Rev Chem Eng 2014; aop
Ali Mohammad Bahmanpour, Andrew Hoadley and Akshat Tanksale*
Critical review and exergy analysis of
formaldehyde production processes
Abstract: Formaldehyde is one of the most important
intermediate chemicals and has been produced industri-
ally since 1889. Formaldehyde is a key feedstock in several
industries like resins, polymers, adhesives, and paints,
making it one of the most valuable chemicals in the world.
However, not many studies have been dedicated to review-
ing the production of this economically important prod-
uct. In this review paper, we study the leading commercial
processes for formaldehyde production and compare
them with recent advancements in catalysis and novel
processes. This paper compares, in extensive detail, the
reaction mechanisms and kinetics of water ballast process
(or BASF process), methanol ballast process, and Formox
process. The thermodynamics of the reactions involved
in the formaldehyde production process was investigated
using HSC Chemistry™ software (Outotec Oyj, Espoo,
Finland). Exergy analysis was carried out for the natural
gas to methanol process and the methanol ballast process
for formaldehyde production. The former process was sim-
ulated using Aspen HYSYS™ and the latter using Aspen
Plus™ software (Aspen technology, Burlington, MA, USA).
The yield and product specifications from the simulation
results closely matched with published experimental data.
The exergy efficiencies of the natural gas to synthesis gas
via steam reforming, methanol synthesis, and formalde-
hyde synthesis processes were calculated as 60.8%, 61.6%,
and 66%, respectively. The overall exergy efficiency of
natural gas conversion into formaldehyde was found to
be only 43.2%. The main sources of exergy losses were the
steam reformer and methanol loss in formaldehyde syn-
thesis process. Despite high conversions and selectivities
of these processes, the low exergy efficiency suggests that
innovations in formaldehyde production processes could
give a more sustainable product. Novel methods of direct
conversion of natural gas or synthesis gas into formalde-
hyde will improve the exergy efficiency, but the conver-
sion rate must also be increased with advancements in
catalysis.
*Corresponding author: Akshat Tanksale, Department of Chemical
Engineering, Monash University, Clayton, Victoria 3800, Australia,
e-mail: akshat.tanksale@monash.edu
Ali Mohammad Bahmanpour and Andrew Hoadley: Department of
Chemical Engineering, Monash University, Clayton, Victoria 3800,
Australia
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Keywords: exergy analysis; formaldehyde; kinetics and
mechanism; methanol ballast process.
DOI 10.1515/revce-2014-0022
Received May 28, 2014; accepted August 25, 2014
1 Introduction
Formaldehyde is one of the simplest molecules in organic
chemistry, which has a wide range of applications in chem-
ical processes. It is produced in nature by photochemical
processes in atmosphere or by incomplete combustion of
organic materials (Reuss et al. 2003). Formaldehyde gas is
colorless at ambient temperature with an irritating odor
that unfavorably affects eyes and skin. The effects of for-
maldehyde on human health have been studied. Formal-
dehyde is toxic and probably a carcinogen because there is
enough evidence that it can cause nasopharyngeal cancer
(Cogliano et al. 2005). Some physical properties of mono-
meric formaldehyde can be found in Table 1 (Reuss et al.
2003).
Formaldehyde’s heat of formation, heat capacity, and
entropy are given in Table 2 for a wide range of tempera-
tures and atmospheric pressure (Walker 1967).
The gas mixture with air is flammable at 293.15  K
or higher (National Fire Protection Association 1994).
Formaldehyde is considered as a reactive compound.
At high temperatures ( > 423.15 K), it tends to undergo
heterogeneous decomposition to produce methanol and
carbon dioxide. However, if the temperature goes higher
( > 623.15 K), it may tend to form synthesis gas (hydrogen
and carbon monoxide mixture) (Bone and Smith 1905,
Calvert and Steacie 1951). It can be easily involved in both
oxidation and reduction reactions. For example, in the
presence of hydrogen, it can be reduced to form metha-
nol over a nickel catalyst. Nitric acid, potassium per-
manganate, potassium dichromate, or oxygen can readily
oxidize formaldehyde to form formic acid, carbon dioxide,
and water (Walker 1967).
At atmospheric pressure, formaldehyde condenses at
253.95  K and freezes at 155.15  K as a white paste. In the
liquid phase, its density is 0.8153  g/cm3 at 253.15  K and
2      A.M. Bahmanpour et al.: Critical review and exergy analysis of formaldehyde production processes

Table 1 Physical properties of monomeric formaldehyde (Reuss Table 3 Partial pressure of formaldehyde for the temperature range
et al. 2003). of -109.4°C to -22.3°C (Spence and Wild 1935).

Properties   Values Temperature (K)  Pressure (kPa)

Heat of formation at 298.15 K   -115.9 ± 6.3 kJ/mol 163.75  0.13

Gibbs energy at 298.15 K   -109.9 kJ/mol 168.75  0.25
Entropy at 298.15 K   218.8 ± 0.4 kJ mol-1 K-1 174.85  0.48
Heat of combustion at 298.15 K   -561.5 kJ/mol 177.95  0.65
Heat of vaporization at 253.95 K   23.32 kJ/mol 184.05  1.16
Specific heat capacity at 298.15 K, Cp   35.425 J mol-1 K-1 187.55  1.63
Heat of solution at 296.15 K   194.25  2.80
 In water   -62 kJ/mol 194.85  2.95
 In methanol   -62.8 kJ/mol 201.25  4.72
 In 1-propanol   -59.5 kJ/mol 204.65  6.19
 In 1-butanol   -62.4 kJ/mol 207.85  7.86
Cubic expansion coefficient   2.83 × 10-3 K-1 208.55  8.22
Specific magnetic susceptibility   -0.62 × 106 209.45  8.69
Vapor density relative to air   1.04 217.35  14.80
219.15  16.62
223.85  21.74
232.55  35.54
234.05  38.74
Table 2 Heat of formation, heat capacity, and entropy of formalde-
238.85  49.17
hyde (Walker 1967).
250.85  88.55

Temperature  Heat of formation  Heat capacity  Entropy

(K) (kJ/mol) (J/mol·K) (J/mol·K)

100  113.5  33.3  182.0
200  114.5  33.5  205.1
298.15  116.0  35.4  218.8
300  116.0  35.5  219.0
400  117.7  39.3  229.7
500  119.3  43.8  239.0
600  120.8  48.2  247.4
800  123.3  56.0  262.3
1000  125.0  62.0  275.5
2000  128.6  754.0  323.8
3000  130.9  79.6  355.4
4000  134.6  81.1  378.5
5000  140.5  81.9  396.7
6000  148.6  82.3  411.7
0.9172 g/cm3 at 193.15 K. The vapor pressure of the lique-
fied formaldehyde has been measured for a wide range of
temperatures by Spence and Wild (1935). Measured partial
pressures for the temperature range of 163.75 K to 250.85 K
are given in Table 3.
According to the measured values, the vapor pressure
of liquid formaldehyde can be determined using the fol-
lowing equation (Spence and Wild 1935):
log10 p* = -1429 / T + 1.75 log T -0.0063T + 5.023 (1)
where p* is the formaldehyde vapor pressure in kPa and
T is in K.
Many different common uses and industrial applica-
tions can be named for formaldehyde because it is one
of the most important compounds in chemical manufac-
turing industry. Formaldehyde is a building block in the
synthesis of industrial resins such as melamine-formal-
dehyde, urea-formaldehyde, and phenol-formaldehyde.
Owing to the applications of formaldehyde derivatives in
wood processing and furniture, carpeting and textiles,
and construction, this chemical is considered as an impor-
tant material in the global economy (Tang et  al. 2009).
Formaldehyde can also be used directly to produce other
chemicals; glycolonitrile can be produced by formalde-
hyde reaction with hydrocyanic acid (Kirk and Othmer
1991). Acid-catalyzed reaction between formaldehyde and
olefins may lead to the production of α-hydroxymethylated
adducts (Walker 1967). Methylamine can also be produced
by the reaction of formaldehyde with amines.
Owing to its high ability to polymerize during long-
term storage, formaldehyde is commercially available as
an aqueous solution of 37–50 wt% concentration known
as formalin. Methanol is usually added (10–12 wt%) in the
solution as the polymerization inhibitor.
The formaldehyde production and consumption rates
have significantly increased during recent years. From
2003 to 2006, the formaldehyde consumption rate grew
at an average of 5.4% worldwide (Bizzari 2007). In 2007,
China, as the largest formaldehyde producer and con-
sumer, produced 12 million metric tons of formaldehyde

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 A.M. Bahmanpour et al.: Critical review and exergy analysis of formaldehyde production processes      3

(Tang et al. 2009). Total global formaldehyde production the other one is partial oxidation of methanol [eq. (3)].
is approximately 25–27 million metric tons per year, and These reactions are as follows:
the growth of the consumption rate of this chemical has
ˆ o = + 84 kJ/mol,
CH 3OH  ↔ CH 2O +  H 2 ΔH (2)
been fairly steady over the past 20  years (Ulukardesler r

et  al. 2010). Considering its steady consumption rate

and its application as a base chemical in more than 50
industries (Reuss et al. 2003), it is important to review the
current production processes and identify novel technolo-
gies that may lead to more efficient and sustainable pro-
duction in the future.
2 Formaldehyde production
2.1 Industrial methods
The sequence of formaldehyde production is made of
three main stages – steam reforming of natural gas leads
to the production of synthesis gas, which is converted to
methanol via methanol synthesis reaction (hydrogenation
of carbon monoxide), and eventually partial oxidation of
methanol leads to formaldehyde production. Formalde-
hyde is industrially produced mainly through two major
reactions: one is methanol dehydrogenation [eq. (2)] and
1 ˆ o = -159 kJ/mol.
CH 3OH +   O2  →CH 2O + H 2O ΔH r (3)
2
Currently, formaldehyde is industrially produced from
methanol using two major processes: the air-deficient
process or silver contact process through which methanol
goes through both dehydrogenation and partial oxidation
reaction to produce formaldehyde [used by BASF, Borden,
Bayer, Degussa, Imperial Chemical Industries (ICI), Cela-
nese, DuPont, Mitsubishi, and Mitsui] (Qian et  al. 2003,
Brenk 2010). The other process involves an excess of air,
known as the Formox process, in which only partial oxi-
dation of methanol takes place (used by Lummus, Monte-
catini, Hiag/Lurgi, and Perstorp/Reichold) (Qian et  al.
2003, Reuss et  al. 2003, Brenk 2010). These two process
routes are shown in a tree diagram in Figure 1. The air-
deficient process can be further classified into two types –
the methanol ballast process and the water ballast process
(or BASF process). In the methanol ballast process, only
methanol and air are used in the reactant feed stream, and

ICI

Methanol ballast
process

Degussa
Air deficient process
(silver contact
process)

Water ballast process BASF process

Formaldehyde
production processes Lummus

Hiag/Lurgi

Formox process

Montecatini

Perstorp/Reichold

Figure 1 Tree diagram of industrial processes for formaldehyde production.

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4      A.M. Bahmanpour et al.: Critical review and exergy analysis of formaldehyde production processes
low single-pass methanol conversion is achieved (used by
ICI and Degussa). In the water ballast process, steam is
also added to the feed stream, and comparatively higher
single-pass methanol conversion is achieved.
2.1.1 Methanol ballast process
Methanol ballast process has been mentioned as one of
the common methods of formaldehyde production in
industry, used by some of the known producers of for-
maldehyde (e.g., ICI and Degussa) (Qian et  al. 2003).
In the ICI process, first patented in 1940 (Arthur and
Maurice 1940), the silver crystals are formed in a 1-cm-
thick layer inside the reactor, which is directly mounted
on the heat recovery system. Silver crystal held by silver
metal gauze is used in the Degussa process. The reactor
operates at 788.15–823.15  K in this method, and heat is
immediately recovered after the product stream leaves
the reactor (Chauvel and Lefebvre 1989). Single-pass con-
version is relatively low in the methanol ballast process,
and unconverted methanol is recycled for higher overall
conversion achievement.
Steam
Scheme A
Reactor
Steam
Cooler
Water
Air
Steam
Evaporator Heat exchanger
Methanol + Water
Scheme B
Figure 2 BASF process schematic diagram.
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2.1.2 BASF process
The BASF process is the most widely applied industrial for-
maldehyde synthesis process and involves passing metha-
nol over a silver catalyst. A schematic diagram of the BASF
process (Figure 2) shows that a fresh mixture of methanol
and water enters an evaporator along with process air and
is mixed with off-gas recycled from the absorption column.
Part of the required heat in the evaporator is supplied using
the first stage of the absorption column. The reactor used
in this process contains a thin layer of silver grains placed
between silver gauze. A cooler is located immediately after
the reactor to prevent further possible reactions.
To control the temperature of the reactor, the water
content of the fresh feed and methanol-to-oxygen ratio
can be adjusted. The ratio controls the temperature of
the process and determines the dominant reaction [either
eq. (2) or (3)] through which formaldehyde is produced.
“Scheme A” shown in Figure 2 contains overhead light
components of the absorption column, and heavier com-
ponents can be recycled in “Scheme B”. The desirable com-
position of the final formalin solution defines whether, or
not any of the mentioned streams should be used.
Combusted off-gas
Steam generator
Water
Cooler
Cooler
Absorption
Column
Formaldehyde
solution
 A.M. Bahmanpour et al.: Critical review and exergy analysis of formaldehyde production processes      5
The role of each reaction in this process can be deter-
mined by controlling the temperature of the reactor,
amount of water entering with methanol as the fresh
feed, and the methanol-to-oxygen ratio. Depending on
the methanol-to-oxygen ratio, at high temperatures,
methanol may be dehydrogenated directly [eq. (2)]. The
effect of water content was studied in a research made by
Qian et  al. (2003). It was claimed that methanol conver-
sion and formaldehyde selectivity increase by addition of
water compared with the same case with no added water.
However, some aspects such as the concentration of the
final product are affected by the water content of the fresh
feed. Therefore, an optimum ratio should be used. The
water-to-methanol ratio of 2:3 or 0.67 has been suggested
in literature (Reuss et al. 2003).
As mentioned before, both partial oxidation and direct
dehydrogenation of methanol take place when silver cata-
lysts are used. However, the selectivity of formaldehyde
can be limited considering the following reactions:
ˆ o = 12.5 kJ/mol,
CH 2O →CO + H 2 ΔH (4)
r trial processes, a combination of Fe2(MoO4)3 and MoO3 has
3 ˆ o = -674 kJ/mol,
CH 3OH +  O2  →CO2 + 2H 2O ΔH r (5)
2
ˆ o = -519 kJ/mol.
CH 2O +  O2  →CO2 +  H 2O ΔH (6)
r selectivity toward formaldehyde have been investigated in
Methyl formate and formic acid are the other main
by-products of this process and are generally removed as
impurities by anion exchange.
2.1.3 Formox process
Many researchers have discussed the effects of using other
catalysts. The most important catalysts that have been
discussed are iron/molybdenum or vanadium oxide in the
Formox process. The Mo/Fe atomic ratio in this process is
usually between 1.5 and 3. Small amounts of other materi-
als such as V2O5, Cr2O3, CuO, P2O5, and CoO are also present
in the catalyst. At atmospheric pressure, methanol is
almost completely converted in the temperature range
of 543.15–673.15 K. However, if the temperature exceeds
743.15 K, oxidation of formaldehyde to carbon monoxide
becomes significant:
1 ˆ o = -215 kJ/mol.
CH 2O + O2 ↔ CO + H 2O ΔH r (7)
2 nol and cupric nitrate tri-hydrate complex at 298.15 K, an
A schematic diagram of the Formox process is shown
in Figure 3. As can be seen, the methanol feed stream
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passes through a steam evaporator and enters the reactor.
Similar to the BASF process, a cooler is located directly
after the reactor. Products are cooled down to 383.15  K
before entering the absorption column. One of the key
controllers of the formaldehyde concentration in this
process is the amount of water added at the top of absorp-
tion column. The product stream goes through an anion
exchange to minimize the formation of formic acid. The
final product stream contains up to 55 wt% formaldehyde
and 0.5–1.5 wt% methanol. Methanol conversion is around
98–99% in case of high selectivity and activity. The overall
plant yield can be between 88% and 91%.
Owing to the lower temperature and the higher sta-
bility of the catalysts in the direct oxidation of methanol
to formaldehyde, this method is attracting more attention
compared with the silver-based catalytic process (Adkins
and Peterson 1931) reported iron-molybdenum as a suit-
able catalyst for methanol oxidation to formaldehyde. It
was commercially used as one of the main catalysts in the
formaldehyde production process in the 1950s. In indus-
been used as the catalyst; this combination may have a
longer lifetime and higher selectivity compared with pure
Fe2(MO4)3 catalyst. The effects of different Mo-to-Fe atomic
ratios in iron molybdate catalysts on catalyst activity and
literature and will be discussed in the Kinetics and Mecha-
nism section. Ratios above 1.5:1 provide desirable results
(Soares et al. 2001).
2.2 Other methods
There are many other methods through which formalde-
hyde can be produced. In many of these methods, either
methanol or hydrocarbon gases are used as the source of
formaldehyde production. Therefore, these methods are
categorized in two groups as indicated below.
2.2.1 Other formaldehyde production methods from
methanol
Many researchers have investigated other methods of
formaldehyde production from methanol using different
operating conditions. Brackman (1959) reported that by
passing oxygen through a stirred mixture of liquid metha-
80% yield of formaldehyde based on the amount of oxygen
consumed can be achieved. Dehydrogenation of metha-
nol is another subject that has been discussed by some
6      A.M. Bahmanpour et al.: Critical review and exergy analysis of formaldehyde production processes

Tail gas
Steam

Reactor
Water

Formaldehyde absorption column

Circulation
system for heat
transfer oil

Air Water

Cooler

Steam
Evaporator

Anion
Methanol exchange
unit
Basic
materials

Formalin

Figure 3 Formox process schematic diagram.

researchers (Sabatier and Mailhe 1910, Newton and Dodge
1933, Sexton 1981, Su et al. 1992, Zaza et al. 1994); Sabatier
and Mailhe (1910) studied this process and declared that
this reaction is a reversible one. Later, Newton and Dodge
(1933) derived the following equilibrium relation for this
reversible reaction:
⎛ 4600 ⎞ (8)
log10 K p = ⎜ -8.48⎟ ,
⎝ T ⎠
where T (K) is the equilibrium temperature and Kp is the
equilibrium constant for this reaction. However, there
are three undesirable side reactions that might occur
during this process. They can be controlled by control-
ling the operating conditions. These reactions are pyro-
lytic decomposition of formaldehyde and oxidation
to formic acid, carbon monoxide, carbon dioxide, and
water:
CH 2O →CO + H 2 ,
1
CH 2O + O2 → HCOOH,
2
CH 2O + O2 →CO2 + H 2O. (11)
Aries (1960) described that elevated pressures in
methanol dehydrogenation prevent the formation of
formic acid in the products stream. Passing methanol and
air over a finely divided silver catalyst at 202.65–1013.25
kPa and 973.15–1073.15 K, the product gas mixture con-
tained formaldehyde, traces of water, and unreacted
methanol, but no formic acid.
Punderson (1960) suggested a combination of silver,
copper, and silicon as a new methanol dehydrogenation
catalyst. According to his patent, by combination of 98.8%
silver, 1% copper, and 0.2% silicon, an active catalyst was
made, through which a 70% methanol conversion and 82%
formaldehyde yield was possible. Using the combination
of 97.8% silver, 2% copper, and 0.2% silicon, even better
results were achieved; 71.5% methanol conversion at the
end of the seventh cycle in the process was achieved using
(9) the latter catalyst while it was exposed to pure methanol
vapor in the temperature range of 873.15–973.15 K.
(10) Considering the difficulty of the separation of formal-
dehyde from the water produced by partial oxidation of

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 A.M. Bahmanpour et al.: Critical review and exergy analysis of formaldehyde production processes      7
methanol to formaldehyde, methanol dehydrogenation
has been studied as an alternative method using types of
reactors such as inorganic membrane reactors (Deng and
Wu 1994) and slurry reactors (Shreiber and Roberts 2000)
using different catalysts.
2.2.2 Formaldehyde production from methane
Direct oxidation of methane to form formaldehyde is
another method that has been extensively discussed (Blair
and Wheeler 1923, Zhang et al. 2003, 2006, Polnišer et al.
2011). This process has the obvious advantage of produc-
ing formaldehyde in a single stage; however, low selectiv-
ity and yield of formaldehyde are the main issues faced
in this process (Bobrova et al. 2007). Many attempts have
been made to increase the selectivity of formaldehyde,
and in some studies, approximately 80% selectivity was
achieved (Zhang et al. 2011), but the issue of low methane
conversion ( < 2%) remained unresolved. In a recent study
(Zhang et  al. 2012a), NO2 has been introduced as a pro-
moter, and the process took place in a very short residence
time. The highest methane conversion (24.3%) and yield
(9%) was achieved in this study for this process so far.
Carbon monoxide is the main by-product of this process.
Among the catalysts that have been used for partial
oxidation of methane to formaldehyde, iron oxide, molyb-
denum oxide, and vanadium oxide are the most common
catalysts (Zhang et al. 2003, Launay et al. 2007, He et al.
2009). It is difficult to activate the relatively inert methane
on the surface of a catalyst to make formaldehyde, consid-
ering the weak chemisorption of methane on the catalyst
surface (Michalkiewicz et  al. 2008). Methane oxidation
[eq. (12)] and formaldehyde oxidation [eq. (6)] occur in
this process dominantly:
ˆ o = -319 kJ/mol.
CH 4 + O2 → HCHO+H 2O ΔH (12)
r Excess methanol is used instead of water to facilitate heat
As can be seen, further oxidation of formaldehyde
may lead to carbon dioxide production for which oxygen
should be the limiting reactant, which significantly
affects methane conversion. Further considerations are
that metal-oxygen bonds on the catalyst surface may lead
to higher catalyst activity, but lower formaldehyde selec-
tivity (Fajardo et  al. 2008). High temperature increases
the methane activation and the kinetics of the process,
but also leads to complete oxidation of methane to carbon
dioxide, instead of formaldehyde synthesis (Sexton et al.
1998). To prevent unfavorable oxidation of formaldehyde
to carbon dioxide, a short residence time is required. One
positive effect is that the high surface area of the catalyst
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support has been shown to improve methane conversion
(Bobrova et al. 2007).
3 Exergy analysis
Exergy analysis is a method for comparison of two different
processes. Exergy is the maximum useful work possible
during a process that brings the system from its initial state
into equilibrium (Christopher and Dimitrios 2012). Unlike
energy, exergy can be destroyed in different systems.
Exergy loss and exergy efficiency are two criteria that can
be used to study the efficiency of a process. In this section,
methanol synthesis from natural gas is simulated using
Aspen HYSYS™ software (Aspen technology, Burlington,
MA, USA). The kinetic expressions of the Aspen HYSYS
library are used for this part of the simulation. The pro-
duced methanol is used in a methanol ballast process to
produce formaldehyde. This process is simulated using
Aspen Plus™ software (Aspen technology, Burlington,
MA, USA). In the formaldehyde synthesis reaction, a fixed
conversion based on the available data is used. The simu-
lation data are used for exergy analysis. The methanol
ballast process is chosen due to the availability of the nec-
essary data for simulation (Turton et al. 2009).
3.1 Simulation results
To do an exergy analysis on the formaldehyde production
process, methanol production from natural gas and, suc-
cessively, formaldehyde production from the produced
methanol are simulated. Data are obtained for the metha-
nol ballast process by simulating this section using the
Aspen Plus software. The industrial data used for simula-
tion is obtained from the literature (Turton et  al. 2009).
transfer. Figure 4A shows the natural gas steam reform-
ing process. Figure 4B shows the simulated methanol
synthesis process in Aspen HYSYS software. It is split into
two parts because the simulation figure is too large to be
shown in one figure. Figure 4C shows the formaldehyde
production process simulated in Aspen Plus. Model vali-
dation is demonstrated in Table 4 based on a compari-
son between the simulation and the experimental results
(Turton et al. 2009).
The results of these simulations are given in Tables 5
and 6.
Separation of the unreacted methanol from water/
methanol/formaldehyde mixture is a complicated process
to study. This mixture is non-ideal, and therefore, no
8      A.M. Bahmanpour et al.: Critical review and exergy analysis of formaldehyde production processes

A
Q5
NG Heated NG
E-100 Saturated NG
MIX-103
Syngas
Steam2 Q11
To 2nd HE To 3rd HE
E-105 E-108
V-104
To syngas
seperator
Pre-heated
SNG
MIX-104 Liquid outlet
RCY-2 Steam3
To 2nd HE
recycle Q10
Produced SG
to pre heater Q8 E-107
ERV-101
To steam
reformer
E-106

Q9

HE
RCY-1 out
B Q4
Cold Liquid Recycle2
liquid CO2 E-101 CO2 To
Compressed Co2+syn gas MIX-102 reactor
MIX-101
Q2 syn gas
To To To
Vapour
intercooler Inter second second
out Q3
cooler drum stage
Second
Syn First Q1
V-100 V-101 stage
gas stage

Liq. out2

Water
Liq. MIX-100 out
out

To To Purge
HE Q7 compressor
Recycle TEE-100
compressor To be
returned

Saturation V-102
Q6
water Cooled Cooled Outlet
E-103 products2 E-104 products3 vapour
HE Products To Light
out Cooled products V-103
To next end
VLV-100 Crude methanol LP
valve drum Qc
To
reactor E-102 Methanol
ERV-100

Steam Fusel
Crude Qr oil
methanol VLV-101 Water
T-100

Meth

Heater

Recycle2 Recycle1
C

Vent
Mixer Reactor Water Absorber
Methanol Cooler Dist-CLM
Mixture
Reac-out
Air To-ABS
To-Dist

Formal

Figure 4 Natural gas to synthesis gas process simulation (A), methanol synthesis process simulation (B), methanol ballast process
simulation (C).

conventional physical property table like the vapor-liquid- in the aqueous phase. As a result, many different inter-
equilibrium exists to predict the instability of formalde- mediate species may be formed that affect the simula-
hyde in the vapor phase and its readiness to polymerize tion results. Many studies have been done to predict the

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 A.M. Bahmanpour et al.: Critical review and exergy analysis of formaldehyde production processes      9

Table 4 Model validation for methanol ballast process simulation (Turton et al. 2009).

Parameters   Simulation results  Experimental results

Formaldehyde yield (%)   26  28

Formalin stream (%)
 Formaldehyde (mol%)   37.5  36
 Water (mol%)   61.4  63.5
 Methanol (mol%)   1.1  0.5
Methanol-to-carbon monoxide molar ratio  1.73  1.73
Formaldehyde-to-methane molar ratio   0.26  0.27

Table 5 Methanol synthesis simulation results.

  Natural gas  Synthesis gas  Carbon dioxide  Purge gas  Methanol

Mole flow (kmol/h)

 CO   0.00  44.06  0.00  3.20  0.00
 CO2   1.53  22.88  18.44  5.85  0.00
 H2O   0.00  1.14  0.00  0  0.00
 H2   0.00  207.96  0.00  26.98  0.00
 N2   0.95  0.94  0.00  0.81  0.00
 CH4   64.10  8.36  0.00  7.18  0.00
 CH3OH   0.00  0.00  0.00  0.13  76.37
Total flow (kg/h)   1122.30  2842.04  811.54  544.04  2447.00
Total flow (kmol/h)  66.58  285.34  18.44  44.15  76.37
Temperature (K)   283.15  313.15  241.26  310.93  348.95
Pressure (kPa)   2914.00  1866.00  8582.00  7886.00  140.30

Table 6 Methanol ballast process simulation results. these studies, a data package has been developed for the
Aspen Plus software, which was used in this simulation.
  Methanol  Formalin UNIFAC is used as the base physical property, and many
Mole flow (kmol/h) other reactions that occur simultaneously are considered
 CH2O   0.00  59.61 in the separation process. The most important reactions
 CH3OH   76.37  1.75 are listed below:
 H2O   0.00  97.35
 O2   0.00  0.00 CH 2O + H 2O ↔ HO-CH 2 -OH (13)
 N2   0.00  0.00
Total flow (kg/h)   2447.00  3600.00 HO-( CH 2O)n-1 -H + HO-CH 2 -OH
Total flow (kmol/h)  76.37  158.71
Temperature (K)   303.15  308.15 ↔ HO-( CH 2O)n -H + H 2O (14)
Pressure (kPa)   120.00  315.00
2CH 2O + H 2O ↔ CH 3OH + HCOOH (15)

2CH 3OH + CH 2O ↔ CH 3O-CH 2 -OCH 3 + H 2O (16)

behavior. Maurer (1986) developed a physicochemical
model in which physical forces and chemical reactions CH 3OH + CH 2O ↔ CH 3O-CH 2 -OH (17)
of binary mixtures of water-formaldehyde and methanol-
formaldehyde were considered. His proposed vapor-liquid CH 3O-( CH 2O)n-1 -H + CH 3O-CH 2 -OH
equilibrium was revised and modified for wider range
↔ CH 3O-(CH 2O)n -H + CH 3OH (18)
of temperatures in his further works (Hasse et  al. 1990,
Hasse and Maurer 1991, Albert et al. 1996, 2000, Kuhnert HO(CH 2O)2 H ↔ HCOOCH 3 + H 2O (19)
et  al. 2006). He and his colleagues also considered the
kinetics of formaldehyde polymer formation in water in 2CH 2O ↔ CH 3OH + CO (20)
their research (Albert et al. 1999). Based on the result of

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10      A.M. Bahmanpour et al.: Critical review and exergy analysis of formaldehyde production processes
3.2 Exergy analysis of the simulated
processes
Considering a process as an open system, physical and
chemical exergies are the two main types of exergies
that are involved in the calculation in each part. Physical
exergy can be calculated based on the physical properties
of each flow stream according to the following equation
(Christopher and Dimitrios 2012):
e ph = ( h-h0 )-T0 ( s-s0 ), (21)
where h, s, and T are enthalpy, entropy, and temperature,
respectively, and the subscript 0 refers to the standard
condition (T = 298.15 K, P = 101.25 kPa). However, for a cold
gas stream, physical exergy can be calculated based on
the following equation derived by Wang et al. (2005).
⎡⎛ T ⎞ T ⎤ P the system can be directly counted as another source of
e ph = ⎢⎜ 0 -1⎟ r -c p ( T0 -T ) + c pT0 ln 0 ⎥ + zRT0 ln , (22)
⎝
⎣ T ⎠ T⎦ P0
where r is the heat of vaporization and z is the compress-
ibility factor. Chemical exergy is the maximum amount of
work achieved from the deviation of the chemical com-
position of a system from the reference state (Tsatsaronis
2007). The reference state used for comparison is chosen
to be the earth’s atmosphere, seawater, and the earth’s
crust (Szargut et  al. 1988). The specific chemical exergy
can be defined based on the chemical potential of a sub-
stance according to the following equation if the tempera-
ture and pressure are constant and equal to the reference
conditions (Demirel 2013):
ci
ech = ∑ ( μi0 -μi 0 0 ) + RT0 ∑ ln (23)
i i ci 0
For a pure component in ideal gas state, the following
equation can be derived:
Pi
ech = RT0 ln , (24)
Pi 0
where Pi and Pi0 refer to the partial pressure of the gas in
the system and in the reference state, respectively. Based
on the availability of a species in standard air, chemical
exergy also can be defined as follows (Bejan 1997):
1 provide enough energy for the high-temperature (over
ech = RT0 ln , (25)
Xi
where R is the universal gas constant and Xi is the mole
fraction of species i in the standard air. Therefore, the
exergy of each flow stream is the addition of physical and
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chemical exergies. For a gas mixture, chemical exergy is
calculated as follows (Dincer and Rosen 2013):
ech = ∑ xi ech
i
+ RT0 ∑ xilnxi , (26)
i i
where xi is the mole fraction of the component i in the gas
mixture. In a control volume, one of the main sources of
exergy is heat transferred to or from the control volume.
The proportion of the transferred heat that can be con-
verted into work based on a Carnot cycle is defined as
follows (Bejan 1997):
⎛ T⎞
eth = Q ⎜ 1- 0 ⎟ (27)
⎝ T⎠
where T is the temperature of the control volume where
the energy transfer is assumed to be at the same tem-
perature. The amount of work done on the system or by
exergy gain or loss. Therefore, the exergy loss and exergy
efficiency can be calculated as follows:
 ⎛ ∑( e ph + ech + eth +W )-∑( e ph + ech + eth +W )⎞
Eloss = m ⎜⎝ ⎟⎠ (28)
in out
Eloss
Eeff =1- . (29)
Ein
Considering the above definitions, an exergy analysis
is undertaken for the steam reforming process, the metha-
nol synthesis process, and the formaldehyde production
process based on the mass of formalin produced. A block
flow diagram is presented in Figure 5, which provides an
overview of the exergy analysis based on the three sepa-
rate processes used for the manufacture of formaldehyde
from natural gas.
The result of the analysis is shown in details in
Table  7. As shown below, the exergy efficiencies of
the steam reforming process, the methanol synthesis
process and the methanol ballast process are 60.8%,
61.6%, and 66%, respectively. The overall exergy effi-
ciency is therefore 43.2%.
In the steam reforming process, it can be noticed from
Table 7 that the highest proportion of exergy loss relates to
the chemical and thermal exergy of the system. The highest
exergy loss in this process is over the steam reformer. To
1073.15 K) reforming process, natural gas is burnt in the
reformer, destroying some chemical exergy, and flue gas
leaves the reformer as a thermal exergy stream. In the
methanol synthesis process, the purge gas leaving the
system is the main source of chemical exergy loss. The
 A.M. Bahmanpour et al.: Critical review and exergy analysis of formaldehyde production processes      11

Carbon dioxide Purge gas

Natural gas Formalin

Synthesis gas
Natural gas to Synthesis gas to Methanol to
synthesis gas methanol formaldehyde
Methanol

Figure 5 Block flow diagram.

purge stream is mainly used as a supplementary fuel for stream has no fuel value. The overall exergy efficiency of
the steam reformer. Another source of exergy loss in the the system is calculated based on all exergy entering the
methanol synthesis process is the distillation column. formaldehyde production sequence and all exergy leaving
Work is done in a distillation column to create a pure this sequence. The results of the exergy analysis calcula-
methanol product. In the formaldehyde synthesis process tions can be summarized using a Sankey diagram (pre-
(methanol ballast process), it can be noticed that the sented in Figure 6), which explains the overall exergy of
main proportion of exergy loss is the chemical exergy loss the whole sequence.
from the unreacted methanol leaving the process in the The results show that increasing the overall exergy
purge stream from the absorber column. Unlike the purge efficiency of formaldehyde production should be studied
stream from the methanol synthesis process, this purge in future works. Although optimization of these processes
has a positive effect on the exergy efficiency of the system,
the exergy loss due to the high energy consumption of the
Table 7 Exergy analysis results. steam reformer or loss of methanol in the purge stream
of the absorber column in the formaldehyde synthesis
Exergy   Exergy in  Exergy out
process limits the extent of improvement to the existing
(kW/kg formalin) (kW/kg formalin)
processes. Because of this, reducing the number of the
Physical exergy process steps to produce formaldehyde can increase the
 NG to synthesis gas process   2.96 × 103  1.16 × 102
exergy efficiency of this process. One possibility is the
 Methanol synthesis process   1.45 × 102  1.63 × 102
 Formalin synthesis process   2.62 × 101  2.73 × 101 direct formation of formaldehyde from natural gas or syn-
Chemical exergy thesis gas, which will save the exergy loss associated with
 NG to synthesis gas process   2.26 × 104  1.71 × 104 the methanol synthesis process. So far, the direct produc-
 Methanol synthesis process   2.69 × 104  1.63 × 104 tion of formaldehyde from natural gas or synthesis gas
 Formalin synthesis process   1.53 × 104  9.32 × 103
has not achieved a competitive conversion or selectivity.
Work
 NG to synthesis gas process   0  0
Therefore, a potential solution might be to study methods
 Methanol synthesis process   5.25 × 102  0 of increasing the conversion and selectivity of natural gas
 Formalin synthesis process   1.84 × 102  0 or synthesis gas into formaldehyde.
Thermal exergy
 NG to synthesis gas process   6.18 × 103  2.05 × 103
 Methanol synthesis process   6.82 × 102  8.34 × 102
 Formalin synthesis process   1.95 × 102  1.38 × 103 4 Kinetics and mechanism
Total
 NG to synthesis gas process   3.17 × 104  1.93 × 104
In the following section, the reactions through which
 Methanol synthesis process   2.81 × 104  1.73 × 104
 Formalin synthesis process   1.57 × 104  1.07 × 104 formaldehyde is being produced in industrial processes
– namely partial oxidation and dehydrogenation of meth-
Exergy loss and efficiency
anol – are investigated and the kinetics and mechanism of
 Exergy loss (kW)
  NG to synthesis gas process  1.24 × 104  the mentioned reactions are discussed.
  Methanol synthesis process  1.08 × 104 
  Formalin synthesis process   0.50 × 104 
 Exergy efficiency (%)
  NG to synthesis gas process  60.8  4.1 Thermodynamic investigation
  Methanol synthesis process  61.6  of the reactions
  Formalin synthesis process   66 
Total   43.2%  The two main reactions that participate in formaldehyde
NG, natural gas. production in industrial processes are partial oxidation

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12      A.M. Bahmanpour et al.: Critical review and exergy analysis of formaldehyde production processes

Figure 6 Sankey diagram for exergy efficiency.

of methanol and methanol dehydrogenation. Therefore,
these reactions will be investigated thermodynamically in
this section. The specifications of each reaction, including
enthalpy, entropy, Gibbs free energy change, and equi-
librium coefficients at different temperatures have been
investigated using HSC Chemistry™ software (Outotec
Oyj, Espoo, Finland). The results for the range of tempera-
ture of 273.15 to 1273.15 K for these reactions are given in
Tables 8 and 9.
As can be seen, the reaction is promising from the
thermodynamics point of view. Enthalpy change does not
change significantly with temperature. High equilibrium
coefficients and highly negative Gibbs free energy change
show high possibility of reaction. Negative Gibbs free
energy change, which decreases with temperature, shows
that increasing temperature makes the reaction “more
spontaneous”. However, considering the reaction as an
exothermic one, temperature increase lowers the equilib-
rium coefficient based on Le Chatelier’s principle.
In this reaction, methanol is dehydrogenated on the
surface of the catalyst. The temperature increase is clearly
in favor of this reaction. At low temperatures, the low
equilibrium coefficient and the high positive Gibbs free
energy show that the reaction may not occur at ambient
conditions. In the temperature range of 1123.15–1173.15 K,
the reactions become fairly spontaneous. However, being
non-spontaneous does not mean that the reaction cannot
take place. As can be seen in Table 9, the methanol dehy-
drogenation reaction seems to be feasible only at very
high temperatures, but this reaction actually occurs at
relatively low temperatures with the assistance of indus-
trial catalysts.
4.2 Kinetics of reactions and mechanism
Regarding the kinetics and mechanism of methanol con-
version to formaldehyde, the reactions will be discussed
in different groups classified based on the catalysts used:
copper, silver, and metal oxides. Because in the classical
process of formaldehyde production silver or copper cata-
lysts have been used, first, the kinetics and mechanism

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 A.M. Bahmanpour et al.: Critical review and exergy analysis of formaldehyde production processes      13

Table 8 Partial oxidation of methanol.

1
CH3OH(g)+   O2 ↔ CH2O(g)+ H2O(g)
2

T (K)  ΔH (kJ/mol)  ΔS (J/mol·K)  ΔG (kJ/mol)  K  log(K)

273.15  -149.694  64.454  -167.299  9.896E+031  31.995

323.15  -149.182  66.180  -170.568  3.743E+027  27.573
373.15  -148.761  67.392  -173.909  2.220E+024  24.346
423.15  -148.424  68.243  -177.301  7.732E+021  21.888
473.15  -148.162  68.829  -180.729  8.988E+019  19.954
523.15  -147.971  69.214  -184.180  2.462E+018  18.391
573.15  -147.845  69.446  -187.647  1.267E+017  17.103
623.15  -147.777  69.560  -191.123  1.052E+016  16.022
673.15  -147.760  69.586  -194.602  1.264E+015  15.102
723.15  -147.788  69.546  -198.080  2.037E+014  14.309
773.15  -147.854  69.458  -201.556  4.154E+013  13.618
823.15  -147.952  69.336  -205.026  1.027E+013  13.011
873.15  -148.075  69.191  -208.489  2.975E+012  12.474
923.15  -148.219  69.030  -211.944  9.851E+011  11.993
973.15  -148.382  68.858  -215.392  3.650E+011  11.562
1023.15  -148.561  68.679  -218.830  1.489E+011  11.173
1073.15  -148.754  68.495  -222.260  6.595E+010  10.819
1123.15  -148.961  68.307  -225.680  3.138E+010  10.497
1173.15  -149.172  68.123  -229.090  1.589E+010  10.201
1223.15  -149.388  67.943  -232.492  8.500E+009  9.929
1273.15  -149.610  67.765  -235.885  4.772E+009  9.679

Table 9 Methanol dehydrogenation reaction.

CH3OH(g)↔CH2O(g)+H2(g)

T (K)  ΔH (kJ/mol)  ΔS (J/mol·K)  ΔG (kJ/mol)  K  log(K)

273.15  91.887  108.018  62.382  1.174E-012  -11.930

323.15  92.895  111.409  56.893  6.352E-010  -9.197
373.15  93.805  114.030  51.254  6.678E-008  -7.175
423.15  94.619  116.079  45.500  2.415E-006  -5.617
473.15  95.346  117.706  39.654  4.188E-005  -4.378
523.15  95.993  119.008  33.734  4.280E-004  -3.369
573.15  96.566  120.054  27.757  2.952E-003  -2.530
623.15  97.071  120.899  21.732  1.507E-002  -1.822
673.15  97.513  121.583  15.670  6.081E-002  -1.216
723.15  97.901  122.139  9.576  2.033E-001  -0.692
773.15  98.238  122.589  3.458  5.840E-001  -0.234
823.15  98.530  122.956  -2.681  1.480E+000  0.170
873.15  98.782  123.254  -8.837  3.378E+000  0.529
923.15  98.998  123.494  -15.006  7.065E+000  0.849
973.15  99.180  123.686  -21.185  1.372E+001  1.137
1023.15  99.329  123.836  -27.374  2.498E+001  1.398
1073.15  99.446  123.948  -33.568  4.306E+001  1.634
1123.15  99.532  124.026  -39.768  7.074E+001  1.850
1173.15  99.595  124.081  -45.971  1.114E+002  2.047
1223.15  99.633  124.113  -52.176  1.692E+002  2.228
1273.15  99.649  124.125  -58.382  2.486E+002  2.395

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14      A.M. Bahmanpour et al.: Critical review and exergy analysis of formaldehyde production processes

related to the reactions of this group will be discussed, 2CH 3O( a ) → 2H 2CO( g ) + 2H( a ) (34)
and then metal oxide catalytic reactions for formaldehyde
production are extensively studied. H( a ) + H( a ) → H 2( g ) (35)

A similar study was done by Wachs and Madix (1978a) on

4.2.1 Copper and silver as catalysts
Formaldehyde was first produced commercially by cata-
lytic partial oxidation of methanol with air over an unsup-
ported copper catalyst at atmospheric pressure. Later,
copper was replaced by silver due the higher yield when
using the latter as the catalyst (43–47% yield obtained
using copper and 67% using silver) (Trillat 1903, Roeda
2003). Silver is also more selective toward forming formal-
dehyde compared with copper (Thomas 1920). A detailed
study on kinetics and mechanism of methanol oxidation
on the surface of copper (110) by flash decomposition
spectroscopy was done by Wachs and Madix (1978b). To
distinguish between the hydrogen atom on the hydroxyl
group and the methyl group for mechanistic study, deute-
rium-substituted methanol (CH3OD) was used. According
to this study, chemisorption of methanol on the surface
of oxygen-free copper was lower compared with the
surface of pre-oxide copper (110). Methanol was oxidized
while adsorbed to make methoxide and deuterium oxide.
Adsorption occurs at 180 K on the surface and produced
methoxide, which was then decomposed to form formal-
dehyde and hydrogen at 365 K. In a parallel way, but to
a lesser extent, some of the chemisorbed methanol was
oxidized to form formate, which in turn decomposed to
carbon dioxide and hydrogen. Based on this study, both
decomposition reactions occurred at a first-order rate with
the following rate constants:
⎛ -92.5 ±0.4( kJ/mol ) ⎞
⎜⎝
k⎛ H 2 CO ⎞
= 5.2 ± 1.6 × 10 12 e
⎜ ⎟
⎝ CH 3 OH ⎠
⎛ -129.3±0.8( kJ/mol ) ⎞
⎜ ⎟⎠
k⎛ CO2 ⎞
= 8.0 ± 2.0 × 10 13 e ⎝
⎜ ⎟
⎝ CH 3 OH ⎠
As the researchers mentioned, the formaldehyde selec-
tivity of the oxidation of deuterated methanol on copper
(110) was 80%, and carbon dioxide selectivity was 20%.
Based on this study, the following mechanism was pro-
posed for formation of formaldehyde from methanol on a
copper surface:
CH 3OH( g ) + O( a ) →CH 3O( a ) + OH( a )
CH 3OH( g ) + OH( a ) →CH 3O( a ) + H 2O( g )
a silver surface, using temperature programmed reaction
spectroscopy to distinguish between hydroxyl and methyl
hydrogen atoms. They showed that the pre-oxide silver
surface showed a higher ability to dissociatively chem-
isorb methanol on the catalyst surface. The process of
methanol oxidation on silver (110) and copper (110) was
investigated, and similarities and differences are veri-
fied. Based on this research, the following reactions are
observed for silver (110):
CH 3OD( g ) + O( a ) →CH 3O( a ) + OD( a ) (36)
CH 3OD( g ) + OD( a ) →CH 3O( a ) + D2O( a ) (37)
D2O( a ) → D2O( g ) (38)
CH 3O( a ) → H( a ) + H 2CO( a ) (39)
H 2CO( a ) → H 2CO( g ) (40)
H 2CO( a ) + CH 3O( a ) → H 2COOCH 3( a ) (41)
H 2COOCH 3( a ) → HCOOCH 3( a ) + H( a ) (42)
HCOOCH 3( a ) → HCOOCH 3( a ) (43)
H( a ) + H( a ) → H 2( g ) (44)
H( a ) + CH 3O( a ) →CH 3OH( g ) (45)
⎟⎠
RT
( s-1 ) (30)
The amount of adsorbed methanol increases as the
oxygen exposure increases as a result of the interaction
of the hydroxyl group of methanol and surface oxygen
RT
( s-1 ) (31) atom. Methoxide and deuterium oxide form on the cata-
lyst surface in both cases. However, unlike copper, the
adsorbed deuterium oxide and oxygen on the silver surface
desorb eventually due to weaker binding compared with
copper. Based on the work by Wachs and Madix, the
mechanism of methanol oxidation over copper and silver
does not differ significantly. However, considering differ-
ent activities of these catalysts, a different selectivity for
each material is achieved. The silver surface is more active
for decomposition of intermediate products compared
(32)
with copper. Reaction (41) between methoxide and for-
maldehyde to form methyl formate was observed on the
(33)
silver surface, but not on copper. This is due to the higher

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 A.M. Bahmanpour et al.: Critical review and exergy analysis of formaldehyde production processes      15
activity of silver for the decomposition of adsorbed meth-
oxide to formaldehyde, and hence, formaldehyde is pro-
duced at a lower substrate temperature, which increases
the residence time of formaldehyde on the silver surface.
A study by Francis et  al. (1994) on methanol oxida-
tion over oxygenated copper surface confirmed the results
achieved earlier (Leibsle et  al. 1994) that the kinetics of
this reaction depends on initial oxygen exposure of the
copper surface and the surface temperature. At low tem-
peratures (150–350 K), methanol reacts with adsorbed
oxygen in a 2:1 ratio to generate the adsorbed methoxy
species based on the following reaction:
2CH 3OH( g ) + O( a ) → 2CH 3O( a ) + H 2O( g )
The formed methoxy is stable at this temperature range,
however, as the temperature increases the stability of the
formed methoxy decreases, and at medium temperatures
(350–400 K), methoxy decomposes to form formalde-
hyde and hydrogen. Therefore, the following reaction is
achieved:
2CH 3OH( g ) + O( a ) → 2H 2CO( g ) + H 2( g ) + H 2O( g )
At high temperatures (above 500 K), the stoichiometry of
the reaction changes and methanol reacts with adsorbed
oxygen atom in a 1:1 ratio to form formaldehyde according
to the following reaction:
CH 3OH( g ) + O( a ) → H 2CO( g ) + H 2O( g )
This mechanism is confirmed by Barnes et  al. (1990)
because of the lack of hydrogen production at tempera-
tures below 320  K and above 470 K. The presence of
surface oxygen is believed to be critical in this process. It
is believed that pre-oxidizing is necessary to activate the
surface of the catalyst. However, overexposure of the cata-
lyst to oxygen can poison the active sites and reduce the
catalyst activity. Researchers proposed that as a dual-site
combination is necessary for high reactivity, overloading
the catalyst with surface oxygen may disable the Cu0 sites
and consequently reduce the activity of the catalyst.
The effect of oxygen on the activation of silver catalyst
in the methanol oxidation reaction has been investigated
by many researchers. Based on the study done by Schlögl
et  al. (Bao et  al. 1993a,b, Nagy et  al. 1998, 1999), three
types of oxygen-silver interactions can be found: (1) Disso-
ciative chemisorption of molecular oxygen leads to atomic
oxygen species adsorbed on the surface of the silver (111)
and silver (110). This species is referenced as Oα and it
participates in the methanol oxidation mechanism and
oxygen desorption proposed by Wachs and Madix (1978a).
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(2) Atomic oxygen species, referenced as Oβ, dissolves in
silver bulk and does not participate in the oxidation reac-
tion directly. (3) Investigation of silver (111) at temperatures
around 900 K shows that atomic oxygen segregates from
the bulk catalyst to the surface by interstitial diffusion to
form the atomic oxygen species referenced as Oγ. There is
a general agreement among the researchers that Oβ does
not participate in the oxidation reaction directly. However,
there is a discussion about the effects of Oα and Oγ on
the mechanism of this reaction. Some researchers have
claimed that Oγ is likely to be the active agent in methanol
oxidative dehydrogenation because Oα desorbs at 600  K
and it cannot be the dominant species on the catalyst
(46)
surface for methanol oxidation at 900 K (Bao et al. 1993b).
Based on Wachs and Madix (1978a), Andreasen et  al.
(2003) asserted that presence of Oα can justify the indus-
trial formaldehyde synthesis process and Oγ is not neces-
sarily involved and that Schlögl group’s conclusion about
the leading role of Oγ is only valid at ultrahigh vacuum in
which they have conducted their research. According to
the study done by Waterhouse et al. (2004), the population
of each atomic oxygen species depends on the tempera-
(47)
ture and structure of the silver catalyst. They declared that
Oα species is dominant at low temperatures, whereas at
industrial operating conditions, Oγ plays the leading role
and drives the process toward oxidative dehydrogenation
reaction. Van Veen et al. (2002) used a temporal analysis
of products method and pulse experiment to investigate
(48)
the mechanism of oxidative hydrogenation of methanol
on silver catalyst. Based on their findings, at temperatures
higher than 550 K, Oγ provides a highly selective oxidative
hydrogenation reaction to generate formaldehyde where
at lower temperatures Oα plays an important role in non-
selective oxidation of methanol at high surface coverage.
However, according to their research, low coverage of Oα
may improve the selectivity significantly.
Some researchers have investigated the effects of
different operating conditions on oxidation of methanol
and formaldehyde production using silver catalyst. Based
on a study done by Cao and Gavriilidis (2005), as reactor
temperature increases from 500 to 620 K, carbon dioxide
production rate increases and formaldehyde selectivity
decreases. This is in agreement with the results achieved
by Van Veen et al. (2002), as they indicated a strong role
of Oα in carbon dioxide production and low selectivity
toward formaldehyde, which is unlike the role of Oγ. As the
reactor temperature exceeds 620 K, formaldehyde selectiv-
ity increases and carbon dioxide concentration decreases,
which prove the role of Oγ as indicated in the results by
Van Veen et  al. (2002). The oxygen concentration in the
gas phase was another aspect that was investigated by
16      A.M. Bahmanpour et al.: Critical review and exergy analysis of formaldehyde production processes

Cao and Gavriilidis (2005). As the oxygen concentration According to their study, the following rate of reaction was
increased from 1.6 to 3.68 vol%, carbon dioxide concen- obtained assuming a steady-state pattern:
tration and methanol conversion increased and formalde-
2 k1k2 Pm PO
hyde selectivity decreased. r= 2
(51)
Qian et al. (2003) investigated the effects of tempera- k1 Pm + 2 k2 PO
2

ture on methanol oxidation process and formaldehyde

where k1 and k2 refer to rate constants for the first and
yield. Formaldehyde yield gradually increased until it
second step, respectively, which were evaluated at each
reached its maximum at 923 K. At higher temperatures, for-
temperature at which the reaction was investigated. The
maldehyde yield decreased, which was accompanied by
results are given in Table 10.
an increase in the yield of carbon monoxide and hydrogen,
In a more detailed study, Mann and Dosi (1973)
which showed formaldehyde decomposition. They also
studied the kinetics of the same reaction on vanadium
investigated the effects of residence time on methanol con-
oxide-molybdenum oxide (V2O5-MoO3) in the temperature
version and formaldehyde selectivity, which showed that in
range of 523.15–803.15 K, catalyst metal oxides ratio of
the range of 0.06–0.45 s residence time, methanol conver-
0–1, and methanol concentration in air of 5–10%. Based
sion increased while formaldehyde selectivity decreased at
on their study, the best results were obtained at 733.15 K
higher residence times. The effect of water vapor was also
and by V2O5/MoO3 weight ratio of 1/4. Optimum methanol
quantified by increasing the H2O/CH3OH molar ratio from 0
concentration in air is detected to be 8%. The same two-
to 2. While methanol conversion constantly increased with
stage redox mechanism that was applied by Bhattachar-
water-to-methanol ratio, formaldehyde selectivity reached
yya et al. (1967) has been considered in this study as well:
its maximum at around the molar ratio of 0.75.
k1
Although many studies have discussed the kinetics,
First step: CH 3OH + (catalyst)ox → HCHO + H 2 O
mechanism, and optimum operating conditions of the
oxidation reaction on copper and silver catalysts, partial +(catalyst)red (52)
oxidation of methanol on metal oxides has attracted more k2
attention. In the following section, we discuss the applica- Second step: 0 .5O2 + (catalyst)red → (catalyst)ox (53)
tion of metal oxides as catalysts.

Based on this research, the following rate equation is

achieved for this reaction:
4.2.2 Metal oxides as catalysts
k1 Pm
r=
⎛ kP ⎞ (54)
Bailey and Craver (1921) patented a method of methanol 1 + ⎜ 1 m0.5 ⎟
oxidation into formaldehyde using metal oxides (vana- ⎝ 2 k2 PO2 ⎠
dium oxide in particular) as catalysts. Since then, many
where k1 and k2 are the rate constants for the first and
researchers have investigated the kinetics and mechanism
second steps, respectively. The value of k1 and k2 can be
of the reactions that occur on the surface of these metal
found using the Arrhenius law-based equations given for
oxides in the presence of methanol and other materials.
these two rate constants:
In a kinetic study done by Bhattacharyya et al. (1967), the
methanol oxidation reaction was investigated at 519.15, 2.358 × 10 3 (55)
log k1 = 0.773-
537.15, and 554.15 K using vanadium oxide as the catalyst. T( K )
Based on their study, the Mars-van Krevelen redox mech- 2.04 × 10 3
anism (Mars and van Krevelen 1954) was suggested in log k2 = 0.157- (56)
T( K )
which methanol reduced the catalyst and formed formal-
dehyde and water [eq. (49)], and in the next step, oxygen
exposure reoxidized the reduced catalyst [eq. (50)]: Table 10 Values for first and second rate constants (Bhattacharyya
et al. 1967).
k1

First step: CH 3OH + ( catalyst )ox → HCHO + H 2 O Rate constants   Temperature (K)

+( catalyst )red (49) 3
Moles of HCHO/(mole CH3OH.s. m .kPa)   519.15  537.15  554.15
k2
k1   2.96  5.93  15.3
Second step: O2 + (catalyst)red → ( catalyst)ox (50) k2   0.26  0.49  1.09

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 A.M. Bahmanpour et al.: Critical review and exergy analysis of formaldehyde production processes      17

Tatibouët and Germain (1981) investigated molybdenum CH 3O-V + Oads →CH 2O +V-OH (58)
oxide as catalyst for methanol oxidation reaction. They
used dilute methanol-oxygen mixture (methanol/oxygen/ S-OH +V-O-H → H 2O +V-O-S (59)
helium molar ratio, 8.2/19.7/72) in the range of 473.15–
573.15 K and at atmospheric pressure and concluded that where S is the support cation.
reaction may take two different paths based on the poly- SiO2-, ZrO2-, TiO2-, Nb2O5-, and Al2O3-supported V2O5
morphic crystalline form of molybdenum oxide. On the were investigated by Deo and Wachs (1994), and the best
hexagonal surface of a molybdenum oxide surface, meth- results for each catalyst based on formaldehyde selectivity
anol goes through dehydration path and dimethyl ether is are given in Table 11.
produced, whereas on orthorhombic molybdenum oxide, According to the results, the highest formaldehyde
methanol goes through partial oxidation to form formal- selectivity (more than 99%) and the highest turnover
dehyde, which may react further with methanol to form frequency (2 s-1) was achieved using titanium dioxide as
its acetal: the support. Niobium pentoxide also showed high selec-
+MeOH tivity toward formaldehyde (97%). Based on the results
HCHO CH2(OMe)2
+O 2 gained, the reactivity of the supported vanadium oxide
as methanol oxidation catalyst depended on the strength
CH3OH
of the V-O-support bond, meaning that the weaker the
-H2O
V-O-support bond was, the higher catalytic reactivity
(CH3)2O
achieved.
Adkins and Peterson (1931) reported 38% oxygen
In an FTIR study, Busca (1989) observed the formation of
conversion and 100% oxygen selectivity for formalde-
methoxy groups upon methanol adsorption over vana-
hyde production over molybdenum oxide catalyst using
dium oxide catalyst. Methoxy groups, in turn, oxidized
methanol partial oxidation. Higher oxygen conversion
to form dioxymethylene. Formaldehyde adsorption on
was achieved over iron oxide, but mostly carbon dioxide
the surface of vanadium oxide also formed dioxymeth-
was formed, which meant complete oxidation of metha-
ylene, which implies that desorption of dioxymethylene
nol. Mixed oxides of iron and molybdenum showed high
formed during methanol oxidation may lead to formalde-
conversion ( > 90%) and high selectivity for formalde-
hyde formation. However, Forzatti et al. (1997) found that
hyde and carbon monoxide. Soares et al. (2001) studied
at low temperatures ( < 435 K) and high methanol avail-
the effects of Mo-to-Fe atomic ratio by comparing
ability, dioxymethylene may react with methanol to form
industrial iron-molybdenum oxide catalyst (Mo/Fe = 3)
dimethoxymethane (DMM), whereas it can preferably
with stoichiometric composition (Mo/Fe = 1.5). Higher
desorb as formaldehyde at high temperatures ( > 435 K)
Mo/Fe atomic ratio resulted in higher surface area and
and low methanol availability. Therefore, high selectivity
higher selectivity of the catalyst toward formaldehyde
toward formaldehyde is achieved over weak formalde-
production. However, the activity of the catalyst did not
hyde binding sites of the catalyst. The type of support –
change significantly. Therefore, it can be concluded that
such as acidic, basic, or redox – also affects the reaction
the Fe2(MoO4)3 stoichiometric phase is the active phase of
pathways substantially. Deo and Wachs (1994) showed
the catalyst. Wachs’ group (Routray et al. 2010) showed
that different products such as formaldehyde, DMM,
that if excess MoOx is added to crystalline Fe2(MoO4)3, it
DME, methyl formate, and oxides of carbon can be pro-
duced over different supports. These products depend
upon the pathways taken by surface methoxy over differ-
Table 11 Effects of different supports on vanadium oxide perfor-
ent supports. Acid sites cause methanol dehydration and mance (Deo and Wachs 1994).
DME production. Basic sites oxidize methanol to formate
and further converts into carbon monoxide and carbon Sample   TOF (s-1)  Selectivity (%)
dioxide. On redox sites, partial oxidation occurs, and  
FA  MF  DMM  DME  COx
formaldehyde, DMM, and methyl formate can be pro-
5% V2O5/SiO2   15.1 × 10-3  88  0  2  8  2
duced. The desired pathway for formaldehyde formation
5% V2O5/ZrO2   1.6  94  5  Trace  Trace  Trace
is shown below in eqs. (57) to (59) (Burcham and Wachs 1% V2O5/TiO2   2  99+  0  0  Trace  0
1999). 2% V2O5/Nb2O5   1.2  97  0  1  2  0
20% V2O5/Al2O3   6.8 × 10-2  46  0  3  50  1
CH 3OH +V-O-S→CH 3O-V + S-O-H (57)

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18      A.M. Bahmanpour et al.: Critical review and exergy analysis of formaldehyde production processes
is deposited as a surface monolayer, which improves the
catalytic performance toward formaldehyde production.
Contrary to Soares et al. (2001), Wach’s group (Routray
et  al. 2010) found that stoichiometric Fe2(MoO4)3 (Mo/
Fe = 1.5) has higher surface area compared with catalysts
with excess molybdenum oxide. Wach’s group (Routray
et al. 2010) achieved highest selectivity toward formal-
dehyde using the catalyst Mo/Fe = 2. However, the turno-
ver frequency was higher when using the catalyst Mo/
Fe = 1.7. Based on the mechanism suggested for metha-
nol oxidation reaction over iron oxide and the one for
iron-molybdenum oxide by Wachs’ group (Routray et al.
2010), they have concluded that due to the dependence
of the formaldehyde production pathway on the presence
of bulk lattice oxygen and considering the incapability
of iron oxide to supply bulk lattice oxygen, the chance of
formation of formaldehyde on iron oxide is low. Mean-
while, considering the high availability of bulk lattice
oxygen on the surface of the iron-molybdenum catalyst,
formaldehyde and probably DMM may form on the
surface of the iron-molybdenum catalyst. The following
rate of reaction is suggested by the researchers:
r = krds K ads PCH OH N s
3 ers because it avoids the formation of water, a recent
where krds is the first-order rate constant (s-1), Kads is the
methanol adsorption equilibrium constant (kPa-1), P is
methanol partial pressure (kPa), and Ns is the surface
density of redox sites (μmol/m2).
Based on the studies done by many researchers,
many improvements and developments have occurred in
this field. However, there are still some issues that can be
addressed.
4.3 Latest advancements in formaldehyde
production
The recent studies done on formaldehyde production can
mainly be divided into two sections; some of these studies
investigated the effects of different modifications done
on industrial catalysts for partial oxidation of methanol
to produce formaldehyde. Bell’s group (Vining et al. 2011,
2012) investigated the effects of additional zirconium
dioxide and cerium dioxide on silica supported vanadium
oxide catalyst for methanol partial oxidation. They found
out that using these bilayered catalysts, the turnover fre-
quency increased by nearly two orders of magnitude for
methanol oxidation compared with monolayered cata-
lyst. They proposed that the addition of cerium and zir-
conium dioxide can affect the rate-limiting step in the
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mechanism of methanol partial oxidation, which is hydro-
gen abstraction from the V-OCH3 group. Other researchers
have studied other methods for formaldehyde production.
Some recent studies (Beznis et al. 2011, Polnišer et al. 2011,
Carlsson et al. 2012, Wang et al. 2012, Zhang et al. 2012a,b)
have targeted the methane reactivity and the selectivity
toward formaldehyde production in the process of direct
oxidation of methane to formaldehyde. Exposing the reac-
tants to nitrogen oxide using low residence time (Zhang
et al. 2012a,b), using periodic operating conditions (Carls-
son et al. 2012), and using copper-iron pyrophosphate as
the catalyst (Polnišer et al. 2011) were suggested. However,
simultaneous increase of methane conversion and formal-
dehyde selectivity remained unsolved. Lou et al. (2007a,b)
suggested using ethane instead of methane. They used a
mesoporous silica supported molybdenum oxide catalyst
to achieve 30% formaldehyde yield by oxidation of ethyl-
ene to formaldehyde at 836 K. Using a double-bed catalyst
for simultaneous dehydrogenation of ethane to ethylene
and oxidation of ethylene to formaldehyde, a maximum of
14% formaldehyde yield was achieved.
As anhydrous dehydrogenation of methanol to for-
maldehyde has been an interesting process for research-
(60)
study was dedicated to the theoretical investigation of this
process using a web-based application called “CatApp”
(Lausche et  al. 2012). Based on this study, the mecha-
nism of methanol dehydrogenation reaction and different
binding energies were investigated over different metal
surfaces. They claimed that on the surface of platinum,
palladium, and rhodium, there is a higher tendency to
dehydrogenate formaldehyde compared with desorption
of this chemical. This may lead to carbon monoxide for-
mation on the surface of these metals as indicated in a
study by Tolmacsov et al. (2009).
Although hydrogenation of carbon dioxide to for-
maldehyde was investigated before (Lunev et al. 2001), a
high yield of formaldehyde was never achieved. Recently,
Nakata et  al. (2014) succeeded to produce formaldehyde
by reduction of carbon dioxide in an electrochemical
procedure. A boron-doped diamond (BDD) electrode was
used for electrochemical process under ambient condi-
tions, and formic acid was produced as an intermedi-
ate. Relatively high faradaic efficiency (up to 74%) was
achieved using methanol, aqueous salt, or seawater as the
electrolyte. Other electrodes such as glassy carbon (GC),
tin, copper, silver, and tungsten were used for compari-
son. The highest faradaic efficiency (74%) for formalde-
hyde was achieved using BDD electrode, whereas formic
acid faradaic efficiency was 15%. Faradaic efficiency
for formaldehyde was about 20% using GC electrode.
 A.M. Bahmanpour et al.: Critical review and exergy analysis of formaldehyde production processes      19
No formaldehyde production was noticed using metal
electrodes.
Hydrogenation from carbon dioxide is not the only
method of producing formaldehyde from carbon dioxide.
Recently, in a study by Lambert’s group (Gómez-Ramírez
et  al. 2014), low-temperature formaldehyde production
was achieved by partial oxidation of ethane using carbon
dioxide as the oxygen source. The catalyst for this process
was vanadia/alumina, which was dispersed on barium
titanate. The catalyst was loaded on a dielectric barrier
discharge reactor. Catalyst was activated at near-ambient
temperature by plasma-excited carbon dioxide, which led
to the generation of an activated oxide surface. Through
the activated catalyst, oxy-dehydrogenation of ethane
took place to produce ethylene. Discharge-activated
carbon dioxide molecules reacted with the produced eth-
ylene molecules at this level to generate acetaldehyde,
which in turn converted to formaldehyde through oxida-
tive decomposition, and an 11.4% formaldehyde yield was
achieved through this process upon complete conversion
of ethane.
5 Conclusions
Formaldehyde is a highly valuable chemical in the global
economy. This paper presents comprehensive analysis of
the industrial and novel formaldehyde production pro-
cesses. Methanol synthesis followed by partial oxidation
into formaldehyde is still the leading technology after
more than a century; however, new catalysts and process
modifications have been made over the years to increase
conversion and selectivity of formaldehyde synthesis.
Based on our process simulation and exergy analysis, it
was shown that the overall exergy efficiency of formalde-
hyde production from natural gas is only 43.2%. Therefore,
there is significant room for improvement in this process
to achieve higher exergy efficiency. The mechanism of
methanol partial oxidation showed that the reaction pro-
ceeds via oxidation of gaseous methanol by adsorbed
oxygen or hydroxyl species on the catalyst surface to form
adsorbed methoxy species, which decomposes to form
formaldehyde depending upon the reaction temperature.
Pre-oxidation of copper or silver catalysts to form metal
oxides were found to be more active than metals as cata-
lysts for partial oxidation of methanol to formaldehyde.
However, since methoxy is stable at low temperatures, the
reaction is carried out at above 623.15 K, which is one of
the reasons of low exergy efficiency of this process. Dif-
ferent types of atomic oxygen species were found to be
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active in the formaldehyde production reactions when
silver catalyst was used. Mars-van Krevelen redox mecha-
nism was suggested for the formation of formaldehyde on
the surface of metal oxide catalysts by some researchers,
and the effects of the addition of the excess molybdenum
oxide in iron-molybdenum oxide catalysts were argued.
Many recent attempts at improving the formaldehyde syn-
thesis process have focused on developing new redox cat-
alysts to improve the methanol partial oxidation process.
Another approach to improve the low exergy efficiency of
formaldehyde production process in future studies might
be to eliminate the steam reforming process, which is a
major source of exergy loss. Direct methane partial oxida-
tion might be promising in this regard. However, so far,
this process has produced low formaldehyde yield (9%).
Other proposed methods for formaldehyde production
such as hydrogenation of carbon monoxide and carbon
dioxide and oxidation of ethylene hold much promise, but
extensive research is required in catalyst development for
these processes.
Nomenclature
Symbols
BASF Badische Anilin- und Soda-Fabrik
ci concentration of species i, mol/m3
e specific exergy, kJ/kmol
E total exergy, kW
Formox formaldehyde by oxidation
h specific enthalpy, kJ/kmol
ICI Imperial Chemical Industries
ki rate constants, 1/s
K equilibrium constant, 1/kPa
m mole flow, kmol/s
Ns surface density, μmol/m2
P partial pressure, kPa
p* vapor pressure, kPa
Q transferred heat, kJ/kmol
r heat of vaporization, kJ/kmol
s specific entropy, kJ/kmol·K
T temperature, K
W work, kJ/kmol
Xi mole fraction of species i in standard air
xi mole fraction of species i in a gas mixture
z compressibility factor
Subscripts
0 reference state
ads adsorption
ch chemical
20      A.M. Bahmanpour et al.: Critical review and exergy analysis of formaldehyde production processes
eff efficiency
in inlet
loss loss
out outlet
ox oxidized
ph physical
rds reduction
red reduced
th thermal
Greek letter
μ chemical potential, J/mol
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Graphical abstract
Ali Mohammad Bahmanpour,
Andrew Hoadley and Akshat
Tanksale
Critical review and exergy
analysis of formaldehyde
production processes
DOI 10.1515/revce-2014-0022
Rev Chem Eng 2014; xx(x): xxx–xxx
Authenticated | akshat.tanksale@monash.edu author's copy
Rev Chem Eng      2014 | Volume xx | Issue x
Review: The exergy analysis
of the formaldehyde produc-
tion process showed that the
highest exergy loss is in the
process of synthesis gas pro-
duction (25.0%), followed by
the methanol synthesis process
(21.7%), and then the formalin
synthesis process (10.1%).
Keywords: exergy analysis;
formaldehyde; kinetics and
mechanism; methanol ballast
process.
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