ISSN: 2605-6895

Vol. 18, 2023, pp. 01~08

Reactor Design for Formaldehyde Production From Mehanol

Oxidation using Silver Catalyst

Alifa Listina Dewi, Risti Ragadhita, Asep Bayu Dani Nandiyanto*

Departement of Chemistry, Indonesia University of Education, Bandung, Indonesia

Article Info ABSTRACT

Article history:
Chemical reactor is the core of most chemical processes in
industry, where the raw materials react to form required
Received 18/01/2023 product. This study aims to modify and scale up design reactor
Accepted 01/07/2023 formaldehyde production is carried out with silver catalyst
process. Formaldehyde produced by dehydrogenation and
oxidation reaction. Mass balance calculations were also carried
Keyword:
out in this study. Calculations of the reactor design is carried
Formaldehyde out using the Microsoft Excel application with various
Mass balance parameters such as determination of material volume, reactor
Oxidation design, and determination of reactor dimensions. Based on the
Silver catalyst
calculation results, dimensions of reactor for reaction process
in formaldehyde production can be calculated. The reactant
volume is 4.73 m3. Dimensional calculation results obtained
for the diameter, height, thickness of the tank are 1.44 m, 6.16
m, and 0.074 m, respectively. In addition, the stirrer
dimensions such as stirrer diameter and stirrer distance from
the bottom of the tank are 0.94 m and 0.813 m, respectively.
The reactor is equipped with 1 stirrer with 6 blades.

Corresponding Author:
Adress Email: nandiyanto@upi.edu
Phone: +62 22 2000 579

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1. INTRODUCTION

The growth of the chemical industry is very rapid along with the increasing
development of technology. In this era of globalization, the industrial sector is an
alternative pathway that contributes to the economic growth of a country, one of which is
the chemical industry [1]. One of those industries needed is the formaldehyde chemical
industry. Formaldehyde is a compound of the same aldehyde group known as methanal and
is one of the chemicals organic compounds which are very important in the chemical
industry. There are lots of these chemicals used as raw material or auxiliary materials for a
variety of chemical industry [2]. Formaldehyde is a compound that belongs to the aldehyde
group with the chemical formula CH2O known as methanal and is one of the chemicals
organic compounds which are very important in the chemical industry. There are lots of
these chemicals used as raw materials or auxiliary materials for a variety of chemical
industries [2,3].
Formaldehyde is used in manufacture melamine formaldehyde, urea formaldehyde,
phenol formaldehyde, tryoxane. And is also used in the manufacture of chemicals among
others synthesis of 1,4 butadienol, trimethylol propane and neophentyl glycol used in the
manufacture of polyester plastic products, synthetic lubricating oil. In addition,
formaldehyde is used directly, but in small quantities, for example as a preservative in
research materials and a disinfectant in a hospital room [4]. The many uses and roles of
formaldehyde in the production of various other chemical compounds has resulted in an
increase in the need for formaldehyde as a raw material in the production of these
compounds.
Several natural sources of formaldehyde are known cause is a biogenic compound [5].
During the physiological activities of some plant formaldehyde is released into the
atmosphere [6]. Based on the results of studies that have been conducted, it shows that
formaldehyde is produced by conifers [7]. In addition, other researchers have been able to
detect formaldehyde in or on forests [8-9]. Besides sourced from nature, the synthesis of
formaldehyde is also widely known. There are several types of synthesis or production of
formaldehyde, (i) complete conversion of methanol, is a process of dehydrogenation and
oxidation with crystalline silver catalyst, (ii) silver catalyst process, almost the same as the
previous process but the methanol conversion value is around 77-87% and the yield is 91-
92% mol, and (iii) formox process, is the process production of formaldehyde by methanol
and using iron oxide as a catalyst [10]. Based on these three process types, the silver-based
catalytic process has a compact plant size because the amount of air required is partially
reduced compared to the metal oxide process. It appears that silver-based catalyst
processes are more suitable for small-scale production due to their compact size and lower
utility costs [11].
Chemical reactor is the most of chemical processes in industry, where the raw
materials react to form required product. Therefore, this study aims to modify and scale up
design reactor formaldehyde production is carried out with silver catalyst process. Reactor
design approaches often do not allow designing entirely innovative reactors and
considering the impact of uncertainties during the design procedure. Thus, it can be useful
and used as a reference in designing the process of working mechanisms in an industry.

2. RESEARCH METHOD
2.1. Production of formaldehyde
Dehydrogenation and oxidation of formaldehyde production with silver catalyst
process which modified the scale of studies have been carried out [1]. This study explained
that the reaction is mixing in reactor. In the liquid phase, generally what is mixed is a
nonvolatile reactant. This is characteristic of hydrogenation and oxidation reactions.
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However, in this study CH3OH is a volatile reactant in a liquid phase which vaporized in to
gas. Then, passed through the reactor containing silver crystal.
Silver catalyst is used because it is cheap and easy to regenerate. In this reactor
methanol oxidation reaction occurs to formaldehyde. Hydrogenation and oxidation reaction
are exothermic operating conditions and taking place at a temperature of 600-650˚C. In this
process purified air is reacted with methanol in a catalytic reactor. The product is rapidly
cooled by cooling dowterm, then flowed into the absorber tower where methanol, water
and formaldehyde condense at the bottom of the tower. To purify the product as desired,
purification is carried out with a distillation process produce formaldehyde. Theoretically,
the reactor and the rest of the equipment could be made of steel carbon, to protect the silver
catalyst sensitive to metal contamination [10].

2.2. Mathematical design of reactor

The mathematical design form of manual calculation of the reactor is carried out
using the Microsoft Excel application with various parameters according to the given
formula (Table 1).
Table 1. Reactor design parameter calculation
No Parameter Equation Eq
1 Mass balance FA = FA0 – FA0 . X (1)
in term of
conversion
2 Total volume Total volume = reactant volume + free space (2)
in reactor
3 Total volume (3)
vessel

4 Liquid volume Vls = V liquid – V tutup bawah (4)

in cylinder
V tutup bawah =
(Vls) (5)
5 Liquid height Lls = (6)
in cylinder
(Lls)
6 Pressure of Pi = Poperation + Phydrostatic (7)
design (Pi)
7 Cylinder ts = (8)
thickness (ts)
8 Head thickness tha = (9)
(tha)
9 Bottom thb = (10)
thickness (thb)
10 Height of hb = (11)
bottom cap
(hb)
11 Height of h = (tha + height of cylinder + thb) + sf (12)
reactor

3. RESULTS AND ANALYSIS

3.1. Main reaction
This main reaction is shown in Figure 2, showing that the reaction consisting of an
alcohol in the form of methanol reacting with O2 in the presence of an Ag catalyst will
produce formaldehyde. Formaldehyde is produced in 81.9% yield (4). CH2O and CO2 were
the only carbon containing products, and both may be claimed as primary products along

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with H2. It also proves that CO is formed by homogenous decomposition of CH2O and
should not be considered a main precursor to CO2, as assumed in several reaction
mechanisms [12]. The following is the reaction that occurs in the reactor:

Figure 1. Chemical reaction of formation formaldehyde

3.2. Thermodynamics Overview

The laws of thermodynamics apply to all energu conversion system and control
interactions of everything regardless of scale [13]. A thermodynamic overview is used to
determine whether the reaction is endothermic or exothermic and to determine the
direction of the reaction (reversible and irreversible). To determine whether the reaction, it
is necessary to prove it by using the heat of reaction (∆H˚f) which can be determined by
the equation:
H˚f reaction = ∑ H˚f product - H˚f reactant
Price H˚f for each component is shown in Table 2.

Table 2. H˚f values for some components

Component H˚f (kJ/mol)
CH3OH -238.4
O2 0
N2 0
CH2O -115.9
H2O -285.83
CO -110.62
If H˚f reaction = - (negative), then the reaction is exothermic
If H˚f reaction = + (positive), then the reaction is endothermic

Based on the reaction in Figure 1, get H˚f reaction as follows:

H˚f reaction = ∑ H˚f product - H˚f reactant
= -28728.62 – (-16155.18)
= -12573.437 kJ/mol
From the value of H˚f the reaction obtained from the calculation results is negative,
then reaction in the reactor is exothermic and occurs at high temperatures of 600-650°C in
atmospheric pressure [1]. In the reactor is installed with a stirrer which functions to mix
each reactant component. The raw materials involve CH3OH and O2 enter the reactor are in
appropriate with the operating conditions. Raw materials can react immediately, when it
enters the reactor. The reaction took place with a residence time of 1 hour and the resulting
conversion of reaction >95%.

3.3. Effect of heat on reaction rate and equilibrium shift

The equilibrium reactor performance analysis based thermodynamic calculations. The
results define the composition, pressure, and temperature for maxium conversion of the
product [14]. The effect of the initial temperature of the reactor will affect the reaction rate
and the shift in equilibrium. Theoretically, the higher the initial temperature of the reactor,
the temperature of the liquid reaction in the reactor will increase. All formaldehyde
prepared by an exothermic reaction at hight temperature and atmospheric pressure. With
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precise temperature control, methanol conversion greater than 95% can be maintained. The
resulting by-product is carbon monoxide and dimethyl ether, and small amounts of carbon
dioxide and formic acid. When both are combined, higher the reactor temperature causes
the higher the temperature absorbed by the heat exchanger.
Steady-state will be achieved immediately when the initial temperature of the reactor
is higher. This is related to the specification of the reaction rate in the reactor. The higher
the temperature, the faster the reaction rate towards equilibrium, according to the
Arrhenius theory. However, in the oxidation process, the operating conditions and
conversion data are known, so they are chosen with consideration of lower operating
temperatures, safety, and simpler processes [15].

3.4. Reaction product optimization

Various types of calculations such as determination of volumetric velocity,
determination of material volume, reactor design, and determination of reactor dimensions
are carried out as an effort to optimize reaction products. To optimization of reaction
product, there are several assumtion, including:
i) Raw materials used for formaldehyde production are CH3OH, N2, O2, H2O and
silver catalyst
ii) Formaldehyde production process follows Figure 2.
iii) Formaldehyde production is calculated based on the mass balance (Tabel 3-8).
iv) The composition of CH3OH is 72.85%, 21.34% N2, 5.67% O2, dan 0.12% water
v) The composition of the silver catalyst is 100%
vi) The basis for calculations using a mass balance is 8853 kg for mass input.
vii) Reaction process occurs in reactor tank
viii) Contruction material is stainless steel
ix) Operating condition temperature is 600-650°C
x) Retention time is 1 hour
xi) Pressure is 1.3 atm
xii) Conversion from methanol to formaldehyde is 95% before separation process.
xiii) Flowrate methanol is 6449.7 kg/hour
xiv) Moles of methanol are calculated by multiplying the flow rate of methanol
and the molecular weight of the methanol. So, the moles of methanol is 201.6
kmol/hour

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Figure 2. Reactor for formaldehyde production (F1-F6 is the feed flow rate).

Based on Figure 3, the results of the mass balance calculation in the design of
formaldehyde production from methanol are presented in Table 3-8.

Table 3. Mass balance reactor

No Component Input Component Output
Massa Mol Massa Mol
(kg/hour) (mol/hour) (kg/hour) (mol/hour)
1 O2 502.5 15.6 O2 8.1 0.3
2 N2 1890 67.5 N2 1890 22.5
CH2O 4379.7 196.2
3 CH3OH 6449.7 201.6 CH3OH 103.2 3.21
4 H2O 10.8 0.6 H2O 2416.2 201
CO 55.5 2.1
Total 8853 285.3 8852.7 425.31

Table 4. Mass balance in mixer tank

No Component Input Component Output
Massa Mol Massa Mol
(kg/hour) (kmol/hour) (kg) (kmol/hour)
1 O2 502.5 15.6 O2 502.5 15.6
2 N2 1890 67.5 N2 1890 67.5

Table 5. Mass balance in F4

No Component Massa Mol
(kg/hour) (kmol/hour)
1 CH3OH 6449.7 201.6
2 H2O 10.8 0.6

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Table 6. Reactor inlet feed (flow rate F3 and F4)

F3 F4
No Component Massa Mol Massa Mol
(kg/hour) (kmol/hour) (kg/hour) (kmol/hour)
1 O2 502.5 15.6
2 N2 1890 67.5
3 CH3OH 6449.7 201.6
4 H2O 10.8 0.6

Table 7. Mass balance in F5 (out of the reactor) with 95% conversion

No Component Massa Mol (kmol/hour)
(kg/hour)
1 CH2O 4379.7 196.2

Table 8. Mass balance in F6 (waste)

No Component Massa Mol
(kg/hour) (kmol/hour)
1 CH3OH 103.2 3.21
2 N2 1890 22.5
3 O2 8.1 0.3
4 H2O 2416.2 201
5 CO 55.5 2.1

Based on the mass balance calculation, the reactor specifications that must be met for
biodiesel production are obtained in this case. The reactor specifications are shown in
Table 9
Table 9. Reactor specification
No Parameters Value
1 Reactant Volume (m3) 4.73
2 Reactor Volume (m3) 5.92
3 Tank Diameter (m) 1.44
4 Tank Height (m) 6.16
5 Liquid Hydrostatic Pressure (atm) 1.06
6 Design Hydrostatic Pressure (atm) 1.3
7 Tank Thickness (m) 0.074
8 Outer Diameter (m) 1.45
9 Head Thickness (m) 0.073
10 Head Height (m) 0.24
11 Stirrer Diameter (m) 0.94
12 Liquid Height in Stirring (m) 3.8
13 Stirrer Distance from Tank Bottom (m) 0.813
14 Number of Stirrer (pcs) 1
15 Number of Blade (pcs) 6

4. CONCLUSION
Reactor design approaches often do not allow designing entirely innovative reactors
and considering the impact of uncertainties during the design procedure. Based on the

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calculation results, dimensions of reactor for reaction process in formaldehyde production

can be calculated. Dimensional calculation results obtained for the diameter, height,
thickness of the tank are 1.44 m, 6.16 m, and 0.074 m, respectively. In addition, the stirrer
dimensions such as stirrer diameter and stirrer distance from the bottom of the tank are
0.94 m and 0.813 m, respectively. The reactor is equipped with 1 stirrer with 6 blades.

REFERENCES
1. Alan, Ega Erica, and Wahyu Hadi Wijaya. Pabrik Formaldehid dari Methanol dengan Proses Silver
Catalyst. Diss. Institut Teknologi Sepuluh Nopember. 2017.
2. Sulistya
3. Ajidannor, Ajidannor, and Hairullah Hairullah. Prarancangan Pabrik Formaldehid dari Metanol dan
Udara melalui Proses Oksidasi menggunakan Katalis Iron Molybdenum Oxide dengan Kapasitas 50.000
Ton/Tahun. Jurnal Tugas Akhir Teknik Kimia 2.2. 2019: 13-18.
4. Ketta, Mc. Encyclopedia of Chemical Processing and Design. Marcel Dekker., Inc. New York. 1983.
5. Koppmann, R. (Ed.). Volatile organic compounds in the atmosphere. Wiley-Blackwell. 2008.
6. Seco, R., Peñuelas, J., & Filella, I. Formaldehyde emission and uptake by Mediterranean trees Quercus
and Pinus halepensis. Atmospheric Environment. 2008: 42(34), 7907-7914.
7. Müller, K., et al. Biogenic carbonyl compounds within and above a coniferous forest in Germany.
Atmospheric Environment. 2006: 40, 81-91.
8. Smidt, S., Bauer, H., Pogodina, O., & Puxbaum, H. Concentrations of ethene and formaldehyde at a
valley and a mountain top site in the Austrian Alps. Atmospheric Environment. 2005: 39(22), 4087-
4091
9. Solberg, S., Dye, C., Walker, S. E., & Simpson, D. Long-term measurements and model calculations of
formaldehyde at rural European monitoring sites. Atmospheric Environment. 2001: 35(2), 195-207.
10. Kirk, R.E. dan Othmer, D.F. Encyclopedia of Chemical Engineering Technology 1. New York: John
Wiley and Sons Inc. 1967.
11. Shakeel, K., Javaid, M., Muazzam, Y., Naqvi, S. R., Taqvi, S. A. A., Uddin, F & Niazi, M. B. K.
Performance comparison of industrially produced formaldehyde using two different
catalysts. Processes. 2020: 8(5), 571.
12. Lervold, Stine, et al. Partial oxidation of methanol to formaldehyde in an annular reactor. Chemical
Engineering Journal. 2021: 130141.
13. Ragheb, Magdi. Nuclear reactor concepts and thermodynamic cycles. NPRE 402 Course Notes. 2014.
14. Conejo, A. N., and G. P. Martins. Equilibrium reactor performance analysis for production of iron
carbide. Ironmaking & steelmaking. 1999: 111-116.
15. Misran, E. Simulasi Dua Dimensi Reaksi Oksidasi Metanol menjadi Formaldehida pada Reaktor
Unggun Tetap. 2001.

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