DOI: 10.1002/cctc.
201000329
A Novel Synthesis Route for Cu/ZnO/Al2O3 Catalysts used
in Methanol Synthesis: Combining Continuous
Consecutive Precipitation with Continuous Aging of the
Precipitate
Stefan Kaluza,[a] Malte Behrens,[b] Nora Schiefenhçvel,[c] Benjamin Kniep,[c] Richard Fischer,[c]
Robert Schlçgl,[b] and Martin Muhler*[a]
A novel continuous method for the preparation of a ternary
Cu/ZnO/Al2O3 catalyst based on a cascade of micromixers and
a tubular aging reactor is presented as a promising alternative
route to the conventional batch process. Its application, in
combination with immediate spray drying, enables monitoring
of the formation of the final precursor by exchange reactions
between initially separated phases during the aging step.
Introduction
The formation of methanol from synthesis gas (CO/CO2/H2) is
one of the key processes in the chemical industry today. Con-
ventionally, Cu-Zn-Al mixed oxides are used as catalyst precur-
sors in low-pressure methanol synthesis.[1] The industrial impor-
tance is confirmed by the numerous patents granted to vari-
ous manufacturers for the production of ternary catalysts.[2–7] In
most cases, the technical preparation route comprises of the
coprecipitation of a metal nitrate solution with sodium or am-
monium carbonate to generate mixed hydroxy carbonates, fol-
lowed by calcination and reduction of the precursor to form
the active Cu/ZnO/Al2O3 catalyst.[8]
The strict definition for a coprecipitation process is the si-
multaneous precipitation of a normally soluble component
with a macrocomponent from the same solution by the forma-
tion of mixed crystals by adsorption, occlusion, or mechanical
entrapment.[9] However, in the field of catalyst preparation, the
term is used more generally and describes the simultaneous
precipitation of more than one component, although the solu-
bility of products may differ substantially. In the latter case,
constant pH conditions are required to avoid independent or
consecutive precipitation.[10] Large-scale precipitations are usu-
ally operated in batch reactors. The advantages of this opera-
tion mode are product accessibility and simplified-process
piloting.[11]
Precipitation is often followed by an aging period. Aging
refers to the period of time during which the precipitate is left
in its mother liquid either under precipitation or somewhat dif-
ferent conditions. Several processes may take place during
aging, which can strongly affect the properties of the final ma-
terial. The morphology and the size of the particles change as
a result of Ostwald ripening, nonisothermal recrystallization,
agglomeration, or coagulation.[12] Furthermore, the most im-
ChemCatChem 2011, 3, 189 – 199  2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
These exchange reactions were successfully simulated by con-
secutive precipitation by using micromixers in series as analyti-
cal tool. After 60 min of continuous aging, calcination, and re-
duction, a catalyst is produced that exhibits an almost equal
mass-related activity in methanol synthesis compared to a
commercial catalyst and an area-related activity that is about
50 % higher.
portant process—with respect to the performance of the final
catalyst—that can occur during aging is recrystallization ac-
companied by a change in the chemical composition of the
solid phase.[13] The initially formed precipitate is often amor-
phous, and during aging in its mother liquid a conversion to a
crystalline phase occurs. Aging is generally performed after the
completed precipitation by stirring the precipitate for a de-
fined period of time in the same reaction vessel. Nevertheless,
the main disadvantage of this operation mode is the variation
of the batch composition during precipitation and aging. It
can lead to an inhomogeneous product distribution, as the ini-
tially formed precursor may differ significantly from the phase
formed at the end of the process. Furthermore, an accurate
identification and investigation of precursor phases at different
stages of the precipitation is hardly feasible.[9]
To avoid this problem, a continuously operating mode can
be applied for both precipitation and aging, which provides
high supersaturation levels and a high homogeneity of the
final product.[14, 15] In addition, it offers a better process control,
as all parameters such as temperature, pH, and residence time
can be kept constant. Tubular reactors have been already used
[a] Dr. S. Kaluza, Prof. Dr. M. Muhler
Laboratory of Industrial Chemistry, Ruhr-University Bochum
Universitaetsstraße. 150, 44780 Bochum (Germany)
Fax: (+ 49) 234 32 14115
E-mail: muhler@techem.rub.de
[b] Dr. M. Behrens, Prof. Dr. R. Schlçgl
Department of Inorganic Chemistry
Fritz Haber Institute of the Max Planck Society
Faradayweg 4-6, 14195 Berlin (Germany)
[c] Dr. N. Schiefenhçvel, Dr. B. Kniep, Dr. R. Fischer
Research & Development Catalysts, Sd-Chemie AG
Waldheimer Straße 13, 83052 Bruckmhl (Germany)
189

for precipitation reactions on the laboratory scale.[16–19] For the
binary Cu/ZnO catalyst, the use of a micromixer as continuous
precipitation reactor proved to be a promising synthesis
route.[20] The advantage of performing the aging process in a
tubular reactor is the sharp residence time distribution, which
only depends on the length of the aging module, that is, it is
the same for every single particle of the precipitate.
Recently, a novel continuous precipitation process using a
micromixer was developed, in which the continuous precipita-
tion was immediately quenched by a subsequent spray-drying
process.[21] Thus, it was possible to investigate the formation
mechanisms occurring during the first few seconds of the pre-
cipitation, which is hardly feasible in batch-operation mode.
This novel method was successfully used for detailed studies
on the synthesis and aging of ZnO,[22] and the binary Zn-Al
oxide system.[23] The latter plays an important role in the syn-
thesis of the ternary catalyst system, and the following obser-
vations were made: Owing to the immediate quenching of the
precipitation reaction, an X-ray amorphous binary Zn-Al phase
was identified as the initially formed (metastable) precipitation
product. By further thermal treatment, this phase decomposes
to form crystalline ZnO and Zn-Al hydrotalcite. Zn-Al hydrotal-
cite can also be obtained if the single Zn and the single Al pre-
cursors are first precipitated and calcined separately, and then
combined during the subsequent washing/drying step. By the
right choice and sequence of post-precipitation steps, that is,
washing, freeze drying, and calcination, the formation of Zn-Al
hydrotalcite can be suppressed, leading to an X-ray amorphous
material with a high specific-surface area of 144 m2 g 1.[23]
A novel continuously operating process for the synthesis of
the ternary Cu/ZnO/Al2O3 catalyst is presented. This process
combines a continuous consecutive precipitation (CCP)
method by using a micromixer cascade with continuous aging
of the precipitate. The formation and conversion of intermedi-
ates occurring during precipitation and aging have been stud-
ied in detail by using a spray dryer to quench the precipitation,
and their influence on the performance of the final catalyst in
methanol synthesis has been investigated. The continuous pre-
cipitation/aging mode is a promising alternative preparation
method to the conventional batch process.
Results
Continuous precipitation—direct spray drying
The combination of continuous precipitation in a micromixer
with a subsequent spray-drying process offers the unique pos-
sibility of an immediate quenching of precipitation reactions
to investigate the initially formed metastable products. To ac-
quire more information about the formation mechanism that
occurs during the coprecipitation of the ternary Cu-Zn-Al pre-
cursor, this method was applied to three single systems, in ad-
dition to three binary mixtures, followed by the usually applied
post-precipitation steps, and a detailed analysis of the influ-
ence of the latter on the properties of the final product in
each case. Thus, an extended dataset of chemical and structur-
al information was collected. Described is a typical example
190 www.chemcatchem.org  2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
M. Muhler et al.
from this dataset to demonstrate the high benefit of this ap-
proach for the investigation of ternary systems.
The single Cu system
The continuous precipitation of copper nitrate with sodium
carbonate was quenched immediately by the subsequent
spray-drying process to investigate the single Cu system in
more detail. The diffraction pattern of the resulting precursor
phase is shown in Figure 1 a. In addition to the intensive reflec-
tions of the byproduct sodium nitrate (solidified due to spray
drying), crystalline sodium copper carbonate Na2Cu(CO3)2 was
identified as the kinetically metastable precipitation product.
By exposing the product to water again during washing, a
phase transition into the thermodynamically more stable
copper hydroxy carbonate occurred (Figure 1 b), the reflections
of which are attributed to a synthetic type of the mineral mala-
chite Cu2(OH)2CO3. Copper oxide and mixed CuO/ZnO phase
syntheses that include several hours of aging in the mother
liquid after precipitation always produce Cu2(OH)2CO3 mala-
chite and a Zn-enriched type material called zincian malachite,
respectively.[24] The described phase transition of the sodium
copper carbonate into malachite was, therefore, considered to
be the key process during the aging step. According to the
corresponding decomposition curves (Figure 1c,d), this transi-
tion also influences the thermochemistry of the precursor and,
therefore, its chemical and structural properties.
The ternary Cu-Zn-Al system
The ternary catalyst precursor was synthesized by continuous
coprecipitation of a mixed solution of the three metal nitrates
in the nominal composition with sodium carbonate followed
by the immediate spray-drying process. The diffraction pattern
of the resulting phase mixture is shown in Figure 2 a. Surpris-
ingly, instead of a precursor phase consisting of a homogene-
ous distribution of all three components, the single sodium
copper carbonate is observed in addition to an amorphous
phase, assumed to be the X-ray amorphous binary Zn-Al
system discussed in the introductory section. Therefore, calci-
nation, washing and drying of this precursor mixture leads
to the formation of CuO and a Zn-Al hydrotalcite-like species
with a very low specific copper surface area of about 1 m2 g 1
(Figure 2 b).
After the ternary precursor was quenched by spray drying,
phase transitions take place during the washing and drying
process, revealed by analysis of the respective diffraction pat-
terns (Figure 2c,d), before it was calcined. One part of Na2Cu-
(CO3)2 remained unchanged upon washing and decomposed
to CuO during the thermal treatment in the drying oven, while
another part was converted to form a binary Cu-Zn hydroxy
carbonate that did not decompose during the drying step.
After calcination, a less crystalline material was produced with
a specific copper surface area of about 6 m2 g 1, much higher
than the CuO and Zn-Al hydrotalcite-like species.
Exchange reactions between the initially formed metastable
precipitation phases must have taken place during the aging
ChemCatChem 2011, 3, 189 – 199
Cu/ZnO/Al2O3 Catalysts
Figure 1. Diffraction patterns of the single Cu system a) after immediate
spray drying of the precipitate: c spray dried Cu precursor, a NaNO3,
Na2Cu(CO3)2 ; b) after washing/drying of the spray-dried precursor: c
washed/dried Cu precursor, & CuO, & Cu2(OH)2CO3 ; c,d) the corresponding
TG-MS curves for the thermal decomposition of the precursors are also
shown: c H2O, c CO2, c NO.
ChemCatChem 2011, 3, 189 – 199  2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Figure 2. Diffraction patterns of the coprecipitated ternary system a) after
& immediate spray drying: c spray dried Cu/Zn/Al precursor, a NaNO3, &
Na2Cu(CO3)2 ; b) after calcination of the precursor followed by washing and
drying (SCu = 0.6 m2 g 1): c final Cu/Zn/Al precursor, & Zn6Al2(OH)16CO3, &
CuO, & ZnO; c) the ternary precursor after washing/drying of the spray-dried
precursor: c washed/dried Cu/Zn/Al precursor, & CuO, & (Zn,Cu)5(OH)6-
(CO3)2 ; d) calcination (SCu = 5.6 m2 g 1) c final Cu/Zn/Al precursor, &
Zn6Al2(OH)16CO3, & CuO, & ZnO.
www.chemcatchem.org 191

process. A novel CCP method was developed to investigate
those exchange reactions in more detail.
Continuous consecutive precipitation—direct spray drying
To achieve CCP of the ternary system, three micromixers were
connected (Figure 3 a). One micromixer was used for the con-
tinuous precipitation of copper nitrate with sodium carbonate
to generate Na2Cu(CO3)2, while the binary Zn-Al phase was
Figure 3. The micromixer cascade setup used for continuous consecutive
precipitation. a) The precipitation of the system described as Cu + (Zn-Al).
b) Specific Cu surface areas achieved for different precipitation methods, as
well as for different sequences of the post-precipitation steps: & washed
then calcined, & calcined then washed.
continuously precipitated in the second one. Both metastable
precipitates were subsequently mixed in a third micromixer fol-
lowed by immediate spray drying. Owing to the consecutive
precipitation process, the resulting precursor is labeled as
Cu+(Zn-Al). Additionally, the other two possible consecutive
combinations were also synthesized and labeled as (Cu-Zn)+Al
and (Cu-Al)+Zn, respectively. The specific copper surface areas
of the resulting catalysts were determined by using N2O reac-
tive frontal chromatography (N2O-RFC) (Figure 3 b).
All samples prepared by using consecutive precipitation ex-
hibited significantly higher copper surface areas in all cases
compared to the corresponding coprecipitation samples.
Among them, the combination Cu+(Zn-Al) synthesized by con-
secutive coprecipitation produced the highest copper area of
about 22 m2 g 1. Moreover, the samples that were first washed
and subsequently calcined had higher copper areas compared
192 www.chemcatchem.org  2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
M. Muhler et al.
to the corresponding samples that were calcined first and
washed afterwards. These results indicated that influence of
the subsequent aging step with respect to the properties of
the final material was important.
For the continuous process, a continuous aging device was
developed and combined with the micromixer setup.
Continuous consecutive precipitation—continuous aging
Recently, detailed studies revealed that the phase transitions
occurring during aging are activated processes that require in-
creased mass transport,[22] which can be increased mechanical-
ly or thermally. Both were achieved by using a temperature-
controlled ultrasonic bath including a continuous aging device
(a silicone tube of defined length and diameter directly con-
nected to the micromixer). The continuous aging process al-
lowed for an exactly defined aging time by adjusting the
length of the aging device, while the diameter and the flow
rate are kept constant. In contrast to a continuously operated
stirred tank reactor (CSTR) with an exponentially decaying resi-
dence time distribution, the aging device is a laminar-flow tub-
ular reactor, in which all precipitated particles are in contact
with their mother liquid for exactly the same period of time.
Therefore, this experimental approach was able to provide a
detailed investigation of the phase transitions occurring during
the synthesis of the ternary precursor as a function of aging
time.
Characterization of the dried precursor
The following results illustrate that the consecutively precipi-
tated Cu+(Zn-Al) precursor is a model system for the process-
es occurring during the continuous coprecipitation. The diffrac-
tion patterns of the resulting precursors precipitated at differ-
ent temperatures and continuously aged for different periods
of time in comparison to a precursor prepared by the usual
batch process (including 2 h aging) are shown in Figure 4.
As expected, if the precursor was filtered immediately after
the precipitation (0 min), the separation of the single copper
and the binary Zn-Al phase was still observable. Analysis of the
X-ray pattern reveals an amorphous profile assigned to the
binary Zn-Al phase, as well as one sharp reflection at 2 q =
12.88 attributed to the single copper phase Na2Cu(CO3)2. The
different precipitation temperatures did not result in significant
differences in the two corresponding diffraction patterns. After
20 min of continuous aging, analysis by using X-ray diffraction
(XRD) analysis revealed that the intensities of the former reflec-
tions decreased, as new reflections assigned to a hydrotalcite-
like phase were recorded. Additional weak reflections of zin-
cian malachite were also recorded. After the precipitate had
been continuously aged for 60 min, the Na2Cu(CO3)2 reflections
disappeared, and the precursor consisted of the hydrotalcite-
like compound and zincian malachite, as well as a small
amount of aurichalcite. Moreover, the recorded XRD pattern
almost corresponds to that observed for the coprecipitated
precursor, which was aged for 2 h in the usual batch process.
ChemCatChem 2011, 3, 189 – 199
Cu/ZnO/Al2O3 Catalysts
Figure 4. Diffraction patterns of four continuously precipitated Cu+(Zn-Al)
precursors (a–d) in comparison to e) a batch-coprecipitated precursor. Tem-
perature during precipitation and aging (if applied) T = 25, 65, 65, 65, 65 8C
(a–e). The corresponding period of aging t = 0, 0, 20, 60, 120 minutes (a–e).
* amorphous Zn-Al, & NaCu(CO3)2, & hydrotalcite, & Zn malachite, & aurichal-
cite.
The thermogravimetric analysis (TG) data of the precursors
together with the evolved H2O and CO2 curves detected upon
heating by using mass spectrometry (MS) are shown in
Figure 5. The two precursors that were both not aged, but pre-
cipitated at different temperatures exhibited the same phase
composition, as judged by the diffraction patterns. Analysis of
both patterns revealed an elevated background, indicative of a
high amount of X-ray amorphous phases. In contrast, analysis
ChemCatChem 2011, 3, 189 – 199  2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Figure 5. TG data for the differently prepared precursors (a–d) in comparison
to e) a batch-coprecipitated precursor. The MS curves of evolved H2O and
CO2 during the thermal decomposition are shown together with their signifi-
cant peak temperature values. The range of the chosen calcination tempera-
ture (320 8C) is marked. Temperature during precipitation and aging (if ap-
plied) T = 25, 65, 65, 65, 65 8C (a–e). The corresponding period of aging t = 0,
0, 20, 60, 120 minutes (a–e). c H2O, c CO2, c mass loss [%].
of the decomposition curves revealed significant differences
between the two samples. In the low-temperature region
(below the calcination temperature, 320 8C) the behavior was
quite similar and the evolution of water was accompanied by
CO2 over the whole temperature range (T < 320 8C). With in-
creasing temperature, the carbonate species decomposed
without any further release of water. TG analysis of the precur-
sor prepared at room temperature revealed two sharp maxima
at 342 8C and 380 8C. The sample precipitated at 65 8C also
shows two maxima, but they are much broader and shifted to
higher temperatures, indicating that the structural differences
of the precursors were caused by an increase in the precipita-
tion temperature. After aging for 20 min, the decomposition
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 M. Muhler et al.

curve of the so called high-temperature carbonate (HT-CO3)

became even broader and three maxima can be distinguished.
As the aging was increased to 60 min, the TG-MS profile
changed significantly. In the low-temperature region, the sharp
maximum of H2O at 120 8C indicated the evolution of interlayer
water from a hydrotalcite-like compound, which had already
been identified in the respective diffraction pattern of this
sample.[25] Within the region of the calcination temperature a
sharp maximum indicated the spontaneous release of CO2,
which was, in this case, accompanied by the simultaneous re-
lease of water. Thus, these maxima were assigned to the de-
composition of the hydroxy carbonate zincian malachite, iden-
tified by using XRD.[26] Additionally, some HT-CO3 decomposed
in the region above T = 320 8C. The structural similarities be-
tween the continuously aged sample and the sample prepared
by coprecipitation in a batch process were confirmed by analy-
sis of the corresponding diffraction patterns and the TG-MS
data.

Characterization of the calcined precursor

Analysis of the diffraction patterns of the calcined samples re-
vealed an increase in crystallinity with increased aging time,
which matched the analysis of the uncalcined precursors
(Figure 6).
Again, the diffraction patterns of the samples that were not
aged did not differ significantly. Even after calcination, the
samples mostly consisted of X-ray amorphous phases, which
made identification of crystalline species almost unfeasible. In
the diffraction pattern of the sample aged for 20 min, CuO was
identified in the crystalline phase and was still accompanied by
high amounts of X-ray amorphous carbonates. The sample
aged for 60 min also contained residual amounts of HT-CO3,
which was identified in a crystalline malachite-type phase. This
observation became more evident for the sample prepared by
batch coprecipitation. These results indicated that the com-
plete conversion of the hydroxy carbonate-containing precur-
sors into the oxides was not achieved for any of the samples; Figure 6. Diffraction patterns of the differently prepared precursors after cal-
all of the samples contained significant amounts of residual cination at 320 8C for 3 h (a–d) in comparison to e) a batch-coprecipitated
carbonate species. A quantitative determination of the amount precursor. Temperature during precipitation and aging (if applied) T = 25, 65,
of residual HT-CO3 by integration of the CO2 curves was unfea- 65, 65, 65 8C (a–e). The corresponding period of aging t = 0, 0, 20, 60, 120
minutes (a–e). & CuO, & Zn malachite, & ZnO.
sible, as some CO2 maxima overlapped with the calcination
temperature range. Qualitatively, the amount of residual high-
temperature carbonate decreased as the aging time increased, displayed in Figure 8. The specific BET surface areas of the cal-
that is, after calcination there were different copper-precursor cined samples decreased with increasing precursor aging time,
ratios present. Precursors which were then heated in hydrogen whereas the values of the specific copper surface area did not
to reduce copper(II) to copper(0). The structural differences of correlate with the aging time. To study the effect of the
the calcined precursors were also visible in the resultant tem- observed structural differences caused by aging on the activity
perature-programmed reduction (TPR) profiles (Figure 7). By in- of the final catalysts, the samples were tested in methanol
creasing the precipitation temperature from 25 8C to 65 8C, the synthesis.
maximum reduction temperature lowered (from 208 8C to
197 8C), and was reduced further as the aging time increased.
Additionally, there is a shoulder at about T = 208 8C is observed
Catalytic activity
in the profiles of the aged samples (Figure 7d,e).
The specific surface areas of the calcined samples derived Summarized in Table 1 are the results of the catalytic activity
from N2 physisorption, as well as the specific copper surface measurements for the samples described above at a steady
areas of the reduced samples measured by using N2O-RFC are state under isothermal plug–flow conditions.

194 www.chemcatchem.org  2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemCatChem 2011, 3, 189 – 199
Cu/ZnO/Al2O3 Catalysts
Figure 7. TPR profiles for the calcined catalyst precursors (a–d) in compari-
son to d) a batch-coprecipitated precursor. The respective maximum reduc-
tion temperature is given for each sample. Temperature during precipitation
and aging (if applied) T = 25, 65, 65, 65, 65 8C (a–e). The corresponding
period of aging t = 0, 0, 20, 60, 120 minutes (a–e).
ChemCatChem 2011, 3, 189 – 199  2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Figure 8. Specific BET surface areas and specific Cu surface areas of continu-
ously precipitated ternary catalysts with respect to the preparation parame-
ters (a–d) in comparison to e) a batch-coprecipitated precursor. The T value
is the temperature during precipitation and aging (if applied). The t value is
the corresponding period of aging. & SBET, & SCu
The weight-time yield values of methanol are given relative
to a ternary Cu/ZnO/Al2O3 benchmark catalyst of the same
nominal composition provided by Sd-Chemie AG. The meas-
urements at 250 8C are close to the thermodynamic equilibri-
um conditions and are performed as stress tests, whereas the
conditions at 210 8C are far from the thermodynamic equilibri-
um. Therefore, the measured values at 210 8C are representa-
tive of the catalytic activity.
Although sample 1 exhibits the highest specific copper sur-
face area (> 20 m2 g 1), it shows only a very low activity for
methanol synthesis. The values are less than 10 % of the values
measured for the reference catalyst. TG-MS analysis revealed
the structural differences between sample 1 (precipitated at
room temperature) and sample 2 (precipitated at 65 8C). The
differences caused by the higher precipitation temperature
strongly influenced the activity of the final catalyst. The mea-
sured value of the methanol productivity increased up to more
than 50 % of the reference values in the second period at
210 8C. By 20 min continuous aging of the precipitate keeping
the temperature constant at 65 8C, the activity of the resulting
catalyst 3 is slightly increased up to 60 % relative to the refer-
ence catalyst. If the aging time is increased to 60 min the activ-
ity of the resultant catalyst 4 nearly equals that of the commer-
cial catalyst. Moreover, the structural similarities between the
continuously precipitated sample and the batch-precipitated
sample 5 (aged for 2 h) is reflected by comparable activities.
The commercial catalyst exhibits a specific copper surface
area of about 25 m2 g 1, which was significantly higher com-
pared to sample 4. Therefore, the intrinsic activity that corre-
lates the productivity of methanol to the copper-surface area
provided was about 50 % higher for the continuously precipi-
tated sample. Another significant difference is the observed in-
creasing stability of the samples 2, 3, and 4. The stability of a
catalyst can be assessed by comparing the activities in the first
period under synthesis conditions with the values of the
second period. It was unexpected that the consecutively pre-
cipitated catalysts did not deactivate.
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 M. Muhler et al.

The results of the catalytic

Table 1. Catalytic test results for the differently prepared Cu/ZnO/Al2O3 catalysts. The activity values are given
relative to a commercial catalyst of the same nominal composition provided by Sd-Chemie AG. testing revealed that the precipi-
tation temperature had a major
Sample Tprec. Taging SCu First reaction period Second reaction period MeOHfinal/MeOHinitial impact on the performance of
MeOH output[a] MeOH output[a]
2 1 the final catalyst. Sample 2 ex-
[8C] [8C] [m g ] 250 8C 210 8C 250 8C 210 8C 250 8C 210 8C
hibited an activity that was more
1[b] 25 0 21.1 0.05 0.03 0.04 0.02 0.95 0.81
[b] than five times the activity of
2 65 0 20.0 0.53 0.51 0.60 0.57 1.13 1.12
3[b] 65 20 13.3 0.56 0.58 0.65 0.65 1.16 1.13 sample 1, although both sam-
4[b] 65 60 15.3 0.87 0.87 0.95 0.93 1.10 1.08 ples were not aged and the re-
5[c] 65 120 18.3 0.92 0.86 0.90 0.84 0.98 0.97 action time (the residence time
[a] MeOH productivity values are relative to the commercial catalyst; [b] prepared by continuous consecutive of the precipitate inside the mi-
precipitation of the system Cu+(Zn-Al); [c] prepared by conventional batch-coprecipitation. cromixer) was less than 1 s. Even
during a rapid precipitation pro-
cess the reaction temperature
Discussion
was a crucial parameter for the preparation of an active
catalyst.
The initial precipitation step
In general there is correlation between high specific copper
The immediate quenching of the continuous coprecipitation surface area and high catalytic activity in methanol synthesis,
reaction produced Na2Cu(CO3)2 separately from the binary Zn- but this could not be confirmed for the catalyst systems ob-
Al phase. Therefore, in the initial stage of the reaction there tained by CCP combined with immediate spray drying. All sam-
was no coprecipitation of all three components, but a compe- ples exhibited high copper areas, but methanol productivity
tition taking place, which favored a mixed Zn-Al phase and a values were less than 10 % compared to a commercial Cu/
single Cu phase. ZnO/Al2O3 catalyst of the same metal composition. Thus, in ad-
However, the ternary precursor consisted of two binary Cu- dition to a high specific copper surface area, the chemical envi-
Zn phases, zincian malachite (Cu,Zn)2(OH)2CO3 and aurichalcite ronment of each copper particle was important for the activity
(Zn,Cu)5(OH)6(CO3)2, as well as a ternary hydrotalcite-like phase, of the catalyst.
if it was prepared by the usual batch process, which included That in the ternary catalyst ZnO also works as a structural
two hours aging in the mother liquid. Thus, during the aging promoter is widely accepted and also that it exhibits a major
process, exchange reactions between the formerly separated influence on the catalytic activity,[26–29] whereas alumina in-
single copper phase and the binary Zn-Al phase took place creases the long-term stability of the system,[30–34] and influen-
and led to a precursor with a much more homogeneous metal ces its catalytic performance.[35, 36] Therefore, precursors are re-
ion distribution and a higher specific copper surface area. quired that provide an intimate contact between all three
These exchange reactions between the metastable precipita- metal species.
tion phases that were formed initially during the aging pro- The copper phase was initially separated from the binary
cess, were then studied in more detail by the novel CCP Zn-Al phase. Thus, the system required a certain period of
method and, consequently, played a crucial role in the synthe- aging time to allow the phase transitions to occur, which led
sis of the ternary catalyst precursor. to a more homogeneous metal distribution that favored the
The higher copper surface areas of the consecutively precipi- performance of the final catalyst.[37]
tated samples, compared to the corresponding coprecipitated
sample, were assumed to be caused by intensified mass trans-
The role of aging
port; the rate of exchange reactions between the two metasta-
ble precursor phases was greatly increased, owing to the high The CCP method provides the unique possibility to simulate
turbulence created inside the small mixing zone of the third the initial situation during the coprecipitation process, that is,
micromixer. Furthermore, the samples that were first washed the formation of a single Cu phase separated from a binary
and subsequently calcined had higher copper surface areas Zn-Al phase. By applying the novel continuous aging device,
compared to the corresponding samples calcined first and the exchange reactions of these metastable phases can be in-
then washed. In the first case, the washing process not only vestigated as a function of aging time.
led to the removal of sodium nitrate, but also allowed a rear- The observed phase transitions proceed in an analogous
rangement of the initially quenched precipitate and caused way to those described for the separated single copper and
phase transitions for the single Cu and the binary Zn-Al binary Zn-Al systems. Upon aging, the initially formed Na2Cu-
system. Thus, washing provided an aging effect for the sam- (CO3)2 was converted into malachite (Cu2(OH)2CO3).[38] In the
ples, which led to more favorable structures with respect to presence of the binary Zn-Al phase, the same transition took
the specific copper surface area. In contrast, direct calcination place and, additionally, some zinc was incorporated into the
of the quenched precipitate froze the separated state of the structure to form zincian malachite (Cu,Zn)2(OH)2CO3. Further-
different consecutively precipitated phases and was followed more, the amorphous Zn-Al phase changed into a hydrotal-
by conversion into the corresponding oxides. cite-like structure during the aging process. However, the dif-
fraction angles of the hydrotalcite reflections for the ternary

196 www.chemcatchem.org  2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemCatChem 2011, 3, 189 – 199
Cu/ZnO/Al2O3 Catalysts
precursor prepared by CCP differ significantly from those
found for the binary system, which indicated structural
changes in the hydrotalcite-like lattice in the ternary system.
The structural changes could have resulted from a decrease in
the zinc content of the binary Zn-Al hydrotalcite, owing to the
substitution into the malachite structure,[39, 40] or the formation
of a ternary hydrotalcite-like structure by the incorporation of
copper.[41, 42]
The diffraction pattern of the CCP precursor that was aged
for 60 min was almost identical to that observed for the pre-
cursor coprecipitated and aged for 2 h in the usual batch pro-
cess. Thus, this precursor composition represents a thermody-
namic minimum that all ternary precursors of the same molar
ratios approach with increasing time, independent of the pre-
cipitation method. This was also reflected as the crystallinity in-
creased with increasing aging time if compared to the initially
X-ray amorphous precursor mixture.
As revealed by the TG-MS data analysis, all samples exhibit-
ed a relatively large amount of high-temperature carbonates
that qualitatively decreased with increasing aging time. Upon
calcination the conversion was incomplete, which resulted in a
mixture of metal oxides and residual carbonate species and a
shift of the maximum reduction temperature in the profiles of
the subsequent reduction step. This shift towards lower values
qualitatively correlated with the decreasing amount of residual
copper carbonate species. These species were reduced at tem-
peratures above 200 8C, whereas the maximum reduction tem-
perature of the ternary mixture of the oxides was about
170 8C. As a consequence, the two samples with the lowest
amount of residual HT-CO3 exhibited reduction temperatures
near this reference value. Additionally, these profiles clearly
show a shoulder in the temperature range above 200 8C, which
originated from the residual carbonate content.
The decrease of the specific surface area with increasing
aging time can be explained by the different phase composi-
tion of the precursors. Without aging, initially the binary Zn-Al
phase was formed. The calcination of this phase produced a
material with a high specific surface area. As the aging time in-
creased, this metastable phase underwent a phase transition
into a hydrotalcite-like compound. Upon calcination, the hy-
drotalcite-like compound decomposed, which led to a material
with a significantly lower surface area. The differences in
copper-surface area originated from the different copper
phases that were present as a function of the aging time. The
formation of metallic copper particles was highly dependent
on the reduced copper compound and its contact to the struc-
tural promoter ZnO. Therefore, aging was required to form the
precursor phases, such as zincian malachite, aurichalcite, or ter-
nary hydrotalcite, that provide intimate contact between the
three metal species, which then resulted in a highly active final
catalyst. Thus, by 60 min of continuous aging the consecutively
precipitated sample exhibited a catalytic performance that
almost equaled that of the commercial reference catalyst.
All catalysts prepared by using the CCP method have in-
creased stability compared to those prepared by using the
conventional batch process. By using methanol synthesis con-
ditions in the first period, favorable changes in the structure of
ChemCatChem 2011, 3, 189 – 199  2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
the catalyst occurred, which led to increased activity in the
second period. This unexpected catalyst behavior may have or-
iginated from the difference in the reduction temperature, that
is, the reduction may be incomplete for those catalyst precur-
sors before the first period. Owing to the higher temperature
and the reduction conditions during the first period, the resid-
ual amount of copper(II) was reduced, and more copper(0) par-
ticles were generated that were then available in the second
period.
Further investigations are needed to optimize the reduction
procedure for each sample according to its TPR profile. More-
over, a microstructural analysis of the used catalysts after the
first and the second period is needed to clarify the beneficial
changes occurring under methanol synthesis conditions.
Conclusions
A novel, continuously operating process for the synthesis of
the ternary Cu/ZnO/Al2O3 catalyst has been developed, which
combines continuous consecutive precipitation (CCP) using a
micromixer cascade with continuous aging of the precipitate.
Quenching experiments were performed by using a spray
dryer, which revealed a separation of a single Cu phase from a
binary Zn-Al phase in the initial stage of the reaction instead
of the desired coprecipitation of all three cations. With increas-
ing aging time, exchange reactions were found to occur that
led to different precursor compositions including phases with
homogeneous metal ion distribution. These exchange reac-
tions were investigated by using the CCP method, which was
shown to simulate the interactions of the initially formed
metastable precipitate phases. Although the specific copper
surface area decreased with aging time, the increasing homo-
geneity led to an increase of the catalytic activity. Compared
to a commercial ternary catalyst used in methanol synthesis,
the intrinsic real activity is about 50 % higher for the catalyst
prepared by the continuous process.
The combination of continuous precipitation with continu-
ous aging allowed for fast and reproducible parameter screen-
ing during catalyst preparation and a reliable study of the
structure-activity correlations. The high activity and stability of
the catalysts were a direct consequence of the increased con-
trol of the relevant process parameters during catalyst precipi-
tation. Continuous catalyst preparation has proven to be a
promising alternative to the conventional batch process.[43]
Experimental Section
Catalyst preparation: All precursors were prepared by a continuous
precipitation of aqueous metal nitrate solution (c = 0.10 mol L 1)
with sodium carbonate (c = 0.12 mol L 1). The chemicals were ob-
tained from Aldrich and used as received. For continuous copreci-
pitation one mixing tee (VICI) was used as micromixer. For continu-
ous consecutive precipitation the components were separately pre-
cipitated in two different mixing tees that were directly connected
to a third micromixer, where the two initially formed precipitates
were immediately mixed. The flow rates were chosen to achieve a
constant pH of 6.5–7.0 measured online in the effluent of the
micromixer.
www.chemcatchem.org 197

Quenching of the precipitation reaction was achieved by connect-
ing the micromixer directly to the two-fluid nozzle of a bench-top
spray dryer (B-290, Bchi). Continuous aging was achieved by al-
lowing the precipitate to flow through a 7 m or 23 m long silicone
tube with an inner diameter of 5 mm, which provided a residence
time of 20 min or 60 min, respectively. The silicone tube was em-
bedded into a temperature-controlled ultrasonic bath. After leav-
ing the aging module, the precipitate was immediately filtered
under reduced pressure. In the case of no aging, the precipitate
was directly filtered after leaving the micromixer. For filtration a
glass frit (porosity 5, 1.0–1.6 mm) was used.
All precursors were washed three times in distilled H2O (30 mL), fol-
lowed by 20 h of either oven drying at 120 8C or freeze drying at
50 8C and 10 Pa. The final materials were obtained by calcination
of the precursors in a rotary kiln under synthetic air flow (20 % O2
in N2, 100 Nm L min 1) keeping the temperature at 320 8C for 3 h.
Catalyst characterization: Powder X-ray diffraction (XRD) patterns
were recorded in the 2 q range 5–808 (step width of 0.038) by
using a Panalytical MPD diffractometer equipped with a copper
tube, 0.58 divergent and antiscatter slit, a 0.2 mm high receiving
slit, incident and diffracted beam 0.04 rad soller slits and a secon-
dary graphite monochromator. Powder diffraction files (PDF) from
the International Centre of Diffraction Data (ICDD) combined with
the X’Pert Line software (Panalytical, Almelo) were used for qualita-
tive phase analysis.
Thermogravimetric mass spectrometry (TG-MS) analysis was per-
formed by using a Cahn TG 2131 thermobalance, coupled with a
quadrupole mass spectrometer (Balzer, Omnistar). Samples were
heated up to 800 8C at a heating rate of 2 8C min 1.
Static nitrogen physisorption experiments were performed by
using a modified Autosorb 1C set-up (Quantachrome). All samples
were pretreated at 200 8C for 2 h. Data were analyzed according to
the BET equation assuming that the area covered by a nitrogen
molecule equals 0.162 nm2.
The temperature-programmed reduction (TPR) experiments were
performed by heating 100 mg of the sample (sieve fraction 250–
355 mm) to 240 8C (1 8C min 1) in a gas mixture of 4.36 % H2 in Ar
(84.1 Nm L min 1).
The copper-surface area was subsequently determined applying
N2O reactive frontal chromatography (N2O-RFC) according to the
method proposed by Chinchen et al.[44] using adapted reaction
conditions.[45]
Catalytic testing: The catalytic testing was performed by using a 16
parallel reactor flow set-up supplied by Premex Reactor AG/Inte-
grated Lab Solutions. The reactors were filled with 180 mg of the
catalyst (sieve fraction 100–200 mm) including one commercial
sample as reference catalyst. After reduction of the catalysts, a mix-
ture of 7.0 % N2, 6.0 % CO, 19.5 % CH4, 8.0 % CO2, 59.5 % H2 was
used as methanol synthesis feed gas (60 Nm L min 1). The catalytic
activity under steady-state conditions was determined at 250 8C
and 210 8C in the first period of reaction followed by a second
period at the same temperatures. The reaction was performed at
6 MPa pressure with an overall time on stream of 182 h.
Acknowledgements
The authors gratefully acknowledge the financial support by the
Bundesministerium fr Bildung und Forschung (BMBF, project
198 www.chemcatchem.org  2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
M. Muhler et al.
01RI05028 “Entwicklung von Methanolsynthesekatalysatoren als
Basis fr nachhaltige Ressourcennutzung”).
Keywords: aging · heterogeneous catalysis · methanol
synthesis · micromixers · precipitation
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