Republic of the Philippines

Cagayan State University

Carig Campus
COLLEGE OF ENGINEERING AND ARCHITECTURE
CSU Vision

Transforming
lives by
Educating for the DESIGN OF PLUG FLOW REACTOR (PFR) FOR THE PRODUCTION
BEST.
OF FORMALDEHYDE

CSU Mission

CSU is committed A Term Paper

to transform the
lives of people and
communities In partial fulfilment for the requirements of the course
through high
quality instruction Chemical Reaction Engineering
and innovative (ChE 325)
research,
development,
production and
By:
extension.
JHON CARLO T. AGPALZA
MA. VALERIE ELAINE M. BACANI
CSU – IGA
Competence LEUNAM KIER C. CAMAYANG
Social Responsibility

Unifying Presence

ENGR. LEONARD D. AGANA

COE – IGA Subject Adviser
Innovative Thinking
Synthesis
Personal Responsibility
Empathy
Research Skill
Entrepreneurial Skill
June 2021
 TABLE OF CONTENTS

I. INTRODUCTION....................................................................................................................1

II. REVIEW OF RELATED LITERATURE..............................................................................3

A. Process Selection of Producing Formaldehyde.............................................................3

B. Iron-Molybdenum Oxide Catalyst Method for the Production of Formaldehyde. .3
C. Overall Reaction.................................................................................................................4
D. Reaction Kinetics................................................................................................................4
E. Chemical and Physical Properties of Formaldehyde...................................................6
1. Physical Properties.......................................................................................................7
2. Thermal Properties.......................................................................................................7
3. Chemical Properties.....................................................................................................8
F. Manufacturing Process...................................................................................................10
G. Process Description..........................................................................................................11
1. Blower..........................................................................................................................12
2. Vaporizers...................................................................................................................13
3. Reactors........................................................................................................................13
4. Condenser....................................................................................................................15
5. Absorber......................................................................................................................15
6. Heat Exchanger...........................................................................................................16
7. Emission Control System..........................................................................................16
H. Feed and Product Composition.....................................................................................17
1. Feed Composition......................................................................................................17
2. Capacity Selection......................................................................................................17
3. Product Composition.................................................................................................17
III. DESIGN METHODOLOGY.............................................................................................19

I.Using Three Reactors in Parallel.........................................................................................19

A. Reaction Kinetics........................................................................................................19
B. Reactor Design............................................................................................................22
 II. Using Four Reactors in Combined Parallel and Series.................................................32
A. Reaction Kinetics........................................................................................................32
B. Reactor Design............................................................................................................32
C. Summary Sheet...........................................................................................................45
D. Conclusions.................................................................................................................48
REFERENCES.............................................................................................................................49

Books.........................................................................................................................................49
Online Journals........................................................................................................................49
NOMENCLATURE

HCHO /C Formaldehyde
C H 3 OH /A Methanol
O2 / B Oxygen Gas
H 2 O /D Water
C O2 Carbon Dioxide
T Temperature
K ox ∧K red Equilibrium Constant in oxidized and Reduced forms
k 1∧k 2 Equilibrium Constant
r C H OH /r A
3
Reaction rate of methanol
rO 2
Reaction rate of oxygen gas
r HCHO Reaction rate of formaldehyde
rH 2 O Reaction rate of H 2 O
r rxn rate of reaction
pC H OH 3
Partial pressure of methanol

C Concentration
C (C H 3 OH )0
/C Ao Initial Concentration of methanol

C (C H 3 OH )
/C A Concentration of methanol at time (t)

XC H 3 OH /XA Fractional Conversion

FA Flow Rate
εA Fractional change of Methanol
τ Residence Time
s Space velocity
n Amount
V Volume
Vo Initial Volume
Vc Volume of catalyst
VT Volume of a tube
HR Height of the Reactor
R Universal gas constant
HTF Heat Transfer Fluid
PFR Plug Flow Reactor
 Chapter I

INTRODUCTION

Chemical reaction engineering is an engineering discipline that is concerned with

the utilization of chemical reactions on a basis of commercial scale. Its primordial

concern is the successful design and operation of chemical reactors for industrial use.

Chemical reactors are the most important equipments in chemical processes; it is where

raw materials are subjected into chemical transformation to produce a promising

product (Levienspiel, 1999). Chemical reactors are designed to maximize the conversion

of raw materials into a useful product. In consideration with the design of a chemical

reactor, it must possess high efficiency in producing the desired output, and least

amount of expenses to be devoted in purchasing the required materials.

To design a chemical reactor, information and knowledge about

thermodynamics, chemical kinetics, fluid mechanics, heat and mass transfer, and

economics must be considered. One of the types of a chemical reactor is plug flow

reactor. Plug flow reactors are commonly used to validate detailed kinetic mechanisms

and to perform kinetic analysis (Cuoci, 2019). And one of the applications of a plug flow

reactor is in the production of formaldehyde.

Formaldehyde (CH2O) is a colorless, strong-smelling gas with a boiling point of

negative 19℃ and is soluble in water and acetone. Formaldehyde is best known as a

preservative and for its anti-microbial property, it is one of the main components in

medicinal products due to its ability to reduce the toxicity of viruses and venoms; it is

also used in making building materials and many household products specifically in
1
pressed-wood products such as particleboard, plywood, and fiberboard; glues and

adhesives; and paper product coatings (American Cancer Society).

Formaldehyde is used as an antimicrobial agent in many cosmetic products,

including soaps, shampoos, deodorants, lotions, make-up, mouthwashes, and nail

products (Cosmetic Ingredient Review Expert Panel, 1984; Reuss et al., 2003).

Formaldehyde is also used directly to inhibit corrosion in electro-plating and in mirror

finishing, in the electrodeposition of printed circuits, and in the development of

photographic films (Reuss et al., 2003).

Due to the rising mortality rate brought by Covid-19 pandemic, demand of

formaldehyde increased significantly. Formaldehyde itself is used to preserve and

disinfect; for example, human and veterinary drug and biological materials (viral

vaccines contain 0.05% formalin as an inactivating agent), to disinfect hospital wards

and to preserve and embalm biological specimens (Lewis, 1998). Formaldehyde has a

numerous application in both industry and medical field that makes it nearly universal

chemical in today’s environment and highly significant to global economy and health; it

plays a significant role in maintaining the safety of humanity against germs and

diseases when used in drugs, and household disinfectants.

2
 Chapter II

REVIEW OF RELATED LITERATURE

A. Process Selection of Producing Formaldehyde

Choosing the most suitable process for a certain product must be the top priority

to be considered. It is the basic step to attain the desired product with high percent

yield considering the process’ efficiency and cost. Today most of the world’s

commercial formaldehyde is manufactured from methanol and air by using metal or

metal oxide catalyst. The former procedure gives essentially pure formaldehyde

containing methanol and traces of formic acid as a primary product, whereas the latter

gives a mixture of lower aliphatic aldehydes (Engineering Formalin Production).

In this paper, metal oxide catalyst method will be used, specifically Iron-

Molybdenum oxide catalyst method.

B. Iron-Molybdenum Oxide Catalyst Method for the Production of

Formaldehyde

Iron-Molybdenum catalyst is used for the selective oxidation of methanol to

formaldehyde in the presence of an excess air (Journal of Saudi Chemical Society, 2018).

Based from the book entitled “Engineering Formalin production”, the result of using

iron-molybdenum oxide catalyst for the production of formalin showed a total

conversion of methanol about 75% yield, it has an effective life of 12 to 18 months, it is

tolerant in tracing contamination, and it requires less frequent change-outs and lower

down time for each replacement of reactors used.

3
 A study of Baber et al. (2018) from the University of Wah, Pakistan, using the

iron-molybdenum oxide catalyst to produce formaldehyde, under atmospheric pressure

and a temperature of 250-400℃ , it shows that methanol conversion inside a reactor

could reach up to 99% and a yield of 88%-92%.

Another study entitled “Performance Comparison of Industrially Produced

Formaldehyde Using Two Different Catalyst; Silver, and Iron-Molybdenum Oxide” by

Shakeel et al. (2019), showed that the conversion of methanol using the iron-

molybdenum oxide catalyst is 99% and that of the silver oxide process is 85%. The life of

the iron-molybdenum oxide catalyst is 12-18 months and that of the silver catalyst is 3-8

months. And the porosity of the iron-molybdenum oxide catalyst is 0.7 and for the

silver catalyst is 0.5. These different studies manifests that the most suitable process for

the production of formaldehyde is the use of Iron-Molybdenum Oxide catalyst method.

C. Overall Reaction

Methanol + Oxygen Gas → Formaldehyde + Water

D. Reaction Kinetics

Chemical reaction kinetics deals with the rates of chemical processes and the

factors affecting the rates such as concentration, pressure, temperature, stirring and

catalyst or enzymes. The rate of a chemical reaction is the rate at which reactants are

used up, or equivalently the rate at which products are formed (Vallance, 2017).

4
 Chemical kinetics is a tool to understand fundamental aspects of reaction

pathways which provides the valuable information about the rate and mechanism of

chemical reaction which helps in running a chemical reaction successfully by selecting

optimum reaction conditions.

Formaldehyde, as a valuable compound, has been widely used in chemical

processes and is usually produced through the catalytic oxidization of methanol.

1
C H 3 OH + O2 → HCHO+ H 2 O
2

To determine the reaction mechanism, a two-stage oxidation pattern suggested by Mars

and Kerevelen was used. In this pattern, at the first stage, methanol was reacted with

oxygen on the catalytic cell. After oxidation of methanol, catalyst was consumed. This

catalyst was oxidized in the gas phase.

C H 3 OH + K ox →CHOH ( g )+ H 2 O+ K red k1

K red +O2 ( g ) → K ox k2

in which K red and K ox are reduced and oxidized forms of the initial catalyst,

respectively. Considering the equations obtained, the rate of oxidation of methanol is as

follows.

k1 pC H OH
−r C H OH = 3
(1)
3
1+k 2 pC H OH 3

where:

k 1∧k 2 is the rate constant which are defined as

8774
ln ( k 1 )=12.5− (2)
T

5
 7439
ln ( k 2 )=−17.29+ (3)
T

r C H OH refers to rate of reaction for methanol

3

pC H OH is the partial pressure of the methanol

3

Deriving the rate equation in terms of concentration is shown below

k1 p C H OH
−r C H OH = 3

3
1+k 2 pC H OH 3

The operating condition of the production of formaldehyde from the metallic oxidation

of methanol is at atmospheric pressure and a temperature that ranges from 250 ℃ to

400 ℃ which methanol conversion inside the reactor could reach 99% and a yield of

88% - 92%. This condition of the gas inside the reactor is in ideal state. (Baber et al.,

2018)

Ideal gas law equation:

PV =nRT (4)

n
C= (5)
V

Therefore:

PC H OH =C C H
3 3 OH RT (6)

Substituting eq 6 to eq 1

k 1 (C C H OH RT )
−r C H OH = 3

3
1+k 2( CC H OH RT ) 3

Above is the obtained rate expression of methanol in terms of its concentration.

6
 E. Chemical and Physical Properties of Formaldehyde

Formaldehyde is a colorless, pungent, highly flammable, irritating, and

poisonous low molecular weight gas in its pure form, it dissolves very well in water,

alcohols, and other polar solvents. Due to its strong electrophilic properties, it is highly

reactive, readily undergoes polymerization, and can form explosive mixtures in air

(Subasi, 2018).

1. Physical Properties

From Perry’s Chemical Engineers’ Handbook 9 th Ed., at ordinary temperatures

formaldehyde gas is readily soluble in water, alcohols and other polar solvents. It has

the following physical properties:

Boiling Point at 101.325 kPa = −19.2 ℃

Melting Point at 101.325 kPa = −118 ℃

g
Density at −80 ℃ ¿ 0.9151 3
cm

g
at −20 ℃ ¿ 0.8153
c m3

Vapor density relative to air = 1.04

Critical Temperature = 137.2 ¿141.2 ℃

Critical Pressure = 6.784 ¿ 6.637 Mpa

Cubic expansion coefficient = 2.83 ×10−3 K −1

2. Thermal Properties

kJ
Heat of formation at 25 ℃ = −115.9 ±6.3
mol

7
 kJ
Heat of combustion at 25 ℃ = 561.5
mol

kJ
Heat of vaporization at -19.2 ℃ = 23.32
mol

J
Specific heat capacity at 25 ℃ = 35.425
mol−K

Heat of solution at 25 ℃

kJ
In water = 62
mol

kJ
In methanol =62.8
mol

kJ
Entropy at 25 ℃ = 218.8 ± 0.4
mol−K

3. Chemical Properties

Formaldehyde is one of the most reactive organic compounds discovered in this

world. The various chemical reactions of formaldehyde are as follows:

 Decomposition
The thermal decomposition of formaldehyde into carbon monoxide and hydrogen

has been shown to be a homogeneous bimolecular reaction over the pressure range 30-

400 mmHg. Simultaneous condensation reactions occur. The decomposition has been

studied from 510°-607° C, and the energy of activation found to be 44,500 calories

(Fletcher, 1934).

 Polymerization

Formaldehyde is a gas at room temperature and is commercially available as 37%

solution in water, which is called formalin. As a gas, it polymerizes into a white powder

called paraformaldehyde.

8
 nHCHO ⇌ ( CH 2 O ) n

where n is usually about 10. Under alkaline conditions, paraformaldehyde can

easily depolymerize into a gas. It also depolymerizes in the presence of water, and

yields to formalin (Subasi, 2018).

 Reduction and Oxidation

Formaldehyde is readily reduced to methanol with hydrogen over many metals

and metal oxide catalysts. It is oxidized to formic acid or C O2 and H 2 O .

The presence of strong alkalis or when heated in the presence of acids,

formaldehyde undergoes cannizzaro reaction with formation of methanol and formic

acid. In the presence of aluminum or magnesium methylate, paraformaldehyde reacts

to form methyl formate (Tishchenko, 2016).

2 HCHO → HCOOC H 3

 Addition Reaction
The formation of sparingly water-soluble formaldehyde bisulphite is an example of

addition reaction. Hydrocyanic acid reacts with formaldehyde to give glyconitrile.

HCHO+ HCN → C 2 H 3 NO

Formaldehyde undergoes Prins reaction which is an organic reaction consisting of

an electrophilic addition of an aldehyde or ketone to an alkene or alkyne followed by

capture of a nucleophile or elimination of an H+ ion. Acetylene undergoes a Reppe

addition reaction with formaldehyde to form 2- butyne-1,4- diol.

2 CHCHO+C 2 H 2 → C 4 H 6 O2

9
 Strong alkalis or calcium hydroxide convert formaldehyde to a mixture of sugars in

particular hexoses, by a multiple aldol condensation, which probably involves a

glycolaldehyde intermediate. Acetaldehyde, for example reacts with formaldehyde to

give pentaerythritol (S. Gayathr and G. Muthamilarasi, 2005).

 Condensation Reactions

Reaction of formaldehyde with ammonia is an example of condensation reaction.

During the reaction of formaldehyde with ammonia there is a release of water

molecules as the byproducts. In condensation reaction only byproducts are going to

form as the side products. Formaldehyde reacts with ammonia to give hexamethylene

tetraamine and with ammonium chloride to give monomethylamine, dimethylamine, or

trimethylamine and formic acid, depending upon reaction conditions (Walker, 1964).

10
 F. Manufacturing Process
Steam Air

Methanol
Emission
Process Gas Control
Air System

Process &
Vaporizer 1 Reactor 1

Absorber
Aftercooler
Cooling
Pressurization
Water
Blower
Cooling Water
Vaporizer 2 Reactor 2

Recirculation
Blower Vaporizer 3 Reactor 3

Condenser 1

Heat
Water Steam Exchanger
Condenser 2

Water Steam
HTF HTF Formaldehyde
Condenser 3

Water Steam

Proposed Process Flow Diagram for Production of Formaldehyde using Three PFR in Parallel

11
 Steam Air

Methanol
Emission
Process Gas Control
Air System

Process &
Vaporizer 1 Reactor 1 Reactor 2

Absorber
Cooling

Aftercooler
Pressurization Water
Blower
Cooling Water
Vaporizer 2 Reactor 3 Reactor 4

Recirculation
HTF HTF HTF HTF
Blower

Condenser 1 Condenser 2

Water Steam Water Steam

Heat
Condenser 3 Condenser 4
Exchanger

Water Steam Water Steam

Formaldehyde

Proposed Process Flow Diagram for Production of Formaldehyde using Four PFR in Combined

Series and Parallel

Both proposed process flow diagram for the production of formaldehyde is based from

the study of Mohammed Ahmad Sanhoob et al. (2012), and Trine Johansen et al. (2013).

G. Process Description

The oxidation process for formaldehyde making uses a metal oxide (iron-

molybdenum oxide) catalyst. The feed mixture contains steam, air, and minimal

amount of methanol (to prevent the explosive range) results to a 98-99% conversion of

methanol is obtained. The reaction takes place at 250-400°C. All formaldehyde is

1
produced via C H 3 OH + O2 → C H 2 O+ H 2 O (the exothermic dehydrogenation of
2

12
methanol). By-products are carbon monoxide, dimethyl ether, carbon dioxide and

formic acid.

Overall yields are in the range of 88 - 92 %. The process starts with the

vaporization of methanol. It is then mixed with air (and optional exhaust/tail gas) and

passed over catalyst-filled tubes in a heat exchanger reactor. A heat transfer fluid

permits circulates outside the tubes and vaporizes, eliminating the heat of reaction; this

fluid is then condensed to make steam. The gases are cooled to 110°C in a heat exchange

unit and then transportable to the bottom of an absorber. Water is added to the top of

the column, and the quantity can be modified to control the product concentration.

After an exit to the column, the product is fed over in anion exchange unit to decrease

the formic acid content.

The final product includes up to 55 wt% formaldehyde and 0.5-1.5 wt%

methanol. The tail gas from the oxide process will not burn the gas alone due to the

minimal amount of flammable gas (dimethyl ether, carbon monoxide, methanol, and

formaldehyde), but rather, it can be combusted in a catalytic furnace or by adding fuel

(Baber A. A. et al., 2018).

Equipment Description of the Proposed Manufacturing Process

1. Blower

A pressurization blower is a centrifugal fan designed such that the air enters the

fan, is forced around the blower. Air inherently contains impurities such as particulate

matter, volatile organic chemicals, acidic gases, salts and various other substances. The

purpose of the pressurization blower is to clean the fresh air. To maintain a constant

13
pressure in the system, a pressure controller controls the inlet air by adjusting the

blower speed with a frequency converter (Ali Shah, 2012).

The recirculation blowers, which supply the air for the oxidation process are also

a centrifugal type. The measured process gas flow is used for calculating methanol

percent volume in the process. In the process, it is designed to have three small

recirculation blowers, connected in parallel that will push the recirculated gas through

the process. One of the blowers will have a frequency converter controls while the two

have one speed, making it independent of backpressure and will almost give same

volumetric flow rate. Constant conditions on the suction side must be retained to give

constant mass flow rate (Johansen et.al., 2013).

2. Vaporizers

Recirculated gas and methanol will be subjected into three parallel vaporizers.

The vaporizer is a heat exchanger, where in this process, the heat that is used by the

vaporizer comes from cooling of the absorber, making the vaporizer a very energy

efficient. Methanol is being sprayed into the heat exchanger together with the process

gas where it will be vaporized (Perstorp, 2011).

3. Reactors

The process gas with methanol is fed to the reactor, where it enters a heat

exchanger reactor with 14600 vertical tubes filled with Iron-Molybdenum catalyst.

Inside the reactor, the feed is passed through the Fe-Mo catalyst filled tubes where heat

is removed from the exothermic reaction to the outside of the tubes (Sanhoob et al.,

2012). The reaction is exothermic where cooling medium is required. When the gas

14
passes the catalyst, the methanol is being oxidized to form formaldehyde. The process

uses excess air and the temperature in the reactor is isothermally controlled to a

temperature of about 340 ºC. Heat transfer fluid (HTF) is used, which is a mixture of

26.5% biphenyl and 73.5% diphenyl oxide. When heat is evolved due to the reaction

inside the tubes, the HTF will boil on the outside and vaporize (Johansen et al., 2013).

When the gas leaves the reactor, it will be subjected into aftercooler mostly a

vaporizer, for the gas to be cooled. After the gas is cooled, it is fed to the bottom of the

absorption column.

Since, plug flow or tubular, reactors (PFR) consist of a hollow pipe or tube. The

reactor model used is an industrial methanol oxidation reactor which is a plug flow

reactor installed with heat exchangers or a heat exchanger reactor filled with Iron-

Molybdenum catalyst. The advantage of using PFR is that it has a high conversion rate

per reactor volume. Moreover, the total reaction of the oxidation of methanol is highly

exothermic and fast, requiring short contact of time, which a PFR is suited due to its

capability in rapid reaction and can be jacketed with cooling fluid to control the

temperature inside the reactor (Satterfield, 1985).

15
 Model of an Industrial Reactor for Formaldehyde Production with Catalyst Deactivation,

Catarina G. Braz et al., (2017).

4. Condenser

The vaporized HTF from the reactor will flow to the condenser, where it will

condense with the use of water. As the HTF cools down, the water will evaporate and

produce steam, the condensed HTF will then flow back to the reactor (Perstorp, 2011).

5. Absorber

After the product leaving the reactors is cooled in a vaporizer, the product will

be passed to the absorber. The absorber consists of three parts, the lower section

includes valve trays without cooling and can be considered as two theoretical steps. The

middle section is packed section with external cooling by the vaporized, this section can

be considered as two theoretical steps. The top section consists of bubble cup trays that

have internal cooling coils on each tray, this section can be considered as three

theoretical steps. The process water fed to the column and controls the formaldehyde

concentration of the product. The composition of formaldehyde in the absorber is

controlled by the amount of water addition. Almost methanol-free product can be

achieved after the absorber (Sanhoob et al., 2012).

16
 Absorption System for Formaldehyde Production, Catarina G. Braz et al. 2017

The packed-bed absorbers are the most common absorbers used for gas removal.

The absorbing liquid is dispersed over the packing material, which provides a large

surface area for gas-liquid contact. For the sizing of packed tower, the column will be

assumed to be packed with 2 inches Ceramic Berl Saddle (Sanhoob et al., 2012).

6. Heat Exchanger

The recycled formaldehyde stream enters a heat exchanger before being

transported back to the absorber. In the heat exchanger, the formaldehyde product

stream from the absorber is cooled down, while the recycle stream is heated (Perstorp,

2011).

7. Emission Control System

In the formaldehyde production unit generates a vent gas which will passed to a

vent gas treatment unit like Emission Control System (ECS) and discharged to

atmosphere. An emission control system may comprise a catalytic combustor that reacts

with carbon monoxide, methanol, formaldehyde, and dimethyl ether in the vent gas

17
with oxygen. The gas emitted from ECS, comprises carbon dioxide, steam, and nitrogen,

and therefore can be recycled (Erlandsson et al., 2015).

H. Feed and Product Composition

1. Feed Composition

The feed composition to be injected to the reactor will depend on the flow rate of the

methanol inlet and the process gas in kmol per hour. The feed contains methanol, water, oxygen,

and nitrogen gas from air (Sanhood et al., 2012). Other feed composition contains formaldehyde

from the recycle in the absorber.

2. Capacity Selection

The Production of Formaldehyde in the Philippines is about 789 Thousand Metric Tons

while the Demand is about 795 thousand metric tons (Bizzari, 2000).

Capacity of formaldehyde required to produce:

Demand−Production=Capacity

795000−789000=6000 MT / year

The desired capacity of the study is 6000 MT/year or 20 MT/day (Baber et al., 2018).

3. Product Composition

From the study of Johansen et al. (2013), the total flow rate of the product stream was

8,923 kg/h, with a composition of water, formaldehyde and methanol of 51.8 wt%, 47.9 wt% and

0.29wt%, respectively.

From the study of Baber et al. (2018), the final product includes up to 55 wt%

formaldehyde and 0.5-1.5 wt% methanol, the remains are water.

The desired composition of this study is that the formaldehyde is at the range of 50 to

60%. Where nearly 98 to 99% methanol conversion.

18
19
 Chapter III

DESIGN METHODOLOGY

I. Using Three Reactors in Parallel

A. Reaction Kinetics

Formaldehyde is usually produced through the catalytic oxidization of methanol.

The reaction involves in oxidation of methanol is

1
C H 3 OH + O2 → HCHO+ H 2 O
2

It is a pseudo-first order reaction with a rate expression of

k1 p C H OH
−r C H OH = 3

3
1+k 2 pC H OH 3

A pseudo-first order reaction is a second order or bimolecular reaction that

behaves life a first order. The oxidation of methanol to form formaldehyde reaction is

dependent upon the concentrations of both methanol and oxygen but one of the

components is present in large excess and thus its concentration hardly changes as the

reaction proceeds.

If component oxides are in large excess and its concentration is very high as

compared to that of methanol, the reaction is a pseudo-first-order reaction with respect

to methanol. In this report the rate equation is expressed in terms of methanol since, the

oxide only serves as catalyst in the reaction.

20
 The basic mole balances of all components involve in the main reaction are:

d CCH OH
Methanol ( C H 3 OH ) 3
=−r C H OH
dt 3

d CO −1
Oxygen (O2 ) 2
= r
dt 2 O 2

d C HCHO
Formaldehyde (HCHO) =r HCHO
dt

d CH O
Water ( H 2 O) 2
=r H O
dt 2

Since, the rate of reaction is equal with the rate equation of the individual

components;

−1
r rxn =−r C H OH = r =r HCHO=r H
3
2 O 2 2 O

k1 pm
−r C H OH = 3
1+k 2 pm

Therefore,

k 1 pC H OH
r rxn =−r C H OH = 3

3
1+k 2 p C H 3 OH

The derived equation in terms of the concentration of methanol was shown in

reaction kinetics section in chapter 2. The obtained equation is

k 1 (C C H OH RT )
−r C H OH = 3

3
1+k 2( CC H OH RT ) 3

where:

KPa−m3
R is the universal constant (8.314 ¿
kgmol−K

T is the temperature in the reactor ( Kelvin , K )

21
 CCH 3 OH is the concentration of methanol at time T (kgmol/L)

k 1∧k 2 is rate constant

Which defined as

8774
ln ( k 1 )=12.5−
T

7439
ln ( k 2 )=−17.29+
T

Calculating the simultaneously rate constant using the operating temperature of

the reactor at T =340 ℃.

kmol
k 1=0.1637012527 3
m −kPa−kgcatalyst

−3 hr
k 2=5.7556741 x 10 3
kPa−m

0.1637012527(C C H OH )(8.134)( 340+ 273.15) K

−r C H OH = −3
3

3
1+5.7556741 x 10 (C C H 3
OH )(8.134)(340+273.15) K

834.5046396(C C H OH )
−r C H OH = 3

3
1+29.34086735(C C H 3
OH )

Consider the equation in terms of conversion of methanol

C(CH OH ) 0 ( 1−X C H OH )
CCH =
3 3

OH
3
1+ε X C H 3 OH

−r C H OH =
834.5046396
( C( C H 3 OH ) 0

1+ε X C H
( 1− X C H OH )
3 OH
3

)
( C (C H ( 1−X C H OH )
)
3

OH ) 0
1+29.34086735 3 3

1+ ε X C H 3 OH

where:

22
 C (C H 3 OH )0 is the initial concentration of the methanol ( kmol
hr )
XC H 3 OH
is the fractional conversion of methanol to formaldehyde.

Under the atmospheric pressure and temperature ranges from 250 to 400 ℃,

methanol conversion inside the reactor could reach 99% using metal oxides as catalysts.

Based on the obtained rate of reaction, the reactor would be feasible to attain 85 to 99%

conversion of methanol.

B. Reactor Design

The reactor used in the study is plug flow reactor with isothermal temperature

and the design of the reactor is same with shell and tube heat exchanger. The tubes have

Fe-Mo catalysts embedded.

The design aims to determine the volume of the reactor and since it is desired

that the reactors would have the same feed rate and conversion, the reactor will have

the same volume.

It also aims to determine the residence time, space velocity, catalyst volume,

volume of each tube, total number of tubes, and the dimensions of the reactor.

The composition of methanol is assumed theoretically. The pressure of the

reactor is based on the studies and temperature of the reactor is assumed. It is also

assumed that the flow rates leaving the three reactors are equal.

 Capacity Selection

Capacity of formaldehyde required to produce:

Demand−Production=Capacity

23
 795000−789000=6000 MT / year

The desired capacity of the study is 6000 MT/year or 20 MT/day to meet the

desired capacity per year (Baber et al., 2018).

 Reactor Operating Condition

Pressure of the reactor is 182.6 KPa. Temperature of the Reactor is 340ºC

(613.15K) (isothermal).

 Reaction Kinetics

1
C H 3 OH + O2 → HCHO+ H 2 O
2

1
A+ B →C+ D
2

C(CH OH ) 0 ( 1−X C H OH )
CCH OH =
3 3

3
1+ε X C H 3 OH

C A ( 1−X A )
C A= 0

1+ ε X A

−r C H OH =
834.5046396
( C( C H 3 OH ) 0

1+ε X C H
( 1− X C H OH )
3 OH
3

)
( C (C H ( 1−X C H OH )
)
3

OH ) 0
1+29.34086735 3 3

1+ ε X C H 3 OH

−r A =
834.5046396 ( C A ( 1−X A )
0

1+ ε X A )
1+ 29.34086735 ( C A ( 1− X A )
1+ε X A
0

)
24
  Desired Production

Capacity in kg/hr:

Capacity=20
MT
day(1000
kg
MT )( 124dayhr )=833.333 kghr
The desired composition of the study is 51.8%wt formaldehyde, 47.9% wt water

and 0.29% wt methanol based from the study of Johansen et al. (2013).

Average Molecular Weight of the Product:

kg
Average MW =30.026 ( 0.518 ) +18.015 ( 0.479 ) +32.042 ( 0.0029 )=24.276671
kmol

Desired Production in kmol/hr:

833.333
kg
( kmol
hr 24.276671kg
=34.32649394 )
kmol
hr

 Material Balance in the Absorber

Material Balance in the Absorber:

Tail Gas

Process &
Absorber

Cooling
Water

Steam/Cooling Water

Feed, A

Amount of Formaldehyde in the Product:

kmol kmol
34.32649394 ( 0.518 )=17.78112386
hr hr
25
Amount of Process Water Included:

kg
Formaldehyde Solubilty∈Water=550 3
m

Volumetric Flow Rate of Water=

17.78112386
kmol
hr (
30.026
kg
kgmol )
=0.9707200455
m
3

kg hr
550 3
m

The temperature of the Absorber is assumed isothermally at 303 K. The density

of water at 303 K is 994.7196 kg/m3.

( )
3
m kg kg
Rate of Water =0.9707200455 994.7196 3 =965.5942554
hr m hr

Amount of Water Added=965.5942554 (

kg kgmol
hr 18.015 kg )
=53.59945908
kgmol
hr

Approximately 85% of the water added will exhaust as steam and some are

released at cooling liquid.

kgmol kgmol
53.59945908 ( 0.85 )=45.55954022
hr hr

From the study of Baber et al., 55% of the feed in the absorber will be the tail gas.

0.55 A+ water added=tail gas+ cooling water + desired production

kgmol kgmol kmol

A+53.59945908 =0.55 A+ 45.55954022 +34.32649394
hr hr hr

kmol
A=58.41461129
hr

 Mass Balance in Aftercooler

26
 Reactor 1

Aftercooler
Reactor 2

Reactor 3

Entering∈the Aftercooler=Leaving ∈the aftercooler

The product stream of each reactor would be equal to the amount entering the

aftercooler divided by the three reactors. The process is assumed to have equal rates for

all the reactors.

kmol
58.41461129
hr kgmol
Amount leaving∈each Reactor= =19.47152038
3 hr

 Mass Balance in each Reactor

Reactor Feed, nF Reactor

Amount entering the reactor would be the amount leaving the reactor.

kgmol
n F =19.47152038
hr

Amount of Methanol in the Feed:

Desired Composition of the Amount of Feed: 50% Recirculated Gas and 50% Methanol.

kgmol kgmol
F MetOH =F A=19.47152038 ( 0.50 )=9.73576019
hr hr

27
  Residence Time in each Reactor

Basic Performance Equation for Plug Flow Reactor:

XA
V d XA
=∫
F A 0 −r A

τ V
=
CA F A
0

XA
dX
τ =C A 0
∫ −r A
0 A

V x =1−V x =0 ( 1+1 )−(1+0.5) 1

ε A= A A
= =
V x =0
A
(1+0.5) 3

Since the reactor operation condition is at high pressure and temperature is at

ideal range, the reaction behaves as ideal.

Initial Volume:

V 0=
n F RT
=
19.47152038
kgmol
hr
8.314 (
m3−KPa
kgmol−K
( 613.15 K ) )
=543.5954877
m3
P 182.6 KPa hr

Initial Concentration of Methanol:

kgmol
9.73576019
F hr kgmol
CA = A = =0.01790993562
0
V0 m
3
m
3
543.5954877
hr
XA
V d XA
=∫
F A 0 −r A

The desired conversion is 87.4% so X A =0.874 .

28
 XA
V d XA
=∫

( )
FA 0 C A ( 1− X A )
834.5046396 0

1+ε X A

1+ 29.34086735 ( C A ( 1−X A )
1+ε X A
0

)
0.874
V dXA
= ∫

( )
FA 0

834.5046396
( 0.01790993562
hr )
kgmol
( 1−X ) A

1
1+ X A
3

(
( hr )
)
kgmol
0.01790993562 ( 1− X ) A
1+29.34086735
1
1+ X A
3

3
V m −hr
=0.1960341838
FA kgmol

V
τ =C A 0
FA

τ =0.01790993562
kgmol
m3 (
0.1960341838
m3−hr
kgmol
=3.51095961 x 10−3 hr )
τ =0.2106575766 mins

 Space Velocity in Each Reactor

1
s=
τ

1
s=
0.2106575766 mins

−1
s=4.747040273 min s

 Volume of the fluid in each Reactor

29
 τ FA
Vf=
CA 0

Vf=
(
( 3.51095961 x 10−3 hr ) 9.73576019 kgmol
hr )
kgmol
0.01790993562 3
m

3
V f =1.908541802 m

 Volume of the Reactor and Catalyst

Volume of each Reactor:

Voidage = 60% (based from the Voidage Range for Fe-Mo Catalyst 55%-65%)

Vf
=Voidage
VR

1.908541802m3
=0.6
VR

3
V R=3.180903003 m

Volume of the Catalyst:

V C =V R −V f

3 3
V C =3.180903003m −1.908541802 m

V C =1.272361201 m3

30
II. Design Methodology for Using Four Reactors in Combined Parallel and Series

A. Reaction Kinetics

The reaction kinetics for this design is the same in the design methodology for

using three reactors in parallel.

B. Reactor Design
The reactor used, catalyst, reactor operating condition, and aim is the same in the

design methanol using three reactors in parallel.

The total feed of methanol is assumed theoretically. The pressure of the reactor is

based on the studies and temperature of the reactor is assumed.

 Capacity Selection

Capacity of formaldehyde required to produce:

Demand−Production=Capacity (Baber et al., 2018)

795000−789000=6000 MT / year

The desired capacity of the study is 6000 MT/year or 20 MT/day to meet the

desired capacity per year.

 Reactor Operating Condition

Pressure of the reactor is 182.6 KPa. Temperature of the Reactor is 340ºC

(613.15K) (isothermal).

31
  Reaction Kinetics

1
C H 3 OH + O2 → HCHO+ H 2 O
2

1
A+ B →C+ D
2

C(CH OH ) 0 ( 1−X C H OH )
CCH OH =
3 3

3
1+ε X C H 3 OH

C A ( 1−X A )
C A= 0

1+ ε X A

−r A =
834.5046396
( C ( A ) 0 ( 1−X A )
1+ ε X A )
1+ 29.34086735 ( C ( A ) 0 ( 1−X A )
1+ε X A )
 Desired Production

Capacity in kg/hr:

Capacity=20
MT
day (
1000
kg
MT )( 124dayhr )=833.333 kghr
The desired composition of the study is 51.8%wt formaldehyde, 47.9% wt water

and 0.29% wt methanol based from the study of Johansen et al., 2013.

Average Molecular Weight of the Product:

kg
Average MW =30.026 ( 0.518 ) +18.015 ( 0.479 ) +32.042 ( 0.0029 )=24.276671
kmol

Desired Production in kmol/hr:

833.333
kg
( kmol
hr 24.276671kg
=34.32649394
kmol
hr )
32
  Material Balance in the Absorber

Material Balance in the Absorber:

Tail Gas

Process &

Absorber
Cooling
Water

Steam/Cooling Water

Feed, A

Amount of Formaldehyde in the Product:

kmol kmol
34.32649394 ( 0.518 )=17.78112386
hr hr

Amount of Process Water Included:

kg
Formaldehyde Solubilty∈Water=550
m3

Volumetric Flow Rate of Water=

17.78112386
kmol
hr (
30.026
kg
kgmol )
=0.9707200455
m3
kg hr
550 3
m

The temperature of the Absorber is assumed isothermally at 303 K. The density

of water at 303 K is 994.7196 kg/m3.

( )
3
m kg kg
Rate of Water =0.9707200455 994.7196 3 =965.5942554
hr m hr

33
 Amount of Water Added=965.5942554
kg kgmol
hr 18.015 kg (
=53.59945908)kgmol
hr

Approximately 85% of the water added will exhaust as steam and some are

released at cooling liquid.

kgmol kgmol
53.59945908 ( 0.85 )=45.55954022
hr hr

From the study of Baber et al., 55% of the feed in the absorber will be the tail gas.

0.55 A+ water added=tail gas+ cooling water + desired production

kgmol kgmol kmol

A+53.59945908 =0.55 A+ 45.55954022 +34.32649394
hr hr hr

kmol
A=58.41461129
hr

 Mass Balance in Aftercooler

Aftercooler

Reactor 2

Reactor 4

Entering∈the Aftercooler=Leaving ∈the aftercooler

It is assumed that the product stream of the Reactor 2 is higher than the product

stream of Reactor 4.

It is assumed that,

Flow rate∈Reactor 2=33.41461129 kmol / hr

34
 kmol
Flow rate∈ Reactor 4=25
h

 Branch Analysis of Reactors

Branch A
Reactor 1 Reactor 2

Reactor 3 Reactor 4

Branch B

The amount leaving in each Branch is equal to the amount entering in each

branch. The composition of the methanol in each branch is 50%.

kmol
F A =33.41461129× 0.5=16.70730565
A
hr
kmol
F A =25 × 0.5=12.5
B
hr
Where,

F A is the amount of methanol in Branch A.

A

F A is the amount of methanol in Branch B.

B

 Volumes of Reactors in Branch A

Basic Performance Equation for Plug Flow Reactor:

( )
XA
VA V VB d XA
= T
= T =∫ T

F A F A F A 0 −r A
A B

τ V
=
CA F A 0

XA
dX
τ =C A 0
∫ −r A
0 A

35
 V x =1−V x =0 ( 1+1 )−(1+0.5) 1
ε A= A A
= =
V x =0
A
(1+0.5) 3

Since the reactor operation condition is at high pressure and temperature is at

ideal range, the reaction behaves as ideal.

Initial Volume:

( )( )
3
kmol m − KPa
33.41461129 8.314 ( 613.15 K )
n F A RT hr kgmol−K m
3
V 0= = =932.8512395
P 182.6 KPa hr

Initial Concentration of Methanol:

kmol
F A 16.70730565 hr kgmol
CA = = A
=0.0179099356
V0
0
m 3
m3
932.8512395
hr

( )
VT X A
d XA
=∫A

( )
FAA 0 C (C H OH ) 0 ( 1−X C H OH )
834.5046396 3 3

1+ ε X C H OH 3

1+ 29.34086735
( C (C H 3
OH ) 0

1+ε X C H
( 1−X C H OH )
3 OH
3

)
The desired conversion is 87.4% so X A =0.874 .

36
 V A 0.874 d XA
=∫

( )
FA A 0

834.5046396
( 0.01790993562
hr )
kgmol
( 1− X ) A

1
1+ X A
3

(
( hr )
)
kgmol
0.01790993562 ( 1−X ) A
1+29.34086735
1
1+ X A
3

3
V m −hr
=0.1960341838
FA kgmol

V
τ =C A 0
FA

τ =0.01790993562
kgmol
m3 (
0.1960341838
m3−hr
kgmol
−3
=3.51095961 x 10 hr )
VT m −hr
3
=0.1960341838
A

FAA kgmol

3
m −hr
V T =0.1960341838 ( FA )
A
kgmol A

( )
3
m −hr kmol
V T =0.1960341838 16.70730565
A
kgmol hr

V T =3.275203027 m3
A

It is assumed that the volume ratio of Reactor 1 and Reactor 2 from Branch A is

V1 A
=2
V2 A

Therefore:

V 1 =2V 2
A A

V T =V 1 + V 2
A A A

37
 V T =2 V 2 +V 2
A A A

3
3.275203027 m =2 V 2 +V 2 A A

V 2 =1.091734342m3
A

3
V 1 =2.183468685 m
A

 Space Time and Space Velocity of Reactor 1 and Reactor 2

For Reactor 1:

V1
τ 1 =C A A

0
FA A

kgmol 2.183468685 m3 −3
τ =0.01790993562 3
× =2.340639741 x 10 hr
m kgmol
16.70730565
hr

τ 1 =0.1404383845 mins

1
s=
τ

1
s=
0.1404383845 mins

−1
s=7.120560406min s

For Reactor 2:

V2
τ 2=C A A

0
FA A

( )
kgmol 1.091734342m3
τ 2=0.0179099356 =¿
m3 16.70730565 kmol
hr

38
 τ 2=0.07021919221mins

1
s2=
τ2

1
s2=
1.091734342 m1.17031987 x 10−3 hr 3

−1
s=14.24112082min s

The overall space time to take in branch A,

τ A =τ 1+ τ 2

τ A =0.1404383845 mins+ 0.07021919221mins=0.2106575766 mins

 Volume of the fluid in each reactor

τ FA
Vf=
CA 0

V 1 Af =
(
( 2.340639741 x 10−3 hr ) 16.70730565 kgmol
hr )
kgmol
0.01790993562
m3

3
V 1 Af =2.18346865 m

V 2 Af =
(
( 1.17031987 x 10−3 hr ) 16.70730565 kgmol
hr )
kgmol
0.01790993562 3
m

3
V 2 Af =1.094419862 m

 Volume of the Reactor and Catalyst

Volume of each Reactor:

39
Voidage = 60% (based from the Voidage Range for Fe-Mo Catalyst 55%-65%)

Vf
=Voidage
VR

3
2.18346865m
=0.6
V R1 A

3
V R 1 =3.639114417 m
A

3
1.094419862m
=0.6
V R1 A

V R 1 =1.824033103 m3
A

Volume of the Catalyst:

V C =V R −V f

V C =3.639114417m3−2.18346865 m3

3
V C 1 A=1.455645767m

V C =V R −V f

V C =1.824033103 m3−1.094419862 m3

3
V C 2 A =0.729613241m

 Volumes of Reactors in Branch B

Basic Performance Equation for Plug Flow Reactor:

( )
XA
VA VT VB
d XA
= T
= =∫ T

F A F A F A 0 −r A
A B

40
 τ V
=
CA F A
0

XA
dX
τ =C A 0
∫ −r A
0 A

V x =1−V x =0 ( 1+1 )−(1+0.5) 1

ε A= A A
= =
V x =0
A
(1+0.5) 3

Since the reactor operation condition is at high pressure and temperature is at

ideal range, the reaction behaves as ideal.

Initial Volume:

V 0=
n F B RT
=
( 25
kmol
hr )(
8.314
m3−KPa
kgmol−K
( 613.15 K )
=697.9366238
)m
3

P 182.6 KPa hr

Initial Concentration of Methanol:

( )
XA
VT d XA
FAA ∫
=
A

0
834.5046396
( C (C H OH ) 0 ( 1−X C H OH )
3

1+ ε X C H OH 3
3

)
1+ 29.34086735
( C (C H 3
OH ) 0

1+ε X C H
( 1−X C H OH )
3 OH
3

)
The desired conversion is 87.4% so X A =0.874 .

41
 V A 0.874 d XA
=∫

( )
FA A 0

834.5046396
( 0.01790993562
hr )
kgmol
( 1− X ) A

1
1+ X A
3

(
( hr )
)
kgmol
0.01790993562 ( 1−X ) A
1+29.34086735
1
1+ X A
3

3
V m −hr
=0.1960341838
FA kgmol

V
τ =C A 0
FA

VT m −hr
3
=0.1960341838
B

F AB kgmol

3
m −hr
V T =0.1960341838 (F A )
B
kgmol A

V T =0.1960341838
B
m 3−hr
kgmol
12.5
kgmol
hr ( )
3
V T =2.450427298 m
B

It is assumed that the volume ratio of Reactor 3 and Reactor 4 from Branch B is

V3 B
=1
V4 B

Therefore:

V 3 =V 4
B B

V T =V 3 +V 4
B B B

V T =V 3 +V 3
B B B

3
2.450427298 m =V 3 +V 3 B B

42
 3
V 3 =V 4 =1.225213649 m
B B

 Space Time and Space Velocity of Reactor 3 and Reactor 4

For both Reactor 3 and Reactor 4

V3
τ =C A B

0
FA B

( )
3
kgmol 1.225213649m −3
τ 3 =τ 4=0.0179099356 =1.755479804 x 10 hr
m
3
kmol
12.5
hr

τ 3 =τ 4=0.1053287882 mins

1
s=
τ

1
s3=s 4=
0.1053287882 mins

s3=s 4=9.494080552min s−1

The overall space time to take in branch B,

τ B=2 τ

τ B=2 ( 0.1053287882 mins )=0.2106575764 min

 Volume of the fluid in each reactor

τ FA
Vf=
CA 0

43
 V 1 Af =
(
( 1.755479804 x 10−3 hr ) 16.70730565 kgmol
hr )
kgmol
0.01790993562 3
m

3
V f =1.637601512 m

 Volume of the Reactor and Catalyst

Volume of each Reactor:

Voidage = 60% (based from the Voidage Range for Fe-Mo Catalyst 55%-65%)

Vf
=Voidage
VR

3
1.637601512m
=0.6
VR

3
V R 3 B=V R 4 B=2.729335853m

Volume of the Catalyst:

V C =V R −V f

3 3
V C =2.729335853m −1.63760151 m

3
V C 3 B =V C 4 B=1.091734343 m

C. Summary Sheet

Using Three Reactors in Parallel:

Table 1: Operating conditions

44
 Temperature Isothermal at 340 ℃

Operating Pressure 182.6 kPa

Flow Rate 6000 MT/year

Table 2: Initial conditions of Feed

Methanol 50 % wt

Recirculated Gas 50 % wt

Concentration kgmol
0.010790993562
m3

Table 3: Reactor Design

Volume of each reactor 163.378185 m3

Volume of catalyst 63.3495274 m3

Volume of Tubes 0.02780 m3

Number of Tubes 5877 tubes

Diameter of Reactor 5.225 m

Residence time in each reactor 18.0326 mins

Space velocity 0.055455 ¿ min

Table 4: Fe-Mo oxide catalyst dimensions

Voidage 60%

Volume 63.3495274 m3

Table 4: Desired Compositions

45
 Formaldehyde 51.8 %wt recovery

Water 47.9 % wt

Methanol 0.29 % wt

Using Four Reactors in Combined Parallel and Series:

Table 5: Operating conditions

Temperature Isothermal at 340 ℃

Operating Pressure 182.6 kPa

Flow Rate 6000 MT/year

Table 6: Initial conditions of Feed

Methanol 50 % wt

Recirculated Gas 50 % wt

Concentration kgmol
0.010790993562 3
m

Table 7: Reactor Design

Volume of Fluid 1 2.183468685 m3

Volume of Catalyst 1 1.455645767 m3

Volume of Reactor 1 1.824033103 m3

Volume of Fluid 2 1.091734342 m3

Volume of Catalyst 2 0.729613241 m3

46
 Volume of Reactor 2 1.824033103 m3

Volume of Fluid 3 1.225213649m3

Volume of Catalyst 3 1.091734343 m3

Volume of Reactor 3 2.729335853 m3

Volume of Fluid 4 1.225213649 m3

Volume of Catalyst 4 1.091734343 m3

Volume of Reactor 4 2.729335853 m3

Space time in Branch A 0.2106575764 min

Space time in Branch B 0.2106575764 min

Space Velocity of Reactor 1 7.120560406 min s−1

Space Velocity of Reactor 2 14.24112082 min s

−1

Space Velocity of Reactor 3 9.494080552 min s

−1

Space Velocity of Reactor 4 9.494080552 min s−1

Table 8: Desired Compositions

Formaldehyde 51.8 %wt recovery

Water 47.9 % wt

Methanol 0.30 % wt

D. Conclusion

A Plug Flow Reactor was designed using Iron-Molybdenum Catalyst for the

production of Formaldehyde. The operating condition is isothermal with the assumed

47
temperature of 340 ℃ at a pressure of 182.6 kPa respectively. Using three reactors in

parallel and four reactors in combined parallel and series, given an amount of feed in

3
kgmol m
the reactor of 19.47152038 , an initial flowrate of 543.5954877 , an initial
hr hr

kgmol
concentration of methanol 0.01790993562 3 , with a desired conversion of methanol
m

to formaldehyde (87.4%), the computed specifications of the three reactors in parallel

were gathered; a volume of approximately 163.378185 m3, a height of 7.62m, a diameter

of 5.225 m, and a reaction time of 18.0326 minutes. And for the four reactors in

combined parallel and series, the following specifications were calculated; a volume of

approximately 186.9079 m3, 93.4540 m3, 104.8800 m3 and 104.8800 m3 for reactors 1, 2, 3,

and 4 arranged in parallel and series, and a reaction time of 18.0326 minutes in both

branches of the reactor. It is concluded that the proposed design for a plug flow reactor

using three reactors in parallel and four reactors in combined parallel and series has a

MT
good potential for the production of 6000 of formaldehyde.
year

REFERENCES

Books

1. Levenspiel O., Chemical Reaction Engineering, 3rd ed., Wiley, New York, 1999

2. Perry, R.H., and Green, D., Perry’s Chemical Engineers’ Handbook, 8th ed.,

McGraw-Hill Book Company, 2008.

48
 3. Davis, M. E., & Davis, R. J. (2003). Fundamentals of Chemical Reaction

Engineering. 1221 Avenue of the Americas, New York, NY 10020: The McGraw-

Hill Companies, Inc.

4. Geankoplis, C.J., Transport Processes and Unit Operations, 3rd ed., Prentice-Hall

International, Inc., 1993.

5. McCabe, L.B. and Smith, J.C. "unit operation of chemical109 engineering" 5th

Edition McGraw Hill, Inc

6. Austin, G.T. Shreve’s Chemical Process Industries (5th Ed.). McGraw-Hill

Companies, Inc.

7. Carey, F.A. & Giuliano, R.M. (2014). Organic Chemistry (9th Ed.). McGraw-Hill

Companies, Inc.

Online Journals

1. Ali Shah, S. A. Analysis of Opportunities to Implement Steam driven Fans in

new Foarmaldehyde Plants. Chalmers Univerity of Technology, 2012.

2. Ola Erlandsson, Andreas Magnusson, John David Pach, Daniel Sheldon, Process

for the Production of Formaldehyde, 2015

3. Catarina G. Braz, Henrique A. Matos, A. Mendes, Jorge F. Rocha, Ricardo P.

Alvim, Model of an Industrial Reactor for Formaldehyde Production with

Catalyst Deactivation, 2017.

4. C. Satterfield, Heterogeneous Catalysis in Industrial Practice, 2nd. Ed. Mc Graw-

Hill, New York, 1985, p.286.

49
5. Fletcher, C. J., The Thermal Decomposition of Formaldehyde. Royal Society,

1934, p.357.

6. Vallance, C., Reaction Kinetics. 2017

7. Walker, J. F., Formaldehyde. New York,1964

8. Subasi, N. T., Formaldehyde Advantages and Disadvantages: Usage Areas and

Harmful Effects on Human Beings. Retrieved from Intechopen:

https://www.intechopen.com/books/biochemical-toxicology-heavy-metals-

and-nanomaterials/formaldehyde-advantages-and-disadvantages-usage-areas-

and-harmful-effects-on-human-beings, October 5, 2018

9. C. Maldqnado, J.L.G. Fierro, G. Birke, E. Martinez, P. Reyes., Conversion of

methanol to formaldehyde on tio2 supported ag nanoparticles. Retrieved from

Journal of the Chilean Chemical Society: http://dx.doi.org/10.4067/S0717-

97072010000400021, 2010.

50