ACKNOWLEDGEMENTS

We would like to express our sincere thanks to Dr. B.N.THORAT, UICT

for providing us the platform to do the Inplant Training in HOC,Rasayani without
which this project would not have been completed successfully.

We would also like to express our since thanks to Mr.A.M.SATHE, HOC for
his guidance for carrying out this project. We were really honored for the keen interest
he took at each and every step of this work. We would like to express our deepest
gratitude for his encouragement and confidence he showed in us while carrying out
this project without which this work would have not been completed.

We also like to thank Mr. M.S.Patil, for the efforts he has taken to help &
guide us. We would also like to thank Mr. Jirimali and Mr.Virkar for the support they
had given & faith they have shown in us.

INDEX

Sr. No. Contents Pg. No.

1. Introduction to Company
1.1 Company background 3
1.2 Features of the company 5
2. Waste heat boiler design 8
3. Vaporizer design 13
4. Pressure drop calculations 16
5. Formaldehyde plant
 5.1 Formaldehyde-useful industrial product
18
5.2 Introduction 19
5.3 Process flow sheet 20
5.4 Plant- functional description 21
5.5 Equipments used 24
5.6 Product sprcification & storage 30
5.7 Operational features & critical parameters 31
5.8 Material balance 34
5.9 Precautions & safety factors 42
5.10 Future perspectives 43

6. References 44

INTRODUCTION

COMPANY BACKGROUND :

“HINDUSTAN ORGANIC CHEMICAL LTD.” A leader in Indian chemical industry

for over three elected is further expanding its horizons in near future. Earlier company
has to depend upon the imports for its vital organic chemical needs till the
government with a view to making the company self reliant in this field set up HOC
in 1960. Making a beginning as a small chemical unit HOC is today a multi
technology, multi-unit company with three fast growing units.

HOC has following manufacturing units:-

The main organic chemical complex at Rasayani in Raigad District
(Maharastra)
The phenol complex at kochi (Kerala)
The poly tetra Flurothylene at Hyderabad (Andhra Pradesh)

Initiating an era in basic chemical intermediates. Incorporated at rasayani, a backward

area in Maharastra, HOC’s first plant started production in 1970. Between 1970 and
1974 a total of twelve plants were commissioned. Together they produce a large
number of products that serve a wide spectrum of industries, ranging from
pharmaceuticals to defense and space.

After stabilization of the first phase plant in the sixth plan period (1980-85), a number
of expansion and diversification plants were launched at Rasayani. Expansion phase
included doubling of Hydrogen, Aniline, Nitro Benzene and Nitro Toluene and
substantial expansion of Nitroclorobenzene.

HOCL was established on 12th Dec.1960 by the Government of India, with the
view of making the country self-sufficient in the filed of organic chemical
manufacture. Initiating an era in basic chemical complex is a leader in Indian
chemical industries manufacturing a wide range of high quality basic organic
chemical which are required for variety of chemical and pharmaceutical product such
as drugs, medical, dyes, plastics, resins, paints, textile, and explosive.
 The company has a continuous manufacturing process and works for 24hrs.
A day in 3 shifts in all, around 22 plants are functioning at Rasayani. HOC has its
head office situated at Mumbai. The company provides various facilities to its
employees like canteen, transport, residential quarter, library and hospital, etc.

FEATURES OF THE COMPANY :

Training Centre :

HOC has as well-quipped training center, which arranges regular courses for
developing skills of employee at all, level. Periodic in house seminars are held,
workshop are conducted for employees. Which help them sharpen their skills.

Safety department :

In everything HOC does, safety of its employees is a prime consideration. This

concern is manifest is a multitude of ways. Safety department provide Safety devices
to the workers and trains them to work Safety and continuously.

Fire department :

The fire officer train the personnel to deal with an emergency like fire etc. and teach
them to make proper use of fire extinguishers and Safety equipments.

Health center :

The company health center is well equipped with all the medicines and has its
own ambulances. There are qualified doctor in medicals center who examine the
workers regularly during the routing medical check up.

Research & Development :

In order to diversify, lower the costs and increase existing capacities, HOC’s R & D
efforts are being directed toward assimilation and adaptation of most modern
international technologies and development of new and improved processes and
chemicals.

Scale-up studies are being undertaken through pilot plants, while facilities are being
augmented for catalyst testing and sophisticated analysis.

In-house research apart, HOC’s R & D division collaborates with scientists from
Universities, Institutes of technology and National Research Laboratories, involved in
nation building projects. In house in the R & D department has led to the installation
of pilot plant for production of cyclohexyl amine. The R& D department is pursuing
it’s efforts in the development of noble metal catalyst for increased manufacture of
CHA.

By recovering resorcinol- a value added chemical from meta amino phenol

plant, due efforts of R & D department, HOC has won many prestigious award.
Quality Control

HOC is very conscious of maintaining a high quality of its products and for this
purpose right from raw material through processing to finished product, through
checking and stringent tests are carried out at every stage by experts in a modern well-
equipped laboratory.

Quality control:

HOC is very conscious of maintaining a high product, right from raw

materials, to finished products, through checking and experts in a modern well-
equipped laboratory carry out stringent test at every stage.

Export :

What began as an import substitution effort years ago is now an export activity that is
steadily gaining momentum. The fact that HOC has generated self-sufficiency in
chemicals in India is further complimented by its exports to countries like USA,
France, UK, Japan, Germany and many others. Competitive pricing and high quality
make HOC’s prospects excellent on the export scene.

Today HOC stands as a winner of several awards for excellent export performance
from CHEMEXCIL (Basic chemicals, pharmaceuticals and cosmetics export
promotion council), an organization set up by the Government of India.
WASTE HEAT BOILER DESIGN :

In 1-2 Shell and Tube heat exchanger (WHB), on shell side water flows at 2000
Kg/hr while on tube side HTM oil flows. We have to calculate the steam generation
rate.

HTM OIL:

Inlet temperature of HTM oil = 173oC

Outlet temperature of HTM oil = 160oC

WATER:

Inlet temperature of water = 80oC

Outlet temperature of steam = 150oC

Following are the physical properties of the concerned fluids:

PROPERTIES HTM OIL WATER STEAM

Ρ, Kg/m3 1000 1000 1.2
Cp, Kcal/KgK 0.76 1 0.47
µ, Poise 0.3x10-3 10-3 1.42x10-4
K, W/Mk 0.1 0.6 0.02836

TUBES:

Number of tubes = 178

Outer diameter of 1 tube = 1.25in.
Thickness = 10BWG
Inner diameter of tube = 0.982in.
Total heat transfer area for heat exchanger = 117.45m2
Assuming overall heat transfer coefficient, Ud = 240W/m2K
Log mean temperature difference is,

∆Tlm = ((173-150)-(160-80))/ln ((173-150)/ (160-80))

= 45.72oC

So, total heat duty will be,

Q = Ud A ∆Tlm
 = 240 x 117.45 x 45.72

Q = 1288755.36 Watts

Now,
Total heat duty = Specific heat given by HTM oil

Q = mcp∆Tlm = 1288755.36

= m x 0.76 x (173-160)

HTM oil mass flow rate, m = 24.8 Kg/s

= 89,280Kg/hr.

HEAT TRANSFER COEFFICIENTS:

On tube side:

Area of cross section of one tube, a = Π/4x (0.982 x 0.0254)2

= 4.885x
10-4 m2

Velocity, V = volumetric flow rate /area

= 24.8 x 2 / (1000 x 178 x 4.885 x 10-4)

Number of passes = 2 and number of tubes = 178

V = 0.57m/s.

Reynolds number, Re = DVρ/ µ

= (0.0249 x 0.57 x 1000)/ (0.3 x 10-3)

= 47345

Prandtl number, Pr = Cp µ/K

= 0.76 x 4184/0.1

= 7.026

Nusselt number, Nu = 0.023 Re0.8 Pr0.33

= 0.023 x 473450.8 x 7.0260.33

 Since, Nu = hd/k

So,
hd/k = 175.84

h = 706.211

hio = 554.8W/m2K …………. ( hio = h x ID/OD)

So, heat transfer coefficient on tube side, hio = 554.8W/ m2K

Shell side:

Square Pitch = 1.5in.

Shell area = 1.5” x 1.5”

= 2.25sq.in.

Tube area = Π/4 x 1.252

= 1.227sq.in.

Total tube area = 178 x Π/4 x 1.252

= 218.44sq.in.

Shell area = (2.25/1.227)x178 = 326.41sq.in.

326.41 = Π/4x D2s

Ds = 20.39in. = 0.518m

Baffle spacing = 0.5 x Ds

= 0.5 x 20.39

= 10.195in.

= 0.258m

Equivalent diameter, Deq = 4xflow area/wetted parameter

= 4 x (1.52 - Π/4 x 1.252)/ (Π x 1.25)

= 1.04 in.

Flow area = baffle spacing x clearance x shell ID/pitch

 = 10.195 x (1.5 - 1.25) x 20.39/1.5

= 0.0224m2

Velocity, V = Volumetric flow rate / flow area

= 2000/ (3600 x 1000 x 0.0224)

= 0.0248m/s

Reynolds number, Re = DVρ/ µ

= 0.0264 x 0.0248 x 1000/10-3

= 654.72

Prandtl number, Pr = Cp µ/K

= 1 x 4184 x 10-3/0.6

=7

Nusselt number, Nu = 0.36 Re0.55 Pr0.33

= 0.36 x 654.720.55 x 70.33

hd/k = 89.17

ho = 2026.64 W/ m2K

Heat transfer coefficient on shell side, ho = 2026.64 W/ m2K

OVERALL HEAT TRANSFER COEFFCIENT:

Overall clean heat transfer coefficient (Uc),

1/Uc = 1/ hio + 1/ ho

= 1/554.8 + 1/2026.64

= 451.34 W/ m2K

Now dirt factor, Rd = 1.785x10-3K/W m2

So, Overall heat transfer coefficient (Ud),

1/ Ud = 1/ Uc + Rd

= 1/451.34 + 1.785x10-3
 Ud = 242 W/ m2K

So, calculated Ud is fairly matching with the assumed value.

Now,

Total heat duty = (mcp∆T) water + mλ + (mcp∆T) steam

1288755.36 = m x 4184 x (100-80) + m x540x4184 + m x 1967.63x (150-100)

m = 0.5278Kg/s

= 1900 Kg/hr.

So, the required steam generation rate is 1900Kg/hr.

VAPORIZER DESIGN :

VAPORIZER :
To check the design for vaporizer :

There are 3 zones in the vaporizer.

1. preheating zone

2. flashing zone

3. superheating zone

A)
Let UD= 25 w/m2k

So,

Q = UD A ΔTLM = (m CP ΔT)H2

= 446.42 x 3.46 x 4184 x 4

Q = 7180.74 W

7180.7 = 25 x A x 43.5

A = 6.6 m2…. required area.

Provided area = 92.787 m2

B)

m cp (160-T)H2 = m λNB

446.2 x 3.46 x 4184 x (160-T) = 2000 x 334720 / 3600

=> (160-T) = 0.02877

 T = 159.97 oC.

C)

Q = m cp (160-T) H2 + m cp (160-T)NB

= 446.42 x 3.46 x 4184 x 0.02872

+ 2000 x 3.46 x 4184 x 0.02877/ 3600

Q = 1094.3 W

Area provided = 0.6823 x 46 = 31.39 m2

Let, UD = 25 w/m2k

& we calculate ΔTLM = 41.49

1094.3 = 25 x A x41.49

A = 1.055 m2

Zone Area calculated, m2 Actual area, m2

Preheating 6.6 92.787
Superheating 1.055 31.39

PRESSURE DROP CALCULATIONS :

Calculations of pressure drop across 90o bend having 80 mm diameter and with
air flow rate 5000Nm3/hr at 9Kg/cm2 and 50oC.

Assumptions :
 Ideal gas laws such as Boyle’s law are considered to be valid for given air at
NTP

Data: 1. ρair = 1.2 Kg/m3

2. Head loss coefficient for 90o bend (K) = 1

Solution :

22.4 dm3 of gas at NTP = 1gmol

5000Nm3/hr of gas at NTP = X gmol

X = 223214.29 gmol/hr

= 6473.2147 Kg/hr

Air flow rate at NTP (25oC & 1Kg/cm2 pre.) = 6473.2147 Kg/hr

By ideal gas law,

V1/T1 = V2/T2

V2 = V1 x T2/T1

V2 = 1.2 x (273.16 + 50) / (273.16+25)

= 1.3006 m3 for 1 kg of gas at 50oC

From Boyle’s law,

P1V1 = P2V2

V2 = P1V1

= 1 x 1.3006/9

= 0.1445 m3 for 1Kg gas at 50oC and 9Kg/cm2

Now,
Density of air at 50oC and 9Kg/cm2,

ρair =1/V2

= 6.9204 Kg/m3
 6473.2147 Kg of gas = 6473.2147/6.9204

= 935.444 m3

Area of cross section of pipe, A= d2/4

= 5.0265 x 10-3m2

Velocity, V = volumetric flow rate / A

= 935.44/(5.0265 x 10-3 x 1000)

= 51.6917 m/s

Pressure drop (ΔP),

ΔP = ½ ρairV2 K

= ½ x 6.9204 x (51.6917)2 x1

= 9245.76Pa

ΔP = 0.09248 kg/cm2

Therefore, the pressure drop across 90o bend = 0.09248 kg/cm2

FORMALDEHYDE

FORMALDEHYDE – USEFUL INDUSTRIAL PRODUCT:

1. Formaldehyde is useful chemical employed in the manufacture of many

industrial product and consumer articles.
2. Formaldehyde is used in the manufacture of phenolic resins, artificial silk and
cellulose esters, dyes, organic chemicals etc.
3. Formaldehyde is used as agent for improving the fastness of dyes on fabrics.

4. A major application of Formaldehyde in the manufacture of crop protection

and soil disinfections chemicals, fumigants, pharmaceuticals and explosives.
5. It is used for tanning and preserving hides, and for preserving and coagulation
of rubber latex.
INTRODUCTION :

The current plant - formaldehyde phase 2 produces a 37% water solution of

formaldehyde by the vapor phase oxidation of methanol by air in presence of Iron
Oxide-molybdenum oxide catalyst in a fixed bed tubular reactor at 320-400°c and
scrubbing the gas by D.M. water to absorb HCHO gas(formalin gas to get 37%
HCHO. The plant is designed to produce a maximum of 55% HCHO.

Alternative ways :
Following are the two alternative ways of production of formaldehyde.
1. Silver catalyst process in which methanol is oxidized over a silver catalyst at
the atmospheric pressure and 600-650°C.
2. From the Methane by, partial oxidation.
But it was found that the process of production of formaldehyde by using
Iron-molybdenum oxide catalyst was much more efficient. Hence this process was
employed in the plant.

Properties :
1. Nature :- colorless liquid with pungent odors.
2. Density :- 1.08-1.085 gm/cm³ (25°C)
3. Boiling point :- 96°C
4. Refractive index :- 1.3746 (20°C)
5. Flash point :- 60°C.
6. Miscible with water, alcohol and acetone.
7. Hazard : - Toxic by inhalation, skin and eye irritant, moderate fire risk.
Raw materials : Methanol, air and caustic soda.
Utilities : D.M water, cooling water, chilled water, instrument air, power
supply.
PROCESS FLOW SHEET :

PLANT - FUNCTIONAL DESCRIPTION:

The process is accomplished by the oxidation of methanol on a metallic oxide

catalyst, using a fixed-bed vapor-phase oxidation converter, according to formula:
CH3OH + ½O2 CH2O + H2O ∆H= -159 KJ/mol

A low ratio of methanol to air is used to maintain the desired oxidation atmosphere,
and the heat of reaction is removed from the converter by boiling a liquid heat transfer
medium (Dowtherm A or equivalent medium). The methanol content in air is
maintained between about 4 and 9 % by volume. Such a high content can be used
because part of stack gas from the plant is recycled, which decreases the oxygen
concentration sufficiently to avoid explosive mixtures.

The process gives a high yield on a single passage, and also very high conversion
making the recovery of methanol from the final product unnecessary. The actual
formaldehyde yield is in the range of 91-94% of the theoretical. The remainder of the
methanol is accounted for by unreacted methanol, carbon monoxide, dimethyl ether
and a negligible amount of formic acid.

The air is supplied by two root type of blowers, here items C-4 A/B. Methanol to the
plant is supplied by pump, P-1 and is injected into the air stream after the vaporizer
tube bundle through a spray nozzle ring. The air is passed through the methanol
vaporizer, E-1, after which the methanol is vaporized. The gas mixture temperature to
the reactor is now about 120°C.

The oxidation of the methanol takes place in a fixed-bed reactor with 11878 stainless
steel tubes of 21mm. The tubes are loaded with the metallic oxide catalyst to a
specific depth. The bottom and the top sections of the tubes are filled with small inert
rings to improve the heat transfer.The reactor tubes are surrounded by Dowtherm to
remove part of the heat of reaction.

The gas mixture entering the top of the catalyst tube is preheated by the boiling
Dowtherm in the reactor shell, while passing through the upper inert rings in the
catalyst tube. As the gas reaches the heated catalyst, the reaction starts and the
temperature rises rapidly to a maximum. When the main part of the methanol has
reacted, the temperature drops rapidly again and approaches the temperature of the
boiling Dowtherm when the gas leaves the reactor tube.

An additional layer of catalyst is loaded below the reactor tubes in the adiabatic bed.
The reacted gases pass out of the reactor bottom and back to vaporizer again. On the
shell side of the vaporizer the gases are cooled to a temperature of about 110°C,
depending on the flow of methanol. The cooled gases then flow to the absorption
tower.

The absorption takes place in the two columns, T-1 & T-2. The first column consists
of a spray section and above that two packed beds. The second column consists of 15
bubble cap trays. Formalin solution of any desired concentration up to 55% can be
obtained.

The heat of absorption is removed by heat exchanger, E-7 and through cooling water
pumped through coils located below the liquid level on each tray. Water is fed into the
top of the second absorber and flows counter-current to the gas flow at a desired rate,
depending on the formaldehyde concentration of the final product.
The reactor shell is filled with boiling Dowtherm in order to obtain the maximum heat
transfer rate. The Dowtherm is circulated by thermo siphon circulation through the
reactor shell and into the vapor separator, E-3.

The Dowtherm vapors are separated from the liquid in the vapor separator from where
the liquid flows back to the converter. The vapors are condensed in a tube-and-shell
heat exchanger, E-2. During start-up, before the heat of reaction has given sufficient
thermosiphon circulation; the Dowtherm is circulated by pump P-2, and preheated in
the Dowtherm heater. The Dowtherm condenser is also operated as a steam boil
EQUIPMENTS USED :

Following are the equipments used in the plant for the production of formaldehyde.

Air blowers, items C-4 A,B :

The air blowers, which supply the air for the oxidation process, are Roots type of
blowers. The maximum delivery pressure is 88 mbar. The normal air flow is 19200
Nm³/hr, which is achieved with two blowers. The blowers are connected to electrical
motors.
Different air flows are achieved by changing the pulleys of the blowers.

Vaporizer, item E-1 :

The vaporizer used is a shell and tube heat exchanger. It works as a flash vaporizer. A
flash vaporizer is used because it eliminates the fire hazard; the amount of methanol
in the process area is very small.

The gas is heated in the vaporizer and after the tube bundle the methanol is sprayed
into the gas. Then the gas passed a pack section before it enters the reactor. This part
of the vaporizer is equipped with a rupture disc.

The temperature of the gas mixture leaving the vaporizer is about 120°C. The heat to
vaporize the methanol is taken from the hot gases coming from the reactor.

Reactor, item R-1 :

The air-methanol mixture enters the top of the fixed-bed reactor, which is equipped
with 11878 stainless steel tubes, 21.0 mm inside diameter and 1500 mm in length. The
tubes are loaded with the metallic oxide catalyst to a specific depth. The bottom and
the top parts of each length of tubes are filled with small inert rings. The purpose of
these rings is to improve the heat transfer between the boiling Dowtherm and the
incoming gas mixture as well as between the Dowtherm and the exit gas. In this way
the gas mixture is preheated before it enters the reaction zone and the reacted gases
are cooled rapidly upon leaving the catalyst zone.

The reactor top is also equipped with two rupture discs, six of the reactor tubes are
fitted with stainless steel thermocouple wells. Each one equipped with six
thermocouples in fixed positions. Below the tubes in the reactor an additional layer of
catalyst is loaded, the adiabatic bed. There is no cooling in this part; therefore the
temperature of the gas leaving the bed is increased by approx. 10°C

Vapor separator, item E-3 :

The Dowtherm vapor separator is cylindrical, vertical vessel, located besides the
reactor. In the vessel the Dowtherm vapor is separated from the liquid as it is forced
from the converter by the thermo siphon circulation. The Dowtherm vapor from the
vapor separator is condensed in the waste heat boiler, which is located just above the
vapor separator.

The liquid Dowtherm in the vapor separator flows back into the converter and again
into the vapor separator. The vapor separator is maintained about half-filled or
somewhat less with liquid Dowtherm during operation, i.e. when the dowtherm is
boiling.
Condenser , item E-2 :

The Dowtherm vapors from the vapor separator are condensed in a tube-and-shell
heat exchanger, which is also operated as a boiler. The boiling water is kept on the
shell side. The boiler feed water level in the condenser is controlled automatically by
the control loop. Steam of pressure up to 22 Kg/cm² (g) can be produced.

The condenser is equipped with a level glass for the boiler feed water level and two
safety valves for the steam system.

Absorption towers, items T-1, T-2 :

The bottom section of the column T-1 contains 6 spray nozzles through which the
product solution circulates. By means of these nozzles the walls of the bottom section
are continuously sprayed with formalin. This is important in order to prevent
precipitation of Para formaldehyde. All nozzles point upwards. The bottom section of
the column is also equipped with a steam coil intended for heating primarily in case of
an interruption in production. In addition, there is a level glass, a level controller,
alarms for high and low levels and temperature indicators.

Above the spray section there are two packed beds through which the formaldehyde
solution is pumped by means of the circulation pumps. The formaldehyde solution,
which is circulating over the upper packed bed, is cooled by an external plate heat
exchanger, E-7.

The second tower T-2 consists of 15 bubble cap trays, each containing 109 bubble
caps. The trays are equipped with cooling coils for removing the heat of absorption.
When producing formalin, process water is added to the upper tray in the column T-2
and the amount is controlled by the flow controller.
At the top of the columns there are built-in drop separators for separating any
entrainment carried along with the gas flow. In T-1this is only a prolonged pipe and
in T-2 a demister of impingement type.

A high pH value in the column contributes to more efficient absorption of

formaldehyde. For this reason there is a piston pump for adding sodium hydroxide to
the process water. To increase the chemical stability of the formaldehyde for storage,
stabilizer is added in the outgoing product.

Chilled water passes through the cooling coils in the T-2 absorber and back to the
chilled water unit. When having colder cooling water, the chilled water is completely
or partly replaced with this. Absorption heat is also removed in heat-exchanger, E-7,
where circulating formalin from the upper packed bed is cooled with cooling water.

Dowtherm system :

When the formaldehyde plant is not in operation, the Dowtherm stored is stored in a
holding tank, E-6, and kept at a temperature of about 20-40°C, since dowtherm is
solidified at a temperature of approximately 12oC. By storing the Dowtherm in this
manner, it is possible to cool down the production equipment quickly, and there is no
danger of freeing the Dowtherm in the system.

When the formaldehyde plant is ready to go into operation, the Dowtherm is brought
into the Dowtherm circulating system by means of dowtherm circulation pump. The
Dowtherm in the separator is kept at low level in order to allow adequate room for
expansion during the heat-up period. When the Dowtherm has reached the operating
temperature, the Dowtherm level in the circulating system is adjusted, if necessary, to
the proper operating level by adding or removing Dowtherm.

During the operation of the plant, the Dowtherm vapor separator is maintained about
half filled. The Dowtherm liquid in the separator exerts a hydrostatic head on the
Dowtherm in the reactor R-1 and in the ECS heat recovery.

In operation the Dowtherm vapor passes out from the top of the converter shell, R-1
and out from the top of the converter shell, and out from the top of the ECS heat
recovery, sweeping Dowtherm droplets along with it, and enters the vapor separator.

The pressure in the Dowtherm system can be regulated between 0 and 2 kg/cm² (g)
by applying instrument air on the tube side of the Dowtherm condenser. The correct
pressure is controlled by the controller. The Dowtherm condenser is equipped with a
safety relief valve.

During the start-up of the plant the heater located in the Dowtherm circulating system
is turned on. When the Dowtherm has reached its operating temperature and the
methanol feed has been started, the heater is turned off manually. Thermocouples are
installed to check that there is no overheating of Dowtherm.
N2 system :
In case of a temperature surge, the methanol and blowers are shut off by the safety
system. If the temperature still does not decrease, a fire-extinguishing system
consisting of three N2 bottles must be manually opened.
Emission Control System :
The ECS consists of three different items. Item E-15 is a preheater for heating the
gases from the absorber to the ignition temperature of the catalyst. Item E-18 is a
vessel containing the platinium-catalyst. The catalyst bed which is supported on a
screen has a height of approximately 60 mm. The reaction taking place is not cooled,
therefore the gas temperature leaving the bed increases.The item E-17 is a tube heat
exchanger where the hot gases leaving E-18 is cooled. On the tube side of the heat
exchanger the hot gases heat the Dowtherm from the separator E-3.
Caustic pump :
It has been found that a slight adjustment of the pH in the absorber by adding NaOH
improves the absorption of the formaldehyde which is important when producing 55%
formalin. When producing formalin, caustic pump can be used for adding NaOH to
the process water. The feed rate to the absorption tower depends to some extends on
the original pH of the water. However, the caustic forms in contact with formic acid
sodium formate. This will increase the ash content in the product. Approximately 5
kg/h of a 5% NaOH-solution can be added which raise the pH at the top on the tower
to appr. 9, to keep ash content in the product below 100 ppm.
Recycle control valve :
As the methanol oxidation to formaldehyde requires oxygen, fresh air must be
continuously brought into the plant via the filter. Consequently, stack gas must be
emitted via the ECS converter. By recycling about 75% of the exit gases from the
absorber, only about 25% of the blower capacity is fresh air. The recycle control valve
is positioned so that the oxygen analyzer during normal operation indicates 10.5-11.00
percent by volume of oxygen.
PRODUCT SPECIFICATION :
Description: - clear and colorless liquid with pungent odor.
Concentration: - 37% + 0.5
Methanol content: - 0.5 – 0.8 %
Specific gravity at 25/25°C: - 1.097
Acidity: - 0.05% max
Iron (as Fe):- 2ppm max.
Ash content: - 0.01%max

STORAGE :
The product Formaldehyde store in the stainless steel tanks at a temperature of 47-
49°C. With the decrease in temperature and increase in the concentration of aqueous
HCHO solution tend to precipitate to Para formaldehyde. At high temperature, the
tendency to formic acid increased. Hence the appropriate storage temperature must be
maintained. Stabilizer solution methanol serves to inhibit polymer formation. Tank
agitation and steam tracing is also provided for preventing Para formaldehyde
formation.

OPERATIONAL FEATURES AND CRITICAL PARAMETERS :

The plant has been equipped with an interlock system to protect personnel and the
environment as well as to prevent damage to the plant itself.
 The interlock system controls the process either by shutting off methanol flows
to reactor (safety system SWS-B) or airflow from blowers (safety system SS-A).
The interlock system is activated if any- predetermined critical limit is reached on the
parameters as in the following situations:
Methanol flow to the vaporizer is an important control parameter. If there is a
high alarm which is alerted at a methanol inlet of vapoarizer. In combination with O2,
SS-B will be activated and methanol feed will be stopped. The valve is located very
near the vaporizer to ensure that as litttle as possible methanol will enter the
vaporizer. The vaporizer top, where vaporization occurs, has a rupture disc connected
to safety AB, which stops air and methanol flow to reaction line.
The safety system AB activated in case of a too high discharge pressure is obtained
from the blowers and hence the blowers and methanol feed are cut off.
In case of a pressure surge the reactor; safety system AB to which the rupture disc is
connected gets activated in order to shut down the methanol and air to reactor.
In the tubular reactor, six of the tubes are fitted with stainless steel thermocouple
wells, inside of which are fixed thermocouples. The highest temperature of per chosen
thermocouples in each well will alarm if it exceeded the set limit.
Safety system SS-D: In plant shut down stage, the dowtherm is stored in a tank where
its temperature is maintained between 20-40°C (it solidifies at about 12°C
approximately). An electric heater is used to heat the dowtherm about 100°C and
hence it avoids water contamination in fresh dowtherm. This heater is connected with
SS-D, which automatically shuts off heater incase of a high exit temperature.
Oxygen Control:
During operation, the O2 concentration of gas going to the reactor is kept constant, by
an automatic controller at 11 vol%. This concentration means that approximately
1/3rd of fresh air and 2/3rd of recycle gas from absorber is fed to the reactor.
Control of O2 concentration essential. If methanol concentration in the gas to the
reactor is below 7 vol%, then no pressure surge will occur, regardless of O2
concentration. However, when the methanol concentration is above 7 vol %, the O2
concentration must be below 13vol% to avoid the risk of an explosion.
HCHO Concentration control:
A specific concentration profiles is achieved in the absorbers, depending on
parameters such as water supply, temperature and the feed gas.
If product concentration goes up it means the supply of water is insufficient and must
be increased. If the HCHO concentration decreases, then either too much water is
being fed or some of the cooling coils in the absorber are leaking. If decreasing the
water flow at the top does not reverse the trend of down going concentration, then the
coils are to be leak tested.
Caustic soda (5%) is also added to the process water in order to achieve better
absorption. The pH profile in the absorber is important. At a pH of 8.5, absorption is
optional.
Formaldehyde pumps and pipelines:
All pumps in contact with formaldehyde are always to be drained when not in
operation, and thus it assures that no Para formaldehyde formation occurs, which can
damage the pumps. All piping in the circulation system for strong formaldehyde
solution around the absorber is insulated and steam raced. The insulation is 50mm
thick.
These actions and control procedures assure that the plant will not produce any
hazardous substances and will operate without any interruptions.
 Emergency stop :
In the control panel there is a red key operated mushroom push button as emergency
stop together with a push button with light (reset button). If the emergency stop has
been pushed the light in the reset button turns off. To reset the system the key is used
to release the emergency stop and thereafter the reset button is pushed in.

MATERIAL BALANCE :
General process block diagram :

RECYCLE GAS
 COMPOSITION OF AIR :

Blower Discharge i.e. Total air flow rate = 18000Nm3/hr

And 1 gmol = 22.4dm3

Thus,

18000 Nm3/hr = 803.5714 Kgmol/hr

COMPONENTS Kgmol/hr %MOL Kg/hr Wt%

N2 677.7116 84.33744 18975.924 83.96472
O2 88.39286 11.0 2828.5714 12.51587
CO 6.402479 0.79675 179.26943 0.793232
DME 1.713954 0.21329 78.841864 0.34886
CH2O 0.062566 0.00779 1.8769821 0.008305
CH3OH 0.586567 0.073 18.770143 0.08304
H2O 28.70139 3.57173 516.62509 2.285964
TOTAL 803.5714 100 22599.879 100

METHANOL FEED:

% CH3OH in mixed stream = (A*2240)/ ((32*B) + (22.4*A)) =7.5

Where,
A= CH3OH flow rate in Kg/hr

B= Air flow rate in Nm3/hr = 18000Nm3/hr

Here we get, A = 1930Kg/hr

Reactions taking place in Reactor:

92.5 %
1) CH3OH + 1/2O2 CH2O + H2O
3.5 %
2) CH3OH + O2 CO + 2H2O
1.5%
3) CH3OH + CH3OH CH3OCH3 + H2O
 0.03%
4) CH3OH + O2 CHOOH +H2O
2.47 %
5) CH3OH CH3OH

INLET TO REACTOR:

Some CH3OH is coming from the blower and some is coming from CH3OH feed, so

Total CH3OH in = 1935/32 + 803.5714*0.073/100

Input stream
= 60.8995 Kgmol/hr

Following are given the amount of CH3OH, O2 used and other compounds formed:

In Reaction 1 ,
CH3OH used = 56.332Kgmol/hr
O2 used = 28.166Kgmol/hr
CH2O formed = 56.332Kgmol/hr
H2O formed = 56.332Kgmol/hr

In Reaction 2,
CH3OH used = 2.13148Kgmol/hr
O2 used = 2.13148Kgmol/hr
CO formed = 2.13148Kgmol/hr
H2O formed = 2.13148Kgmol/hr

In Reaction 3,
CH3OH used = 1.82699Kgmol/hr
H2O formed = 0.91349Kgmol/hr

In Reaction 4,
CH3OH used = 0.0182699Kgmol/hr
H2O formed = 0.0182699Kgmol/hr

In Reaction 5,
CH3OH used = 1.50422Kgmol/hr

AT OUTLET OF REACTOR:

Outlet of the reactor is used as a heating medium in the evaporator to

evaporate methanol. Following is its composition:

COMPONENTS Kgmol/hr Mol % Kg/hr Wt%

N2 677.7116 75.71395 18975.92 77.26632
O2 58.0773 6.488397 1858.474 7.567348
CO 8.533947 0.953413 238.9505 0.972961
DME 2.62744 0.293538 120.8622 0.4921218
CH2O 56.3942 6.300361 1691.826 6.888791
CH3OH 1.504207 0.16805 48.13462 0.195995
H2O 90.22772 10.08024 1624.099 6.613019
CHOOH 0.01838 0.002053 0.84548 0.003443
TOTAL 895.0948 100 24559.12 100

This outlet stream of reactor is used for vaporizing CH3OH and in turn to reduce
its temperature for better absorption in the two absorbers later. From the absorber we
get the required product i.e. 37% Formaldehyde (wt %).

From the outlet of reactor 2.5Kg/hr CH2O, 25Kg/hr CH3OH and whole N2, O2, CO
and DME goes to T2 outlet thus,

CH2O = 1689.326Kg/hr

Thus for CH2O to be 37% total amount required (X) is,

1689.326 *100/X = 37

X = 4565.779Kg/hr

Water added for absorption is 90.5% of amount of CH3OH feed.

Water required to make product 37% by wt =

4565.779-(1689.326+ 23.13462+0.84548)

Amount of water in the product = 2852.44 Kg/hr

Remaining amount of H2O goes to the T2 stream along with N2, O2, DME, some
amount of CH3OH and CH2O.

FD PRODUCT OUTLET :

COMPONENTS Kgmol/hr Mol% Kg/hr Wt%

CH2O 56.31087 26.12778 1689.326 37
CH3OH 0.722957 0.335446 23.13462 0.5067
H2O 158.4689 73.52825 2852.44 62.47478
CHOOH 0.01838 0.008528 0.84548 0.018518
TOTAL 215.5211 100 4565.746 100

T2 OUTLET STREAM :

COMPONENTS Kgmol/hr Mol% Kg/hr Wt%

N2 677.7116 87. 26417 18975.92 87.25446
O2 58.0773 7.478312 1858.474 8.548629
CO 8.533947 1.098872 238.9505 1.099127
DME 2.62744 0.338322 120.8622 0.555943
CH2O 0.083333 0.01073 2.5 0.0115
CH3OH 0.78125 0.100597 25 0.114995
H2O 28.79494 3.707775 518.309 2.384124
TOTAL 776.6098 100 21740.02 100

T2 outlet stream gets divided into two streams which are as follows:

1. RECYCLE STREAM
2. ECS INPUT STREAM

Amount of fresh air (X) required can be calculated as:

(803.5714-X) x 7.478312 + X x 20.3 = 803.5714 x 11

X = 220.7141Kgmol/hr

Thus, amount of recycle stream = 803.5714-220.7141

= 582.8573Kgmol/hr

Amount of ECS stream = T2 stream - recycle stream

= 776.6098 – 582.8573

= 193.7525Kgmol/hr
EMISSION CONTROL SYSTEM (ECS) :

At equilibrium stage, amount of CO generated in reactor system goes to the ECS

system while the rest gets recycled.

Percentages of all components in T2 stream, Recycle stream, ECS input stream

remains is same.

Following is tabulated the ECS INPUT STREAM :

COMPONENTS Kgmol/hr Mol% Kg/hr Wt%

N2 169.0765 87.26417 4734.143 87.28446
O2 14.48942 7.478312 463.6614 8.548629
CO 2.131467 1.10098 59.68109 1.100354
DME 0.655507 0.338332 30.15332 0.555943
CH2O 0.02079 0.01073 0.623713 0.0115
CH3OH 0.19491 0.100597 6.237126 0.114995
H2O 7.183908 3.70777 129.3103 2.384124
TOTAL 193.7525 100 5423.81 100
 RECYCLE STREAM:

COMPONENTS Kgmol/hr Mol% Kg/hr Wt%

N2 508.6225 87.26417 14241.51 87.28446
O2 43.58788 7.478312 1394.812 8.548629
CO 6.402479 1.10098 179.2694 1.100354
DME 1.971933 0.338332 90.7089 0.555943
CH2O 0.062543 0.01073 1.876287 0.0115
CH3OH 0.58634 0.100597 18.76287 0.114995
H2O 21.61104 3.70777 388.9986 2.384124
TOTAL 582.8573 100 16315.94 100

ECS OUTLET:

In ECS system CO, HCHO, DME, CH3OH are converted to CO2.

Following are the reactions to form CO2 on fixed catalyst bed of Platinum:

1) CO + 1/2O2 CO2

2) HCHO + O2 CO2 + H2O

3) CH3OCH3 +3O2 CO2 + 3H2O

4) CH3OH + 3/2O2 CO2 + 2H2O

However some CO still remains. Standard norm for CO is 50ppm.

0.16% of the CO in the ECS inlet goes in the ECS outlet, while rest all other
compounds get 100% converted to CO2 by above reaction. This hot ECS outlet is
used to heat dowtherm oil .

Following is the composition of the ECS outlet stream:

COMPONENTS Kgmol/hr Mol% Kg/hr Wt%

N2 169.0765 87.632 4734.143 87.75109
O2 11.29901 5.856250 361.5683 6.701956
CO 0.310004 0.160674 8.680114 0.160893
H2O 9.56104 4.955466 172.0987 3.189986
CO2 2.692671 1.395605 118.4775 2.196075
TOTAL 192.9393 100 5394.968 100

Now the blower will discharge mixture of fresh air and recycle stream into the
evaporator.

FRESH AIR COMPOSITION :

As calculated earlier fresh air amount was 220.7141Kgmol/hr.

Following is the composition of fresh air :

COMPONENTS Kgmol/hr Mol% Kg/hr Wt%

N2 170.612 77.3 4777.137 75.75248
O2 44.80497 20.3 1433.759 22.73555
H2O 5.297139 2.4 95.34851 1.51197
TOTAL 220.7141 100 6306.244 100

NEW BLOWER DISCHARGE :

So the new blower discharge will have the following tabulated composition:

COMPONENTS Kgmol/hr Mol % Kg/hr Wt%

N2 679.2375 84.52834 19018.65 84.07302
O2 88.39285 11.00013 2828.571 12.50346
CO 6.402479 0.796762 179.2694 0.792445
DME 1.971933 0.245399 90.7089 0.400971
CH2O 0.062543 0.007783 2.001373 0.008847
CH3OH 0.58634 0.072968 18.76287 0.08294
H2O 26.90817 3.348613 484.3471 2.141015
TOTAL 803.5619 100 22622.31 100

This is the complete material balance for the formaldehyde plant in phase 2.

PRECAUTIONS AND SAFETY FACTORS:

Formaldehyde is highly toxic by inhalation and oral intake. The vapors are very much
irritating to the eye and upper respiratory system. Though liquid is not highly
irritating to skin, it can cause severe eye burns.
Topical application may produce irritant dermatitis ingestion may cause severe
abdominal pain, acidosis, vertigo, coma, death High concentrations are intolerabl.
Explosive limit of formaldehyde in air is: LEL: 7% HEL 73%
So proper precautions need to be taken while working on the formaldehyde plant.
Safety equipments such as gloves, mask, apron, helmet, safety goggles, shoes, etc.
must be used while working on plant.
O2 control :
Control of O2 concentration is essential. If methanol concentration in the gas to the
reactor is below 7 vol%, then no pressure surge will occur, regardless of O2
concentration. However, when the methanol concentration is above 7 vol %, the O2
concentration must be below 13vol% to avoid the risk of an explosion. Because it
forms explosive mixture in such cases. The plant has been equipped with rupture disc
which gets open automatically in case of high pressure to avoid explosion. Also
majority of the part of the stack gas is recycled which makes sure the oxygen
concentration is well below 13% to avoid explosive mixture.
Fire control :
There is always a certain risk at elevated temperatures at the reactor top or at bottom.
The plant has to be shut down in case of too high temperatures. As both methanol and
the gas are stopped by SS-AB, any fire will extinguish itself. In the unlikely event that
the fire does not cease, there is a nitrogen system connected to the reactor top of
purging.
FUTURE PERSPECTIVES :

HOC holds very good reputation of being one of the greats in their field. The
past years of company has been full of glory. Once a time, the company was one of
the leading manufacturer of basic chemical products.
However, the tradition has shown reverse trend these days. Due to immense
competition from private sector & improper management strategy, the company is
finding difficult to hold it’s status of being great in the market.
No question in the world can be unanswered. The company need to be more
reluctant, professional in attitude & have to take some tough decisions. Plants are still
in good condition which can give product of high purity. The proper marketing
strategy is must for any firm, if it has to remain intact in the global market. The
working efficiency of workers as well as the higher officials needs to be improved.
Well, the future of HOC is in the hand of HOC’ians.
REFERENCES :

1. PERRY’S HANDBOOK
2. PHYSICAL PROPERTIES
BY CARL L .YAWS
3. LANGE’S HANDBOOK OF CHEMISTRY-TATA MCGRAW HILL
4. PROCESS HEAT TRANSFER
BY DONALD Q. KERN
ACKNOWLEDGEMENTS

We would like to express our sincere thanks to Dr. B.N.THORAT, UICT

for providing us the platform to do the Inplant Training in HOC,Rasayani without
which this project would not have been completed successfully.

We would also like to express our since thanks to Mr.A.M.SATHE, HOC for
his guidance for carrying out this project. We were really honored for the keen interest
he took at each and every step of this work. We would like to express our deepest
gratitude for his encouragement and confidence he showed in us while carrying out
this project without which this work would have not been completed.

We also like to thank Mr. M.S.Patil, for the efforts he has taken to help &
guide us. We would also like to thank Mr. Jirimali and Mr.Virkar for the support they
had given & faith they have shown in us.

INDEX

Sr. No. Contents Pg. No.

1. Introduction to Company
1.1 Company background 3
1.2 Features of the company 5
2. Waste heat boiler design 8
3. Vaporizer design 13
4. Pressure drop calculations 16
5. Formaldehyde plant
5.1 Formaldehyde-useful industrial product
18
5.2 Introduction 19
5.3 Process flow sheet 20
5.4 Plant- functional description 21
5.5 Equipments used 24
5.6 Product sprcification & storage 30
5.7 Operational features & critical parameters 31
5.8 Material balance 34
5.9 Precautions & safety factors 42
5.10 Future perspectives 43

6. References 44

INTRODUCTION

COMPANY BACKGROUND :

“HINDUSTAN ORGANIC CHEMICAL LTD.” A leader in Indian chemical industry

for over three elected is further expanding its horizons in near future. Earlier company
has to depend upon the imports for its vital organic chemical needs till the
government with a view to making the company self reliant in this field set up HOC
in 1960. Making a beginning as a small chemical unit HOC is today a multi
technology, multi-unit company with three fast growing units.

HOC has following manufacturing units:-

The main organic chemical complex at Rasayani in Raigad District
(Maharastra)
The phenol complex at kochi (Kerala)
The poly tetra Flurothylene at Hyderabad (Andhra Pradesh)

Initiating an era in basic chemical intermediates. Incorporated at rasayani, a backward

area in Maharastra, HOC’s first plant started production in 1970. Between 1970 and
1974 a total of twelve plants were commissioned. Together they produce a large
number of products that serve a wide spectrum of industries, ranging from
pharmaceuticals to defense and space.

After stabilization of the first phase plant in the sixth plan period (1980-85), a number
of expansion and diversification plants were launched at Rasayani. Expansion phase
included doubling of Hydrogen, Aniline, Nitro Benzene and Nitro Toluene and
substantial expansion of Nitroclorobenzene.

HOCL was established on 12th Dec.1960 by the Government of India, with the
view of making the country self-sufficient in the filed of organic chemical
manufacture. Initiating an era in basic chemical complex is a leader in Indian
chemical industries manufacturing a wide range of high quality basic organic
chemical which are required for variety of chemical and pharmaceutical product such
as drugs, medical, dyes, plastics, resins, paints, textile, and explosive.

The company has a continuous manufacturing process and works for 24hrs.
A day in 3 shifts in all, around 22 plants are functioning at Rasayani. HOC has its
head office situated at Mumbai. The company provides various facilities to its
employees like canteen, transport, residential quarter, library and hospital, etc.
FEATURES OF THE COMPANY :

Training Centre :

HOC has as well-quipped training center, which arranges regular courses for
developing skills of employee at all, level. Periodic in house seminars are held,
workshop are conducted for employees. Which help them sharpen their skills.

Safety department :

In everything HOC does, safety of its employees is a prime consideration. This

concern is manifest is a multitude of ways. Safety department provide Safety devices
to the workers and trains them to work Safety and continuously.

Fire department :

The fire officer train the personnel to deal with an emergency like fire etc. and teach
them to make proper use of fire extinguishers and Safety equipments.

Health center :

The company health center is well equipped with all the medicines and has its
own ambulances. There are qualified doctor in medicals center who examine the
workers regularly during the routing medical check up.

Research & Development :

In order to diversify, lower the costs and increase existing capacities, HOC’s R & D
efforts are being directed toward assimilation and adaptation of most modern
international technologies and development of new and improved processes and
chemicals.

Scale-up studies are being undertaken through pilot plants, while facilities are being
augmented for catalyst testing and sophisticated analysis.
In-house research apart, HOC’s R & D division collaborates with scientists from
Universities, Institutes of technology and National Research Laboratories, involved in
nation building projects. In house in the R & D department has led to the installation
of pilot plant for production of cyclohexyl amine. The R& D department is pursuing
it’s efforts in the development of noble metal catalyst for increased manufacture of
CHA.

By recovering resorcinol- a value added chemical from meta amino phenol

plant, due efforts of R & D department, HOC has won many prestigious award.
Quality Control

HOC is very conscious of maintaining a high quality of its products and for this
purpose right from raw material through processing to finished product, through
checking and stringent tests are carried out at every stage by experts in a modern well-
equipped laboratory.

Quality control:

HOC is very conscious of maintaining a high product, right from raw

materials, to finished products, through checking and experts in a modern well-
equipped laboratory carry out stringent test at every stage.

Export :

What began as an import substitution effort years ago is now an export activity that is
steadily gaining momentum. The fact that HOC has generated self-sufficiency in
chemicals in India is further complimented by its exports to countries like USA,
France, UK, Japan, Germany and many others. Competitive pricing and high quality
make HOC’s prospects excellent on the export scene.

Today HOC stands as a winner of several awards for excellent export performance
from CHEMEXCIL (Basic chemicals, pharmaceuticals and cosmetics export
promotion council), an organization set up by the Government of India.

WASTE HEAT BOILER DESIGN :

 In 1-2 Shell and Tube heat exchanger (WHB), on shell side water flows at 2000
Kg/hr while on tube side HTM oil flows. We have to calculate the steam generation
rate.

HTM OIL:

Inlet temperature of HTM oil = 173oC

Outlet temperature of HTM oil = 160oC

WATER:

Inlet temperature of water = 80oC

Outlet temperature of steam = 150oC

Following are the physical properties of the concerned fluids:

PROPERTIES HTM OIL WATER STEAM

Ρ, Kg/m3 1000 1000 1.2
Cp, Kcal/KgK 0.76 1 0.47
µ, Poise 0.3x10-3 10-3 1.42x10-4
K, W/Mk 0.1 0.6 0.02836

TUBES:

Number of tubes = 178

Outer diameter of 1 tube = 1.25in.
Thickness = 10BWG
Inner diameter of tube = 0.982in.
Total heat transfer area for heat exchanger = 117.45m2
Assuming overall heat transfer coefficient, Ud = 240W/m2K
Log mean temperature difference is,

∆Tlm = ((173-150)-(160-80))/ln ((173-150)/ (160-80))

= 45.72oC

So, total heat duty will be,

Q = Ud A ∆Tlm

= 240 x 117.45 x 45.72

Q = 1288755.36 Watts

Now,
Total heat duty = Specific heat given by HTM oil
 Q = mcp∆Tlm = 1288755.36

= m x 0.76 x (173-160)

HTM oil mass flow rate, m = 24.8 Kg/s

= 89,280Kg/hr.

HEAT TRANSFER COEFFICIENTS:

On tube side:

Area of cross section of one tube, a = Π/4x (0.982 x 0.0254)2

= 4.885x
10-4 m2

Velocity, V = volumetric flow rate /area

= 24.8 x 2 / (1000 x 178 x 4.885 x 10-4)

Number of passes = 2 and number of tubes = 178

V = 0.57m/s.

Reynolds number, Re = DVρ/ µ

= (0.0249 x 0.57 x 1000)/ (0.3 x 10-3)

= 47345

Prandtl number, Pr = Cp µ/K

= 0.76 x 4184/0.1

= 7.026

Nusselt number, Nu = 0.023 Re0.8 Pr0.33

= 0.023 x 473450.8 x 7.0260.33

Since, Nu = hd/k

So,
hd/k = 175.84

h = 706.211
 hio = 554.8W/m2K …………. ( hio = h x ID/OD)

So, heat transfer coefficient on tube side, hio = 554.8W/ m2K

Shell side:

Square Pitch = 1.5in.

Shell area = 1.5” x 1.5”

= 2.25sq.in.

Tube area = Π/4 x 1.252

= 1.227sq.in.

Total tube area = 178 x Π/4 x 1.252

= 218.44sq.in.

Shell area = (2.25/1.227)x178 = 326.41sq.in.

326.41 = Π/4x D2s

Ds = 20.39in. = 0.518m

Baffle spacing = 0.5 x Ds

= 0.5 x 20.39

= 10.195in.

= 0.258m

Equivalent diameter, Deq = 4xflow area/wetted parameter

= 4 x (1.52 - Π/4 x 1.252)/ (Π x 1.25)

= 1.04 in.

Flow area = baffle spacing x clearance x shell ID/pitch

= 10.195 x (1.5 - 1.25) x 20.39/1.5

= 0.0224m2

Velocity, V = Volumetric flow rate / flow area

= 2000/ (3600 x 1000 x 0.0224)

 = 0.0248m/s

Reynolds number, Re = DVρ/ µ

= 0.0264 x 0.0248 x 1000/10-3

= 654.72

Prandtl number, Pr = Cp µ/K

= 1 x 4184 x 10-3/0.6

=7

Nusselt number, Nu = 0.36 Re0.55 Pr0.33

= 0.36 x 654.720.55 x 70.33

hd/k = 89.17

ho = 2026.64 W/ m2K

Heat transfer coefficient on shell side, ho = 2026.64 W/ m2K

OVERALL HEAT TRANSFER COEFFCIENT:

Overall clean heat transfer coefficient (Uc),

1/Uc = 1/ hio + 1/ ho

= 1/554.8 + 1/2026.64

= 451.34 W/ m2K

Now dirt factor, Rd = 1.785x10-3K/W m2

So, Overall heat transfer coefficient (Ud),

1/ Ud = 1/ Uc + Rd

= 1/451.34 + 1.785x10-3

Ud = 242 W/ m2K

So, calculated Ud is fairly matching with the assumed value.

Now,

Total heat duty = (mcp∆T) water + mλ + (mcp∆T) steam

 1288755.36 = m x 4184 x (100-80) + m x540x4184 + m x 1967.63x (150-100)

m = 0.5278Kg/s

= 1900 Kg/hr.

So, the required steam generation rate is 1900Kg/hr.

VAPORIZER DESIGN :

VAPORIZER :
To check the design for vaporizer :

There are 3 zones in the vaporizer.

1. preheating zone

2. flashing zone

3. superheating zone

A)
Let UD= 25 w/m2k

So,

Q = UD A ΔTLM = (m CP ΔT)H2

= 446.42 x 3.46 x 4184 x 4

Q = 7180.74 W

7180.7 = 25 x A x 43.5

A = 6.6 m2…. required area.

Provided area = 92.787 m2

B)

m cp (160-T)H2 = m λNB

446.2 x 3.46 x 4184 x (160-T) = 2000 x 334720 / 3600

=> (160-T) = 0.02877

T = 159.97 oC.

C)

Q = m cp (160-T) H2 + m cp (160-T)NB
 = 446.42 x 3.46 x 4184 x 0.02872

+ 2000 x 3.46 x 4184 x 0.02877/ 3600

Q = 1094.3 W

Area provided = 0.6823 x 46 = 31.39 m2

Let, UD = 25 w/m2k

& we calculate ΔTLM = 41.49

1094.3 = 25 x A x41.49

A = 1.055 m2

Zone Area calculated, m2 Actual area, m2

Preheating 6.6 92.787
Superheating 1.055 31.39

PRESSURE DROP CALCULATIONS :

Calculations of pressure drop across 90o bend having 80 mm diameter and with
air flow rate 5000Nm3/hr at 9Kg/cm2 and 50oC.

Assumptions :

Ideal gas laws such as Boyle’s law are considered to be valid for given air at
NTP

Data: 1. ρair = 1.2 Kg/m3

2. Head loss coefficient for 90o bend (K) = 1

Solution :

22.4 dm3 of gas at NTP = 1gmol

5000Nm3/hr of gas at NTP = X gmol

X = 223214.29 gmol/hr

= 6473.2147 Kg/hr

Air flow rate at NTP (25oC & 1Kg/cm2 pre.) = 6473.2147 Kg/hr

By ideal gas law,

V1/T1 = V2/T2

V2 = V1 x T2/T1

V2 = 1.2 x (273.16 + 50) / (273.16+25)

= 1.3006 m3 for 1 kg of gas at 50oC

From Boyle’s law,

P1V1 = P2V2

V2 = P1V1

= 1 x 1.3006/9

= 0.1445 m3 for 1Kg gas at 50oC and 9Kg/cm2

Now,
Density of air at 50oC and 9Kg/cm2,

ρair =1/V2

= 6.9204 Kg/m3

6473.2147 Kg of gas = 6473.2147/6.9204

= 935.444 m3

Area of cross section of pipe, A= d2/4

= 5.0265 x 10-3m2
Velocity, V = volumetric flow rate / A

= 935.44/(5.0265 x 10-3 x 1000)

= 51.6917 m/s

Pressure drop (ΔP),

ΔP = ½ ρairV2 K

= ½ x 6.9204 x (51.6917)2 x1

= 9245.76Pa

ΔP = 0.09248 kg/cm2

Therefore, the pressure drop across 90o bend = 0.09248 kg/cm2

FORMALDEHYDE

FORMALDEHYDE – USEFUL INDUSTRIAL PRODUCT:

1. Formaldehyde is useful chemical employed in the manufacture of many

industrial product and consumer articles.
2. Formaldehyde is used in the manufacture of phenolic resins, artificial silk and
cellulose esters, dyes, organic chemicals etc.
3. Formaldehyde is used as agent for improving the fastness of dyes on fabrics.

4. A major application of Formaldehyde in the manufacture of crop protection

and soil disinfections chemicals, fumigants, pharmaceuticals and explosives.
5. It is used for tanning and preserving hides, and for preserving and coagulation
of rubber latex.

INTRODUCTION :

The current plant - formaldehyde phase 2 produces a 37% water solution of

formaldehyde by the vapor phase oxidation of methanol by air in presence of Iron
Oxide-molybdenum oxide catalyst in a fixed bed tubular reactor at 320-400°c and
scrubbing the gas by D.M. water to absorb HCHO gas(formalin gas to get 37%
HCHO. The plant is designed to produce a maximum of 55% HCHO.

Alternative ways :
 Following are the two alternative ways of production of formaldehyde.
1. Silver catalyst process in which methanol is oxidized over a silver catalyst at
the atmospheric pressure and 600-650°C.
2. From the Methane by, partial oxidation.
But it was found that the process of production of formaldehyde by using
Iron-molybdenum oxide catalyst was much more efficient. Hence this process was
employed in the plant.

Properties :
1. Nature :- colorless liquid with pungent odors.
2. Density :- 1.08-1.085 gm/cm³ (25°C)
3. Boiling point :- 96°C
4. Refractive index :- 1.3746 (20°C)
5. Flash point :- 60°C.
6. Miscible with water, alcohol and acetone.
7. Hazard : - Toxic by inhalation, skin and eye irritant, moderate fire risk.
Raw materials : Methanol, air and caustic soda.
Utilities : D.M water, cooling water, chilled water, instrument air, power
supply.
PROCESS FLOW SHEET :

PLANT - FUNCTIONAL DESCRIPTION:

The process is accomplished by the oxidation of methanol on a metallic oxide

catalyst, using a fixed-bed vapor-phase oxidation converter, according to formula:
CH3OH + ½O2 CH2O + H2O ∆H= -159 KJ/mol

A low ratio of methanol to air is used to maintain the desired oxidation atmosphere,
and the heat of reaction is removed from the converter by boiling a liquid heat transfer
medium (Dowtherm A or equivalent medium). The methanol content in air is
maintained between about 4 and 9 % by volume. Such a high content can be used
because part of stack gas from the plant is recycled, which decreases the oxygen
concentration sufficiently to avoid explosive mixtures.

The process gives a high yield on a single passage, and also very high conversion
making the recovery of methanol from the final product unnecessary. The actual
formaldehyde yield is in the range of 91-94% of the theoretical. The remainder of the
methanol is accounted for by unreacted methanol, carbon monoxide, dimethyl ether
and a negligible amount of formic acid.

The air is supplied by two root type of blowers, here items C-4 A/B. Methanol to the
plant is supplied by pump, P-1 and is injected into the air stream after the vaporizer
tube bundle through a spray nozzle ring. The air is passed through the methanol
vaporizer, E-1, after which the methanol is vaporized. The gas mixture temperature to
the reactor is now about 120°C.
The oxidation of the methanol takes place in a fixed-bed reactor with 11878 stainless
steel tubes of 21mm. The tubes are loaded with the metallic oxide catalyst to a
specific depth. The bottom and the top sections of the tubes are filled with small inert
rings to improve the heat transfer.The reactor tubes are surrounded by Dowtherm to
remove part of the heat of reaction.

The gas mixture entering the top of the catalyst tube is preheated by the boiling
Dowtherm in the reactor shell, while passing through the upper inert rings in the
catalyst tube. As the gas reaches the heated catalyst, the reaction starts and the
temperature rises rapidly to a maximum. When the main part of the methanol has
reacted, the temperature drops rapidly again and approaches the temperature of the
boiling Dowtherm when the gas leaves the reactor tube.

An additional layer of catalyst is loaded below the reactor tubes in the adiabatic bed.
The reacted gases pass out of the reactor bottom and back to vaporizer again. On the
shell side of the vaporizer the gases are cooled to a temperature of about 110°C,
depending on the flow of methanol. The cooled gases then flow to the absorption
tower.

The absorption takes place in the two columns, T-1 & T-2. The first column consists
of a spray section and above that two packed beds. The second column consists of 15
bubble cap trays. Formalin solution of any desired concentration up to 55% can be
obtained.

The heat of absorption is removed by heat exchanger, E-7 and through cooling water
pumped through coils located below the liquid level on each tray. Water is fed into the
top of the second absorber and flows counter-current to the gas flow at a desired rate,
depending on the formaldehyde concentration of the final product.
The reactor shell is filled with boiling Dowtherm in order to obtain the maximum heat
transfer rate. The Dowtherm is circulated by thermo siphon circulation through the
reactor shell and into the vapor separator, E-3.

The Dowtherm vapors are separated from the liquid in the vapor separator from where
the liquid flows back to the converter. The vapors are condensed in a tube-and-shell
heat exchanger, E-2. During start-up, before the heat of reaction has given sufficient
thermosiphon circulation; the Dowtherm is circulated by pump P-2, and preheated in
the Dowtherm heater. The Dowtherm condenser is also operated as a steam boil
EQUIPMENTS USED :

Following are the equipments used in the plant for the production of formaldehyde.

Air blowers, items C-4 A,B :

The air blowers, which supply the air for the oxidation process, are Roots type of
blowers. The maximum delivery pressure is 88 mbar. The normal air flow is 19200
Nm³/hr, which is achieved with two blowers. The blowers are connected to electrical
motors.
Different air flows are achieved by changing the pulleys of the blowers.

Vaporizer, item E-1 :

The vaporizer used is a shell and tube heat exchanger. It works as a flash vaporizer. A
flash vaporizer is used because it eliminates the fire hazard; the amount of methanol
in the process area is very small.

The gas is heated in the vaporizer and after the tube bundle the methanol is sprayed
into the gas. Then the gas passed a pack section before it enters the reactor. This part
of the vaporizer is equipped with a rupture disc.

The temperature of the gas mixture leaving the vaporizer is about 120°C. The heat to
vaporize the methanol is taken from the hot gases coming from the reactor.

Reactor, item R-1 :

The air-methanol mixture enters the top of the fixed-bed reactor, which is equipped
with 11878 stainless steel tubes, 21.0 mm inside diameter and 1500 mm in length. The
tubes are loaded with the metallic oxide catalyst to a specific depth. The bottom and
the top parts of each length of tubes are filled with small inert rings. The purpose of
these rings is to improve the heat transfer between the boiling Dowtherm and the
incoming gas mixture as well as between the Dowtherm and the exit gas. In this way
the gas mixture is preheated before it enters the reaction zone and the reacted gases
are cooled rapidly upon leaving the catalyst zone.

The reactor top is also equipped with two rupture discs, six of the reactor tubes are
fitted with stainless steel thermocouple wells. Each one equipped with six
thermocouples in fixed positions. Below the tubes in the reactor an additional layer of
catalyst is loaded, the adiabatic bed. There is no cooling in this part; therefore the
temperature of the gas leaving the bed is increased by approx. 10°C
 Vapor separator, item E-3 :

The Dowtherm vapor separator is cylindrical, vertical vessel, located besides the
reactor. In the vessel the Dowtherm vapor is separated from the liquid as it is forced
from the converter by the thermo siphon circulation. The Dowtherm vapor from the
vapor separator is condensed in the waste heat boiler, which is located just above the
vapor separator.

The liquid Dowtherm in the vapor separator flows back into the converter and again
into the vapor separator. The vapor separator is maintained about half-filled or
somewhat less with liquid Dowtherm during operation, i.e. when the dowtherm is
boiling.
Condenser , item E-2 :

The Dowtherm vapors from the vapor separator are condensed in a tube-and-shell
heat exchanger, which is also operated as a boiler. The boiling water is kept on the
shell side. The boiler feed water level in the condenser is controlled automatically by
the control loop. Steam of pressure up to 22 Kg/cm² (g) can be produced.

The condenser is equipped with a level glass for the boiler feed water level and two
safety valves for the steam system.

Absorption towers, items T-1, T-2 :

The bottom section of the column T-1 contains 6 spray nozzles through which the
product solution circulates. By means of these nozzles the walls of the bottom section
are continuously sprayed with formalin. This is important in order to prevent
precipitation of Para formaldehyde. All nozzles point upwards. The bottom section of
the column is also equipped with a steam coil intended for heating primarily in case of
an interruption in production. In addition, there is a level glass, a level controller,
alarms for high and low levels and temperature indicators.

Above the spray section there are two packed beds through which the formaldehyde
solution is pumped by means of the circulation pumps. The formaldehyde solution,
which is circulating over the upper packed bed, is cooled by an external plate heat
exchanger, E-7.

The second tower T-2 consists of 15 bubble cap trays, each containing 109 bubble
caps. The trays are equipped with cooling coils for removing the heat of absorption.
When producing formalin, process water is added to the upper tray in the column T-2
and the amount is controlled by the flow controller.

At the top of the columns there are built-in drop separators for separating any
entrainment carried along with the gas flow. In T-1this is only a prolonged pipe and
in T-2 a demister of impingement type.

A high pH value in the column contributes to more efficient absorption of

formaldehyde. For this reason there is a piston pump for adding sodium hydroxide to
the process water. To increase the chemical stability of the formaldehyde for storage,
stabilizer is added in the outgoing product.
Chilled water passes through the cooling coils in the T-2 absorber and back to the
chilled water unit. When having colder cooling water, the chilled water is completely
or partly replaced with this. Absorption heat is also removed in heat-exchanger, E-7,
where circulating formalin from the upper packed bed is cooled with cooling water.

Dowtherm system :

When the formaldehyde plant is not in operation, the Dowtherm stored is stored in a
holding tank, E-6, and kept at a temperature of about 20-40°C, since dowtherm is
solidified at a temperature of approximately 12oC. By storing the Dowtherm in this
manner, it is possible to cool down the production equipment quickly, and there is no
danger of freeing the Dowtherm in the system.

When the formaldehyde plant is ready to go into operation, the Dowtherm is brought
into the Dowtherm circulating system by means of dowtherm circulation pump. The
Dowtherm in the separator is kept at low level in order to allow adequate room for
expansion during the heat-up period. When the Dowtherm has reached the operating
temperature, the Dowtherm level in the circulating system is adjusted, if necessary, to
the proper operating level by adding or removing Dowtherm.

During the operation of the plant, the Dowtherm vapor separator is maintained about
half filled. The Dowtherm liquid in the separator exerts a hydrostatic head on the
Dowtherm in the reactor R-1 and in the ECS heat recovery.

In operation the Dowtherm vapor passes out from the top of the converter shell, R-1
and out from the top of the converter shell, and out from the top of the ECS heat
recovery, sweeping Dowtherm droplets along with it, and enters the vapor separator.

The pressure in the Dowtherm system can be regulated between 0 and 2 kg/cm² (g)
by applying instrument air on the tube side of the Dowtherm condenser. The correct
pressure is controlled by the controller. The Dowtherm condenser is equipped with a
safety relief valve.

During the start-up of the plant the heater located in the Dowtherm circulating system
is turned on. When the Dowtherm has reached its operating temperature and the
methanol feed has been started, the heater is turned off manually. Thermocouples are
installed to check that there is no overheating of Dowtherm.
N2 system :
In case of a temperature surge, the methanol and blowers are shut off by the safety
system. If the temperature still does not decrease, a fire-extinguishing system
consisting of three N2 bottles must be manually opened.
Emission Control System :
The ECS consists of three different items. Item E-15 is a preheater for heating the
gases from the absorber to the ignition temperature of the catalyst. Item E-18 is a
vessel containing the platinium-catalyst. The catalyst bed which is supported on a
screen has a height of approximately 60 mm. The reaction taking place is not cooled,
therefore the gas temperature leaving the bed increases.The item E-17 is a tube heat
exchanger where the hot gases leaving E-18 is cooled. On the tube side of the heat
exchanger the hot gases heat the Dowtherm from the separator E-3.
 Caustic pump :
It has been found that a slight adjustment of the pH in the absorber by adding NaOH
improves the absorption of the formaldehyde which is important when producing 55%
formalin. When producing formalin, caustic pump can be used for adding NaOH to
the process water. The feed rate to the absorption tower depends to some extends on
the original pH of the water. However, the caustic forms in contact with formic acid
sodium formate. This will increase the ash content in the product. Approximately 5
kg/h of a 5% NaOH-solution can be added which raise the pH at the top on the tower
to appr. 9, to keep ash content in the product below 100 ppm.
Recycle control valve :
As the methanol oxidation to formaldehyde requires oxygen, fresh air must be
continuously brought into the plant via the filter. Consequently, stack gas must be
emitted via the ECS converter. By recycling about 75% of the exit gases from the
absorber, only about 25% of the blower capacity is fresh air. The recycle control valve
is positioned so that the oxygen analyzer during normal operation indicates 10.5-11.00
percent by volume of oxygen.
PRODUCT SPECIFICATION :
Description: - clear and colorless liquid with pungent odor.
Concentration: - 37% + 0.5
Methanol content: - 0.5 – 0.8 %
Specific gravity at 25/25°C: - 1.097
Acidity: - 0.05% max
Iron (as Fe):- 2ppm max.
Ash content: - 0.01%max

STORAGE :
The product Formaldehyde store in the stainless steel tanks at a temperature of 47-
49°C. With the decrease in temperature and increase in the concentration of aqueous
HCHO solution tend to precipitate to Para formaldehyde. At high temperature, the
tendency to formic acid increased. Hence the appropriate storage temperature must be
maintained. Stabilizer solution methanol serves to inhibit polymer formation. Tank
agitation and steam tracing is also provided for preventing Para formaldehyde
formation.

OPERATIONAL FEATURES AND CRITICAL PARAMETERS :

The plant has been equipped with an interlock system to protect personnel and the
environment as well as to prevent damage to the plant itself.
The interlock system controls the process either by shutting off methanol flows
to reactor (safety system SWS-B) or airflow from blowers (safety system SS-A).
The interlock system is activated if any- predetermined critical limit is reached on the
parameters as in the following situations:
Methanol flow to the vaporizer is an important control parameter. If there is a
high alarm which is alerted at a methanol inlet of vapoarizer. In combination with O2,
SS-B will be activated and methanol feed will be stopped. The valve is located very
near the vaporizer to ensure that as litttle as possible methanol will enter the
vaporizer. The vaporizer top, where vaporization occurs, has a rupture disc connected
to safety AB, which stops air and methanol flow to reaction line.
The safety system AB activated in case of a too high discharge pressure is obtained
from the blowers and hence the blowers and methanol feed are cut off.
In case of a pressure surge the reactor; safety system AB to which the rupture disc is
connected gets activated in order to shut down the methanol and air to reactor.
In the tubular reactor, six of the tubes are fitted with stainless steel thermocouple
wells, inside of which are fixed thermocouples. The highest temperature of per chosen
thermocouples in each well will alarm if it exceeded the set limit.
Safety system SS-D: In plant shut down stage, the dowtherm is stored in a tank where
its temperature is maintained between 20-40°C (it solidifies at about 12°C
approximately). An electric heater is used to heat the dowtherm about 100°C and
hence it avoids water contamination in fresh dowtherm. This heater is connected with
SS-D, which automatically shuts off heater incase of a high exit temperature.
Oxygen Control:
During operation, the O2 concentration of gas going to the reactor is kept constant, by
an automatic controller at 11 vol%. This concentration means that approximately
1/3rd of fresh air and 2/3rd of recycle gas from absorber is fed to the reactor.
Control of O2 concentration essential. If methanol concentration in the gas to the
reactor is below 7 vol%, then no pressure surge will occur, regardless of O2
concentration. However, when the methanol concentration is above 7 vol %, the O2
concentration must be below 13vol% to avoid the risk of an explosion.
HCHO Concentration control:
A specific concentration profiles is achieved in the absorbers, depending on
parameters such as water supply, temperature and the feed gas.
If product concentration goes up it means the supply of water is insufficient and must
be increased. If the HCHO concentration decreases, then either too much water is
being fed or some of the cooling coils in the absorber are leaking. If decreasing the
water flow at the top does not reverse the trend of down going concentration, then the
coils are to be leak tested.
Caustic soda (5%) is also added to the process water in order to achieve better
absorption. The pH profile in the absorber is important. At a pH of 8.5, absorption is
optional.
Formaldehyde pumps and pipelines:
All pumps in contact with formaldehyde are always to be drained when not in
operation, and thus it assures that no Para formaldehyde formation occurs, which can
damage the pumps. All piping in the circulation system for strong formaldehyde
solution around the absorber is insulated and steam raced. The insulation is 50mm
thick.
These actions and control procedures assure that the plant will not produce any
hazardous substances and will operate without any interruptions.

Emergency stop :
In the control panel there is a red key operated mushroom push button as emergency
stop together with a push button with light (reset button). If the emergency stop has
been pushed the light in the reset button turns off. To reset the system the key is used
to release the emergency stop and thereafter the reset button is pushed in.
MATERIAL BALANCE :
General process block diagram :

RECYCLE GAS

COMPOSITION OF AIR :
Blower Discharge i.e. Total air flow rate = 18000Nm3/hr

And 1 gmol = 22.4dm3

Thus,

18000 Nm3/hr = 803.5714 Kgmol/hr

COMPONENTS Kgmol/hr %MOL Kg/hr Wt%

N2 677.7116 84.33744 18975.924 83.96472
O2 88.39286 11.0 2828.5714 12.51587
CO 6.402479 0.79675 179.26943 0.793232
DME 1.713954 0.21329 78.841864 0.34886
CH2O 0.062566 0.00779 1.8769821 0.008305
CH3OH 0.586567 0.073 18.770143 0.08304
H2O 28.70139 3.57173 516.62509 2.285964
TOTAL 803.5714 100 22599.879 100

METHANOL FEED:

% CH3OH in mixed stream = (A*2240)/ ((32*B) + (22.4*A)) =7.5

Where,
A= CH3OH flow rate in Kg/hr

B= Air flow rate in Nm3/hr = 18000Nm3/hr

Here we get, A = 1930Kg/hr

Reactions taking place in Reactor:

92.5 %
1) CH3OH + 1/2O2 CH2O + H2O
3.5 %
2) CH3OH + O2 CO + 2H2O
1.5%
3) CH3OH + CH3OH CH3OCH3 + H2O

0.03%
4) CH3OH + O2 CHOOH +H2O
2.47 %
5) CH3OH CH3OH

INLET TO REACTOR:
Some CH3OH is coming from the blower and some is coming from CH3OH feed, so

Total CH3OH in = 1935/32 + 803.5714*0.073/100

Input stream
= 60.8995 Kgmol/hr

Following are given the amount of CH3OH, O2 used and other compounds formed:

In Reaction 1 ,
CH3OH used = 56.332Kgmol/hr
O2 used = 28.166Kgmol/hr
CH2O formed = 56.332Kgmol/hr
H2O formed = 56.332Kgmol/hr

In Reaction 2,
CH3OH used = 2.13148Kgmol/hr
O2 used = 2.13148Kgmol/hr
CO formed = 2.13148Kgmol/hr
H2O formed = 2.13148Kgmol/hr

In Reaction 3,
CH3OH used = 1.82699Kgmol/hr
H2O formed = 0.91349Kgmol/hr

In Reaction 4,
CH3OH used = 0.0182699Kgmol/hr
H2O formed = 0.0182699Kgmol/hr

In Reaction 5,
CH3OH used = 1.50422Kgmol/hr

AT OUTLET OF REACTOR:

Outlet of the reactor is used as a heating medium in the evaporator to

evaporate methanol. Following is its composition:

COMPONENTS Kgmol/hr Mol % Kg/hr Wt%

N2 677.7116 75.71395 18975.92 77.26632
O2 58.0773 6.488397 1858.474 7.567348
CO 8.533947 0.953413 238.9505 0.972961
DME 2.62744 0.293538 120.8622 0.4921218
CH2O 56.3942 6.300361 1691.826 6.888791
CH3OH 1.504207 0.16805 48.13462 0.195995
H2O 90.22772 10.08024 1624.099 6.613019
CHOOH 0.01838 0.002053 0.84548 0.003443
TOTAL 895.0948 100 24559.12 100
 This outlet stream of reactor is used for vaporizing CH3OH and in turn to reduce
its temperature for better absorption in the two absorbers later. From the absorber we
get the required product i.e. 37% Formaldehyde (wt %).

From the outlet of reactor 2.5Kg/hr CH2O, 25Kg/hr CH3OH and whole N2, O2, CO
and DME goes to T2 outlet thus,

CH2O = 1689.326Kg/hr

Thus for CH2O to be 37% total amount required (X) is,

1689.326 *100/X = 37

X = 4565.779Kg/hr

Water added for absorption is 90.5% of amount of CH3OH feed.

Water required to make product 37% by wt =

4565.779-(1689.326+ 23.13462+0.84548)

Amount of water in the product = 2852.44 Kg/hr

Remaining amount of H2O goes to the T2 stream along with N2, O2, DME, some
amount of CH3OH and CH2O.

FD PRODUCT OUTLET :

COMPONENTS Kgmol/hr Mol% Kg/hr Wt%

CH2O 56.31087 26.12778 1689.326 37
CH3OH 0.722957 0.335446 23.13462 0.5067
H2O 158.4689 73.52825 2852.44 62.47478
CHOOH 0.01838 0.008528 0.84548 0.018518
TOTAL 215.5211 100 4565.746 100

T2 OUTLET STREAM :

COMPONENTS Kgmol/hr Mol% Kg/hr Wt%

N2 677.7116 87. 26417 18975.92 87.25446
O2 58.0773 7.478312 1858.474 8.548629
CO 8.533947 1.098872 238.9505 1.099127
DME 2.62744 0.338322 120.8622 0.555943
CH2O 0.083333 0.01073 2.5 0.0115
CH3OH 0.78125 0.100597 25 0.114995
H2O 28.79494 3.707775 518.309 2.384124
TOTAL 776.6098 100 21740.02 100

T2 outlet stream gets divided into two streams which are as follows:
1. RECYCLE STREAM
2. ECS INPUT STREAM

Amount of fresh air (X) required can be calculated as:

(803.5714-X) x 7.478312 + X x 20.3 = 803.5714 x 11

X = 220.7141Kgmol/hr

Thus, amount of recycle stream = 803.5714-220.7141

= 582.8573Kgmol/hr

Amount of ECS stream = T2 stream - recycle stream

= 776.6098 – 582.8573

= 193.7525Kgmol/hr
EMISSION CONTROL SYSTEM (ECS) :

At equilibrium stage, amount of CO generated in reactor system goes to the ECS

system while the rest gets recycled.

Percentages of all components in T2 stream, Recycle stream, ECS input stream

remains is same.

Following is tabulated the ECS INPUT STREAM :

COMPONENTS Kgmol/hr Mol% Kg/hr Wt%

N2 169.0765 87.26417 4734.143 87.28446
O2 14.48942 7.478312 463.6614 8.548629
CO 2.131467 1.10098 59.68109 1.100354
DME 0.655507 0.338332 30.15332 0.555943
CH2O 0.02079 0.01073 0.623713 0.0115
CH3OH 0.19491 0.100597 6.237126 0.114995
H2O 7.183908 3.70777 129.3103 2.384124
TOTAL 193.7525 100 5423.81 100

RECYCLE STREAM:

COMPONENTS Kgmol/hr Mol% Kg/hr Wt%

N2 508.6225 87.26417 14241.51 87.28446
O2 43.58788 7.478312 1394.812 8.548629
CO 6.402479 1.10098 179.2694 1.100354
DME 1.971933 0.338332 90.7089 0.555943
CH2O 0.062543 0.01073 1.876287 0.0115
CH3OH 0.58634 0.100597 18.76287 0.114995
H2O 21.61104 3.70777 388.9986 2.384124
TOTAL 582.8573 100 16315.94 100

ECS OUTLET:

In ECS system CO, HCHO, DME, CH3OH are converted to CO2.

Following are the reactions to form CO2 on fixed catalyst bed of Platinum:

1) CO + 1/2O2 CO2

2) HCHO + O2 CO2 + H2O

3) CH3OCH3 +3O2 CO2 + 3H2O

4) CH3OH + 3/2O2 CO2 + 2H2O

However some CO still remains. Standard norm for CO is 50ppm.

0.16% of the CO in the ECS inlet goes in the ECS outlet, while rest all other
compounds get 100% converted to CO2 by above reaction. This hot ECS outlet is
used to heat dowtherm oil .

Following is the composition of the ECS outlet stream:

COMPONENTS Kgmol/hr Mol% Kg/hr Wt%

N2 169.0765 87.632 4734.143 87.75109
O2 11.29901 5.856250 361.5683 6.701956
CO 0.310004 0.160674 8.680114 0.160893
H2O 9.56104 4.955466 172.0987 3.189986
CO2 2.692671 1.395605 118.4775 2.196075
TOTAL 192.9393 100 5394.968 100

Now the blower will discharge mixture of fresh air and recycle stream into the
evaporator.
 FRESH AIR COMPOSITION :

As calculated earlier fresh air amount was 220.7141Kgmol/hr.

Following is the composition of fresh air :

COMPONENTS Kgmol/hr Mol% Kg/hr Wt%

N2 170.612 77.3 4777.137 75.75248
O2 44.80497 20.3 1433.759 22.73555
H2O 5.297139 2.4 95.34851 1.51197
TOTAL 220.7141 100 6306.244 100

NEW BLOWER DISCHARGE :

So the new blower discharge will have the following tabulated composition:

COMPONENTS Kgmol/hr Mol % Kg/hr Wt%

N2 679.2375 84.52834 19018.65 84.07302
O2 88.39285 11.00013 2828.571 12.50346
CO 6.402479 0.796762 179.2694 0.792445
DME 1.971933 0.245399 90.7089 0.400971
CH2O 0.062543 0.007783 2.001373 0.008847
CH3OH 0.58634 0.072968 18.76287 0.08294
H2O 26.90817 3.348613 484.3471 2.141015
TOTAL 803.5619 100 22622.31 100

This is the complete material balance for the formaldehyde plant in phase 2.

PRECAUTIONS AND SAFETY FACTORS:

Formaldehyde is highly toxic by inhalation and oral intake. The vapors are very much
irritating to the eye and upper respiratory system. Though liquid is not highly
irritating to skin, it can cause severe eye burns.
Topical application may produce irritant dermatitis ingestion may cause severe
abdominal pain, acidosis, vertigo, coma, death High concentrations are intolerabl.
Explosive limit of formaldehyde in air is: LEL: 7% HEL 73%
So proper precautions need to be taken while working on the formaldehyde plant.
Safety equipments such as gloves, mask, apron, helmet, safety goggles, shoes, etc.
must be used while working on plant.
O2 control :
Control of O2 concentration is essential. If methanol concentration in the gas to the
reactor is below 7 vol%, then no pressure surge will occur, regardless of O2
concentration. However, when the methanol concentration is above 7 vol %, the O2
concentration must be below 13vol% to avoid the risk of an explosion. Because it
forms explosive mixture in such cases. The plant has been equipped with rupture disc
which gets open automatically in case of high pressure to avoid explosion. Also
majority of the part of the stack gas is recycled which makes sure the oxygen
concentration is well below 13% to avoid explosive mixture.
Fire control :
There is always a certain risk at elevated temperatures at the reactor top or at bottom.
The plant has to be shut down in case of too high temperatures. As both methanol and
the gas are stopped by SS-AB, any fire will extinguish itself. In the unlikely event that
the fire does not cease, there is a nitrogen system connected to the reactor top of
purging.
FUTURE PERSPECTIVES :

HOC holds very good reputation of being one of the greats in their field. The
past years of company has been full of glory. Once a time, the company was one of
the leading manufacturer of basic chemical products.
However, the tradition has shown reverse trend these days. Due to immense
competition from private sector & improper management strategy, the company is
finding difficult to hold it’s status of being great in the market.
No question in the world can be unanswered. The company need to be more
reluctant, professional in attitude & have to take some tough decisions. Plants are still
in good condition which can give product of high purity. The proper marketing
strategy is must for any firm, if it has to remain intact in the global market. The
working efficiency of workers as well as the higher officials needs to be improved.
Well, the future of HOC is in the hand of HOC’ians.

REFERENCES :

1. PERRY’S HANDBOOK
2. PHYSICAL PROPERTIES
BY CARL L .YAWS
3. LANGE’S HANDBOOK OF CHEMISTRY-TATA MCGRAW HILL
4. PROCESS HEAT TRANSFER
BY DONALD Q. KERN