Applied Catalysis A: General 238 (2003) 211–222

Formaldehyde synthesis from methanol over silver catalysts

Min Qian∗ , M.A. Liauw, G. Emig
Institute of Chemical Technology I, University Erlangen-Nuremberg, Egerlandstr. 3, D-91058 Erlangen, Germany
Received 5 February 2002; received in revised form 11 March 2002; accepted 10 June 2002
Dedicated to Professor J. Weitkamp on the occasion of his 60th birthday

Abstract
The formaldehyde synthesis from methanol was investigated over a polycrystalline silver catalyst at temperatures up to
993 K. Water was added to the feed (water ballast process) like in the commercial BASF process. The conversion of methanol
and the selectivity to formaldehyde appeared to increase with respect to the methanol ballast process with no added water. A
long-time experiment was carried out lasting over more than 300 days time-on-stream. While the methanol conversion does
not change significantly, there is a pronounced change in hydrogen and CO2 selectivity. A most noteworthy observation is
that over months of operation, the width of the temperature region where formic acid is formed increases in a linear manner.
Finally, interrupting the oxygen supply for a few hours led to a temporary deterioration of the product selectivity after oxygen
re-admittance. All observations may well be interpreted in the framework of the commonly discussed silver–oxygen chemistry
with its three different oxygen species (O␣ , O␤ and O␥ ).
© 2002 Elsevier Science B.V. All rights reserved.
Keywords: Methanol oxidation; Oxidative dehydrogenation; Formaldehyde; Silver catalyst; Catalyst deactivation; Oxygen species

1. Introduction route is performed over an electrolytic silver catalyst

With an ever increasing production of (2.5–2.7) ×
107 t per year worldwide in 2000 for the production of
urea–phenolic, melamine and acetal resins, formalde-
hyde is one of the world’s most important chemicals
[1]. It may be synthesized by either dehydrogenation
(Eq. (1)) or partial oxidation (Eq. (2)) of methanol:
CH3 OH
CH2 O + H2 , H = +84 kJ/mol
CH3 OH + 21 O2 → CH2 O + H2 O,
H = −159 kJ/mol
Two important routes are prominent in the industrial
formaldehyde production [2–6]. The first synthesis
∗ Corresponding author. Tel.: +49-9131-85-27-426;
fax: +49-9131-85-27-421.
E-mail address: min.qian@rzmail.uni-erlangen.de (M. Qian).
at air-lean conditions, which has been commercial-
ized at the beginning of the 20th century. The second
route, industrialized since the 1950s, is by the oxi-
dation in excess air over a ferric molybdate catalyst.
Other routes have not yet been commercialized, e.g.
the sodium catalyzed dehydrogenation of methanol
to anhydrous formaldehyde [7] and the partial oxida-
(1) tion of methane over silica catalysts [8]. With about
55% of the industrial production capacity in western
Europe being based on the silver-catalyzed route in
(2) 2000 [1], it plays an important role. Its advantages
are the relatively low investment cost, the high yield
and the stable production.
In commercial production, the strongly exothermic
reaction is carried out under adiabatic conditions [2].
A selection of parallel and consecutive reactions is
given in Table 1. They may inevitably lead to many

0926-860X/02/$ – see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 8 6 0 X ( 0 2 ) 0 0 3 4 0 - X
212 M. Qian et al. / Applied Catalysis A: General 238 (2003) 211–222
Table 1
Some possible secondary reactions in the system with the compo-
nents formic acid, hydrogen, carbon dioxide and carbon monoxide,
coke, etc. [2,4]
Number Reaction HR,973 K (kJ/mol)
(3) CH2 O → CO + H2 +12
(4) CH3 OH + 23 O2 → CO2 + 2H2 O −676
(5) CH2 O + O2 → CO2 + H2 O −519
(6) CH2 O + 21 O2 → CH2 O2 −314
(7) CH3 OH → C + H2 O + H2 −31
(8) CO + H2 C + H2 O −136
(9) CO + H2 O CO2 + H2 −35
byproducts, e.g. carbon dioxide, carbon monoxide,
formic acid, hydrogen, coke, etc. The combination
of the reactions yields a rather complex reaction
network.
Various versions of the conventional silver-catalyzed
process are adopted commercially, described in many
different patents [9–14]. Two main variations are used
industrially. The first process (hereafter referred to
as methanol ballast process) in which only air and
pure methanol are fed is used in numerous companies
(e.g. ICI and Degussa). Features are an incomplete
conversion of methanol and its distillative recov-
ery. BASF uses another important process (hereafter
referred to as water ballast process) feeding extra
water with the reactant mixture, thereby achieving a
complete conversion of methanol [2,9,15]. However,
water addition is limited by the requirement of the
final products strength and of the additional water
needed for tail-gas scrubbing. Normally, the commer-
cial production is carried out with a H2 O/CH3 OH
molar ratio of 40/60 or 0.67 [2]. Due to its large
heat capacity, water vapor may remove a great deal
of reaction heat, thereby both preventing detrimen-
tal overheating as well as sintering of the catalyst.
Moreover, because addition of water vapor helps to
burn away the coke on the catalyst surface, it is re-
ported for the industrial production that the life time
of Ag catalyst in the water ballast process is signifi-
cantly longer than that in the methanol ballast process
[5].
In the present study, both methanol and water bal-
last processes were investigated comparatively in the
same laboratory-scale setup. The influence of water
addition on catalyst life time, formaldehyde selectiv-
ity and generation of byproducts was studied.
Despite a century of industrial production, still
no comprehensive insight into the silver-catalyzed
formaldehyde synthesis is available. It has been
pointed out for the methanol oxidation that the high
yields and selectivities may seem to render any at-
tempt to study the reaction with the aim to improve it
superfluous, but that, considering the potential market
demand of formaldehyde, even small improvements
will be economically interesting [16]. This is certainly
one of the reasons that quite some research work is
devoted to this system.
One approach is the surface science approach where
the interaction of reactants and well-defined single
crystal surfaces is studied under high vacuum condi-
tions. In order to move to industrially more relevant
conditions, some studies have been carried out with
polycrystalline electrolytic silver at atmospheric pres-
sure and temperatures up to 930 K. From the body of
literature, a mechanistic model begins to emerge that
may explain a number of experimental observations.
A brief outline will be given in the next paragraphs.
It is generally accepted that understanding well the
interaction of oxygen with silver is a prerequisite to ex-
plain the mechanism of total reaction routes [17–30].
Three different oxygen species O␣ , O␤ and O␥ are as-
sumed to form during the reaction [31,32]. Molecular
oxygen dissociates on the silver and forms the weakly
bound atomic surface oxygen species O␣ which bene-
fits especially the formation of HCOOH and the com-
plete oxidation of products to H2 O and CO2 . Deng
et al. even supposed that molecularly adsorbed oxygen
acts as a precursor and transforms to atomic oxygen
in this process [33]. With similar atomic dimensions
(φ Ag : 60 Å, φ O : 62 Å), oxygen may dissolve in the
silver lattice. This O␤ cannot participate directly in
the reaction. The strongly bound oxygen species O␥
is formed from O␤ , when the latter segregates from
the bulk to the surface. O␥ exists predominantly in
the uppermost layer of silver catalyst and tends to
only catalyze the dehydrogenation of methanol. The
oxygen–silver chemistry also seems to influence the
adsorption of methanol which has been found to hardly
occur on an oxygen-free silver surface [34]. Under
reaction conditions, the silver is constantly exposed to
oxygen, part of which will penetrate into the crystal
lattice of silver and form the oxygen species of O␣ , O␤
and O␥ species that are depleted by the corresponding
reactions, which shows a dynamic equilibrium [35].
 M. Qian et al. / Applied Catalysis A: General 238 (2003) 211–222
The population is a strong function of parameters
and pre-treatment. The three oxygen species have,
e.g. stability regions at different temperatures. Another
factor is the dynamic restructuring of the silver: SEM
images reveal that the morphology of silver catalyst
changes strongly during the reaction [32,36–39]. Mil-
lar et al. observed that “pinholes” appear firstly pre-
dominantly in the vicinity of initial surface defects
and spread gradually from the region of defects to the
entire silver surface [40]. This reaction-induced mor-
phological restructuring reinforces the formation of
grain boundary defects over the catalyst, which en-
ables more oxygen to penetrate into the silver lattice
and, in turn, to intensify the reaction [30,31,41–43].
Recent studies have focused on using silver sup-
ported catalysts [44], on elucidating the mechanism
with sophisticated vacuum experiments, such as tem-
poral analysis of products (TAPs) [45] or on optimiz-
ing the thermal management [46]. The present exper-
imental work addresses three industrially relevant is-
sues that have been little studied in the past:
• the investigation of the water ballast process with
H2 O/CH3 OH of 0–2.0;
• (detrimental) formic acid formation as a function of
control parameters and time;
• long-time behavior (10 months) of conversion and
selectivities.
Two byproducts that were closely monitored were
carbon dioxide and formic acid. Carbon dioxide,
one of the major byproducts, was monitored with
time-on-stream to gauge the catalyst activity during a
long-time operation. Formic acid is a strongly corro-
sive byproduct and an undesired contaminant of the
final product. It is, therefore, also strictly controlled
in commercial operation (normally <0.01 wt.% in
the product [2]). Before the onset of catalyst deacti-
vation, the formation of formic acid is restricted to
only a limited temperature range. After deactivation,
normally 4–9 months, formic acid is formed at all
temperatures, which forces a shutdown and catalyst
replacement in industrial production.
2. Experimental
Catalytic partial oxidation of methanol was carried
out over an electrolytic silver powder (Bayer AG, 20
213
Table 2
Standard settings and operation range in the laboratory-scale setup
Standard Operation
setting range
Temperature (K) 823 473–993
Residence time (s; at 823 K) 0.085 0.06–0.45
GHSV (h−1 ; at 298 K) 1.5 × 104
WHSV (h−1 ; at 298 K) 440
CH3 OH fraction in the feed (vol.%) 17.5
O2 fraction in the feed (vol.%) 7
CH3 OH/O2 molar ratio 2.5
H2 O/CH3 OH molar ratioa 0.67 0–2.0
a In the methanol ballast process, no water was fed and the
other conditions were the same as those in the water ballast
process. The space velocity was kept constant by varying the N2
flow accordingly.
mesh) in a tubular fixed-bed reactor. With the help of
two HPLC pumps, methanol and water were pumped
separately into the two different vaporizers (kept at 363
and 393 K, respectively) which were set up in series.
Assisted by N2 as a carrier gas, evaporation yielded
partial pressures with a standard deviation of ±1.5%.
Oxygen was added behind the second vaporizer and
the mixture flowed through the catalyst bed from the
top of the reactor. Table 2 gives the range and stan-
dard settings of all relevant operating parameters. In
this paper, yields and selectivities are expressed with
respect to the excess component CH3 OH and not with
respect to oxygen.
The reactor was made of a 50 cm long Al2 O3 tube
and had an inner diameter of 10 mm. The blank ac-
tivity proved negligible. The reactor was filled with
quartz chips (Ø 1 mm) before the catalyst bed to im-
prove the mixing and pre-heating of the feed. The 3 cm
long Ag catalyst bed was strongly diluted with quartz
chips (Ag/quartz: 0.1 g/3 g) in order to weaken the lo-
cal heating effects.
Heating was provided by an electric heat coil con-
trolled by a Eurotherm temperature controller, which
monitored the temperature with the help of a thermo-
couple, located directly in the middle of catalyst bed
through a capillary Al2 O3 tube. At the given param-
eter settings, no isothermal operation was possible
(see Section 4). The temperatures given in this paper
are those located on the centerline, at an axial posi-
tion of approximately 1 cm into the catalyst bed (T1 ).
In order to prevent the product formaldehyde from
decomposing at the high temperature, the reaction
214 M. Qian et al. / Applied Catalysis A: General 238 (2003) 211–222
was carried out with a very short residence time of
<0.086 s. Moreover, the product mixture was rapidly
quenched to about 413 K subsequently with a cooling
jacket behind the catalyst bed. The quench down-
stream caused a strong axial temperature gradient: the
temperature on the centerline 2 cm downstream of T1 ,
just before the quench (T2 ), was about 42 K higher.
This strong gradient is the reason that, compared with
the results of Panzer [31], different runs may exhibit
relative shifts on the temperature axis even if their
qualitative behavior is identical.
Analysis of the products was made by online gas
chromatography (HP 5890 series II) with two TCD de-
tectors. Qualitative and quantitative separation of both
high and low boiling point compounds was possible
in this setup with a mol-sieve (5A, HP) and a polar
capillary column (Poraplot-Q, HP). The separation of
formaldehyde and water is relatively difficult, but was
attained in this study within a reasonable accuracy
(see error bars in Fig. 3). The carbon balance is about
100 ± 5% with an acceptable margin of error. For the
temperature variation, a heating rate of 0.16 K/min was
selected. Combined with a sampling period of 45 min
and a sampling time of seconds, it may be safely as-
sumed that the values obtained at this extremely slow
heating rate are representative of the steady state val-
ues with a temperature resolution of 7.5 K.
Fig. 1. Variation of the operating temperature in the water ballast process with 225 days time-on-stream.
3. Results
3.1. Influence of operating parameters
3.1.1. Influence of reaction temperature
Fig. 1 depicts conversions and yields as a function of
temperature. A light-off temperature was observed at
about 570 K. CO2 displayed a maximal yield at the rel-
atively low temperature of 575 K and then dropped off
with temperature. The yield of formaldehyde increased
gradually with temperature and reached a maximum
at about 923 K, which corresponds well with the com-
mercial operation temperature. The abrupt decrease
of the formaldehyde yield above 923 K was accom-
panied by a yield increase of CO and H2 , suggesting
a gas phase decomposition of formaldehyde to CO
and H2 at the high temperature. Formic acid appeared
only in a limited temperature region (approximately
570–850 K) and could not be observed in the high
temperature region before the deactivation of catalyst
(see Section 3.3).
3.1.2. Influence of residence time
Methanol conversion and the selectivities to
formaldehyde and hydrogen were determined at dif-
ferent residence times (0.06–0.45 s; Fig. 2). The
higher the residence time was, the more methanol
 M. Qian et al. / Applied Catalysis A: General 238 (2003) 211–222 215

Fig. 2. Variation of the residence time (823 K).

was converted (open triangles). However, the longer
residence time was not beneficial for the formalde-
hyde formation: its selectivity decreased apparently
under the longer residence time, which may be partly
due to the fast decomposition of formaldehyde in the
gas phase to H2 and CO at high operation tempera-
tures. The H2 selectivity did increase with residence
time, albeit not to the extent that the formaldehyde
selectivity decreased.
3.1.3. Influence of molar ratio of H2 O/CH3 OH in
the feed
The influence of water vapor in the reaction gas on
the formaldehyde selectivity was estimated. Water va-
por content was varied in the region of H2 O/CH3 OH
molar ratio of 0–2.0. The space velocity was kept
constant by varying the N2 flow accordingly. This
led to a constant CH3 OH/O2 molar ratio. Each re-
sult was an average over a 15 h lasting stationary

Fig. 3. Selectivity to HCHO and CO2 vs. the molar ratio of H2 O/CH3 OH (823 K; CH3 OH, 8.5%; O2 , 3.5%).
216 M. Qian et al. / Applied Catalysis A: General 238 (2003) 211–222

test. Fig. 3 indicates that the conversion of methanol

increased with the H2 O/CH3 OH molar ratio, how-
ever, the selectivity to formaldehyde passed through
a maximum around a H2 O/CH3 OH molar ratio of
about 0.75, which corresponds basically well with
the above-mentioned molar ratio of 0.67 in industrial
formaldehyde manufacture (indicated by the vertical
dashed line). Because of the experimental error in the
formaldehyde detection, the experiment was repro-
duced at different feed concentrations, supporting the
conclusions reported above. It is also shown in Fig. 3
that the selectivity to CO2 decreased with the molar
ratio of H2 O/CH3 OH. The more water vapor was fed
in the reaction gas, the less CO2 was detected.

3.2. Comparison of water and methanol ballast

Fig. 4. Comparison between the water and methanol ballast pro-
processes
cess.

In order to estimate the effect of water vapor on

the reaction, during the long-time water ballast study
some experiments were carried out where methanol
ballast conditions were ensured. The two modes of
operation were, therefore, studied at identical space
velocity in the same setup. The gradual decrease of
catalyst activity (see Section 3.3) was slow com-
pared to the time elapsed between the two experi-
ments carried out subsequently and could be neg-
lected.
In comparison with the methanol ballast process,
the water ballast process displayed a higher conversion
of methanol and selectivity to formaldehyde. Fig. 4
shows the methanol conversion rose by 10% and the
formaldehyde selectivity increased by 4% at 823 K, if

Fig. 5. Comparison of HCOOH selectivity between the water and methanol ballast process (lines indicate a moving average over a 10 K
temperature interval).
 M. Qian et al. / Applied Catalysis A: General 238 (2003) 211–222 217

Fig. 6. The life time of silver catalyst in the water ballast process (823 K).

adding water vapor to the reaction gas. The selectivity
to CO2 , the product of total oxidation, was obviously
suppressed in the water ballast process as compared
to the methanol ballast process.
In addition, the selectivity to formic acid was also
clearly smaller in the water ballast process. Fig. 5
shows the result of two experiments carried out one
immediately after the other. The selectivity to formic
acid in the water ballast process was almost 30% lower
at 620 K than that in the methanol ballast process.
3.3. Aging behavior
In order to gauge the long-time behavior, conver-
sions and selectivities were measured for over 300
days time-on-stream. After a short initialization, both
methanol conversion and formaldehyde selectivity
were basically constant (steady state performance).
The latter may have displayed a slight decrease
(Fig. 6). A much more pronounced change was ob-
served for the selectivities to CO2 and H2 (Fig. 7).

Fig. 7. Selectivity to CO2 and H2 vs. time-on-stream in the water ballast process (823 K).
218 M. Qian et al. / Applied Catalysis A: General 238 (2003) 211–222

Fig. 8. Selectivity to HCOOH vs. time-on-stream in the water ballast process.

S(CO2 ) increased gradually over the entire experi- two trends made the region of HCOOH formation
ment. S(H2 ) decreased from 14 to 8% during the first broader with time.
100 days. It then dropped to about 5–6%, where it To study the nature of this deactivation, the opera-
remained basically constant for the remainder of the tion was interrupted once during the time while the up-
experiments. per limit still changed (180 days time-on-stream) and
Fig. 8 shows the selectivity to formic acid as a once when it was constant (280 days time-on-stream).
function of temperature for various times-on-stream. The interruption consisted of 4 weeks during which
No formic acid was detected during the first 100 the catalyst bed was kept under flowing N2 at 523 K.
days. After this period, formic acid appeared, but only In both cases, after the experimental conditions had
in a limited temperature region of 600–690 K with
S(HCOOH) < 0.05. However, this region grew with
time, such that after 8 months (240 days), formic acid
could be observed over a wide range of temperatures
(580–870 K). In order to visualize the slow extension
of formic acid formation into the high temperature
region, we define an upper (Tupper ) and a lower
(Tlower ) temperature limit such that these two bound
the region where formic acid could be detected in the
outlet with S(HCOOH) > 0.01. The two tempera-
tures are plotted in Fig. 9 versus time-on-stream. The
upper temperature increased linearly to 870 K during
the first 8 months with a correlation coefficient of
R 2 > 0.97. After this time, the shift into the higher
temperature region stopped and the upper tempera-
ture stayed constant with time. The lower temperature
limit decreased with time-on-stream, but in a less Fig. 9. Upper and lower detection temperature of HCOOH vs.
pronounced manner and without a discontinuity. The time-on-stream.
 M. Qian et al. / Applied Catalysis A: General 238 (2003) 211–222 219

been restored, no marked discontinuities were ob-
served (Fig. 9).
3.4. Oxygen-free treatment
For more insight into the interaction between oxy-
gen and silver during the partial oxidation of methanol,
the catalyst was temporarily exposed to an oxygen-free
atmosphere. Starting from steady state, the oxygen
feed was interrupted for 5 h. Methanol, water vapor
and nitrogen kept flowing over the catalyst. After this,
oxygen (and hence the normal feed composition) was
switched back on. The exit gas composition was av-
eraged over 5 h following the oxygen-free treatment.
Fig. 10a shows that, at three different temperatures
(623, 773 and 823 K, respectively), the conversion of
methanol and the yield of CH2 O decreased strongly af-
ter oxygen-free treatment as compared to steady state.
In addition, the yields of carbon dioxide and formic
acid had increased while the hydrogen yield was lower.
The decrease of the ratio of S(CH2 O)/S(CO2 ) after
oxygen-free treatment is depicted in Fig. 10b.

Fig. 10. Influence of oxygen-free treatment on: (a) the conversion and the yield; (b) the ratio of S(CH2 O)/S(CO2 ) as compared to steady
state in the water ballast process.
220 M. Qian et al. / Applied Catalysis A: General 238 (2003) 211–222
4. Discussion
In order to classify the results, it should firstly be
noted that laboratory-scale operation was neither adi-
abatic nor isothermal. Like in [25], a pronounced tem-
perature gradient was measured in the catalyst bed.
When discussing the results, it should be kept in mind
that the temperatures given are those measured at T1
and used for the temperature control. Rather than the
absolute values of T1 , the trend should be considered.
The excellent isothermicity of catalytic wall reactors
as reported by Redlingshöefer et al. [47] has also been
used for the methanol oxidation to formaldehyde [31].
However, more development is required for the sys-
tem prior to publication.
A second caveat is that even if we will discuss the re-
ported findings in the framework of the state-of-the-art
of silver–oxygen chemistry, it should be obvious that
due to the absence of spectroscopic evidence, this pa-
per cannot contribute much to the body of evidence.
However, the phenomenological approach taken here
may indeed give suggestions for new experiments. As
a matter of fact, transferring promising results with
fiber-optic in situ spectroscopy [48] to this reaction
system is currently underway. Raman spectroscopy
seems to be an appropriate method [49].
The comparison of water and methanol ballast pro-
cesses indicates that an appropriate water vapor ad-
dition plays a great role in the reaction. Bao et al.
[35] found the oxygen-induced restructuring process
can be greatly enhanced by adding a small amount
of water vapor to O2 , which makes the formation of
oxygen species more favorable. An evident increase
of CH3 OH conversion shown in Fig. 4 supports this
hypothesis. As well as reinforcing the conversion of
methanol, water vapor can suppress effectively the to-
tal oxidation and reduce consequently the generation
of CO2 shown in Figs. 3 and 4. Various tentative ex-
planations can be given: water vapor may block spe-
cific surface sites at which total oxidation takes place;
it may help burn away the coke on the catalyst surface
to expose more active sites.
The study shows an initialization phase to ignite
the silver catalyst, which was also observed by Nagy
et al. [32]. This is necessary not only in the methanol
ballast process but also in the water ballast process,
which was also observed in the industrial plants from
some hours to several days. The in situ Raman studies
of Millar et al. demonstrated that subsurface OH(a)
species were formed very rapidly in a well-defected
Ag sample, whereas extremely slowly over the smooth
surface of a fresh Ag sample [50]. It is assumed that
the initial activation of silver catalysts is due to the
diffusion of OH(a) species and the consequent forma-
tion of defected sites.
A notable trend is that S(CO2 ) increased with time
whereas S(H2 ) decreased (Fig. 7). This may point to
an increase of the number of weakly bound atomic
O␣ on the silver surface with time. The degree of
total oxidation is commonly attributed to the surface
adsorbed atomic O␣ . While this is particularly true
in the low temperature region, after extended times it
may also hold in the high temperature region, where
O␥ plays the prominent role in the dehydrogenation
of methanol.
HCHO is normally unstable at high temperatures,
being easily decomposed to H2 and CO or, in the pres-
ence of oxygen, even totally oxidized to CO2 and H2 O.
It is also assumed that HCHO could be further oxi-
dized to HCOOH in the presence of the weakly bound
surface atomic O␣ [31]:
HCHO + O␣ → HCOOH
As mentioned above, the influence of O␣ became
more and more notable with time, HCOOH was con-
sequently formed in a wider temperature region and
even at high temperatures after several months of op-
eration (Fig. 8). Because the O␣ species plays an im-
portant role mainly in the lower temperature region,
it is reasonable that the amount of HCOOH increased
particularly at low temperatures around 600 K with
time-on-stream. The reason that no formic acid was
detected above 870 K is that this is the decomposition
temperature and does not reflect a discontinuity in the
deactivation process.
The experimental results after oxygen-free treat-
ments confirmed this hypothesis well on another as-
pect. The dynamic equilibrium of the O-development
is disturbed during treatment with N2 gas only. Since
oxygen species could not evolve well during nitro-
gen treatment, the dominant oxygen species in the
subsequent oxidative reaction would initially be the
weakly bound atomic O␣ , which shows high oxidative
power and helps promoting the formation of carbon
dioxide and formic acid. With the help of in situ Ra-
man spectroscopy, Pettinger et al. discerned a gradual
 M. Qian et al. / Applied Catalysis A: General 238 (2003) 211–222
re-development of O␥ formation over the Ag catalyst
when it was exposed again to O2 after a 30 min treat-
ment with pure N2 [51]. As a result, treatment un-
der oxygen-free conditions followed by re-admission
of oxygen should temporarily lead to an increase of
O␣ -catalyzed formation of carbon dioxide and formic
acid as well as a decrease of O␥ -catalyzed hydrogen
formation as compared to the steady state. This is in-
deed found (Fig. 10a). Consequently, the oxygen-free
treatment should lead to an Ag catalyst on which the
steady state distribution of oxygen species does not
fully develop immediately. Hence, a temporary de-
crease of methanol conversion and CH2 O yield would
be expected after oxygen-free treatment. This is also
supported well by Fig. 10a. A decrease of the ratio of
S(CH2 O)/S(CO2 ) appeared after the treatment under
oxygen-free condition, especially with almost 50% at
low temperature where O␣ is normally developed well
and plays a dominant role (shown in Fig. 10b).
5. Conclusions
The silver-catalyzed synthesis of formaldehyde
from methanol was studied at near industrial condi-
tion. The reaction proves sensitive to some operating
parameters, e.g. reaction temperature, residence time
and molar ratio of H2 O/CH3 OH.
Methanol can be converted more completely and
the selectivity to formaldehyde increased if water is
added to the reaction gas. In addition, an appropriate
amount of water vapor decreases the total oxidation
in the reaction system and suppresses the generation
of formic acid. Besides removing a great deal of heat
to avoid the sintering of the catalyst, water vapor may
also block total oxidation sites, or burn off coke, to
improve the silver activity significantly.
The amount of carbon dioxide, the main byprod-
uct, grew with time-on-stream, revealing a gradual en-
hancement of oxidation in the reaction system. An-
other major byproduct, formic acid, was first formed
in a narrow temperature region. However, the region
grew wider for more than 10 months.
Acknowledgements
Ernst Panzer is thanked for invaluable groundwork
and advice regarding this reaction system. Financial
221
support by the Bayerische Forschungsstiftung in the
framework of FORKAT and by the DFG (Li 669/2-1)
is gratefully acknowledged. The authors thank their
industry partners H.-G. Pirkl (Bayer), A. Nagy (for-
merly Bayer), and G. Stochniol and J. Sauer (Degussa
AG) for their support.
References
[1] E. Burridge, Eur. Chem. News 75 (1983) 16.
[2] G. Reuss, W. Disteldorf, A.O. Gamer, A. Hilt, Formaldehyde,
in: Ullmann’s Encyclopedia of Industrial Chemistry, 6th
Edition, Vol. A11, VCH, Weinheim, 2001, p. 619.
[3] B.A.J. Fischer, Formaldehyde, in: Encyclopaedia of Chemical
Technology, 4th Edition, Vol. 11, Wiley, New York, 1992,
p. 929.
[4] M.V. Twigg, Catalyst Handbook, 2nd Edition, Manson
Publishing, London, 1996, pp. 490.
[5] K. Weissermel, H.-J. Arpe, Industrielle Organische Chemie,
5th Edition, Wiley/VCH, New York/Weinheim, 1998, pp. 40–
41.
[6] A.R. Chauvel, P.R. Courty, R. Maux, C. Petitpas, Hydrocarbon
Process. 9 (1973) 180.
[7] S. Ruf, A. May, G. Emig, Appl. Catal. A 213 (2001) 203.
[8] F. Arena, F. Frusteri, A. Parmaliana, Appl. Catal. A 197
(2000) 239.
[9] G. Halbritter, W. Mühlthaler, H. Soerber, H. Diem, C. Dudeck,
G. Lehmann, Verfahren zur herstellung von Formaldehyd, DE
Patent 2,442,231 (1974).
[10] K. Yoshikawa, T. Matsuzawa, Process for producing aqueous
formaldehyde solution, US Patent 4,594,457 (1985).
[11] A. Aicher, G. Lehmann, N. Petri, W. Pitteroff, V. Reuss,
V. Schreiber, R. Sebastian, Preparation of formaldehyde, US
Patent 4,584,412 (1986).
[12] W.P. McMillan, C.C. Hobbs Jr., H.R. Gerberich, M.L. Junker,
Process for converting methanol to formaldehyde, US Patent
4,450,301 (1984).
[13] B. Knuth, R. Diercks, Process for the preparation of
formaldehyde, US Patent 5,990,358 (1999).
[14] I.E. Wachs, C.-B. Wang, Formaldehyde production, US Patent
6,147,263 (1999).
[15] H. Sperber, Chem. Ing. Tech. 41 (1969) 962.
[16] G. Centi, F. Cavani, F. Trifirò, Selective oxidation by
heterogeneous catalysis, Kluwer Academic Publishers/Plenum
Press, Dordrecht/New York, 2001, pp. 441.
[17] L. Lefferts, J.G. van Ommen, J.R.H. Ross, Appl. Catal. A 23
(1986) 385.
[18] C.T. Au, S. Singh-Boparai, M.W. Roberts, R.W. Joyner, J.
Chem. Soc., Faraday Trans. 79 (1983) 1779.
[19] G. Rovida, F. Pratesi, M. Maglietta, E. Ferroni, Surf. Sci. 43
(1974) 230.
[20] X. Bao, J.V. Barth, G. Lehmpfuhl, R. Schuster, Y. Uchida,
R. Schlögl, G. Ertl, Surf. Sci. 283 (1993) 14.
[21] A. Nagy, G. Mestl, D. Herein, G. Weinberg, E. Kitzelmann,
R. Schlögl, J. Catal. 182 (1999) 417.
222 M. Qian et al. / Applied Catalysis A: General 238 (2003) 211–222
[22] J.-H. Wang, W.-L. Dai, J.-F. Deng, X.-M. Wei, Y.-M. Cao,
R.-S. Zhai, Appl. Surf. Sci. 126 (1998) 148.
[23] J.-H. Wang, X.-H. Xu, J.-F. Deng, Y. Liao, B.-F. Hong, Appl.
Surf. Sci. 120 (1997) 99.
[24] B. Pettinger, X. Bao, I. Wilcock, M. Muhler, R. Schlögl, G.
Ertl, Angew Chem. 106 (1994) 113.
[25] A. Nagy, G. Mestl, Appl. Catal. 188 (1999) 337.
[26] C.-B. Wang, G. Deo, I.E. Wachs, J. Phys. Chem. B 103
(1999) 5645.
[27] G.J. Millar, J.B. Metson, G.A. Bowmaker, R.P. Cooney, Appl.
Catal. 147 (1994) 385.
[28] X.-D. Wang, W.T. Tysoe, R.G. Greenler, K. Truszkowska,
Surf. Sci. 258 (1991) 335.
[29] M. Voß, D. Borgmann, G. Wedler, Surf. Sci. 465 (2000)
211.
[30] L. Lefferts, J.G. van Ommen, J.R.H. Ross, Appl. Catal. A 31
(1987) 291.
[31] E. Panzer, Reaktionstechnische Untersuchungen zur kataly-
tischen Oxidation von Methanol zu Formaldehyd an Silber,
Doctoral thesis, Universität Erlangen-Nuremberg, Germany,
2000.
[32] A. Nagy, G. Mestl, T. Rühle, G. Weinberg, R. Schlögl, J.
Catal. 179 (1998) 548.
[33] J.-F. Deng, X.-H. Xu, J.-H. Wang, Y.-Y. Liao, B.-F. Hong,
Catal. Lett. 32 (1995) 159.
[34] J.-F. Deng, X. Bao, J. Catal. 99 (1986) 391.
[35] X. Bao, M. Muhler, B. Pettinger, R. Schlögl, G. Ertl, Catal.
Lett. 22 (1993) 215.
[36] L. Lefferts, J.G. van Ommen, J.R.H. Ross, Appl. Catal. A 34
(1987) 329.
[37] P.J.R. Uwins, G.J. Millar, M.L. Nelson, Microsc. Res. Tech.
36 (1997) 382.
[38] X. Bao, G. Lehmpfuhl, G. Weinberg, R. Schlögl, G. Ertl, J.
Chem. Soc., Faraday. Trans. 88 (1992) 865.
[39] G.J. Millar, M.L. Nelson, P.J.R. Uwins, J. Chem. Soc.,
Faraday Trans. 94 (1998) 2015.
[40] G.J. Millar, M.L. Nelson, P.J.R. Uwins, J. Catal. 169 (1997)
143.
[41] C. Rehren, G. Isaac, R. Schlögl, G. Ertl, Catal. Lett. 11 (1991)
253.
[42] I.E. Wachs, R.J. Madix, Surf. Sci. 76 (1978) 531.
[43] G.J. Millar, M.L. Nelson, P.J.R. Uwins, Catal. Lett. 43 (1997)
97.
[44] W.-L. Dai, J.-L. Li, Y. Cao, Q. Liu, J.-F. Deng, Catal. Lett.
64 (2000) 37.
[45] A.C. van Veen, H.W. Zanthoff, O. Hinrichsen, M. Muhler, J.
Vac. Sci. Technol. A 19 (2001) 651.
[46] G. Groppi, E. Tronconi, Catal. Today 69 (2001) 63.
[47] H. Redlingshöefer, O. Kröcher, W. Böck, K. Huthmacher, G.
Emig, Ind. Eng. Chem. Res. 41 (2002) 1445.
[48] R. Philipps, S. Walter, M. Liauw, Chem. Eng. J., in press.
[49] G. Mestl, J. Mol. Catal. A Chem. 158 (2000) 45.
[50] G.J. Millar, J.B. Metson, G.A. Bowmaker, R.P. Cooney, J.
Chem. Soc., Faraday Trans. 91 (22) (1995) 4149.
[51] B. Pettinger, X. Bao, I.C. Wilcock, M. Muhler, G. Ertl, Phys.
Rev. Lett. 72 (10) (1994) 1561.