INTEGRATED DESIGN PROJECT

JANUARY 2019 SEMESTER

CDB 2013 SEPARATION PROCESS I

CDB 2043 REACTION ENGINEERING

PREPARED BY: GROUP B4

ONG WEI HANG 24819

HATEEM BIN FEROZE 25178
NUR FAZREEN ADLENA BINTI RAHMAN 25383
MUHAMMAD ANWAR BIN HAIZAL 25202
HAMSHA VATHANA RAJENDRAN 17009523

PREPARED FOR:

DR KHAIRIRAIHANNA BT JOHARI
DR LAM MAN KEE
DR MUHAMMAD AYOUB
DR AQSHA AQSHA
 TABLE OF CONTENTS

No. Content Page

1. Executive Summary 2-3

2. Chapter 1: Introduction 4-7
3. Chapter 2: Process Flow Diagram and Simulation 8-14
4. Chapter 3: Separation Process I 15-18
5. Chapter 4: Reaction Engineering 19-26
6. Chapter 5: Conclusion 27
7. Chapter 6: References 28-29
8. Appendix 30-33

1
 Executive Summary

The Integrated Design Project for the Chemical Engineering students in the January 2019
semester integrates the knowledge gained and the application of the knowledge from the two
courses undertaken during this semester that is: Separation Process I and Reaction Engineering.
The task of this project is to design a process plant to produce 37% formalin from methanol.
Students are required to design the process flow diagram, calculate the mass balance, run
simulation on HYSYS and finally design a catalytic reactor system with suitable calculations,
justifications and assumptions for the Reaction Engineering part of this project whereas for the
Separation Process I part, the number of stages of one separation unit must be calculated and
determined and compared with the simulated results.

According to Amin, Islam, Imtiaz, Saeed and Unaiza (n.d.), formaldehyde is produced from
the exothermic oxidation and endothermic hydrogenation of methanol. There are two main
routes for formaldehyde production which are oxidation-dehydrogenation process using a
silver catalyst which involves both the complete or incomplete conversion of methanol; and
also the direct oxidation of methanol to formaldehyde using metal oxide catalysts which is
being carried out in this Integrated Design Project. In the oxidation-dehydrogenation route,
vaporized methanol with air is passed over a thin bed of silver-crystal catalyst at about 650ºC.
Formaldehyde is then formed by the dehydrogenation of methanol. The other route which is
the focus route involves the oxidation of methanol over a catalyst of molybdenum and iron at
350ºC. The yield from the reaction is 88 to 92 percent with conversion of 99 percent. The
catalyst is easily poisoned so stainless-steel equipment must be used to protect the catalyst from
metal contamination. Another method of producing formaldehyde is through the oxidation of
hydrocarbon gases. An increase in the amount produced of formaldehyde is expected in this
process. However, the hydrocarbon formaldehyde is usually obtained as dilute solution which
is not economically concentrated.

The metal oxide catalyst reaction process is also known as the FORMOX process. FORMOX
is a registered trademark owned by Johnson Matthew and is an abbreviation for Formaldehyde
by Oxidation. According to Sanoob, Al-Sulami, Al-Shehri and Al-Rasheedi (2012), the first

2
commercial plant for the production of formaldehyde using the iron-molybdenum oxide
catalyst was put into action in 1952. Unlike the silver based catalyst process, the iron-
molybdenum oxide catalyst makes formaldehyde from the exothermic reaction entirely. The
advantage of this process compared to the silver based catalyst is the absence of the distillation
column to separate unreacted methanol and formaldehyde product after the reaction in the
reactor. It also has a life span of 12 to 18 months, which is larger than the sliver catalyst.
However, the disadvantage of this process design is the need for significantly large equipment
to accommodate the increased flow of gases (3 times larger) compared to the original silver
catalyst process design. This increase in equipment sizing obviously increases the construction
cost of the reactor making it less feasible to be used.

The reactions that are undergone in the reactor for the FORMOX process are as follows:

CH3OH + ½ O2 ➔ HCHO + H2O

HCHO + ½ O2 ➔ CO + H2O

3
 Chapter 1: Introduction

1.1 Introduction about formaldehyde and formalin

Formaldehyde plays a major role in the synthesis of many important compounds which causes
its worldwide to grow day by day. Formaldehyde is a substance that is readily soluble in water
and it has many uses in the industrial applications. Formaldehyde is a simple chemical
compound used in certain sectors such as the building and construction, health care
applications, food additives and ingredients and others. Growth in formaldehyde consumption
is generally correlated with growth in the construction industry. The chemical formula of
formaldehyde is CH2O with the molecular weight of 30.026 g/mol. Formaldehyde has high
solubility with water and when it is dissolved in water, it forms a hydrate called formalin.
Formalin composes of 37% of formaldehyde in aqueous solution. A concentration of 37 wt %
formaldehyde is used as a standard for pricing or production data.

Just like formaldehyde, formalin serves many purposes in industries too like in agricultural,
food production and automobile sectors. Besides, formalin is used to make fertilizers, drugs,
dye, antiseptic perfume and rubber chemicals. The demand for formalin has increased due to
its high application in many sectors and thus it has entered in the economical market. Countries
like India and China have reported and expected to have the highest growth in formalin market.
Regions like North America and Europe also have expected to have growth spurt due to high
demand in drug and dye industries.

1.2 Market analysis of formalin

Based on the statistic reported by IHS Markit in 2017, the single largest market for high
consumption of formaldehyde is conquered by China accounting for 47% of world
consumption in 2017. Not only is China the greatest consumers but China continues to add
capacity for formaldehyde, as the largest producer globally. Moreover, demand for 37% of
formaldehyde which is formalin has been forecasted to grow moderately in United States.

4
 Figure 1.1: Chart of World Consumption of Formaldehyde in 2017

One of the most prominent companies when it comes to designing and constructing
formaldehyde production plant is Dynea AS. Dynea is a well known company the chemistry
and chemical plants construction field. Dynea has more than 60 years of experience in process
development, design and operation of both synthetic resin production, formaldehyde silver and
metal-oxide plants. Dynea have designed, constructed and started up more than 40
formaldehyde plants worldwide.

Figure 1.2: Locations of Formaldehyde Production Plants by Dynea

5
 Figure 1.3: Global Methanol Derivative Chart

It can be seen from the figure above based on a research by Dynea on the forecast of
formaldehyde production that most of the methanol is used for the production of formaldehyde.
This shows that globally, formaldehyde plays an important role in various industries and will
be a key chemical as it continues the dominate the market economically.

Generally, in Malaysia, the consumption of formaldehyde mainly used as the preservative in

hair product, skin product, eye products and aslo in nail treatment. According to SAIR, both
locally-manufactured formalin which are the laboratory-grade and industrial grade are
inexpensive. The current cost of laboratory-grade formalin is reported to be about $3/L
meanwhile the industrial grade formalin is available at $16.00/25 kg/drum. Statistics of
Malaysia trade of formaldehyde from year 2001 to 2017 is shown in the picture below.

Figure 1.4: Malaysia trade of formaldehyde from 2001 to 2017

6
1.3 General block flow diagram of formalin production

P-100: Pump
C-100: Compressor
E-100: Heater
E-101: Heater
MIX-100: Mixer
PFR-100: PFR Reactor
VLV-100: Valve
T-100: Absorber
MIX-101: Mixer

7
 Chapter 2: Process Flow Diagram and Simulation

2.1 Process flow diagram

Process Flow Diagram Description

1. P-100- Methanol Pump

2. C-100 -Air Compressor
3. MIX-100- Mixer
4. E-100 – Heater
5. R-101 – PBR Reactor
6. E-101- Cooler
7. VLV-100 – Gate Valve
8. T-100 – Absorption Column

Figure 2.1: Process Flow Diagram developed in Microsoft Visio 2010

8
2.2 Mass balance calculations

Basis: 10,000,000 kg per annum of formalin (37 % formaldehyde) and 3, 700, 000 kg per
annum formaldehyde gas and 300 working days and one day with 24 working hours.

Formaldehyde produced per annum = 0.37 x 10, 000,000 kg

= 3, 700, 000 kg per annum
Thus, formalin produced per hr = (10, 000,000 kg/yr) x (1 yr/300 days) x (1 day/24 hr)
= 1388.889 kg/hr
And formaldehyde produced per hr = (3, 700, 000 kg/yr) x (1 yr/300 days) x (1 day/24 hr)
= 513.889 kg/hr

MASS BALANCE FOR R-101

The reactions that are undergone in the reactor are as follows:

CH3OH + ½ O2 ➔ HCHO + H2O ---------- (1)

HCHO + ½ O2 ➔ CO + H2O ---------- (2)

Mol wt. of methanol = 32.04 kg/kmol

Mol wt. of formaldehyde = 30.026 kg/kmol
Mol wt. of water = 18.02 kg/kmol
Mol wt. of carbon monoxide = 28.01 kg/kmol
Mol wt. of nitrogen = 28.02 kg/kmol
Mol wt. of oxygen = 32 kg/kmol

Based on specific references (refer References section), the following ASSUMPTIONS were
made:

• Conversion of first reaction = 99 %

• Yield = 90 %
• Composition of air = 0.21 mol% O2 and 0.79 mol% N2
Formaldehyde produced = (513.889 kg/hr) / (30.026 kg/kmol)
= 17.115 kmol/hr

9
Assume ‘y’ to be the amount of formaldehyde used in the second reaction:

𝑓𝑜𝑟𝑚𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒 𝑓𝑜𝑟𝑚𝑒𝑑 𝑖𝑛 𝑓𝑖𝑟𝑠𝑡 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛

𝑌𝑖𝑒𝑙𝑑 % =
𝑓𝑜𝑟𝑚𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒 𝑓𝑜𝑟𝑚𝑒𝑑 𝑖𝑛 𝑓𝑖𝑟𝑠𝑡 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 + 𝑓𝑜𝑟𝑚𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒 𝑢𝑠𝑒𝑑 𝑖𝑛 𝑠𝑒𝑐𝑜𝑛𝑑 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛

0.90 = 17.115 / (17.115 + y)

y = 1.901 kmol/hr ➔ amount of formaldehyde used in second reaction

Total formaldehyde produced in first reaction = 17.115 + 1.901 = 19.016 kmol/hr.

According to stoichiometry of reaction and the conversion as assumed earlier to be 99 %,

The amount of methanol fed is = 19.016 / 0.99

= 19.208 kmol/ hr
Therefore, the amount of unreacted methanol = 19.208 – 19.016
= 0.192 kmol/hr

Excess air is used.

Air = 85 kmol/hr

Therefore, oxygen present in the stream = 0.21 x 85 kmol/hr

= 17.850 kmol/hr
And nitrogen present in the stream = 0.79 x 85 kmol/hr
= 67.150 kmol/hr

Oxygen

According to the stoichiometry of reaction 1, one mole of methanol reacts with 0.5 mole of
oxygen.

Total formaldehyde produced in first reaction

Therefore, oxygen reacted in first reaction = 2

= 19.016 / 2
= 9.508 kmol/hr
According to stoichiometry of reaction 2, one mole of formaldehyde reacts with 0.5 mole of
oxygen.

10
 Total formaldehyde used in seccond reaction
Therefore, oxygen reacted in second reaction =
2

= 1.901 / 2
= 0.951 kmol/ hr
Therefore total oxygen used in both reactions = oxygen reacted in first reaction +
oxygen reacted in second reaction
= 9.508 + 0.951
= 10.459 kmol/hr
Hence, the total amount of unreacted oxygen = 17.850 – 10.459
= 12.403 kmol/hr
Nitrogen

Nitrogen is not involved in the reaction.

Hence, the total amount of unreacted nitrogen = 67.15 kmol/hr

Water

Based on the stoichiometry of both the reactions,

The amount of water formed in both the reactions = methanol reacted in first reaction
+ formaldehyde reacted in second
reaction
= 19.016 + 1.901
= 20.917 kmol/hr
Carbon Monoxide

Amount of CO formed = amount of formaldehyde used in second reaction

= 1.901 kmol/hr

S6 S7/S9 S10 S11 S12

(kmol/hr) (kmol/hr) (kmol/hr) (kmol/hr) (kmol/hr)
CH3OH 19.208 0.192 0 0 0.192
O2 17.850 7.391 0 0 7.391
N2 67.150 67.150 0 0 67.150
HCHO 0 17.115 0 17.115 0
CO 0 1.901 0 0 1.901
H2O 0 20.917 27.640 48.557 0

Table 2.1: Flowrates of Streams based on Mass Balance Calculations

11
2.3 Simulation of the Process Flow using Aspen HYSYS

Stream Number 1 2 3 4 5 6
Overall
Temperature(ºc) 25 25 25.07 142.2 28.14 178.1
Pressure(kPa) 100 100 250 250 250 200
Vapor Frac 0 1 0 1 0.8864 1
Entalphy(kJ/mole) -2.394e5 0.00 -2.394e5 3458 -4.131e+4 -3.199e4
Std Liq Vol 0.7735 2.835 0.7735 2.835 3.608 3.608
(m3/hr)

Mass Flow (kg/hr)

Methanol 615.5 0 615.5 0 615.5 615.5
Oxygen 0 571.07 0 571.07 571.07 571.43
Nitrogen 0 1881.29 0 1881.29 1881.29 1881.29
Water 0 0 0 0 0 0
Formaldehyde 0 0 0 0 0 0
Carbon Monoxide 0 0 0 0 0 0
Total Flow (kg/hr) 615.5 2452.36 615.5 2452.36 3068 3068

Stream Number 7 8 9 10 11 12
Overall
Temperature(ºc) 300 170 170 27 72.48 53.86
Pressure(kPa) 150 150 120 100 100 50
Vapor Frac 1 1 1 0 0 1
Entalphy(kJ/mole) -5.126e4 -5.559e4 -5.559e4 -2.847e5 -2.45e5 -7.081e6
Std Liq Vol 3.678 3.678 3.678 1.19 1.71 3.158
(m3/hr)

Mass Flow (kg/hr)

Methanol 1.23 1.23 1.23 0 0 1.23
Oxygen 264.46 264.46 264.46 0 0 264.46
Nitrogen 1881.29 1881.29 1881.29 0 0.05 1881.24
Water 345.44 345.44 345.44 1182 954.04 573.4
Formaldehyde 575.56 575.56 575.56 0 562.96 12.60
Carbon Monoxide 0.029 0.029 0.029 0 0 0.029
Total Flow (kg/hr) 3068. 3068. 3068. 1182 1517 2733
Table 2.2 and 2.3 :Mass and Energy Balance from Aspen HYSYS Simulation

12
2.4 Process flow and equipment description.

The simulation process was carried out in Aspen Hysys V10. At first we added the
basic components which is methanol , oxygen , formaldehyde ,water and carbon monoxide.

Figure 2.2: Chemical components involve in formalin production.

Then we specify the fluid package as NRTL(Non-Random-Two -Liquid). According to

Renon and Prausnitz, 1968, the NRTL model can handle any combination of polar and non-
polar compounds, up to very strong non-ideal components. Parameters should be fitted in the
temperature, pressure, and composition range of operation.

Figure 2.3: Properties method selection in Aspen Plus V10.0.

13
 Figure 2.4: Flowsheet diagram of simulated process in Aspen Hysys V10.0

As simulation started, air was sucked in by a compressor at temperature of 25ºC and

pressure 200kPA with mass flowrate of 2452.36 kg /hr to provide excess oxygen. Pure
methanol was pumped with mass flowrate of 615.5kg/hr at 25ºC with 200kPa as oulet pressure.
Both of the air and pure methanol were mixed in mixing chamber, MIX-100.

The mixture of air and methanol is preheated in E-100 heater to 178ºC to reduce the
reactor duty itself. As the mixture was preheated, it flowed to the reactor itself. The temperature
of the reactor is specified to 300ºc to maximise the coversion and selectivity ( Tesser.R et
al,2003).This reactor applied the concept partial oxidation of methanol using metal oxide as
catalyst. The catalyst specified as iron oxide–molybdenum oxide catalyst with a little present
of vanadium-pentaoxide. By proper temperature control, the methanol conversion at 99% can
be maintained (Gerberich et al.,2000). Then , the product stream that flow out of reactor
specified to have 300ºC as temperature and pressure drop of 50kPa as catalyst was present in
the reactor.

The product stream was cooled down to 170ºC before entering the absorption column.
Followed by a gate valve, VLV-100, the pressure specified to decrease to 120kPa. As the
product stream enter the absorber column, simultaneously with water feed at stream 10 at 25ºC
and 100kPa form the top of the column. The pressure on the overhead product of absorber
column was specified to 50kPa while bottom product was specified 100kPa . The formaldehyde
in stream 9 was almost completely removed by counter-current with clean water feed from top.
The water feed help to control desired concentration in bottom stream of absorption column .
For the absorption column, we use try and error method and grpahical method , we conclude
that 9 stages is optimum for absorber to absorb formaldehyde as only 0.5% formaldehyde lost
as flue gas.

14
 Chapter 3: Separation Process

The separation unit selected based on the process flow diagram is the absorption tower.
Absorption is a process that involves the transfer of one or more species from the gas phase to
a liquid phase. The species transferred to the liquid phase are referred to as solutes or absorbate
while the liquid phase itself is known as solvent or absorbent. This process requires no change
in the chemical species present in the system. Absorption is commonly used to separate gas
mixtures, remove impurities, or recover valuable chemicals.

The absorption tower is a long vertical column that is used to absorb impurities from gas
streams in oil refineries and natural gas processing stations. These towers have the function to
be scrubbers as their main purpose of the absorption tower is to scrub the gas stream and
remove impurities by trapping the components of the rising gas with a falling liquid. The
equipment is also used in many more industries, for example the industry of purification and
material processing.

The type of absorption tower used was the tray absorption tower, an equipment commonly used
in the production of formalin from formaldehyde. The conditions implied to the tower,
temperature was fixed to maintain isothermal condition of 150°C and pressure used was
approximate to 101kPa.

15
Table 3.1: Raw Data Obtained from HYSYS Stimulation to plot Equilibrium Line

Equilibrium Line (Coordinates Selected)

0 0
0.3000 0.2718
Table 3.2: Coordinate Selected from Raw Data to plot Equilibrium Line.

16
 T-100

Figure 3.1: Data Obtained from HYSYS Simulation to Plot the Operating Line.

Operating Line (Coordinates Obtained)

0 0.0039
0.2607 0.1687
Table 3.3: Coordinate Obtained from Data to plot Operating Line.

17
 Figure 3.2: Graph of XA vs. YA and Number of Stages

Observation:

Hence, after plotting both the equilibrium and the operating lines, the number of stages
obtained were 9 STAGES.

Explanation and Comparison with Aspen HYSYS Simulation:

The number of stages obtained is 9 STAGES too after trial and error method (refer appendix)
in the simulation of Aspen HYSYS. Both the manual calculation and simulation gave the same
number of stages because theoretically both methods should give nearly the same results as the
manual calculation and plotting of the graph is an accurate method to obtain the number of
stages too.

18
 Chapter 4: Reaction Engineering

4.1 Type of reactor used

Reactor selection depends on several criteria such as the type of reaction, type of catalyst,
size and methods of charging and discharging. In this chemical process, Packed Bed Reactor
(PBR) is chosen. Generally, in industrial packed bed reactor the flow velocity is so high that
the temperature and concentration drop over the film surrounding the catalyst is small in
steady-state operation (Froment, 1972). PBR usually consists of a cylindrical vessel packed
with catalyst pellets and it is easy to design as well as operate. Inert ceramic balls are usually
placed above the catalyst bed to ensure the feed is distributed evenly.

Figure 4.1: Illustrated packed bed reactor

In this process, PBR is the most suitable reactor because the reaction type was selected as
kinetic heterogenous catalytic reaction. For the first reaction, formaldehyde was resulted
from the exothermic oxidation (dehydration) of methanol. The chemical equation as
follows:
CH3OH +1/2 O2 CH2O + H2O ΔH = -159 kJ/mol

Arrhenius constant mole (Bhattacharyya, S, et el, 2000):

A= 1.9600e+06 E= 65000 KJ/Kg mole

For the side reaction, CO was generated while the other side reactions were neglected.
19
 CH2O + 1/2 O2 CO + H2O

Arrhenius constant mole (Bhattacharyya, S, et el, 2000):

A= 1.00 E= 56266 KJ/Kg

It is compatible for solid catalyst to be tested which in this case, Fe-Mo-oxide is used. The
void fraction of the catalyst is ɛ= 0.57 with a density of 𝜌 = 2000𝑘𝑔/𝑚3 . By using PBR,
high conversion per unit mass of catalyst can be achieved which is highly recommended for
a better quality of the end-product.

However, there are few of disadvantages of using this type of reactor. Due to coke
deposition, the reactor will experience plugging of bed which will lead to high pressure
drop. In fact, small beads or pellet catalyst also will cause the same problem. Besides, for a
case where the catalysts are packed non-uniformly, it can cause channelling of fluids to poor
heat and mass transfer. Nonetheless, to ensure the plug flow behaviour, the ratio of reactor
length to catalyst particle diameter should be maintained with greater value.

Heat management is also a very essential aspect in designing packed bed reactor in order to
decrease the cost of running equipment. According to Braz, Matos, Mendes, Rocha and
Alvim (2017), the methanol partial oxidation to formaldehyde is a highly exothermic
reaction. This condition causes the temperature difficult to control. Consequently, the
regeneration or replacement of catalyst is difficult to the point where the process needs to
be shutdown. However, to overcome this problem, the multitubular reactor with catalyst
packed inside the tubes can be used in this reaction for better heat management.

20
4.2 Type of catalyst used

In industrial chemical processes, an efficient choice of catalyst will give higher value
products as well as having significant economics benefits in this modern world. The choice
of the catalyst cannot only be based on the economic aspects in facts, the product end-use,
size of plant and type of operation should be put under consideration. In order to control
kinetics and directions of chemical reaction, heterogenous catalyst in industrial scale has
been used.

In this chemical reaction, Fe-Mo-oxide which doped together with small amounts of other
transition metals has been selected to be the catalyst. Usually, the oxide mixture has an
Mo:Fe atomic ratio of 1.5-2.0, small amounts of V2O5, CuO, Cr2O3, CoO and P2O5 also
presents (Reuss, n.d.). It is used due to its ability in oxidizing the methanol efficiently at a
reactor temperature of 300°C to 400°C. In contrast to the silver catalyst, an almost
complete conversion of methanol could be achieved when using Fe-Mo-oxide which is
99%. Thus, the required amount of methanol would be lesser to get better results. Based
on Phoenix Equipment Corporation (2018), low quantities of methanol in the feed mixture
ensure relatively pure, with only minimal amount of by products would be produced in the
end. This is because of the feed stock itself is the major input cost in formaldehyde
production. Hence, Fe-Mo-oxide would give the best rate in converting the methanol in
this reaction.
Apart from that, the presence of Fe-Mo-oxide catalyst in this reaction causes a distillation
column to be excluded. The reaction products are directly fed to the absorber. This is due
to the almost complete methanol conversion in the reactor thus the purification steps
become simpler.
However, based on Kamlesh (2015), there are few major drawbacks when Fe-Mo-oxide is
used. Due to air is fed in excess quantities, a very dangerous reaction might take place
therefore proper care has to be taken in operating the plant. In fact, the equipment sizes
had to be increased to accommodate the compounds.
Despite many issues arose saying that Fe-Mo-oxide catalysts cost higher than silver
catalyst, it is still the best choice as it usually has an effective lifetime of between 12 to 18
months (Johansen, Johnsen & Christiansen, 2013). The amount of catalyst can last for a
year or more. Only after this range of time, the amount of catalyst needs to be replaced.
Therefore, the utilization of Fe-Mo-oxide in this reaction will make the operating process
easier.

4.3 Description of how the chosen reactor-separator system works

In this chemical process, Packed Bed Reactor (PBR) is used because it is very versatile
and usually used in many other chemical processing applications. In this part, the

21
 preheated gaseous mixture consist of air and methanol from the heater is fed to the reactor.
These gaseous flow through the bed of Fe-Mo-oxide catalyst and rest on a perforated tray.
Immediately, the bed will be placed directly above a water boiler. Here, the hot reaction
gaseous will be cooled so that it can be passed to the absorption column for further
operation.
Apart from that, the separator involved in this process is only an absorber column. Due to
high methanol conversion which is 99% from the first reaction, there is no economical
amount of methanol that required to be recycled thus no distillation column is needed.
In the process of formaldehyde absorption by water, it depends on several factors which
are concentration of formaldehyde in the solution, concentration of methanol in the
solution and temperatures. When all the factors are low, the equilibrium constant value is
very small (Kuramshina & Pavlova, 2016).

4.4 Strategy to maximize desired and minimize undesired product

1
CH3OH + 2 O2 HCHO + H2O (1)

1
HCHO + 2 O2 CO + H2O (2)

Shown above are the two chemical reactions involved in the production of formaldehyde. Chemical
equation (1) is the desired reaction to produce formaldehyde whereas chemical equation (2) represents
the undesired chemical reaction in which the formaldehyde formed in the first reaction is converted into
carbon monoxide and water. Since reaction (2) consumed formaldehyde to produce carbon monoxide
and water, it is undesirable and methods to minimize the undesired product is taken into consideration
thus increasing the desired product which is formaldehyde.

(a) Increase the concentration of methanol and manipulate the concentration of excess oxygen

Based on the both reactions involved, methanol which is the reactant of reaction (1) is not
involved in reaction (2). However, oxygen is required in both reactions. Therefore, increasing
the concentration of methanol would favour the first reaction because by increasing the
concentration of methanol, the chances of methanol reacting with the oxygen will increase.
Besides, the concentration of oxygen which is in excess should be reduced to a ratio of 1.5:1
compared to methanol as too much concentration of oxygen will allow the reaction (2) to take
place at a higher rate. Therefore, if concentration of oxygen is lowered to a level where it is
optimum, reaction (2) might be reduced while reaction (1) is not affected.

(b) Increase the amount of molybdenum in iron-molybdenum oxide

22
 Iron molybdate has been established as an effective methanol partial oxidation catalyst since it
was reported in 1931. The catalyst itself composed of two phases: Fe2(MoO4) with excess of
MoO3. The excess MoO3 have two function which is increase selectivity towards formaldehyde
and maintain high selectivity. Based on the research conducted, the SEM (scanning electron
microscope), when there is increment of molybdenum ration to iron, the number of pores
increased which lead to increase in surface area (Yeo,B.R et al,2016).

Figure 4.2 Formaldehyde Selectivity and Conversion of the Catalysts

4.5 Sizing of the reactor

1
CH3OH + 2 O2 HCHO + H2O (1)

1
HCHO + 2 O2 CO + H2O (2)

For the above reactions, we neglect the 2nd reaction because the yield of the reaction is 0.9. The
above reaction is assumed to be an elementary reaction thus the rate of reaction is proportional
to the concentration of the reactants. When the reaction is assumed to be an elementary reaction
the order agrees with the stoichiometry. The above assumptions are done to ease the
calculation.

Mole Balance of Packed Bed Reactor

𝒅𝑿
FA0∙𝒅𝒘 = -rA’
23
Rate Law based on elementary reaction

-rA’ = kCACB0.5
k = Ae-Ea/RT
= (1.96x106) ∙ e-65000/ (8.314) (573)
= 2.326 unit/hr
Thus,

𝑢𝑛𝑖𝑡
-rA’ = (5x10-7 ) ∙ CACB0.5
ℎ𝑟

Stoichiometry

𝟏
𝟏−𝒙 𝑷 𝑻 𝚯𝐁− 𝒙 𝑷 𝑻
CA = CA0 ∙ (𝟏−𝜺𝒙) ∙ 𝑷 ∙ 𝑻 CB = CA0 ∙ ( 𝟏−𝜺𝒙 ) ∙ 𝑷 ∙ 𝑻
𝟐
𝟎 𝟎 𝟎 𝟎

ε = yA ∙ δ

Based on the reaction,

1
δ = (1 - 1 - -1)
2

= 0.5
Based on the mass balance,
𝑘𝑚𝑜𝑙
Molar flowrate of methanol from the inlet of reactor : 19.21 ℎ𝑟
𝑘𝑚𝑜𝑙
Molar flowrate of mixture from the inlet of reactor : 104.21 ℎ𝑟

19.21𝑘𝑚𝑜𝑙
ℎ𝑟
yA = = 0.184
104.21𝑘𝑚𝑜𝑙
ℎ𝑟

ε = (0.5) ∙ (0.184) = 0.092

𝐹𝐵
ΘB = 𝐹𝐴

17.85𝑘𝑚𝑜𝑙
ℎ𝑟
=
19.21𝑘𝑚𝑜𝑙
ℎ𝑟

= 0.9293

To calculate CA0, the molar density flowrate of mixture is obtained from stream 6 of Hysys and
is taken to multiply the composition, x of methanol in the mixture.

CA0 = x ∙ CT0

x = composition of methanol in the mixture in stream 6

24
 𝑘𝑔𝑚𝑜𝑙
CT0 = molar density flowrate ( )
𝑚3

The composition of methanol in the mixture of stream 6 is,

19.21𝑘𝑚𝑜𝑙
ℎ𝑟
x =
104.21𝑘𝑚𝑜𝑙
ℎ𝑟

= 0.1843
𝑘𝑔𝑚𝑜𝑙
The molar density flowrate of the mixture in stream 6 from HYSYS is: 5.33 x 10-2 𝑚3

Thus,

CA0 = x ∙ CT0
𝑘𝑚𝑜𝑙 1000 𝑚𝑜𝑙
= (0.1843) ∙ (5.33 x 10-2 )∙ ( )
𝑚3 𝑘𝑚𝑜𝑙
𝑚𝑜𝑙
= 9.823 𝑚3

The data below is the data retrieved from the simulation of HYSYS:

Temperature of inlet (stream6) 178.1 °C

Temperature of outlet (stream7) 300 °C
Pressure of inlet (stream6) 200 kPa
Pressure of outlet (stream7) 150 kPa

Thus,

1−𝑥 𝑃 𝑇
CA = CA0 ∙ (1−𝜀𝑥) ∙ 𝑃 ∙ 𝑇
0 0

𝑚𝑜𝑙 1−𝑥 150𝑘𝑃𝑎 178.10 𝐶

= 9.823 ∙ (1−0.092𝑥) ∙ 200𝑘𝑃𝑎 ∙
𝑚3 3000 𝐶
1
ΘB− 𝑥 𝑃 𝑇
CB = CA0 ∙ ( 1−𝜀𝑥 ) ∙ 𝑃 ∙ 𝑇
2
0 0
1
𝑚𝑜𝑙 0.9293− 𝑥 150𝑘𝑃𝑎 178.10 𝐶
= 9.823 ∙ ( 1−0.092𝑥 ) ∙ 200𝑘𝑃𝑎 ∙
2
𝑚3 3000 𝐶

Substitute CA and CB into rate law:

-rA’ = kCACB0.5
1
𝑢𝑛𝑖𝑡 𝑚𝑜𝑙 1−𝑥 150𝑘𝑃𝑎 178.10 𝐶 𝑚𝑜𝑙 0.9293− 𝑥
= (2.326 ) ∙ [9.823 ∙ (1−0.092𝑥) ∙ (200𝑘𝑃𝑎) ∙ ( 3000 𝐶 ) ] ∙ [9.823 ∙ ( 1−0.092𝑥
2
)∙
ℎ𝑟 𝑚3 𝑚3
150𝑘𝑃𝑎 178.10 𝐶
(200𝑘𝑃𝑎) ∙ ( 3000 𝐶 ) ] 0.5
1
1−𝑥 0.9293− 𝑥
= 21.28 ∙ (1−0.092𝑥 ) ∙ ( 1−0.092𝑥 ) 0.5 2

25
Substitute rate law into the mole balance of PBR:

𝑑𝑋
FA0∙𝑑𝑤 = -rA’
𝐹
𝐴0
𝑑𝑤 = −𝑟′ dx
𝐴

𝑤 19.21 𝑘𝑚𝑜𝑙 0.99 1

∫0 𝑑𝑊 = ℎ𝑟
∙ ∫0 1
21.28 1−𝑥 0.9293− 𝑥
2 )0.5
( )∙(
1−0.092𝑥 1−0.092𝑥

W = 3323.65 kg

Weight of catalyst = 3 323.65 kg

𝑘𝑔
Density of catalyst (iron-molydenum oxide) = 4500 𝑚3

1𝑚3
∴ Volume of catalyst = 3 323.65 kg x 4500𝑘𝑔

= 0.7384 m3

Calculation of total volume of reactor based on the void of 0.5

𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒃𝒆𝒅−𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒄𝒂𝒕𝒂𝒍𝒚𝒔𝒕
𝜺 =1- 𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒃𝒆𝒅
𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒄𝒂𝒕𝒂𝒍𝒚𝒔𝒕
0.5 =1- 𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒃𝒆𝒅

𝟎.𝟕𝟑𝟖𝟒 𝒎𝟑
0.5 = 1 - 𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒃𝒆𝒅

Volume of Reactor = 1.477 𝒎𝟑

26
 Chapter 5: Conclusion

In conclusion, this report includes the calculations to determine the number of stages for the
reactor which is 9 stages. The mole balance of the flow is also calculated manually to produce
10,000,000 kg of formalin in a year. Based on the calculations, the volume of the reactor is also
calculated and 1.477m3 is obtained. In the process of formalin production, Packed Bed Reactor
is chosen as the operating reactor because in the production of formaldehyde from methanol
and oxygen, the catalyst used which is iron molybdenum is present as a solid catalyst which
will not be used up during the reaction as it does not need to be recycled and only stays in the
reactor itself. By using the PBR reactor, it can maximize the amount of catalyst that can be
used and further reducing cost. The catalyst chosen is iron molybdenum because of its higher
selectivity and conversion rate compared to silver catalyst. In addition, iron molybdenum
catalyst also has a longer lifespan compared to silver catalyst thus reducing cost of
maintenance. The concentration of methanol can be increased, and the concentration of excess
oxygen can be reduced to an optimum level to maximize desired and minimize undesired
product. Increasing the amount of molybdenum in iron-molybdenum oxide will also increase
the desired product.

27
 Chapter 6: References

BHATTACHARYYA, S. (1967). Kinetics of the vapor-phase oxidation of methyl alcohol on

vanadium pentoxide catalyst. Journal of Catalysis, 8(2), pp.128-136. (2019). Formalin Market:
Global Industry Analysis 2012 - 2016 and Opportunity Assessment; 2017 – 2027. Future
Market Insights. Retrieved from https://www.futuremarketinsights.com/reports/formalin-
market

Froment, F., G., (1972). Analysis and Design of Fixed Bed Catalytic Reactors. Washington:
Bischoff; Chemical Reaction Engineering. Module 2: Heterogeneous catalysis (n.d). Retrieved
from https://nptel.ac.in/courses/103103026/module2/lec18/3.html

Gerberich, H. R., Seaman, G. C., & Staff, U. B. (2013). Formaldehyde. Kirk-Othmer Encyclopedia
of Chemical Technology. doi:10.1002/0471238961.0615181307051802.a01.pub3

H. Renon and J.M. Prausnitz, (1968). "Local Compositions in Thermodynamic Excess Functions
for Liquid Mixtures," AIChE J., Vol. 14, No. 1, pp. 135 – 144.

Johansen, T., Johnsen, A., & Christiansen, A. (2013). A Comparison of Training Simulators for
the Formox Process. NTNU.

Kamlesh, S.K. 2016. Production of formalin from methanol oxidation. Department of Chemical
Engineering Faculty of Technology and Engineering the M.S. University of Baroda, pp 1-75.

Reuss, G., (n.d). Formaldehyde. Aktiengesellschaft, Ludwigshafen, Federal Republic of

Germany.

Kuramshina, K. S., & Pavlova, K. A., (2016). Physical and Chemical Analysis of Formaldehyde
Absorption Process. ARPN Journal of Engineering and Applied Sciences, vol. 11, no. 16.
Russia: University Kazan.

Millar, G.J., & Collins, M., (2017). Industrial Production of Formaldehyde Using Polycrystalline
Silver Catalyst. Brisbane: Ind. Eng. Chem. Res., 56 (33), pp 9247–9265.

Mohamed, S., Nagaraj, G., Chua, F.H.C., & Wang, Y.G. (2000). The use of chemicals in
aquaculture in Malaysia and Singapore. In: J.R. Arthur, C.R. Lavilla-Pitogo, & R.P.
Subasinghe (Eds.) Use of Chemicals in Aquaculture in Asia: Proceedings of the Meeting on
the Use of Chemicals in Aquaculture in Asia 20-22 May 1996, Tigbauan, Iloilo, Philippines

28
 (pp. 127-140). Tigbauan, Iloilo, Philippines: Aquaculture Department, Southeast Asian
Fisheries Development Center.

Phoenix Equipment Corporation (2018). Comparing the different formaldehyde production

processes. Retrieved from https://www.phxequip.com/resource-detail.40/comparing-the-
different-formaldehyde-production-processes.aspx

Raun, K. V. (2018). Understanding the Deactivation of the Iron Molybdate Catalyst and its
Influence on the Formox Process. Kgs. Lyngby: Technical University of Denmark (DTU).

Tesser, R., Serio, M. D., & Santacesaria, E. (2003). Catalytic oxidation of methanol to
formaldehyde: An example of kinetics with transport phenomena in a packed-bed reactor.
Catalysis Today, 77(4), 325-333. doi:10.1016/s0920-5861(02)00377-2

Thulin, M. (2016). Fe-Mo of spinel structure for methanol oxidation – synthesis development and
catalytic performance. Lund University.

Yeo, B., Pudge, G., Bugler, K., Rushby, A., Kondrat, S., Bartley, J., Golunski, S., Taylor, S.,
Gibson, E., Wells, P., Brookes, C., Bowker, M. and Hutchings, G. (2016). The surface of iron
molybdate catalysts used for the selective oxidation of methanol. Surface Science, 648, pp.163-
169.

29
 APPENDIX

1
Case Name: formaldehyde production.hsc
2
Company Name Not Available Unit Set: SI
3 Bedford, MA
USA
Date/Time: Sun Mar 24 13:04:42 2019
4
5
6
7 Workbook: Case (Main)
8
9
Material Streams Fluid Pkg: All
10
Name 1 2 3 4 5
11
Vapour Fraction 0.0000 1.0000 0.0000 1.0000 0.8864
12
Temperature (C) 25.07 142.2 28.14
13 25.00 * 25.00 *

Pressure (kPa) 250.0 250.0 250.0

14 100.0 * 100.0 *

Molar Flow (kgmole/h) 19.21 85.00 104.2

15 19.21 * 85.00 *

Mass Flow (kg/h) 615.5 2452 615.5 2452 3068

16
Liquid Volume Flow (m3/h) 0.7735 2.835 0.7735 2.835 3.608
17
Heat Flow (kJ/h) -4.599e+006 0.0000 -4.599e+006 2.940e+005 -4.305e+006
18
Name 6 7 8 10 11
19
Vapour Fraction 1.0000 1.0000 1.0000 0.0000 0.0000
20
Temperature (C) 178.1 170.0 72.49
21 300.0 * 27.00 *

Pressure (kPa) 200.0 150.0 100.0

22 150.0 * 100.0 *

Molar Flow (kgmole/h) 104.2 113.8 113.8 71.70

23 65.60 *

Mass Flow (kg/h) 3068 3068 3068 1182 1517

24
Liquid Volume Flow (m3/h) 3.608 3.678 3.678 1.184 1.704
25
Heat Flow (kJ/h) -3.334e+006 -5.829e+006 -6.325e+006 -1.868e+007 -1.738e+007
26
Name 12 9
27
Vapour Fraction 1.0000 1.0000
28
Temperature (C) 53.86 170.0
29
Pressure (kPa) 50.00 120.0
30

30
 Molar Flow (kgmole/h) 107.7 113.8
31
Mass Flow (kg/h) 2733 3068
32
Liquid Volume Flow (m3/h) 3.158 3.678
33
Heat Flow (kJ/h) -7.626e+006 -6.325e+006
34

35
Compositions Fluid Pkg: All
36
Name 1 2 3 4 5
37
Comp Mole Frac (Methanol) 1.0000 0.0000 0.1843
38 1.0000 * 0.0000 *

Comp Mole Frac (Oxygen) 0.0000 0.2100 0.1713

39 0.0000 * 0.2100 *

Comp Mole Frac (Formaldehyde) 0.0000 0.0000 0.0000

40 0.0000 * 0.0000 *

Comp Mole Frac (H2O) 0.0000 0.0000 0.0000

41 0.0000 * 0.0000 *

Comp Mole Frac (CO) 0.0000 0.0000 0.0000

42 0.0000 * 0.0000 *

Comp Mole Frac (Nitrogen) 0.0000 0.7900 0.6444

43 0.0000 * 0.7900 *

Name 6 7 8 10 11
44
Comp Mole Frac (Methanol) 0.1843 0.0003 0.0003 0.0000
45 0.0000 *

Comp Mole Frac (Oxygen) 0.1713 0.0726 0.0726 0.0000

46 0.0000 *

Comp Mole Frac (Formaldehyde) 0.0000 0.1685 0.1685 0.2615

47 0.0000 *

Comp Mole Frac (H2O) 0.0000 0.1685 0.1685 0.7385

48 1.0000 *

Comp Mole Frac (CO) 0.0000 0.0000 0.0000 0.0000

49 0.0000 *

Comp Mole Frac (Nitrogen) 0.6444 0.5901 0.5901 0.0000

50 0.0000 *

Name 12 9
51
Comp Mole Frac (Methanol) 0.0003 0.0003
52
Comp Mole Frac (Oxygen) 0.0767 0.0726
53
Comp Mole Frac (Formaldehyde) 0.0039 0.1685
54
Comp Mole Frac (H2O) 0.2955 0.1685
55
Comp Mole Frac (CO) 0.0000 0.0000
56
Comp Mole Frac (Nitrogen) 0.6235 0.5901
57

58
Energy Streams Fluid Pkg: All
59

31
 Name Q-100 Q-101 Q-102 E-103 E-104
60
Heat Flow (kJ/h) 156.6 2.940e+005 9.708e+005 2.495e+006 4.959e+005
61

62

63 Aspen Technology Inc. Aspen HYSYS Version 10 Page 1 of 2

Licensed to: Company Name Not Available * Specified by user.

1
Case Name: formaldehyde production.hsc
2
Company Name Not Available Unit Set: SI
3 Bedford, MA
USA
Date/Time: Sun Mar 24 13:04:42 2019
4
5
6
7 Workbook: Case (Main) (continued)
8
9
Unit Ops
10
Operation Name Operation Type Feeds Products Ignored Calc Level
11
1 3
12
P-100 Pump Q-100 No 500.0 *
13
2 4
14
K-100 Compressor Q-101 No 500.0 *
15
3 5
16
MIX-100 Mixer 4 No 500.0 *
17
5 6
18
E-100 Heater Q-102 No 500.0 *
19
6 7
20
R-101 Plug Flow Reactor E-103 No 500.0 *
21
10 11
22
T-100 Absorber No 2500 *
9 12
23
7 8
24
E-101 Cooler E-104 No 500.0 *
25
VLV-100 Valve 8 9 No
26 500.0 *

27

28 Aspen Technology Inc. Aspen HYSYS Version 10 Page 2 of 2

Licensed to: Company Name Not Available * Specified by user.

Table A.1: HYSYS Simulation Result

32
Method of Trial and Error to Find Number of Stages in the Absorption Column

The number of stages was varied and analysis was done on how much formaldehyde being
absorb and lost in flue gas.

Composition of Percent of
Composition of Formaldehyde loss
Formaldehyde at
Number of Stages Formaldehyde at at Flue Gas
Upper (Flue
bottom ,kg/hr stream.,%
Gas),kg/hr

6 563.07 12.57 2.18

7 568.00 7.64 1.32

8 570.74 4.90 0.85

9 572.64 3.00 0.52

Table A.2: Trial and Error Data

33