Summer training report

Increase in steam generation in

formaldehyde production plant
Submitted by:
Rajat Punia
2013CH10100
B.Tech Chemical Engineering
Indian Institute Of Technology Delhi
Under the supervision of:
Apurva Prabhakar
DGM, Jubilant Life Sciences Ltd.

Contents
1 Process overview
1.1 Problem statement . . . . . . . . . . . . . . . . . . . . . . . .
1.2 Process flow diagram . . . . . . . . . . . . . . . . . . . . . . .

3
3
4

Mass balance
2.1 Mass balance over reactor . . . . . . . . . . . . . . . . . . . .
2.2 Mass balance over absorber . . . . . . . . . . . . . . . . . . .
2.3 Actual vs. theoretical comparison . . . . . . . . . . . . . . . .

5
5
6
7

3 Energy Balance
3.1 Heat of reaction . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2 Actual vs Theoretical comparison . . . . . . . . . . . . . . . .

8
8
9

4 Heat Exchanger Design

11
4.1 Tube side Design . . . . . . . . . . . . . . . . . . . . . . . . . 11
4.2 Shell side Design . . . . . . . . . . . . . . . . . . . . . . . . . 11
4.3 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
5 Process Safety Considerations

14

29

Results & Conclusions

Chapter 1
Process overview
Formaldehyde is a simplest form of aldehyde produced industrially by catalytic oxidation of methanol.It is an important precursor to many industrial
process like formation of pyridine, production of industrial resins etc. Its
chemical formula is CH2 O and the name is derived from its similarity and
relation to formic acid. In this plant Metal Oxide is used as a catalyst which
provides higher yield & selectivity and amount of methanol in product is
very less compared to Silver catalyst.The high yield & selectivity comes at
cost of higher air flow rate. Reaction occur in this process is
1
CH3 OH + 12 O2 HCHO + H2 O
Hrxn = 159 KJ/mol
The reaction is exothermic and heat generated in this process is carried out
by cooling oil and used to generate steam.Also this process involves a side
reaction which leads to the formation of Carbon Monoxide.

1.1

Problem statement

The purpose of this project is conduct a comprehensive study of process,

identify the heat losses and resolve them to increase steam generation. This
project is conducted chronologically as per the following activities:
To understand formaldehyde production plant
To make Process flow diagram(PFD)
To perform mass and relevant energy balance over plant
To compare theoretical compositional and temp. values with actual process
To identify the problem & scheme preparation to troubleshoot them
Sizing and cost estimation
Benefit evaluation

1.2

Process flow diagram

F igure1 P rocessF lowDiagram

Chapter 2
Mass balance
Percentage yield of formaldehyde = 93%
Percentage of CO in Stream 9 = 1.2%
Methanol feed in Stream 3 = 1340Kg/hr
Methanol feed in Stream 7 = 1700Kg/hr
Air Input, Stream 1 = 6000N m3 /hr
Flow rate of stream 2 = 14425N m3 /hr

2.1

Mass balance over reactor

Percentage yield of HCHO = 1

Percentage yield of CO = 2
1 &
2
From reaction
5

1 +2
100

nM 6 = nM 5 nM 5
nF 6 = nF 5 + nM 5

1
100

nC6 = nC5 + nM 5

2
100

nW 6 = nW 5 + nM 5
nO6 = nO5 nM 5

1 +2
100
1 +2
200

nN 6 = nN 5 where,
M Methanol, F Formaldehyde, C Carbon Monoxide, W Water
and N Nitrogen

2.2

Mass balance over absorber

Process gas from reactor 2 is cooled in After cooler to significant amount

and then passed on to absorber to separate formaldehyde from other gases.
Since formaldehyde and methanol has higher solubility in water compared
6

to sparingly soluble gases like nitrogen and oxygen, we use water to make
approx. 48 wt% formaldehyde solution.The basis for mass balance across
absorber is
95% absorption of formaaldehyde
0.8 wt% Methanol in stream 12
0.8 wt% Methanol in stream 12 72% absorption of methanol (Hit & trial
method)
So, nF 12 = 0.95 nF 10
nM 12 = 0.72 nM 10
nW 12 = nW 10 + nW 11
ni13 = ni10 + ni11 ni12
i = M,F,W,O,C&N
where, M Methanol, F Formaldehyde, C Carbon Monoxide, W
Water and N Nitrogen

2.3

Actual vs. theoretical comparison

Theoretically percentage oxygen is found significantly less compared to actual

present value in stream-2. Stream-2 passes through a blower and pressure
drop across the blower is such that it drives a flow of approx. 14400N m3 /hr.
A flow measuring device is attached across stream-15 and oxygen % measuring device is attached across stream-2(Note:- There is no flow measuring
device across stream-1 ). So, there can be 3 possibilities...
1. Oxygen measuring device in stream-2 is not calibrated.
2. Flow-meter in stream-15 is not calibrated.
3. Possibility of dehydrogenation reaction
CH3 OH HCHO + H2

Chapter 3
Energy Balance
3.1

Heat of reaction

Standard Enthalpy of Formation:

Gas
Methanol
Formaldehyde
Heat of formation -201 KJ/mol -115.9 KJ/mol

Oxygen
Water(g)
0
-241.8 KJ/mol

CH3 OH + 21 O2 HCHO + H2 O
0
Hrxn
= Hf0 (P roducts) Hf0 (Reactants)
0
= 156.718KJ/mol
Hrxn

By Hesss Law,
Hrxn (T = 300C) = 156.424KJ/mol
Similarly for,
HCHO + 21 O2 CO + H2 O
Hrxn (T = 300C) = 233KJ/mol

CO
-110.5 KJ/mol

Heat carried by oil from reactor-1 and reactor-2 is used to heat the water
in in boiler.

At 15 Kg/cm2 , boiling point is, Tb = 200 deg. C

Heat carried by oil from reactor 1 = Ho1 = H5 - H6
Heat carried by oil from reactor 2 = Ho2 = H8 - H9
Water is heated by pre-heater upto 80 deg. Celcius. In waste heat boiler
steam pressure is 15 Kg/cm2 at which boiling pt. is 200 deg. Celcius.
Ho1 + Ho2 = m(C
p (200 80) + )
At T= 2000 C, = 1993 KJ/Kg
Cp (avg.) = 4.354 KJ/Kg.K

m
=

3.2

Ho1 + Ho2
2455.5

Actual vs Theoretical comparison

Process gas heater is used to heat the process gas to desired temperature
rquired in reactor. But due to its small size compared to designed one, desired
value of temperature is not obtained. Some portion of heat liberated by the
reaction is consumed in heating the process gas to desired temperature. So,
it decreases the amount of steam production compared to designed process.
To increase the temperature of process gas to desired value, an introduction
of heat exchanger is proposed as given below:
9

Proposal
Product from reactor-2 i.e. stream-9 can be splitted to heat both inlet of
reactor-1 and reactor-2. In this case 1 baffle is ther on shell side to increase
heat transfer coefficient and reduce area.

Heat exhanger would be Shell & Tube type and designing of this heat exchanger is done in the next chapter.

10

Chapter 4
Heat Exchanger Design
4.1

Tube side Design

1 inch OD tubes with 1 14 inch triangular pitch
Reynolds No., Re = Gs d
p
Prandtl No., Pr = C
K

Petukhov-Kirillov correlation:
Friction factor, f = (1.58ln(Re) 3.28)2

f
2

Nusselt No., Nu =

104 < Re < 5 106 and 0.5 < Pr < 2000

Heat transfer coefficient, hi =
Pressure drop:

N uK
di

P = (4f dLi + 4) U2m

4.2

.Re.Pr/[1.07 + 12.7 ( f2 ) 2 (P r 3 1)]

Shell side Design

Tube-pitch = PT
Clearance, C = PT - do
Baffle spacing = B
Shell diameter = Ds
As =

Ds CB
PT
11

Gs =

As

4(PT2 d20 /4)

d0
De Gs 0.55 Cp 1/3
h0 De
= 0.36h
i h
i
K

K
De =

for 2 103 < Res < 1 106

Pressure drop:
Friction factor f = exp(0.576 - 0.19ln(Res ))
Number of baffles Nb = BL - 1
f G2s (Nb + 1)Ds
2De s
b
where, s = ( )0.14 1
w
Ps =

Overall heat transfer coefficient (Uo ):

1
Uo A o

1
hi Ai

ln(ro /ri )
2Ks L

1
ho Ao

Thermal Conductivity of steel,Ks at 225 deg C = 17.45 W/m.K

Calculations are done for different tube thickness & different no. of tubes
and best option is chosen.

12

4.3

Results

Proposal 2
Material of Construction
Tube OD
BWG
Tube thickness
Pitch
Number of tubes
Length
Shell ID
Shell thickness
Tube-side velocity
Shell-side velocity
Tube-side pressure
Shell-side pressure
Tube pressure drop
Shell pressure drop
Overall heat transfer cefficient
Area
Heat transfer rate
LMTD
No. of Baffles

HX-1
Stainless steel
1 in
16
0.065 in
1.25 in
538
4m
33 in
6 mm
22.59 m/s
9.11 m/s
1.25 atm
0.75 atm
0.017 Kg/cm2
0.03 Kg/cm2
37.81 W/m2.K
171.6 m2
1067500 KJ/hr
45.68 K
1

13

HX-2
Stainless steel
1 in
16
0.065 in
1.25 in
538
4m
33 in
6 mm
22.59 m/s
9.11 m/s
1.25 atm
0.75 atm
0.017 Kg/cm2
0.03 Kg/cm2
37.95 W/m2.K
171.6 m2
1025107 KJ/hr
43.71 K
1

Chapter 5
Process Safety Considerations
If gas composition lies in flammability limit and ignition energy is provide,
it will catch fire but if compositio lies outside the region of flammability, no
matter how much ignition energy we provide, gas will not catch fire.
Problem:

Stream
Fuel %
Oxygen %

5
6
8
9
6.36 5.88 12.8 11.98
14.5 11
9.5
6.5

Below given is the composition of process streams 5,6,8 & 9 on flammability

diagram and how process occur outside the flammability limit.

14

Note:- The flammability region shown in above figure is for illustration, it

may not represent the exact LFL and UFL
One of the main problem arises in the plant is when catalyst get old i.e.
degraded. Low conversion in reactor-1 increase the oxygen percentage in
stream-8, which bring the gas in flammable limit.If it catches fire, pressure
increases suddenly and for safety purpose rupture disc is fitted on the top
of reactor bursts and production stops, leading to plant shutdown. Also replacement of rupture disc is both time and money consuming.
Solution:
According to design the oxygen percentage in stream-8 should be 9.36% at
this capacity(178). Oxygen level greater than this can be risky. So the solution to this problem is to maintain the oxygen level to desired value. It
require oxygen measuring device in stream 8. If oxygen percentage increase
then we can increase the flow rate of recycle stream which automatically decreases the flow rate of fresh air and oxygen percentage goes down.
Amount of pressure increase in reactor when gas catches fire depends on
where gas lie in the flammability region. Following graph shows the pressure
increase vs. composition of gas

15

Results & Conclusions

1.The mismatch in oxygen percentage in reactor inlet between actual and
theoretical values can be due to
a) Flowrate measuring device is not properly calibrated.
b) Oxygen measuring device is not properly calibrated.
2.Steam generation can be increased by introduction of heat exchangers
a) Total heat carried by oil in current process
Heat carried by oil from reactor-1 = Qo1 = 3969690 kJ/hr
Heat carried by oil from reactor-2 = Qo2 = 5970557 kJ/hr
Steam generated = m
= 4048 kg/hr
Norm = 0.545
b) Proposal 1: Introduction of Single heat exchanger
Heat carried by oil from reactor-1 = Qo1 = 5219375 kJ/hr
Heat carried by oil from reactor-2 = Qo2 = 5970557 kJ/hr
Steam generated = m
= 4557 kg/hr
Norm = 0.614
c) Proposal 2: Introduction of 2 heat exchangers
Heat carried by oil from reactor-1 = Qo1 = 5045133 kJ/hr
Heat carried by oil from reactor-2 = Qo2 = 6989824 kJ/hr
Steam generated = m
= 4901 kg/hr
Norm = 0.660
3. Bursting of rupture disc in reactor due to increase in O2 % and gas shifting
towards flammability zone can be prevented by controlling the flowrate of
recycled stream according to O2 % in Stream-8.

16