, J. G. Adsorption and dehydration of methanol on Al2O3 catalyst. Chin.
J. Catal. 2004, 25, 403. IE800777T