Simulation of Formaldehyde Production Process

Ruhul Amin, Nazibul Islam, Rezwanul Islam, Yusuf Imtiaz, Saeed M., Unaiza M.
Department of Chemical Engineering
Bangladesh University of Engineering and Technology, Dhaka-1000, Bangladesh

Abstract
Formaldehyde plays a major role in the synthesis of many important compounds. Worldwide production
of formaldehyde is growing day bay day. There are various industrial processes for the production of
formaldehyde. This article starts with an overview of formaldehyde and the history of formaldehyde
production. Subsequently, production of formaldehyde using silver catalyst is simulated with the help of
Aspen Hysys 7.1. Important parameters such as temperature profile, pressure profile, fluid properties etc
were investigated with this simulation process. The effect of temperature in the reaction was also
examined. The simulation process validated that for maximum conversion to take place, the reaction must
occur in 550C. Finally, 74% formaldehyde was obtained as product.
Key Words: Formaldehyde, Oxidation-dehydrogenation, NRTL, Simulation
products generated from formaldehyde include

1. Introduction

urea formaldehyde resin, melamine resin, phenol

Formaldehyde was discovered in 1859 by a

formaldehyde resin,poly-oxy-methylene plastics,

Russian chemist named Aleksandr Butlerov.

1,4-butane-di-ol, and methylene-di-phenyl-di-

However it was in 1869, that German chemist

iso-cyanate.[5]

August Hofmann developed a practical method

formaldehyde is used in vaccines, medicines,

to synthesis formaldehyde from methanol. [1] It is

plastics and in x-ray machines. The phenolic

a colorless gas with a distinctive pungent order.

molding resins produced from formaldehyde are

In

biomedical

industry,

It is highly flammable with a flashpoint of 50 C;

used in appliances, electrical control, telephone

the heat of combustion is 134.1kcal/mol or

and wiring devices.

4.47kcal/g.[2] Formaldehyde is soluble in a

building industries, formaldehyde-based acetal

variety of solvents and is miscible in water. [2, 3]

resins are used in the electrical system,

Formaldehyde is a key chemical component in

many manufacturing processes. It is used as a
building block for the synthesis of more
complex compounds and materials.

[4]

[6]

In the automotive and

transmission, engine block, door panels and

break shoes. [7]
The total annual formaldehyde capacity in 1998

In

was estimated by 11.3 billion pounds. Since then

approximate order of decreasing consumption,

and the production capacity around the globe is

1

expanding exponentially reaching a worlds

every process

production of 32.5 million metric tons by 2012.

calculation. It calculates as much as it can at all

[7, 8]

There are two main routes for formaldehyde

time and results are always available, even

production: oxidation-dehydrogenation using a

during calculation. Any changes that one makes

silver catalyst involving both the complete or

to the data are automatically propagated

incomplete conversion of methanol; and the

throughout the program to anywhere that entry

direct oxidation of methanol to formaldehyde

appears and all necessary recalculations are

using metal oxide catalysts.

oxidation-dehydrogenation

[9,

10]

route,

Formaldehyde

catalyst
is

at

formed

about
by

before

beginning

In the

instantly carried out. It tends to be a lot easier to

vaporized

catch errors as one gradually converge the

methanol with air is passed over a thin bed of

silver-crystal

condition

process simulation.

650 C.
the

de-

hydrogenation of methanol. [11, 12] The other route

involves the oxidation of methanol over a
catalyst of molybdenum and iron at 3500C. [13]

The Fluid package used in this simulation is

NRTL. The non-random two-liquid model is
known as NRTL equation in short[14]. NRTL is
an activity coefficient model that correlates
the activity coefficients of a compound i with

This article deals with the detailed study of the

its mole fractions in the liquid phase concerned.

simulation of formaldehyde production from

The concept of NRTL is based on the hypothesis

methanol. Simulation has been done with the

of Wilson that the local concentration around a

help of Aspen Hysys v7.2. Although simulation

molecule

does not give the real world performance or the

concentration. This difference is due to a

real life production environment but if the basic

difference between the interaction energy of the

process is known and related data are available,

central molecule with the molecules of its own

it is the best way by which an individual can get

kind Uii and that with the molecules of the other

ideas of an industrial process without conducting

kind Uij. The energy difference also introduces a

any experiment.

non-randomness at the local molecular level.

2. Methodology
The process of producing formaldehyde from
methanol is simulated in Simulation software
Aspen Hyssy 7.1. Aspen Hysys is a simulationsoftware which comes along with excellent
reference & tutorial manuals for simulating a
process. Hysys does not wait until entering

is

different

from

the

bulk

The NRTL model belongs to the so-called localcomposition models. Other models of this type
are

the Wilson model,

the UNIQUAC model,

and the group contribution model UNIFAC.

These

local-composition

thermodynamically

models

consistent

due

are

not

to

the

assumption that the local composition around

molecule

is

independent

of

the

local

composition around molecule j. This assumption

2

is not true, as was shown by Flemmer in

formalin). The yield from the reaction is 85 to

1976[15, 16].

90 percent. The catalyst is easily poisoned so

stainless-steel equipment must be used to protect
the catalyst from metal contamination.

2.1 Process Description

Formaldehyde results from the exothermic
oxidation and endothermic hydrogenation of
methanol.

These

two

reactions

occur

simultaneously in commercial units in a

balanced reaction, called auto thermal because

2.2 Simplified Block Diagram

the oxidative reaction furnishes the heat to cause

the dehydrogenation to take place. About 50 to
60 percent of the formaldehyde is formed by the
exothermic reaction. The oxidation requires
1.6m3 of air per kilogram of methanol reacted, a
ratio that is maintained when passing separate
streams of these two materials forward. Fresh &
recycled methanol are vaporized, superheated
and

passed

into

the

methanol-air

mixer.

Atmospheric air is purified, compressed and preheated to 540C in a finned heat exchanger. The

Figure 1: Block diagram of the total process

products leave the converter at 620 oC and at 34

to 69 KPa absolute. The converter is a small
water-jacketed vessel containing the silvercatalyst. About 65 percent of the methanol is
converted per pass. The reactor effluent contains
about 25% formaldehyde, which is absorbed
with the excess methanol and piped to the make
tank. The latter feeds the methanol column for

2.3 Set Stoichiometry and Rate of

separation of recycle methanol overhead, the

Reaction

bottom stream containing the formaldehyde and

a few percent methanol. The water intake adjusts
the formaldehyde to 37% strength (marketed as
3

As mentioned earlier, Formaldehyde results

from the exothermic oxidation and endothermic
de-hydrogenation of methanol.
CH3OH + 1/2 O2

CH2O + H2O;

H = -156 KJ

mole
gcatalyst
K 1 pm
rm2 [
]=
hr
1+ K 2 pm
Where,

lnK 1=16.9

CH3OH

CH 2O + H2;

H = +85 KJ

12500
T

And

So the stoichimetry for Methanol in the 1st and

nd

2 reaction would be -1
For Formaldehyde it would be +1 for the both
reactions.

lnK 2=25.0

15724
T

For all the equations, T is in Kelvin. [8]

2.4 The Simulation Environment

st

For Oxygen it would be -0.5 in the 1 reaction

1. First Methanol and feed air are delivered
And for water and Hydrogen it would be +1 for
st

nd

the 1 and 2 reaction respectively.

The rate of reaction for the first reaction will be:

mole
gcatalyst
k 1 pm
r m 1[
]=
hr
1+k 2 pm

and delivered to the reactor.

2. In the first step of the reaction, methanol
reacts with oxygen to give formaldehyde
and water
3. In the 2nd stage some of the methanol
breaks

up

to

formaldehyde

and

hydrogen.
4. The vapor from the reactor outlet is

Where,

8774
lnk 1=12.50
T

cooled to 10 C and delivered to a

separator.
5. The Hydrogen is separated from the
mixture.
6. The remaining mixture is heated to 100

And

lnk 2=17.29+

to a mixer and later preheated to 55 C

7439
T

C and fed to the distillation column.

7. From the distillation column, we get the
liquid product of 83.2% formaldehyde

The rate of reaction for the second reaction will

be:

and

vapor

product

of

44.1%

formaldehyde.
8. The vapor product is heated to 35 C
and delivered to a storage tank.
4

Final composition of Formaldehyde obtained is

74.8%.
200

Different parameters of the distillation

column are shown in different graphs below-

100
Temperature

0
-100

10

15

-200
-300
Number of Tray

3.1 Temperature Profile of Distillation

2.

Column

5 Importance of Temperature in the

Simulation
Figure 2: Graphical representation of

The heated feed that is delivered to the

first reactor is heated to a temperature of
55 C by delivering the feed to a heater.
It is heated to 55 C because this is the

Temperature vs Tray position from top

From figure 2 we can see that the condenser

temperature

is

around

-2500C.

The

optimum temperature of reactor inlet.

The final top product from the

temperature rises rapidly from the condenser

distillation column is delivered to a

tray after the condenser. From tray 2, the

heater before it is stored in the storage

temperature rise is linear and is around

tank. The outlet from the heater is

heated to a temperature between 35-45

and reaches near 1000C at stage 2 that is first

1100C in the reboiler.

C. At temperatures below 35 C, the

product forms formaldehyde polymer
which

is

not

desired.

Storage

at

temperatures between 35-45 C further

inhibits the formation of formaldehyde
polymers[2].

3. Results and Discussions

5

1.00E+030
1.00E+027
1.00E+024
1.00E+021
1.00E+018
1000000000000000
Light liquid
1000000000000
1000000000
1000000
1000
1
0 5 1015

20
15
Pressure(psia) 10
5
0
-2

13

Number of Tray

3.2
Pressure profile of Distillation column

Figure 3: Graphical representation of

Temperature vs Tray position from top
From this graph we can visualize the pressure
profile of the distillation column. Here we see
that the pressure profile is almost linear. The
linear equation for this curve is,

Figure 4: Graphical representation of light

liquid (mole fraction) vs Tray position from top

Y=0.6081X+10.551

Here, we see that there is a slight rise of mole

With, R2= 0.9946

fraction of the light liquid from condenser to

3.3 Light Liquid Composition

tray 1. After that up to tray 7 this value remains

somewhat constant. From tray 7, which is the
feed tray we again see a perfect linear increase
in light liquid mole fraction right up to the
reboiler.

3.4 Flow rate vs. Tray Position

8.00E+03

0.8

7.00E+03

0.7

6.00E+03

0.6

5.00E+03

0.5

4.00E+03

0.4

3.00E+03

0.3

2.00E+03

0.2

1.00E+03

0.1

0.00E+00
0

8 10 12 14 16

Figure 5: Graphical representation of flow vs

Tray position from top

0
0

10 12 14 16

Figure 6: Graphical representation of

composition (light liquid) vs Tray position from
top

In the case of molar flow, we see that the

vapor flow starts from zero at tray 1 and
increases rapidly up to tray 3. From tray 3

1.00E+05
1.00E-03
1.00E-11

this increase in flow is much sluggish. For

1.00E-19

the liquid however, there are rapid increases

1.00E-27

in flow from reboiler to tray 1 and also in

these rapid increases, the flow is somewhat

1.00E-59

3.5 Light Liquid Composition vs. Tray

Position

10 12 14 16

1.00E-43
1.00E-51

the flow of liquid at the reboiler.

1.00E-35

tray 7 which is the feed tray. In between

constant. Finally there is a drastic drop in

1.00E-67

For the light liquid, we see that water

composition is higher than Formaldehyde in the
condenser. But from the condenser a gradual
increase in Formaldehyde composition takes
place right up to theFormaldehyd
reboiler. Evidently the
water composition decreases
from the condenser
e
to reboiler.

they decrease a little and remain perfectly

constant.

3.6 Heavy Liquid Compositon vs. Tray

Position

3.8 Transports Properties of the

Distillation Column

0.8

120

0.7
100

0.6
0.5

80

0.4
0.3

Column Properties

0.2

60
40

0.1
20

0
0

10 12 14 16

0
0

5 10 15

Figure 7: Graphical representation of

composition (vapor) vs Tray Position from top
Here we also see that starting from zero in the
condenser; the composition of formaldehyde

Figure 9: Graphical representation of column

properties vs tray position from top

gradually increases. In the case of water, the

If we analyze the properties of the light liquid in

composition reaches its maximum at tray 2 and

the distillation column, we find that the surface

from there it gradually decreases.

tension decreases dramatically from condenser

3.7 K-values vs tray position

Figure 8: Graphical representation of k-values
vs Tray position from top

to tray 2 and from there, this decrease in surface

tension is gradual.
The molecular weight increases linearly with the
equation:

In the case of k-values (Distribution Co-

Y=0.2622X+23.182

efficient), we see that the distribution co-

And, R2=0.9981

efficient of hydrogen (present in the feed)

remains constant with respect to water and
formaldehyde. The k-values for the letter two
increase dramatically up to tray 2 from where

The heat capacity increases with the linear

equation:
Y=0.0643X+3.698
8

And, R2=0.8865

amount of product. This in turn will help to

calculate the cost required to operate a

3.9 Effect of Temperature on Feed

formaldehyde production plant.

References

-1.15E+08
20 40 60
-1.20E+08

1.

-1.25E+08
Heat flow (kJ/h)
-1.30E+08
-1.35E+08

2.

-1.40E+08
Temperature of heated feed (C)

3.

Figure 10: Graphical representation of heated

flow vs temperature of heated feed
In case of the heated feed, the heat flow keeps
increasing with the increase of temperature of

4.
5.

the heated feed. After 45 C the heat flow does

not increase too much with the change in

6.

temperature and becomes constant. So the

heated feed is heated to a temperature of 55 C.

4. Conclusion

7.
8.

The simulation developed by AspenHYSYS is

useful to understand the detailed environment of
the production process of formaldehyde. The

9.

tray-by-tray characteristics of the distillation

column can be visualized using simulation.
Similarly the products of the reactors can be
anticipated. Thus using this simulation, one can
easily calculate the material and energy feed

10.

CECIL H. , Frank B., JOHN W.,

PETER P. Formaldehyde
Fixation The Journal of
Histochemistry and
Cytochemistry 1985. 33(8): p.
845-853.
Inc. S.A., Formaldehyde,
Material Safety Data Sheet
version 1.10. 2007: Missouri,
USA.
NCDOL, A Guide to
Formaldehyde. North Carolina
Dept. of Labor: 1101 Mail
Service Center Raleigh, NC
27699-1101.
Robert C., CRC Handbook of
Chemistry and Physics 62 ed.
1981.
Jacqueline I., Seidel A.,
Encyclopedia of Chemical
Technology. 1997, John Wiley
and Sons.
Natz B., FORMALDEHYDE:
FACTS AND BACKGROUND
INFORMATION. 2007: Arlington.
Bizzari S.N., Formaldehyde.
Chemical Industries Newletter
2007.
Sanhoob M A., Sulami A., Shehri
F., Rasheedi S., Production of
Formaldehyde from Methanol
Integrated Final Report. 2012,
KFUPM.
Austin T.G., Shreve's Chemical
Process Industries. 5th ed.
Chemical Engineering Seris.
1984, United States: McGrawHill Book Company.
Perry R.H., Green D.W., Perrys
chemical engineers Handbook.
7th ed. 1997: McGraw-Hill.

required for the production of any specific

9

11.
12.
13.

14.

15.
16.

Dryden.C.E., Outlines of
Chemical Technology for 21st
Century. 1997, New York press.
Ketta Mc., Encyclopedia of
Chemical Technology,. 1997.
Mccabe W. L., Smith J.C., Harriot
P., Unit Operations in Chemical
Engineering. 6th ed. 2001:
McGraw Hill.
Renon H. Prausnitz J. M., Local
Compositions in
Thermodynamic Excess
Functions for Liquid Mixtures.
AIChE Journal, 1968. 14(1): p.
135-144.
Flemmer, Collection of
Czechoslovak Chemical
Communications. 1976. p. 3347.
McDermott C.M., Fluid Phase
Equilibrium 1ed. Vol. 33. 1977.

10