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Critical Review and Exergy Analysis of Formaldehyde Production Processes
Critical Review and Exergy Analysis of Formaldehyde Production Processes
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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).
100 113.5 33.3 182.0 Many different common uses and industrial applica-
200 114.5 33.5 205.1 tions can be named for formaldehyde because it is one
298.15 116.0 35.4 218.8 of the most important compounds in chemical manufac-
300 116.0 35.5 219.0
turing industry. Formaldehyde is a building block in the
400 117.7 39.3 229.7
500 119.3 43.8 239.0
synthesis of industrial resins such as melamine-formal-
600 120.8 48.2 247.4 dehyde, urea-formaldehyde, and phenol-formaldehyde.
800 123.3 56.0 262.3 Owing to the applications of formaldehyde derivatives in
1000 125.0 62.0 275.5 wood processing and furniture, carpeting and textiles,
2000 128.6 754.0 323.8 and construction, this chemical is considered as an impor-
3000 130.9 79.6 355.4
tant material in the global economy (Tang et al. 2009).
4000 134.6 81.1 378.5
5000 140.5 81.9 396.7 Formaldehyde can also be used directly to produce other
6000 148.6 82.3 411.7 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
0.9172 g/cm3 at 193.15 K. The vapor pressure of the lique- adducts (Walker 1967). Methylamine can also be produced
fied formaldehyde has been measured for a wide range of by the reaction of formaldehyde with amines.
temperatures by Spence and Wild (1935). Measured partial Owing to its high ability to polymerize during long-
pressures for the temperature range of 163.75 K to 250.85 K term storage, formaldehyde is commercially available as
are given in Table 3. an aqueous solution of 37–50 wt% concentration known
According to the measured values, the vapor pressure as formalin. Methanol is usually added (10–12 wt%) in the
of liquid formaldehyde can be determined using the fol- solution as the polymerization inhibitor.
lowing equation (Spence and Wild 1935): The formaldehyde production and consumption rates
have significantly increased during recent years. From
log10 p* = -1429 / T + 1.75 log T -0.0063T + 5.023 (1) 2003 to 2006, the formaldehyde consumption rate grew
at an average of 5.4% worldwide (Bizzari 2007). In 2007,
where p* is the formaldehyde vapor pressure in kPa and China, as the largest formaldehyde producer and con-
T is in K. sumer, produced 12 million metric tons of formaldehyde
(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
ICI
Methanol ballast
process
Degussa
Air deficient process
(silver contact
process)
Formaldehyde
production processes Lummus
Hiag/Lurgi
Formox process
Montecatini
Perstorp/Reichold
Combusted off-gas
Steam
Steam generator
Scheme A Water
Reactor
Steam
Cooler
Cooler
Water
Cooler
Air
Steam
Absorption
Column
Evaporator Heat exchanger
Methanol + Water
Formaldehyde
solution
Scheme B
The role of each reaction in this process can be deter- passes through a steam evaporator and enters the reactor.
mined by controlling the temperature of the reactor, Similar to the BASF process, a cooler is located directly
amount of water entering with methanol as the fresh after the reactor. Products are cooled down to 383.15 K
feed, and the methanol-to-oxygen ratio. Depending on before entering the absorption column. One of the key
the methanol-to-oxygen ratio, at high temperatures, controllers of the formaldehyde concentration in this
methanol may be dehydrogenated directly [eq. (2)]. The process is the amount of water added at the top of absorp-
effect of water content was studied in a research made by tion column. The product stream goes through an anion
Qian et al. (2003). It was claimed that methanol conver- exchange to minimize the formation of formic acid. The
sion and formaldehyde selectivity increase by addition of final product stream contains up to 55 wt% formaldehyde
water compared with the same case with no added water. and 0.5–1.5 wt% methanol. Methanol conversion is around
However, some aspects such as the concentration of the 98–99% in case of high selectivity and activity. The overall
final product are affected by the water content of the fresh plant yield can be between 88% and 91%.
feed. Therefore, an optimum ratio should be used. The Owing to the lower temperature and the higher sta-
water-to-methanol ratio of 2:3 or 0.67 has been suggested bility of the catalysts in the direct oxidation of methanol
in literature (Reuss et al. 2003). to formaldehyde, this method is attracting more attention
As mentioned before, both partial oxidation and direct compared with the silver-based catalytic process (Adkins
dehydrogenation of methanol take place when silver cata- and Peterson 1931) reported iron-molybdenum as a suit-
lysts are used. However, the selectivity of formaldehyde able catalyst for methanol oxidation to formaldehyde. It
can be limited considering the following reactions: was commercially used as one of the main catalysts in the
formaldehyde production process in the 1950s. In indus-
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
been used as the catalyst; this combination may have a
3 ˆ o = -674 kJ/mol,
CH 3OH + O2 →CO2 + 2H 2O ΔH r (5) longer lifetime and higher selectivity compared with pure
2
Fe2(MO4)3 catalyst. The effects of different Mo-to-Fe atomic
ratios in iron molybdate catalysts on catalyst activity and
ˆ o = -519 kJ/mol.
CH 2O + O2 →CO2 + H 2O ΔH (6)
r selectivity toward formaldehyde have been investigated in
literature and will be discussed in the Kinetics and Mecha-
Methyl formate and formic acid are the other main nism section. Ratios above 1.5:1 provide desirable results
by-products of this process and are generally removed as (Soares et al. 2001).
impurities by anion exchange.
Tail gas
Steam
Reactor
Water
Air Water
Cooler
Steam
Evaporator
Anion
Methanol exchange
unit
Basic
materials
Formalin
researchers (Sabatier and Mailhe 1910, Newton and Dodge CH 2O + O2 →CO2 + H 2O. (11)
1933, Sexton 1981, Su et al. 1992, Zaza et al. 1994); Sabatier
and Mailhe (1910) studied this process and declared that Aries (1960) described that elevated pressures in
this reaction is a reversible one. Later, Newton and Dodge methanol dehydrogenation prevent the formation of
(1933) derived the following equilibrium relation for this formic acid in the products stream. Passing methanol and
reversible reaction: air over a finely divided silver catalyst at 202.65–1013.25
kPa and 973.15–1073.15 K, the product gas mixture con-
⎛ 4600 ⎞ (8)
log10 K p = ⎜ -8.48⎟ , tained formaldehyde, traces of water, and unreacted
⎝ T ⎠
methanol, but no formic acid.
Punderson (1960) suggested a combination of silver,
where T (K) is the equilibrium temperature and Kp is the
copper, and silicon as a new methanol dehydrogenation
equilibrium constant for this reaction. However, there
catalyst. According to his patent, by combination of 98.8%
are three undesirable side reactions that might occur
silver, 1% copper, and 0.2% silicon, an active catalyst was
during this process. They can be controlled by control-
made, through which a 70% methanol conversion and 82%
ling the operating conditions. These reactions are pyro-
formaldehyde yield was possible. Using the combination
lytic decomposition of formaldehyde and oxidation
of 97.8% silver, 2% copper, and 0.2% silicon, even better
to formic acid, carbon monoxide, carbon dioxide, and
results were achieved; 71.5% methanol conversion at the
water:
end of the seventh cycle in the process was achieved using
CH 2O →CO + H 2 , (9) the latter catalyst while it was exposed to pure methanol
vapor in the temperature range of 873.15–973.15 K.
1
CH 2O + O2 → HCOOH, (10) Considering the difficulty of the separation of formal-
2
dehyde from the water produced by partial oxidation of
methanol to formaldehyde, methanol dehydrogenation support has been shown to improve methane conversion
has been studied as an alternative method using types of (Bobrova et al. 2007).
reactors such as inorganic membrane reactors (Deng and
Wu 1994) and slurry reactors (Shreiber and Roberts 2000)
using different catalysts. 3 Exergy analysis
Exergy analysis is a method for comparison of two different
2.2.2 Formaldehyde production from methane processes. Exergy is the maximum useful work possible
during a process that brings the system from its initial state
Direct oxidation of methane to form formaldehyde is into equilibrium (Christopher and Dimitrios 2012). Unlike
another method that has been extensively discussed (Blair energy, exergy can be destroyed in different systems.
and Wheeler 1923, Zhang et al. 2003, 2006, Polnišer et al. Exergy loss and exergy efficiency are two criteria that can
2011). This process has the obvious advantage of produc- be used to study the efficiency of a process. In this section,
ing formaldehyde in a single stage; however, low selectiv- methanol synthesis from natural gas is simulated using
ity and yield of formaldehyde are the main issues faced Aspen HYSYS™ software (Aspen technology, Burlington,
in this process (Bobrova et al. 2007). Many attempts have MA, USA). The kinetic expressions of the Aspen HYSYS
been made to increase the selectivity of formaldehyde, library are used for this part of the simulation. The pro-
and in some studies, approximately 80% selectivity was duced methanol is used in a methanol ballast process to
achieved (Zhang et al. 2011), but the issue of low methane produce formaldehyde. This process is simulated using
conversion ( < 2%) remained unresolved. In a recent study Aspen Plus™ software (Aspen technology, Burlington,
(Zhang et al. 2012a), NO2 has been introduced as a pro- MA, USA). In the formaldehyde synthesis reaction, a fixed
moter, and the process took place in a very short residence conversion based on the available data is used. The simu-
time. The highest methane conversion (24.3%) and yield lation data are used for exergy analysis. The methanol
(9%) was achieved in this study for this process so far. ballast process is chosen due to the availability of the nec-
Carbon monoxide is the main by-product of this process. essary data for simulation (Turton et al. 2009).
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 3.1 Simulation results
catalysts (Zhang et al. 2003, Launay et al. 2007, He et al.
2009). It is difficult to activate the relatively inert methane To do an exergy analysis on the formaldehyde production
on the surface of a catalyst to make formaldehyde, consid- process, methanol production from natural gas and, suc-
ering the weak chemisorption of methane on the catalyst cessively, formaldehyde production from the produced
surface (Michalkiewicz et al. 2008). Methane oxidation methanol are simulated. Data are obtained for the metha-
[eq. (12)] and formaldehyde oxidation [eq. (6)] occur in nol ballast process by simulating this section using the
this process dominantly: Aspen Plus software. The industrial data used for simula-
tion is obtained from the literature (Turton et al. 2009).
ˆ o = -319 kJ/mol.
CH 4 + O2 → HCHO+H 2O ΔH (12)
r Excess methanol is used instead of water to facilitate heat
transfer. Figure 4A shows the natural gas steam reform-
As can be seen, further oxidation of formaldehyde ing process. Figure 4B shows the simulated methanol
may lead to carbon dioxide production for which oxygen synthesis process in Aspen HYSYS software. It is split into
should be the limiting reactant, which significantly two parts because the simulation figure is too large to be
affects methane conversion. Further considerations are shown in one figure. Figure 4C shows the formaldehyde
that metal-oxygen bonds on the catalyst surface may lead production process simulated in Aspen Plus. Model vali-
to higher catalyst activity, but lower formaldehyde selec- dation is demonstrated in Table 4 based on a compari-
tivity (Fajardo et al. 2008). High temperature increases son between the simulation and the experimental results
the methane activation and the kinetics of the process, (Turton et al. 2009).
but also leads to complete oxidation of methane to carbon The results of these simulations are given in Tables 5
dioxide, instead of formaldehyde synthesis (Sexton et al. and 6.
1998). To prevent unfavorable oxidation of formaldehyde Separation of the unreacted methanol from water/
to carbon dioxide, a short residence time is required. One methanol/formaldehyde mixture is a complicated process
positive effect is that the high surface area of the catalyst to study. This mixture is non-ideal, and therefore, no
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
Table 4 Model validation for methanol ballast process simulation (Turton et al. 2009).
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)
3.2 Exergy analysis of the simulated chemical exergies. For a gas mixture, chemical exergy is
processes calculated as follows (Dincer and Rosen 2013):
ech = ∑ xi ech
i
+ RT0 ∑ xilnxi , (26)
Considering a process as an open system, physical and i i
chemical exergies are the two main types of exergies
that are involved in the calculation in each part. Physical where xi is the mole fraction of the component i in the gas
exergy can be calculated based on the physical properties mixture. In a control volume, one of the main sources of
of each flow stream according to the following equation exergy is heat transferred to or from the control volume.
(Christopher and Dimitrios 2012): The proportion of the transferred heat that can be con-
verted into work based on a Carnot cycle is defined as
e ph = ( h-h0 )-T0 ( s-s0 ), (21)
follows (Bejan 1997):
⎛ T⎞
where h, s, and T are enthalpy, entropy, and temperature, eth = Q ⎜ 1- 0 ⎟ (27)
respectively, and the subscript 0 refers to the standard ⎝ T⎠
condition (T = 298.15 K, P = 101.25 kPa). However, for a cold
where T is the temperature of the control volume where
gas stream, physical exergy can be calculated based on
the energy transfer is assumed to be at the same tem-
the following equation derived by Wang et al. (2005).
perature. The amount of work done on the system or by
⎡⎛ 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 exergy gain or loss. Therefore, the exergy loss and exergy
efficiency can be calculated as follows:
where r is the heat of vaporization and z is the compress- ⎛ ∑( e ph + ech + eth +W )-∑( e ph + ech + eth +W )⎞
Eloss = m ⎜⎝ ⎟⎠ (28)
ibility factor. Chemical exergy is the maximum amount of in out
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
of methanol and methanol dehydrogenation. Therefore, in favor of this reaction. At low temperatures, the low
these reactions will be investigated thermodynamically in equilibrium coefficient and the high positive Gibbs free
this section. The specifications of each reaction, including energy show that the reaction may not occur at ambient
enthalpy, entropy, Gibbs free energy change, and equi- conditions. In the temperature range of 1123.15–1173.15 K,
librium coefficients at different temperatures have been the reactions become fairly spontaneous. However, being
investigated using HSC Chemistry™ software (Outotec non-spontaneous does not mean that the reaction cannot
Oyj, Espoo, Finland). The results for the range of tempera- take place. As can be seen in Table 9, the methanol dehy-
ture of 273.15 to 1273.15 K for these reactions are given in drogenation reaction seems to be feasible only at very
Tables 8 and 9. high temperatures, but this reaction actually occurs at
As can be seen, the reaction is promising from the relatively low temperatures with the assistance of indus-
thermodynamics point of view. Enthalpy change does not trial catalysts.
change significantly with temperature. High equilibrium
coefficients and highly negative Gibbs free energy change
show high possibility of reaction. Negative Gibbs free 4.2 Kinetics of reactions and mechanism
energy change, which decreases with temperature, shows
that increasing temperature makes the reaction “more Regarding the kinetics and mechanism of methanol con-
spontaneous”. However, considering the reaction as an version to formaldehyde, the reactions will be discussed
exothermic one, temperature increase lowers the equilib- in different groups classified based on the catalysts used:
rium coefficient based on Le Chatelier’s principle. copper, silver, and metal oxides. Because in the classical
In this reaction, methanol is dehydrogenated on the process of formaldehyde production silver or copper cata-
surface of the catalyst. The temperature increase is clearly lysts have been used, first, the kinetics and mechanism
1
CH3OH(g)+ O2 ↔ CH2O(g)+ H2O(g)
2
CH3OH(g)↔CH2O(g)+H2(g)
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)
activity of silver for the decomposition of adsorbed meth- (2) Atomic oxygen species, referenced as Oβ, dissolves in
oxide to formaldehyde, and hence, formaldehyde is pro- silver bulk and does not participate in the oxidation reac-
duced at a lower substrate temperature, which increases tion directly. (3) Investigation of silver (111) at temperatures
the residence time of formaldehyde on the silver surface. around 900 K shows that atomic oxygen segregates from
A study by Francis et al. (1994) on methanol oxida- the bulk catalyst to the surface by interstitial diffusion to
tion over oxygenated copper surface confirmed the results form the atomic oxygen species referenced as Oγ. There is
achieved earlier (Leibsle et al. 1994) that the kinetics of a general agreement among the researchers that Oβ does
this reaction depends on initial oxygen exposure of the not participate in the oxidation reaction directly. However,
copper surface and the surface temperature. At low tem- there is a discussion about the effects of Oα and Oγ on
peratures (150–350 K), methanol reacts with adsorbed the mechanism of this reaction. Some researchers have
oxygen in a 2:1 ratio to generate the adsorbed methoxy claimed that Oγ is likely to be the active agent in methanol
species based on the following reaction: oxidative dehydrogenation because Oα desorbs at 600 K
and it cannot be the dominant species on the catalyst
2CH 3OH( g ) + O( a ) → 2CH 3O( a ) + H 2O( g ) (46)
surface for methanol oxidation at 900 K (Bao et al. 1993b).
Based on Wachs and Madix (1978a), Andreasen et al.
The formed methoxy is stable at this temperature range,
(2003) asserted that presence of Oα can justify the indus-
however, as the temperature increases the stability of the
trial formaldehyde synthesis process and Oγ is not neces-
formed methoxy decreases, and at medium temperatures
sarily involved and that Schlögl group’s conclusion about
(350–400 K), methoxy decomposes to form formalde-
the leading role of Oγ is only valid at ultrahigh vacuum in
hyde and hydrogen. Therefore, the following reaction is
which they have conducted their research. According to
achieved:
the study done by Waterhouse et al. (2004), the population
2CH 3OH( g ) + O( a ) → 2H 2CO( g ) + H 2( g ) + H 2O( g ) of each atomic oxygen species depends on the tempera-
(47)
ture and structure of the silver catalyst. They declared that
At high temperatures (above 500 K), the stoichiometry of Oα species is dominant at low temperatures, whereas at
the reaction changes and methanol reacts with adsorbed industrial operating conditions, Oγ plays the leading role
oxygen atom in a 1:1 ratio to form formaldehyde according and drives the process toward oxidative dehydrogenation
to the following reaction: reaction. Van Veen et al. (2002) used a temporal analysis
of products method and pulse experiment to investigate
CH 3OH( g ) + O( a ) → H 2CO( g ) + H 2O( g ) (48)
the mechanism of oxidative hydrogenation of methanol
on silver catalyst. Based on their findings, at temperatures
This mechanism is confirmed by Barnes et al. (1990) higher than 550 K, Oγ provides a highly selective oxidative
because of the lack of hydrogen production at tempera- hydrogenation reaction to generate formaldehyde where
tures below 320 K and above 470 K. The presence of at lower temperatures Oα plays an important role in non-
surface oxygen is believed to be critical in this process. It selective oxidation of methanol at high surface coverage.
is believed that pre-oxidizing is necessary to activate the However, according to their research, low coverage of Oα
surface of the catalyst. However, overexposure of the cata- may improve the selectivity significantly.
lyst to oxygen can poison the active sites and reduce the Some researchers have investigated the effects of
catalyst activity. Researchers proposed that as a dual-site different operating conditions on oxidation of methanol
combination is necessary for high reactivity, overloading and formaldehyde production using silver catalyst. Based
the catalyst with surface oxygen may disable the Cu0 sites on a study done by Cao and Gavriilidis (2005), as reactor
and consequently reduce the activity of the catalyst. temperature increases from 500 to 620 K, carbon dioxide
The effect of oxygen on the activation of silver catalyst production rate increases and formaldehyde selectivity
in the methanol oxidation reaction has been investigated decreases. This is in agreement with the results achieved
by many researchers. Based on the study done by Schlögl by Van Veen et al. (2002), as they indicated a strong role
et al. (Bao et al. 1993a,b, Nagy et al. 1998, 1999), three of Oα in carbon dioxide production and low selectivity
types of oxygen-silver interactions can be found: (1) Disso- toward formaldehyde, which is unlike the role of Oγ. As the
ciative chemisorption of molecular oxygen leads to atomic reactor temperature exceeds 620 K, formaldehyde selectiv-
oxygen species adsorbed on the surface of the silver (111) ity increases and carbon dioxide concentration decreases,
and silver (110). This species is referenced as Oα and it which prove the role of Oγ as indicated in the results by
participates in the methanol oxidation mechanism and Van Veen et al. (2002). The oxygen concentration in the
oxygen desorption proposed by Wachs and Madix (1978a). gas phase was another aspect that was investigated by
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
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)
is deposited as a surface monolayer, which improves the mechanism of methanol partial oxidation, which is hydro-
catalytic performance toward formaldehyde production. gen abstraction from the V-OCH3 group. Other researchers
Contrary to Soares et al. (2001), Wach’s group (Routray have studied other methods for formaldehyde production.
et al. 2010) found that stoichiometric Fe2(MoO4)3 (Mo/ Some recent studies (Beznis et al. 2011, Polnišer et al. 2011,
Fe = 1.5) has higher surface area compared with catalysts Carlsson et al. 2012, Wang et al. 2012, Zhang et al. 2012a,b)
with excess molybdenum oxide. Wach’s group (Routray have targeted the methane reactivity and the selectivity
et al. 2010) achieved highest selectivity toward formal- toward formaldehyde production in the process of direct
dehyde using the catalyst Mo/Fe = 2. However, the turno- oxidation of methane to formaldehyde. Exposing the reac-
ver frequency was higher when using the catalyst Mo/ tants to nitrogen oxide using low residence time (Zhang
Fe = 1.7. Based on the mechanism suggested for metha- et al. 2012a,b), using periodic operating conditions (Carls-
nol oxidation reaction over iron oxide and the one for son et al. 2012), and using copper-iron pyrophosphate as
iron-molybdenum oxide by Wachs’ group (Routray et al. the catalyst (Polnišer et al. 2011) were suggested. However,
2010), they have concluded that due to the dependence simultaneous increase of methane conversion and formal-
of the formaldehyde production pathway on the presence dehyde selectivity remained unsolved. Lou et al. (2007a,b)
of bulk lattice oxygen and considering the incapability suggested using ethane instead of methane. They used a
of iron oxide to supply bulk lattice oxygen, the chance of mesoporous silica supported molybdenum oxide catalyst
formation of formaldehyde on iron oxide is low. Mean- to achieve 30% formaldehyde yield by oxidation of ethyl-
while, considering the high availability of bulk lattice ene to formaldehyde at 836 K. Using a double-bed catalyst
oxygen on the surface of the iron-molybdenum catalyst, for simultaneous dehydrogenation of ethane to ethylene
formaldehyde and probably DMM may form on the and oxidation of ethylene to formaldehyde, a maximum of
surface of the iron-molybdenum catalyst. The following 14% formaldehyde yield was achieved.
rate of reaction is suggested by the researchers: As anhydrous dehydrogenation of methanol to for-
maldehyde has been an interesting process for research-
r = krds K ads PCH OH N s (60)
3 ers because it avoids the formation of water, a recent
study was dedicated to the theoretical investigation of this
where krds is the first-order rate constant (s-1), Kads is the process using a web-based application called “CatApp”
methanol adsorption equilibrium constant (kPa-1), P is (Lausche et al. 2012). Based on this study, the mecha-
methanol partial pressure (kPa), and Ns is the surface nism of methanol dehydrogenation reaction and different
density of redox sites (μmol/m2). binding energies were investigated over different metal
Based on the studies done by many researchers, surfaces. They claimed that on the surface of platinum,
many improvements and developments have occurred in palladium, and rhodium, there is a higher tendency to
this field. However, there are still some issues that can be dehydrogenate formaldehyde compared with desorption
addressed. 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).
4.3 Latest advancements in formaldehyde Although hydrogenation of carbon dioxide to for-
production maldehyde was investigated before (Lunev et al. 2001), a
high yield of formaldehyde was never achieved. Recently,
The recent studies done on formaldehyde production can Nakata et al. (2014) succeeded to produce formaldehyde
mainly be divided into two sections; some of these studies by reduction of carbon dioxide in an electrochemical
investigated the effects of different modifications done procedure. A boron-doped diamond (BDD) electrode was
on industrial catalysts for partial oxidation of methanol used for electrochemical process under ambient condi-
to produce formaldehyde. Bell’s group (Vining et al. 2011, tions, and formic acid was produced as an intermedi-
2012) investigated the effects of additional zirconium ate. Relatively high faradaic efficiency (up to 74%) was
dioxide and cerium dioxide on silica supported vanadium achieved using methanol, aqueous salt, or seawater as the
oxide catalyst for methanol partial oxidation. They found electrolyte. Other electrodes such as glassy carbon (GC),
out that using these bilayered catalysts, the turnover fre- tin, copper, silver, and tungsten were used for compari-
quency increased by nearly two orders of magnitude for son. The highest faradaic efficiency (74%) for formalde-
methanol oxidation compared with monolayered cata- hyde was achieved using BDD electrode, whereas formic
lyst. They proposed that the addition of cerium and zir- acid faradaic efficiency was 15%. Faradaic efficiency
conium dioxide can affect the rate-limiting step in the for formaldehyde was about 20% using GC electrode.
No formaldehyde production was noticed using metal active in the formaldehyde production reactions when
electrodes. silver catalyst was used. Mars-van Krevelen redox mecha-
Hydrogenation from carbon dioxide is not the only nism was suggested for the formation of formaldehyde on
method of producing formaldehyde from carbon dioxide. the surface of metal oxide catalysts by some researchers,
Recently, in a study by Lambert’s group (Gómez-Ramírez and the effects of the addition of the excess molybdenum
et al. 2014), low-temperature formaldehyde production oxide in iron-molybdenum oxide catalysts were argued.
was achieved by partial oxidation of ethane using carbon Many recent attempts at improving the formaldehyde syn-
dioxide as the oxygen source. The catalyst for this process thesis process have focused on developing new redox cat-
was vanadia/alumina, which was dispersed on barium alysts to improve the methanol partial oxidation process.
titanate. The catalyst was loaded on a dielectric barrier Another approach to improve the low exergy efficiency of
discharge reactor. Catalyst was activated at near-ambient formaldehyde production process in future studies might
temperature by plasma-excited carbon dioxide, which led be to eliminate the steam reforming process, which is a
to the generation of an activated oxide surface. Through major source of exergy loss. Direct methane partial oxida-
the activated catalyst, oxy-dehydrogenation of ethane tion might be promising in this regard. However, so far,
took place to produce ethylene. Discharge-activated this process has produced low formaldehyde yield (9%).
carbon dioxide molecules reacted with the produced eth- Other proposed methods for formaldehyde production
ylene molecules at this level to generate acetaldehyde, such as hydrogenation of carbon monoxide and carbon
which in turn converted to formaldehyde through oxida- dioxide and oxidation of ethylene hold much promise, but
tive decomposition, and an 11.4% formaldehyde yield was extensive research is required in catalyst development for
achieved through this process upon complete conversion these processes.
of ethane.
Nomenclature
5 Conclusions
Symbols
Formaldehyde is a highly valuable chemical in the global
BASF Badische Anilin- und Soda-Fabrik
economy. This paper presents comprehensive analysis of
ci concentration of species i, mol/m3
the industrial and novel formaldehyde production pro- e specific exergy, kJ/kmol
cesses. Methanol synthesis followed by partial oxidation E total exergy, kW
into formaldehyde is still the leading technology after Formox formaldehyde by oxidation
more than a century; however, new catalysts and process h specific enthalpy, kJ/kmol
ICI Imperial Chemical Industries
modifications have been made over the years to increase
ki rate constants, 1/s
conversion and selectivity of formaldehyde synthesis. K equilibrium constant, 1/kPa
Based on our process simulation and exergy analysis, it m mole flow, kmol/s
was shown that the overall exergy efficiency of formalde- Ns surface density, μmol/m2
hyde production from natural gas is only 43.2%. Therefore, P partial pressure, kPa
there is significant room for improvement in this process p* vapor pressure, kPa
Q transferred heat, kJ/kmol
to achieve higher exergy efficiency. The mechanism of
r heat of vaporization, kJ/kmol
methanol partial oxidation showed that the reaction pro- s specific entropy, kJ/kmol·K
ceeds via oxidation of gaseous methanol by adsorbed T temperature, K
oxygen or hydroxyl species on the catalyst surface to form W work, kJ/kmol
adsorbed methoxy species, which decomposes to form Xi mole fraction of species i in standard air
xi mole fraction of species i in a gas mixture
formaldehyde depending upon the reaction temperature.
z compressibility factor
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 Subscripts
reaction is carried out at above 623.15 K, which is one of 0 reference state
the reasons of low exergy efficiency of this process. Dif- ads adsorption
ferent types of atomic oxygen species were found to be ch chemical
eff efficiency Bizzari SN. CEH marketing research report: formaldehyde. Chemical
in inlet Industries Newsletter, 2007.
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Graphical abstract