ISSN 20700504, Catalysis in Industry, 2010, Vol. 2, No. 4, pp. 320–328. © Pleiades Publishing, Ltd., 2010.

Original Russian Text © E.V. Danilevich, G.Ya. Popova, I.A. Zolotarskii, A. Ermakova, T.V. Andrushkevich, 2010, published in Kataliz v Promyshlennosti.

CATALYSIS IN CHEMICAL
AND PETROCHEMICAL INDUSTRY

Kinetics of formaldehyde Oxidation on a Vanadia–Titania catalyst

E. V. Danilevich, G. Ya. Popova, I. A. Zolotarskii, A. Ermakova, and T. V. Andrushkevich
Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, 630090 Russia
Received June 15, 2010

Abstract—The heterogeneous catalytic oxidation of formaldehyde in the gas phase may be considered as an
alternative to the multistep liquidphase synthesis of formic acid. Monolayer vanadia–titania catalysts are
active and selective in the oxidation of formaldehyde to formic acid. Detailed investigation of kinetics of
formaldehyde oxidation over a monolayer vanadia–titania catalyst was carried out. It was established that by
product form via a consecutive–parallel reaction network. CO2 results from formaldehyde oxidation via par
allel pathway and from formic acid overoxidation via consecutive pathway; CO forms from formic acid via
consecutive pathway. It was shown that oxygen and water accelerate formic acid formation and that water
retards CO formation. Based on experimental data, a kinetic model of formaldehyde oxidation was devel
oped. The kinetic model was used in the mathematical simulation of the formaldehyde oxidation process and
in the determination of dynamic and design parameters of the reactor. Formic acid production by the gas
phase oxidation of formaldehyde is unique and does not have any analogue. As opposed to conventional tech
nologies, it is energysaving, environmentally friendly, and technologically simple. An enlargedscale pilot
plant using this technology is under construction.

Keywords: formaldehyde, formic acid, vanadia–titania catalyst, kinetics, kinetic model.

DOI: 10.1134/S2070050410040057

INTRODUCTION distributed on the TiO2 (anatase) surface [6].

Formic acid in an important organic product
widely used in the pharmaceutical, leather, and cellu
lose industries; in the production of pentaerythritol,
latexes, etc.; and as a feedstuff preservative in agricul
ture. Formic acid is industrially obtained by the liquid
phase oxidation of butane and light naphtha (as a by
product), by the direct hydrolysis of methyl formate,
by the acidolysis of formic acid salts, and by CO
hydration [1]. Russia does not produce formic acid on
the industrial scale and satisfies its demand in part
through import.
The heterogeneous catalytic gasphase oxidation of
formaldehyde [2–4] is an alternative to multistep liq
uidphase formic acid synthesis [1]. This new catalytic
formic acid synthesis technology has the following
advantages over the liquidphase methods: it is tech
nologically simpler, consisting of a small number of
steps; it is environmentally friendlier; it yields no
wastewater, solid waste, or hazardous gas emissions;
the final product has a low cost; and the process needs
only small capital investments. A further advantage of
the new technology is that it can be implemented at
existing facilities producing formaldehyde by metha
nol oxidation over a Fe–Mo catalyst.
Among the supported vanadium catalysts for form
aldehyde oxidation to formic acid, the V–Ti catalysts
are the most efficient [3, 5]. The active species in these
catalysts are nanosized VOx particles homogeneously
With these catalysts, the formic acid yield at 110–
140°C and atmospheric pressure is above 85%.
The kinetics of formaldehyde oxidation into formic
acid has not been reported in the literature. Sparse
information has been provided by kinetic studies of the
oxidative dehydrogenation of methanol and formalde
hyde burning on oxide catalysts—processes in which
formic acid is an intermediate product of formalde
hyde oxidation to carbon oxides [7–10]. There has
been a study on partial formaldehyde oxidation to CO
over a Fe–Mo catalyst in a flow circulation reactor [7].
The CO formation rate at 200–300°C was found to
obey a firstorder law with respect to the formaldehyde
concentration (1–6 mol % CH2O). The reaction rate
as a function of the oxygen concentration at a constant
formaldehyde concentration is described by a Lang
muir–Hinshelwood type equation. The apparent acti
vation energy of CO formation is 72 kJ/mol [7]. The
kinetics of formaldehyde oxidation to CO2 was studied
with an Au/CeO2 catalyst in excess hydrogen at low
formaldehyde concentrations (0.083–0.88 mmol/m3)
between 303 and 413°C [8]. Under these conditions,
the reaction obeys a firstorder rate equation with
respect to formaldehyde and the calculated activation
energy is 14.61 kJ/mol at 303–363°C and
34.18 kJ/mol at 363–413°C [8]. The authors of that
study hypothesize that the low and hightemperature
CH2O oxidation mechanisms can be different.

320
 KINETICS OF FORMALDEHYDE OXIDATION ON A VANADIA–TITANIA CATALYST
H H
C O
H C
n+ n+
O V O V
Fig. 1. Mechanism of formaldehyde oxidation into formic acid over the vanadia–titania oxide catalyst.
There has been a kinetic and mechanistic study of
formaldehyde oxidation with air over a hydrophobic
catalyst (0.1% Pt on Raschig rings covered with fluor
inated carbon) [9]. A kinetic model was suggested, and
it provided a good fit to selectivity and reaction rate
data obtained at 60–150°C. According to this model,
the reaction between adsorbed oxygen and CH2O pro
ceeds via two pathways: one is partial oxidation, yield
ing formic acid, and the other leads to the total oxida
tion product—CO2. It was demonstrated that CO2
forms via parallel pathways, resulting both from CH2O
oxidation and from the oxidation of adsorbed formic
acid.
The mechanism of CH2O oxidation over a Pt/TiO2
catalyst at room temperature was investigated by IR
spectroscopy [10]. It was shown that the major reactive
intermediates in CH2O oxidation are surface formates
and CO. Formaldehyde oxidizes to form surface for
mates at room temperature. The formates decompose,
yielding adsorbed CO species in the absence of O2 in
the gas phase, and CO is then oxidized to CO2 by O2 of
the gas phase.
In situ spectroscopic kinetic studies [11–13] eluci
dated the mechanism of selective formaldehyde oxida
tion into formic acid over the V–Ti–O catalyst
(Fig. 1). In this reaction, the surface intermediates are
vanadium ions–stabilized formates. The conversion of
adsorbed formaldehyde to the surface formates
involves oxygen of the catalyst. Formic acid results
from the recombination of the formates with surface
protons as the catalyst is oxidized by oxygen of the gas
phase at 100–140°C. Raising the temperature to 150–
180°C leads to the thermal decomposition and oxida
tion of the formates to carbon oxides.
Structurally similar surface formates result from
formic acid adsorption on the V–Ti–O catalyst. The
mechanism of the decomposition of these formates is
similar to the mechanism observed for the decomposi
tion of the formates resulting from formaldehyde
adsorption [14, 15].
The advantages and practical value of the above
formic acid synthesis method and good prospects for
putting it into practice prompted us to study the kinet
ics of formaldehyde oxidation into formic acid over
the vanadia–titania catalyst.
CATALYSIS IN INDUSTRY Vol. 2 No. 4
321
HCOOH
O2
H O O
n+
V O Vm+ 䊐 Vn+ O Vn+ O
EXPERIMENTAL
Catalyst. A (11% V2O5)/(89% TiO2) catalyst was
prepared as described in an earlier study [6]. The cat
alyst contained vanadium as polymeric VOx species
uniformly covering the support surface [6]. The VOx
coverage density was 5.2 (at V)/nm2, which is close to
the monolayer coverage by polymeric vanadium spe
cies [16, 17]. The specific surface area of the catalyst
was 140 m2/g.
Experiments. Kinetic experiments were carried out
using a flow circulation setup [18, 19] with a differen
tial reactor at atmospheric pressure in the temperature
range of 120–140°C. The particle size of the catalyst
was 0.25–0.50 mm, and the catalyst weight charged
into the reactor was 0.5–3.0 g.
The formaldehyde concentration in the feed was
varied between 7 × 10–4 and 3.3 × 10–4 mol/l (1.5–
7.5 mol %); the oxygen concentration, between 10 ×
10–4 and 111 × 10–4 mol/l (2.5–25 mol %); the water
vapor concentration, between 4.5 × 10–4 and 89 ×
10 ⎯4 mol/l (1–20 mol %).
The experimental setup is schematized in Fig. 2.
Water was dosed by saturating the air or oxygen +
nitrogen stream from cylinders (1) with H2O vapor in
an evaporator (3) at a preset temperature.
Gaseous formaldehyde for catalytic experiments
was obtained by the thermal decomposition of
paraformaldehyde (Methyl Co., Russia) [20]. The
water concentration in the initial paraformaldehyde
was 4.9 wt %. Before feeding formaldehyde into the
reactor, water was distilled from paraformaldehyde at
100°C. During distillation, the water vapor concentra
tion in the formaldehyde–air mixture gradually
decreased to 0.5 vol % and then remained practically
invariable. Formaldehyde was dosed from an evapora
tor (4) by passing dry air or the vapor–air mixture over
a paraformaldehyde layer at a preset temperature. The
reaction mixture stream, which contained formalde
hyde, oxygen, nitrogen, and water vapor, was intro
duced into the circulation circuit. The circulation cir
cuit consisted of a circulation pump (7), a valve unit
(8), a rotameter (9), and a molybdenum glass reactor
(6) (inner diameter of 12 mm, length of 50 mm) with
a coaxial thermocouple well for measuring the catalyst
bed temperature. The reactor was airheated in a resis
tance furnace (5). The circulation ratio of the reaction
mixture was VC/V = 50–100. In order to prevent the
2010
322 DANILEVICH et al.

12
Exit

Porapak T
10
Na X

10 10
11

 8 
 
10 10 9
7

2 2 2

5
1 N 1 O 1 Air 6
2 2 3 4

Fig. 2. Experimental setup: (1) gas cylinders, (2) mass flow controllers, (3) water evaporator, (4) paraformaldehyde evaporator,
(5) resistance furnace, (6) reactor, (7) circulation pump, (8) valve unit, (9) rotameter, (10) sixway valves, (11) calibrated chro
matographic sampler, and (12) Tsvet500 chromatograph.

condensation of the reaction products and reactants,
all reaction lines and the circulation circuit were
maintained at 120°C. The gases (air, oxygen, and
nitrogen) were dosed using mass flow controllers (2).
The components of the reaction mixture were
quantified chromatographically. The chromato
graphic procedure is described elsewhere [21].
CALCULATIONS
The following quantities were determined:
formaldehyde conversion, %,
X = 100 ( C °CH2 O – C CH2 O )/C °CH2 O ;
ith product selectivity, %,
S i = 100Ci/ ( C °CH2 O – C CH2 O );
formaldehyde oxidation rate, mol/(m2 s),
C °CH2 O XV
r = 

,
22.4 × 3600 × 10 gS sp
4 At 120°C, the formic acid selectivity in the 30–
r i = rS i /100.
Here, C °CH2 O and C CH2 O are the inlet and outlet
formaldehyde concentrations (vol %), Ci is the steady
state concentration of the ith product in the mixture
(vol %), V is the reaction mixture flow rate under nor
mal conditions (l/h), g is the catalyst weight (g), and
Ssp is the specific surface area of the catalyst (m2/g).
The carbon balance was 98 ± 2% in all runs.
The component concentration measurement error
due to the changes in the volume of the reaction mix
ture did not exceed the error of the chromatographic
analysis.
RESULTS AND DISCUSSION
Figure 3 plots the HCOOH, CO, and CO2 forma
tion rates and product selectivities versus the CH2O
(1) conversion at different temperatures and a constant
mixture composition: 5% CH2O, 10% H2O, and air as
the balance gas.
(2) The major reaction product throughout the con
version range examined is formic acid. The byprod
ucts are carbon monoxide and dioxide and traces of
methyl formate.
(3)
70% conversion range is 95%. Raising X to 90%
(4) reduces S to 90%. The decrease in the formic acid
selectivity caused by the increase in the formaldehyde
conversion is due to the decomposition of the acid,
which mainly yields CO. Accordingly, the CO selec
tivity increases from 0.5 to 5.5% as X increases from 35
to 90%.

CATALYSIS IN INDUSTRY Vol. 2 No. 4 2010

 KINETICS OF FORMALDEHYDE OXIDATION ON A VANADIA–TITANIA CATALYST 323

80 (a)
60
40 HCOOH
3
20 2
0 1

W, 10−9 mol/m2 s
4 3
CO
2 2
1
0
6 CO2
4
2 3
2
1
0 10 20 30 40 50 60 70 80 90 100
Conversion (X), %
(b)
100 HCOOH 1
90 2
80 3
70
60
50
15 3
Selectivity, %

CO
10
2
5 1
0
7
6 CO2
3
5
4 2
3 1
2
0 10 20 30 40 50 60 70 80 90 100
Conversion (X), %

Fig. 3. HCOOH, CO, and CO2 (a) formation rates and (b) selectivities as a function of the CH2O conversion at (1) 120, (2) 130,
and (3) 140°C.

An opposite trend is observed for CO2 formation: grew and the CO2 selectivity decreased. The contribu
the CO2 selectivity decreases from 5 to 3% as X tion from the consecutive COx formation pathway
increases from 35 to 90%. Similar dependences of the increases with an increasing reaction temperature.
selectivities on X are observed at 130 and 140°C.
Thus, the observed dependences of the selectivities
The extrapolation of the selectivities to the zero on the formaldehyde conversion suggest that formal
conversion indicates that HCOOH and CO2 form dehyde oxidizes via a consecutive–parallel reaction
from CH2O via parallel pathways. At nearzero CH2O network (Fig. 4). Formic acid and CO2 form via paral
conversions and temperatures of 120, 130, and 140°C, lel pathways, and CO and CO2 form via consecutive
the HCOOH selectivity is 97, 95, and 93% and the reactions through HCOOH decomposition.
CO2 selectivity is 3, 5, and 7%, respectively. The initial
CO selectivities are close to zero, which indicates that
w1
CO forms via a consecutive pathway through the CH2O HCOOH
decomposition of formic acid. Direct experiments on w3 w4 w2
formic acid decomposition over the vanadia–titania
CO2 CO
catalyst demonstrated that CO2 can also result from
formic acid decomposition. In these experiments, as Fig. 4. Scheme of formaldehyde oxidation over the vana
the HCOOH conversion increased, the CO selectivity dia–titania catalyst.

CATALYSIS IN INDUSTRY Vol. 2 No. 4 2010

324 DANILEVICH et al.

(a) (b)
60 HCOOH 3 100 HCOOH 1
2 2
40
1 90 3
20
W, 10−9 mol/m2 s0 80
4 CO 8

Selectivity, %
3 CO
3 4 3
2
2
1
0 1 0 1 2
4 CO2
8
3 CO2 3
2 4 3
1 2
0 1 2 1
0 5 10 15 0 5 10 15
CH2O concentration, (10−4) mol/l CH2O concentration, (10−4) mol/l

Fig. 5. HCOOH, CO, and CO2 (a) formation rates and (b) selectivities as a function of the CH2O concentration at (1) 120,
(2) 130, and (3) 140°C. The CH2O conversion is 67 ± 2% at 120°C, 51 ± 2% at 130°C, and 57 ± 5% at 140°C.

(a) (b)
HCOOH 3 100 HCOOH
30
20 2 1
1 90 2
10 3
W, 10−9 mol/m2 s

80
5 CO 20 CO
4 3
Selectivity, %

3 3
2 2 10
2 1
1 1
0 0
2 CO2 3 6 CO2
3
1 2 4 2
1 1
2
0
0
0 20 40 60 80 100 0 20 40 60 80 100
O2 concentration, (10−4) mol/l O2 concentration, (10−4) mol/l

Fig. 6. HCOOH, CO, and CO2 (a) formation rates and (b) selectivities as a function of the oxygen concentration in the reaction
mixture at (1) 120, (2) 130, and (3) 140°C. The formaldehyde conversion is 60 ± 5% at 120°C, 70 ± 5% at 130°C, and 80 ± 5%
at 140°C.

Effects of the component (CH2O, O2, H2O) con
centrations in the reaction mixture on the product for
mation rates were studied at 120, 130, and 140°C by
oneparameter experiments.
Effect of the formaldehyde concentration. The
steadystate CH2O concentration varied between 2 ×
10–4 and 1.6 mol/l (0.5–4.0 mol %) at fixed concen
trations of oxygen (89 × 10–4 mol/l, 20 mol %) and
water (45 × 10–4 mol/l, 10 mol %) and a fixed CH2O
conversion at each particular temperature. Figure 5
shows the dependences of the product formation rates
and selectivities on the steadystate CH2O concentra
tion at 120, 130, and 140°C. In the steadystate CH2O
concentration range, these dependences appear as
flattening curves (Fig. 5a). An increase in the formal
dehyde concentration leads to an increase in the for
mic acid selectivity and to a decrease in the CO and
CO2 selectivities (Fig. 5b).
The effect of oxygen was studied at constant inlet
concentrations of formaldehyde (22.3 × 10–4 mol/l,
5 mol %) and water vapor (45 × 10–4 mol/l, 10 mol %)
and a fixed formaldehyde conversion. The steadystate
oxygen concentration varied between 10 × 10–4 and
103 × 10–4 mol/l (2.5–23 mol %).
In the absence of oxygen, the major formaldehyde
conversion product is methyl formate. Only traces of
formic acid are present in the reaction products. The
introduction of oxygen into the reaction mixture
causes the formation of formic acid and carbon oxides.
Figure 6 plots the product formation rates and
product selectivities as a function of the steadystate
oxygen concentration. The steadystate oxygen con
centration varied between 10 × 10–4 and 103 ×
10 ⎯4 mol/l (2.5–23 mol %).
The formation rates of formic acid and carbon
oxides increase with an increasing steadystate oxygen

CATALYSIS IN INDUSTRY Vol. 2 No. 4 2010

 KINETICS OF FORMALDEHYDE OXIDATION ON A VANADIA–TITANIA CATALYST 325

(a) HCOOH (b) 1

70 HCOOH 100 2
60 3 90 3
50 2 80
40 70
30 1 60
W, 10−9 mol/m2 s 20 50
5 CO 15 CO
4 10
3

Selectivity, %
2 3 5 3
1 2
0 1 0 1 2
1
5 CO2 8 CO2
4 3 6 3
3 2 2
2 4
1 1
1 2
0 10 20 30 40 50 60 70 80 90 0 10 20 30 40 50 60 70 80 90 100
H2O concentration, (10−4) mol/l H2O concentration, (10−4) mol/l

Fig. 7. HCOOH, CO, and CO2 (a) formation rates and (b) selectivities as a function of the water vapor concentration in the reac
tion mixture at (1) 120, (2) 130, and (3) 140°C. The formaldehyde conversion is 60 ± 5% at 120°C, 70 ± 5% at 130°C, and 80 ±
5% at 140°C.

concentration (Fig. 6a). At all temperatures exam
ined, the HCOOH selectivity decreases slightly and
then CO and CO2 selectivity increase as the oxygen
concentration is increased (Fig. 6b).
The effect of the water vapor concentration was
investigated at fixed inlet concentrations of formalde
hyde (22.3 × 10–4 mol/l, 5 mol %) and oxygen (89 ×
10–4 mol/l, 20 mol %).
Figure 7 plots the dependences of the formation
rates of formic acid and carbon oxides and their selec
tivities as a function of the steadystate water vapor
concentration.
The introduction of water into the reaction mixture
raises the formic acid formation rate. As is demon
strated in Fig. 7a, the HCOOH formation rate curves
flatten out at an H2O concentration of about 45 ×
10 ⎯4 mol/l (10 mol %).
As the water vapor concentration is increased, the
CO formation rate falls sharply, while the CO2 forma
tion rate is independent of the water concentration
(Fig. 7a). The changes in the product selectivities are
consistent with the changes in the formation rates
(Fig. 7b).
The kinetic model of the process was derived from
the above experimental data and the mechanism of the
reaction [11–15] and includes the following proposi
tions:
(1) Formaldehyde oxidizes via consecutive and
parallel reactions. CO2 forms from CH2O and
HCOOH; CO, from HCOOH only.
(2) HCOOH and CO form on the same sites, ZO,
and CO2 forms on other sites, Z'O, as is indicated by
the significant effect of the H2O concentration on the
HCOOH and CO formation rates and by the indepen
dence of the CO2 formation rate of the H2O concen
tration.
(3) The experimentally observed increase in the
formic acid formation rate upon the introduction of
water vapor into the reaction mixture suggests that
HCOOH formation involves protonated ZO sites,
which will be designated ZOw.
(4) CH2O adsorption involves oxygen of the cata
lyst, yielding surface formates (HCOO–Zw–H and
HCOO–Z'–H), which are characterized by
νas(COO–) and νs(COO–) IR absorption bands at 1567
and 1370 cm–1 for HCOO–Zw–H and at 1555 and
1370 cm–1 for HCOO–Z'–H. These formates differ in
reactivity. In the temperature range dominated by for
mic acid formation (100–140°C), the decomposition
rate constant of the HCOO–Zw–H formates is almost
one order of magnitude larger that of the HCOO–Z'–
H formates.
(5) The recombination of HCOO–Zw–H with
protons in the presence of gasphase oxygen leads to
the release of formic acid into the gas phase. The pro
tons form on the surface via the dissociative adsorption
of formaldehyde and water.
(6) Part of the formic acid is readsorbed on ZO sites
to yield strongly bound formates (HCOO–ZO–H).
The decomposition of these formates releases CO and
H2O into the gas phase. The decelerating effect of
water on CO formation from HCOOH is evidence that
formic acid is adsorbed as the strongly bound species
HCOO–ZO–H on the same ZO sites on which H2O
is adsorbed.
(7) CO2 also forms via the decomposition of the
HCOO–Zw–H and HCOO–Z'–H formates, the sur
face compounds resulting from the adsorption of
formaldehyde and formic acid, respectively. The

CATALYSIS IN INDUSTRY Vol. 2 No. 4 2010

326 DANILEVICH et al.

decomposition of these formates involves oxygen from HCOOH and CO formation (steps 1–5)
the gas phase.
r1
1. ZO + H2O ZOw
r–1 ZO
r2 1 4 5
2. ZOw + CH2O HCOO–Zw– H –1
r3 ZOw HCOO–ZO–H
3. HCOO–Zw–H + 1/2O2 HCOOH + ZOw
r4 2 3
4. ZO + HCOOH HCOO–ZO–H
r5 HCOO–Zw–H
5. HCOO–ZO–H CO + ZO + H2O
Here, ZO is a dehydrated active site, ZOw is a protonated active site, HCOO–Zw–H and HCOO–ZO–H are
bidentate formates, and r1–r5 are the rates of the reaction steps.
CO2 formation (steps 6–9)
r6
6. Z'O + CH2O HCOO–Z'–H
r7 Z'O
7. HCOO–Z'–H + O2 Z'O + CO2 + H2O 6
7 8 9
r8
8. Z'O + HCOOH HCOO–Z'O–H HCOO–Z'–H HCOO–Z'O–H
r9
9. HCOO–Z'O–H + 1/2O2 Z'O + CO2 + H2O

Here, Z'O is an active site, HCOO–Z'–H W CO2 = W 3 + W 4

HCOO–Z'O–H are surface formates, and r6–r9 are
the rates of the reaction steps. K 8 P CH2 O + K 9 P HCOOH (7)
= 
 ,
Step 1 is reversible water adsorption/desorption on 1 + K 6 P CH2 O /P O2 + K 7 P HCOOH /P O2
active sites, which is accompanied by the formation of where K1 = k2, K2 = k–1/k1, K3 = k4/k5, K4 = k2/k3.
ZOw protonated sites. Step 2 is dissociative formalde K5 = k4(k–1/k1), K6 = k6/k7, K7 = k8/k9, K8 = k6, and
hyde adsorption yielding surface formates and pro K9 = k8. ki are the rate constants of steps.
tons. The recombination of the surface formates with
Equation (5) refers to HCOOH formation; Eq. (6),
protons in the presence of gaseous oxygen causes the
to CO formation from HCOOH; Eq. (7), to CO2 for
release of formic acid into the gas phase and catalyst
mation from CH2O and HCOOH.
reoxidation (step 3). Formic acid readsorption on
active sites yielding formates and their subsequent The rate constants in Eqs. (5)–(7) and the corre
decomposition to CO and H2O are steps 4 and 5. The sponding activation energies were determined by min
formation of CO2 from formaldehyde is accounted for imizing the function of relative deviations between the
by steps 6 and 7, and CO2 formation from formic acid calculated and experimental concentrations:
is due to steps 8 and 9. N exp 7

∑ ∑ ((y
exp calc exp 2
The above reaction network and graph theory were S = ij – y ij )/y ij ) min, (8)
used to set up rate equations for product formation j = 1i = 1
[22]. where j = 1, N exp are run numbers; i = 1, 7 are num
The product formation rate equations based on the bers assigned to components of the reaction system
above mechanism (Fig. 1) and the consecutive–paral exp
(CH2O, O2, HCOOH, CO, CO2, N2, H2O); y ij are
lel reaction scheme (Fig. 4) appear as follows: calc
the observed mole fractions of components; and y ij
W HCOOH = W 1 are the mole fractions of components calculated from
K 1 P CH2 O (5) the material balance equations for a perfectly mixed
= 
, reactor,
1 + K 2 ( 1 + K 3 P HCOOH )/P H2 O + K 4 P CH2 O /P O2 0
y i – γy i + q i τ = 0. (9)
W CO = W 2 Here, γ is the ratio of the outlet molar flow rate to
K 5 P HCOOH /P H2 O (6) the inlet molar flow rate; τ ((g s)/mol) is the apparent
= 
, residence time determined as the ratio of the catalyst
1 + K 2 ( 1 + K 3 P HCOOH )/P H2 O + K 4 P CH2 O /P O2 weight to the inlet molar flow rate; and qi (mol/(h/s))

CATALYSIS IN INDUSTRY Vol. 2 No. 4 2010

 KINETICS OF FORMALDEHYDE OXIDATION ON A VANADIA–TITANIA CATALYST 327

W, 10−9 mol/m2 s(calculated) 6

80 (a) CO (b) 6 CO2 (c)
70 HCOOH 5
5
60 4
50 4
40 3 3
30 2 2
20
10 1 1

0 10 20 30 40 50 60 70 80 0 1 2 3 4 5 60 1 2 3 4 5 6
W, 10−9 mol/m2 s(observed)

Fig. 8. Fit between the calculated and observed formation rates of (a) HCOOH, (b) CO, and (c) CO2.

is the formation/disappearance rate of the ith compo
nent,
4 entire experimental data array and on the mechanism
∑z
qi =
ki W i ,
k=1
where zki are stoichiometric coefficients and Wi are
reaction rates in Eqs. (5)–(7).
The minimum point of the objective function S
(formula (8)) was approached by the Gauss–Mar
quardt gradient method. In the iterative procedure,
the set of nonlinear equations (9) was solved by the sta
tionarization method; that is, the set of differential
equations was integrated with the righthand side cor
responding to Eq. (9) until the steady state was
reached.
Figure 8 compares the observed formation rates of
HCOOH (Fig. 8a), CO (Fig. 8b), and CO2 (Fig. 8c) to
those calculated via Eqs. (5)–(7) using the rate con
stants derived from the entire experimental data array
(data obtained at varied residence times, tempera
tures, and concentrations). The standard deviation
between the observed and calculated reaction rates,
determined as
N exp calc 2
1 ⎛ w exp
– w i, j ⎞
Δw i = ∑
N exp ⎝ w calc
i, j
 ⎜ ⎟ ,
i, j ⎠
j=1
is 11% for the HCOOH formation rate, 21% for the
CO formation rate, and 15% for the CO2 formation
rate.
CONCLUSIONS
The kinetics of formaldehyde oxidation over a
vanadia–titania monolayer catalyst was investigated in
detail. A consecutive–parallel reaction network was
deduced for the formation of the formaldehyde oxida
tion products. HCOOH and CO2 form via parallel
pathways, and CO forms via a consecutive pathway
through formic acid decomposition. It was revealed
that oxygen and water vapor accelerate the formation
of formic acid (desired product) and that water retards
the decomposition of HCOOH to CO. Based on the
of the reaction, a kinetic model was constructed for
(10)
formaldehyde oxidation, and this model provided a
satisfactory fit to the experimental data.
Using the kinetic model constructed in this study,
the basic operation and design parameters of the reac
tor equipment at the pilot and commercial scales were
optimized by mathematical modeling. The catalyst
pellet size, the diameter and length of the reactor
tubes, the linear gas velocity, and the heat carrier tem
perature were determined. The Institute of Catalysis is
creating an enlargedscale pilot plant in order to
obtain initial data for commercialscale technology.
ACKNOWLEDGMENTS
This work was supported by the Russian Federal
Agency for Science and Innovation through the fed
eral targeted program “Research and Pedagogical
Cadre of Innovative Russia.”
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