King Fahd University for Petroleum and Minerals

Department of Chemical Engineering

Senior Project

FORMALINE PRODUCTION PROC

HYSYS SIMULATION

Term 121

Abbas Al-Salboukh
200764950
Mostafa Al-Osaif 200779610
Mohammed rajal
Mohammed moaish

GROUP:C
21/11/20

Table of Contents:
I.
II.
III.
1

Summary
Introduction
Formalin Production Process
Process Description
a) compressor
b)
c)
d)
e)
f)

reactor type and methanol conversion

Flash feed condition

Distillation column
Recycle of benzeneAbsorber
Efficiencies of compressor, pumps and heat exchanger pressure difference

2 . Alternative Process Description

IV.

Justification of change in the process

1. Adding cooler before the reactor
2. Adding cooler after reactor
3. Removing air heater

V.
VI.
VII.

Explained Differences and Comparing.

Conclusion
Appendixs

I. Summary:
Process simulation is a model-based representation of chemical, physical,
biological, and other technical processes and unit operations in software. Basic
1

prerequisites are a thorough knowledge of chemical and physical properties of pure

components and mixtures, of reactions, and of mathematical models which, in
combination, allow the calculation of a process in computers. Process simulation
software describes processes in flow diagrams where unit operations are positioned
and connected by product streams. The software has to solve the mass and energy
balances to find a stable operating point.
The goal of a process simulation is to find optimal conditions for an examined
process. This is essentially an optimization problem which has to be solved in an
iterative process. Process simulation always uses models which introduce
approximations and assumptions but allow the description of a property over a
wide range of temperatures and pressures which might not be covered by real data.
Models, also, allow interpolation and extrapolation - within certain limits - and
enable the search for conditions outside the range of known properties.
This report shows the process simulation of formalin production, describes the
process that is done by HYSYS, and shows the comparison between the hand
calculation results and HYSYS results. For example, the flow rate of the fresh
methanol feed was calculated by hand to be 78.56 Kmol/h, unlike HYSYS, which
calculated the flow rate to be 77.24 Kmole/h after adjusting some data.

II. Introduction:
This report focuses on the task of simulating the formalin production process. The
program used for simulation is HYSYS ASPEN which is available at KFUPM
computers Labs. The report is divided into two sections. The first one describes the
2

simulated process and its alternative. The third one compare the results obtained
from the simulation with that obtained in the mass and energy balance.

III. Formalin production process:

Here the simulation was done using the basic PFD with little details using PengRobinson as a fluid package. Below are the process description and the details of
additions and assumptions of the basic PFD.

1. Process Description:
Formaldehyde is manufactured by reacting methanol over the catalyst as follows:

Main reaction

CH 3OH 12 O2 HCHO H 2O

methanol
Side reaction

formaldehyde

CH 3OH HCHO H 2

methanol

formaldehyde

The catalyst used in formalin production is bulk density with 1500 kg catalyst/m3
of reactor volume with void fraction of 0.5 . The catalyst particles are spherical,
with a 1 mm diameter. Fresh methanol is pumped as liquid to increases the driving
force to 3 atm .Then, methanol is heated to 150 C using water with inlet of 200C
and outlet of 150C .Pure air (as a mixture of oxygen and nitrogen) is compressed to
equalize the pressure with the methanol stream . Before introducing methanol and
the compressed air to the reactor we mixes then at 3 atm .The reaction is taken
place inside the conversion reactor to have single pass conversion of methanol to
be 87.4%.The vapor product of the reactor has temperature of 745C and 3 atm
.Then we cooled the product to 200C using a cooler .After the pressure is dropped
to 1 atm using a pressure control valve ,it enter the absorber .80% of the
formaldehyde is absorbed using water at 30C and rate of 100 Kmol/hr in 3 trays
3

absorber .the liquid outlet is heated to 102C before entering the destination
column . In the destination column 93% of the methanol inlet is distillated while
the remaining is recycled to be mixed with the fresh methanol.in the bottom
formaldehyde is mixed with deionized water at 30C and 95.45 Kmol/hr to have
formalin ( 37% of formaldehyde ) . Then it cooled to 40C before storage.

Figure 1: Process Description

a) Compressor :
In the figure of the process flow diagram, it shows that a feed of O2 and N2 were
mixed in the mixture in the compressor, and then used in the reactor. The initial
condition is 25oC and 101.3 kpa , this unit operation yield to a mixture at 168.9 oC
and a pressure of 3 atm , also the pump work used was calculated to have 9.269E5
kJ/hr . Another important parameter of this unit is the efficiency which equal to
75%.

b) Reactor type and methanol conversion :

In this problem we choose a converter reactor for the process because the
statement provides the conversion percent. The condition of the inlet feed was
4

161oC and 3 atm, also the molar flow rate is equal to 310.7 Kmol/hr. As the
problem state that two reaction takes place in the reactor we found that 77.7 of the
conversion from reaction 1 and 9.7 from the second reaction.
Also we got that the total conversion is 87.4% and the selectivity as mentioned
in the problem to be 9:1. The product composition steam has 0.1832 mol% of
formaldehyde with flow rate of 343.7 Kmol/hr at 745.4 oC and the pressure at 3
atm.

c) Flash feed condition :

Before the final operation of the process the feed mixture enters the distillation
column at 102oC and 1 atm .the feed enter the distillation in stage number 3 with
flow rate of 104.8 Kmol/hr.

d) Distillation Column :
The result of the simulation of the process provides that the purity is equal to 93
% using 10 trays, whereas the problem state that the purity is equal to 98 %. And
the reflux ratio is 1.2 to the condenser. Moreover the pressure in the boiler and the
partial condenser is 1 atm. The composition outlet steam has 0.5915 mol% of
formaldehyde with flow rate of 79.15Kmol/hr.

e) Recycle :
An important step in the process is to recycle some of the methanol to the feed
inlet to reduce the amount needed of the raw material and that will help to
minimize the cost. Also the molar composition of recycle stream found to be
5

0.0166 methanol , 0.1377 formaldehyde and 0.8458 H2O at 68.3C and

25.62Kmol/hr.

f) Absorber :
One of the important unit in the process is the absorber, the feed is cooled up to
200oC and the valve is used to decrease the pressure from 3 to 1 atm. we used a 3
trays absorber. The upper feed stream is pure water at temperature of 30 oC and
138 Kpa . The outlet of the convertsion reactor is the inlet of the absorber. Also all
of the N2 , H2 and O2 are all in the off gas stream . The mole fraction of the bottom
stream 0.0663 methanol, 0.4805 formaldehyde and 0.4532 H 2O. the flow rate was
104.8Kmol/hr at 78.92C and 1 atm.

g) The efficiency of the compressor ,pumps and heat exchanger pressure

difference :
In the process we use pump (p-101) to increase the pressure to 3 and have
enough driving force to enter a heat exchanger (E-101) which vaporize the
methanol by increasing the temperature to 150C with duty of 4.048*10 6 kJ/h and
Ft factor of 0.807. Heat exchanger (E-102) used to cool the outlet of the reactor to
200C with duty of 7.142*106 kJ/h. Another Heat exchanger (E-103) used to heat
the outlet of the absorber to 102C with duty of 1.645*10 6 kJ/h .before storing the
formalin it beenig cooled to 40C using Heat exchanger (E-104) with duty of
3.91*105 kJ/h.

2. Alternative Process Description:

Here the simulation was done using the alternative PFD which is similar to the
basic one with the difference of removing the destination column. As result of this
action the recycle is removed. The process description and the details of additions
6

and assumptions of this PFD are the same as the basic PFD exab that a coolar is
added before the reactor to cool the methanol and compressed air to 48.95C . The
outlet temperature of the reactor is adjusted to 103.4C to have 37% of
formaldehyde as a liquid product of the absorber.
This alternative is important in terms of utility which is translated in terms of
money. The use of cooler before the reactor will add expense to the budgeted. Also,
the duty needed to cool the steams before and after the reactor is vary huge which
is about 1754 KW in order to have 37% of formaldehyde as a product.

Figure 2: Alternative Process Description

IV.

Justification of change in the process

1-Adding cooler before the reactor :
A cooler has been introduce for stream# 8 in order to reduce the temperature

that entered the reactor because it was causing a problem where increasing the
7

temperature in stream#8 lead to increase in stream # 9 temperature. The

temperature result without the cooler rise up to 900C which is very critical
where it is need special martial of construction and will increase the production
cost.so, adding the cooler will reduce the temperature entering the reactor
stream #8 and cause the temperature in stream #9 to decrease to 379 C .
2- Adding cooler after reactor:
A cooler has been adding after the reactor to decrease the temperature on stream
#9 as preparation for the absorption process where the cooler reduce the
temperature of absorber feed to 200 C instead of 272.5 C. if we dont use the
cooler a lot of formaldehyde and methanol will go with the off gas as waste which
impact the environment and cost a lot of money.
3-Removing air heater:
Heater E-102 has been removed from the process because there is no need for it
since the temperature of the feed gas is increases in the compressor from 25 C to
168.9 C which is acceptable for the process .so, removing the air heater will not
affect the process and will save energy and money.
V.

Explained Differences and Comparing.

This part compares and explained differences between the results obtained from

mass and energy balance with that obtained from HYSYS simulation with the basic
PFD only. It is expected that there are some differences but also there are a lot of
similarities. Table 1 below shows the comparison and discusses it in terms of the
reasonability.

In the problem given, there has been some changes in terms of

equipments and streams (adding / removing). Due to that, some
flow rates, which have been calculated with certain assumptions,
have some errors when they get compared with the HYSYS
results. Starting from the beginning of the simulations, the flow
rate of the streams 3, 4 and 6 is 91.44 kmol/hr, which equals to
the flow rate assumed in the hand calculation. This equality is
caused because in the HYSYS and the hand calculations the
assumption of the basis was the same flow rate. The same thing
can be applied to stream 1, 5 and 7 which have the flow rate of
217.6 kmol/hr.
As a result of that, the flow rate of stream 8 is the same in both
the hand and the HYSYS calculations. But stream 2, in the HYSYS,
has the flow rate of 66.39 kmol/hr, while using the hand
calculation stream 2 has a flow rate of 78.56 kmol/hr. This
different in the calculations has been caused by the difference in
the recovery value of formaldehyde in the distillation column.
Also, stream 15 has some differences between the HYSYS
calculations and the hand calculations caused by the difference in
the recovery value.
Streams 9 and 10, using HYSYS, have a flow rate of 341.5
kmol/hr, while using the hand calculations the flow rate is 353.5
kmol/hr, which isn't that much difference. This difference in the
flow rate is caused by the difference in the flow rate of the recycle
stream (stream 15).

Stream 11, in HYSYS, has a very low value (100 kmol/hr)

compared to the hand calculations (256.5 kmol/hr). This big
difference caused because if stream 11 flow rate increases, the
composition of the formaldehyde in stream 13 (absorber's stream
outlet) would be lower than 0.3 wt%. As a result of this big
difference in the flow rate of stream 11, the remaining streams
(13, 14, 16, 17, 18, 19 and 20) have a very big difference in
HYSYS calculations compared to the hand calculations. In
addition, this difference can be done because in the hand
calculations there were a lot of assumptions which are rejected
(or not applied) by the HYSYS.

VI.

Conclusion:
To sum up, material and energy balance calculations are shown for the process

with detailed information about the composition of all streams as well as the duty
of equipment. The objective of the process is to produce formalin by reacting
methanol over an Ziegler-Natta catalyst with maximum rate of return on
investment. In order to produce this amount of formalin we should have a full
knowledge about what we are required to have in each stream to produce this
amount which calculated using the material balance.

10

VII. Appendixs :
A. Streams Summary Table
Table A.1: Streams Summary Table.
B. Equipment Summary Tables
Table B.1: Hear Exchangers.
Table B.2: Reactor Column.
Table B.3: Pumps.
Table B.4: Absorber Column.
Table B.5: Distillation Column.
Table B.6: COMPRESSOR.
Table B.7: Valve.

A. Streams Summary Table

11

Table 1: Streams Summary Table.

Name
1
Vapor / Phase Fraction
1
Pressure [Kpa]
101.3
Temperature [C]
25
Molar Enthalpy
190.1
[kJ/kmole*C]
Molar Flow [kmole/h] 217.6
Composition
[%Mole ]
Methanol
0.0000

2
0
101.3
25

3
0
304
33.81

4
0
304
33.89

5
1
304
168.9

6
1
304
150

8
0.836
304
161.0

9
1
304
745.4

46.69

51.14

58.22

192.6

178.3

194.1

218.6

67.64

93.03

93.03

217.6

93.03

304.0

330.1

1.0000

0.7316

0.0000

0.2191

0.0250

0.0112

0.1832

0.0265

0.2164

0.1472

0.0561

0.0000

0.0192

0.5534

0.5002

14
0.4041
101.3
102

0.7316
0.037
5
0.230
9
0.000
0
0.000
0
0.000
0
15
0
101.3
68.30

16
0
101.3
101.6

18
0
101.3
30

Formaldehyde

0.0000

0.0375

Water

0.0000

0.0000

0.2309

Oxygen

0 .201

0.0000

0.0000

Hydrogen

0 .0000

0.0000

Nitrogen

0 .7899

0.0000

0.0000

11
0
138.0
30

12
1
101.3
74.72

0.7316
0.037
5
0.230
9
0.000
0
0.000
0
0.000
0
13
0
101.3
78.92

7.823

179.4

84.17

128.5

36.78

106.0

7.823

100

338.9

104.8

104.8

25.39

79.15

95.45

0.0000 0.0048

0.0663

0.0000

0.4805

0.0167
0.137
3
0.846
0
0.000

0.0824

0.0000

0.0663
0.480
0.0373
5
0.453
0.3744
2
0.0569 0.000

0.5915

0.0000

0.3261

1.000

0.0000

0.0000

Name
10
Vapor / Phase Fraction
1
Pressure [Kpa]
101.3
Temperature [C]
199.8
Molar Enthalpy
198.9
[kJ/kmole*C]
Molar Flow [kmole/h] 343.7
Composition [Mole
%]
Methanol
0.0250
Formaldehyde
Water
Oxygen

0.1832

0.1192 1.0000
0.0561

0.0000
0.0000
0 .2101
0 .0000
0 .7899

0.4532
0.0000

12

Hydrogen
Nitrogen

B.

0
0.000
0.0192
0
0.0195
0.0000
0
0.5002 Name
0.0000 0.507119 0.000
0.0000
20
0
Vapor / Phase Fraction
0
0
Pressure [Kpa]
101.3
101.3
Temperature [C]
67.31
40
Molar Enthalpy
53.97
45.44
[kJ/kmole*C]
Molar Flow [kmole/h] 174.6
174.6
Composition
[%Mole ]
Methanol
0.0374 0.0374
Formaldehyde
0.2681 0.2681
Water
0.6945 0.6945
Oxygen
0.0000 0.0000
Hydrogen
0 .0000 0.0000
Nitrogen
0 .0000 0.0000

0
0.000
0
0.000
0

0.0000

0.0000

0.0000

0.0000

Equipment

Summary Tables
Table B.1: Hear Exchangers.
Name
E-101

Duty[kJ/h]
4.048 E+006

Pressure Drop[Kpa]
0

Delta T [C]
Tube
side=116.1

E-102
E-103
E-104

7.142 E+006
1.645 E+006
4.048 E+005

0
0
0

shell side=-50
-545.4
23.08
-27.31

Table B.2: Reactor Column.

Name
Vessel Temperature
Vessel Pressure
Reaction Heat [kJ/Kmol]
Liquid Volume Percent [%]

CRV-101
304.0
745.4
4.048 E+005
50
13

Table B.3: Pumps.

Name
Delta P [Kpa]
Adiabatic Efficiency [%]

P-100
202.65
75
0.25062
Duty [kW]
3
NPSH available [m]
9.819
Delta T [C]
0
Pressure Head [m]
25.82
-1.597EVelocity Head [m]
06
Friction Loss Power [kW]
0
Table B.4: Absorber Column.
Name
Number of Stage
Top Stage Temperature [C]
Bottom Stage Temperature [C]
Top Stage Pressure [Kpa]
Bottom Stage Pressure [Kpa]
Reflux Ratio
Efficiency

T-101
3
78.9
74.7
101.3
101.3
0.3211
1

Table B.5: Distillation Column.

Name
Number of Stage
Inlet Stage
Top Stage Temperature [C]
Bottom Stage Temperature [C]
Top Stage Pressure [Kpa]
Bottom Stage Pressure [Kpa]
Reflux Ratio
Condenser Duty [kJ/h]
Reboiler Duty [kJ/h]

T-102
10
3
99.67
95.85
101.3
101.3
1.2
14

Table B.6: COMPRESSOR.

Name
Power [kW]
Adiabatic Efficiency[%]
Polytropic Efficiency[%]
Delta T [C]
Delta P [Kpa]
Polytropic Head [m]
Adiabatic Head [m]
Dynamic Head [m]
Polytropic Fluid Head [kJ/kg]
Adiabatic Fluid Head [kJ/kg]
Dynamic Fluid Head [kJ/kg]
Polytropic Head Factor
Polytropic Exponent
Friction Loss Power [kW]
Duty [kJ/h]

K-100
257.481
75
78.405
143.9
202.6
1.18 E+004
1.129 E+004
1.18 E+004
115.8
110.72
115.8
1.0006
1.5589
0
9.269E+005

Table B.7: Valve.

Pressure Drop[Kpa]
Percentage Open[%]
Flow Rate [Kg/h]

202.6
50
8951

15