PRODUCTION OF “ACETIC ACID” BY

METHANOL CARBONYLATION
INTRODUCTION
Acetic acid, also known as ethanoic acid, is an organic
chemical compound with the formula CH3COOH best
recognized for giving vinegar its sour taste and pungent
smell. Pure, water-free acetic acid (glacial acetic acid) is
a colourless liquid that attracts water from the
environment (hygroscopy), and freezes below 16.7°C
(62°F) to a colourless crystalline solid. Acetic acid is
corrosive, and its vapour causes irritation to the eyes, a
dry and burning nose, sore throat and congestion to the
lungs, however, it is considered a weak acid due to its
limited ability to dissociate in aqueous solutions.
Following is the sunnary of its general properties.

• Systematic Names: Acetic Acid

Ethanoic Acid
• Molecular Formula: CH3COOH
• Appearance: Colorless Liquid or Crystals

• Molecular Weight: 60.05 g/mol

• Melting Point: 16.5 oC
• Boiling Point: 118.1 oC
• pKa: 4.76
• EU Classification: Corrosive ( C )

History
Vinegar is as old as civilization itself, perhaps older.
Acetic acid-producing bacteria are present throughout the
world, and any culture practicing the brewing of beer or
wine inevitably discovered vinegar as the natural result of
these alcoholic beverages being exposed to air.The use of
acetic acid in chemistry extends into antiquity. In the 3rd
century BC, the Greek philosopher Theophrastos
described how vinegar acted on metals to produce
pigments useful in art, including white lead (lead
carbonate) and verdigris, a green mixture of copper salts
including copper(II) acetate. Ancient Romans boiled
soured wine in lead pots to produce a highly sweet syrup
called sapa. Sapa was rich in lead acetate, a sweet
substance also called sugar of lead or sugar of Saturn,
which contributed to lead poisoning among the Roman
aristocracy. The 8th century Persian alchemist Jabir Ibn
Hayyan (Geber) concentrated acetic acid from vinegar
through distillation.
In the Renaissance, glacial acetic acid was prepared
through the dry distillation of metal acetates. The 16th
century German alchemist Andreas Libavius described
such a procedure, and he compared the glacial acetic acid
produced by this means to vinegar. The presence of water
in vinegar has such a profound effect on acetic acid's
properties that for centuries many chemists believed that
glacial acetic acid and the acid found in vinegar were two
different substances. The French chemist Pierre Adet
proved them to be identical. In 1847 the German chemist
Hermann Kolbe synthesised acetic acid from inorganic
materials for the first time. This reaction sequence
consisted of chlorination of carbon disulfide to carbon
tetrachloride, followed by pyrolysis to tetrachloroethylene
and aqueous chlorination to trichloroacetic acid, and
concluded with electrolytic reduction to acetic acid.

Frozen acetic acid

FIG 1-1

By 1910 most glacial acetic acid was obtained from the

"pyroligneous liquor" from distillation of wood. The
acetic acid was isolated from this by treatment with milk
of lime, and the resultant calcium acetate was then
acidified with sulfuric acid to recover acetic acid. At this
time Germany was producing 10,000 tons of glacial acetic
acid, around 30% of which was used for the manufacture
of indigo dye.
Chemical properties
Acidity
The hydrogen (H) atom in the carboxyl group (−COOH)
in carboxylic acids such as acetic acid can be given off as
an H+ ion (proton), giving them their acidic character.
Acetic acid is a weak, effectively monoprotic acid in
aqueous solution, with a pKa value of 4.8. Its conjugate
base is acetate (CH3COO−). A 1.0 M solution (about the
concentration of domestic vinegar) has a pH of 2.4,
indicating that merely 0.4% of the acetic acid molecules
are dissociated.

Solvent
Liquid acetic acid is a hydrophilic (polar) protic solvent,
similar to ethanol and water. It can dissolve not only polar
compounds such as inorganic salts and sugars, but also
non-polar compounds such as oils and elements such as
sulfur and iodine. It readily mixes with many other polar
and non-polar solvents such as water, chloroform, and
hexane. This dissolving property and miscibility of acetic
acid makes it a widely used industrial chemical.

Detection
Acetic acid can be detected by its characteristic smell.

Production by region
Acetic acid is a very important commodity. Because of
it’s versatile uses the production of acetic acid is
increasing rapidly.
Production capacity is rapidly increasing in East Asia,
also new plants are being set in Asia. The main
companies producing acetic acid are Celanese (23 %)
and BP (21 %). BP is the fastest growing producer and
2/3 of world uses BP technology. Acetic acid production
by region is statistically shown as below.

FIG 1-2

The overall production capacity of world is about 6.4

million tones. Out of which 1.42 million tones is
produced in Europe. And 0.57 million tones are produces
in UK.
Major uses of acetic acid

 Ethanoic anhydride

Used to manufacture cellulose acetate; pharmaceuticals (aspirin);

 bleaching agents in detergents; agro-chemicals (herbicides) and dyes.

 Vinyl acetate monomer (VAM) -

used to make Polyvinyl alcohol (polyethenol) (PVOH), a safe biodegradable

water soluble polymer, polyvinyl acetate and ethylene vinyl acetate/ethylene
vinyl alcohol - used in manufacturing/ processing a wide range of paints,
adhesives, films, textiles and paper.

Ethanoic acid is one of the world's most important chemicals and serves as an
intermediate in the production of a vast range of products.
 Ethanoate ester solvents - used in the production of many paints, dyes
adhesives and inks.

 Purified terephthalic acid (PTA)- used to make lightweight, recyclable

plastics such as packaging films and plastic PET bottles; and in the
manufacture of polyester fibres/ films.
  Chloroethanoic acid - used in the production of wallpaper adhesives;
herbicides; pharmaceuticals and cosmetics.

FIG 1-3

These wide uses are the cause of increasing world

demand of acetic acid.
TECHNOLOGY SELECTION

Acetic acid can be produced industrially by a number of

methods, some having discrepancies while others are
modern methods. By methanol carbonylation acetic acid
is made by two major methods .The purpose of this
chapter is to show how the best among them t is selected.
The methods or the technologies used to manufacture
acetic acid are as follows.

1. Monsanto Process.
2. Cativa Process
One by one these methods are discussed below.

Methanol carbonylation
1. Monsanto process
The carbonylation of methanol produces acetic acid:

150 - 200 oC
30 - 60 atmosphere
CH3OH + CO CH3COOH
Rhodium/Iodide Catalyst

This is the second largest industrial homogeneous

carbonylation process with over 7 billion pounds of acetic
acid produced each year using this technology. Prior to
1970, acetic acid was made using cobalt catalysts (BASF
process) requiring rather severe conditions. In 1970
Monsanto commercialized a rhodium carbonyl iodide
catalyst that is commonly called the Monsanto Acetic
Acid Process (developed in the late 60’s by James Roth
and his research team at the corporate research center in
St. Louis). In 1986 Monsanto sold the acetic acid plant
and technology to British Petroleum (BP), but it is still
commonly referred to as the Monsanto Acetic Acid
process.

Merits:
 Introduced methanol carbonylation which resulted in
huge reduction of waste.
 The whole process uses less energy as compared to
non methanol carbonylation processes.
  Uses methanol, a cheaper feedstock.
 Although methanol is usually manufactured from
synthesis gas, produced from oil, it can also be
produced from biomass (wood), municipal wastes
and sewage. This may eventually lead to the process
being no longer dependent oil.
Demerits:
 Rhodium metal is very expensive more expensive
than gold.
 Rhodium and iodide form insoluble salts like RhI3.
So water level in the reactor vessel has to be kept
high in order to prevent this.
 A final distillation step has to be added in order to
remove water. Adding to the costs and energy
demands.
 Rhodium is capable of catalyzing a lot of side
reactions.
2. CATIVA PROCESS:
Since 1997, ethanoic acid is
increasingly being produced by the BP Cativa process,
also involving the carbonylation of methanol. The
difference is that it uses an iridium metal iodide complex
ion as a catalyst, with promoters.
190 oC
 27 atmospheres
CH3OH + CO CH3COOH
Iridium Iodide Complex & promoter

Merits:
 The mechanism involving iridium is different to that
of rhodium as catalyst, as iridium works best under
different conditions. The Cativa process also uses
ruthenium compounds as promoters in the reaction.
These increase the reaction rate by three times, even
though ruthenium on its own has negligible catalytic
activity in this system.
 Iridium costs only about one fifth as much as rhodium.
 The process is faster and more effective, requiring less
catalyst to be used.
 Iridium is even more selective for methanol, which
increases the overall yield and reduces by- products,
resulting in lower purification costs and reduced
waste.
 Iridium complexes are more soluble in the reaction
mixture than rhodium complexes. This means that the
catalyst is not lost by precipitation and does not need
replacing so frequently.
 The energy needed at the distillation and purifying
stages.
 Existing plant can be modified to run the Cativa
process at half the cost of building a new plant. This is
referred to as retrofitting.
 Cativa plants have a higher throughput a single plant
can produce up to 75% more ethanoic acid than was
previously possible using the Monsanto process.

BECAUSE OF ALL THESE ADVANTAGES WHICH

CATIVA PROCESS HAS OVER MONSANTO PROCESS WE
SELECTED CATIVA PROCESS.
PROCESS DESCRIPTION
Process for the formation of acetic acid by methanol
and carbon monoxide involves carbonylation process.
Carbonylation is the addition of carbon monoxide to
a molecule. The reaction is given as follows
27 atmospheres, 190 oC
CH3OH + CO CH3COOH
-
[Ir (CO) 2 I2] + Ru (CO) 4I2

Figure 1 is a schematic diagram illustrating the process

flow. Carbon monoxide is bubbled through a liquid
reaction medium in a continuous stirred tank reactor
maintained at 190 oC and 27 atmospheres. The
reaction medium consists of methanol, acetic acid,
iodomethane, methyl acetate, water, and iridium
iodocarbonyl catalyst complex and ruthenium
iodocarbonyl as a promoter (Ru (CO) 4I2).

Side reactions producing byproducts are as follows:

27 atm, 190 oC
1. CH3OH + CH3COOH CH3COOCH3 + H2O
-
[Ir (CO) 2 I2] + Ru (CO) 4I2

27 atm, 190 oC
2. CO + H2O CO2 + H2
-
[Ir (CO) 2 I2] + Ru (CO) 4I2
 27 atm, 190 oC
3. 4CO + 2H2O 3CO2 + CH4
-
[Ir (CO) 2 I2] + Ru (CO) 4I2

Carbon monoxide is the excess reactant and methanol

is the limiting reactant.

As shown in Figure 1 stream A consists of carbon

monoxide entering at pressure of 1 atm and 25 oC into
compressor. The Compressor compresses the gas to 28
atm and temperature after the after cooler is 190 oC
(stream B).

Methanol enters into pump through stream C at 25 oC

and 1 atm. The pump increases the pressure to 28 atm
and temperature to 28 oC (stream D).

All the reactions described above occur at 190 oC and

27 atm. The overall reaction is endothermic.
Dowtherm Q is being used as a heating medium in the
reactor jacket. Dowtherm Q enters into reactor jacket
through stream 1 and leaves through stream 2.

Some of the gases are dissolved or entrained in the

liquid and leave with the stream of liquid going out of
the reactor (stream E).While the rest of gases are used
to build up pressure in the reactor and leave from top
(stream F) through a control valve.
Stream E is than send to the blowdown drum where
the entrained gasses are removed by impingement and
escape from top of blowdown drum (stream G). These
gases combine with the gases from the top of reactor
(stream F) and go to the utility section where there
heat is utilized. After giving there heat these gases are
scrubbed before venting them to the atmosphere.

Liquid stream from the blow down drum (stream H) at

temperature of 190 oC and 27 atmospheres is passed
through the heat exchanger, where it is cooled down
from 190 oC to 110 oC using Dowtherm as cooling
media. Dowtherm enters the heat exchanger (stream 3)
at 30 oC and leaves (stream 4) at 80 oC. Dowtherm
comes to the plant through parallel streams from the
utility section at different temperatures as required.

The cooled liquid stream at 110 oC and 26.4

atmospheres escapes from the heat exchanger
(Stream I) and enters the throttling valve. The
throttling valve reduces the pressure and produces a
vapor liquid mixture (stream J) which is send to the
flash tank operating at 1.4 atmospheres and 110 oC.

Catalyst and promoter are highly non volatile and

along with some liquid proportion consisting of acetic
acid, methyl acetate, water, iodomethane,
(Co-catalyst) iridium iodocarbony catalyst and
ruthenium promoter are recycled back to the reactor
(stream K) at the temperature of 101 oC and 1.4
atmospheres (this stream is first pumped to the
pressure of 28 atmospheres before entering it to the
reactor).

The vapor stream from the top of flash tank at the

temperature of 119 oC through stream L are send to the
distillation column operating at 1 atmospheres.
Stream L consists of acetic acid, methyl acetate, water
and iodomethane (Co-catalyst).

Acetic acid is the required product and the heaviest

among all other components with the boiling point of
about 118 oC. All the other components except water
have boiling point very much less than acetic acid.

99 % acetic acid and 1 % water escape from bottom of

distillation column through stream M at temperature of
118 oC and 1 atmosphere. This stream is first to be
cooled this is done by passing it through a water
cooler. Water enters the cooler at 30 oC (Stream 11)
and leaves a 55oC (Stream 12). Finally Product is
obtained from stream M’ at 35 oC.

Steam is used in reboiler of distillation column and

enters through stream 5 and leaves through stream 6.

And from the top of distillation column methyl

acetate, water, iodomethane and little amount of acetic
acid is obtained ( stream N ) at the temperature of 71
o
C and 1 atmospheres. Cooling water is used as a
coolant in the condenser of distillation column. It
enters the condenser through stream 7 and leaves
through stream 8.

Now we have to obtain our co-catalyst (iodomethane)

from the mixture obtained from the top of distillation
column and recycle it back to the reactor.

Stream N is than send to water cooler. This reduces its

temperature to 35 oC. Cooling water enters the cooler
at 30 oC (stream 9) and leaves at 50 oC
(stream 10).

As there is a large density difference between

iodomethane and other components methyl acetate,
water and little amount of acetic acid which have very
similar density. Iodomethane is heaviest in terms of
density as compared to others. Therefore the stream
from top of distillation column is send to decanter
separator operating at 1 atmosphere.

As iodomethane has high density so it moves to the

bottom of decanter and is obtained in stream O which
is recycled back to the reactor.
A mixture of methyl acetate, water and very little
amount of acetic acid moves to the top of the decanter
and is obtained in stream P.
MATERIAL BALANCE
 MATERIAL BALANCE AROUND REACTOR

O F

D
E
B

K
MATERIAL GOING IN:
Stream Component Mass (Kg/hr) Mass
%
D CH3OH 2470 100

B CO 2250 100

O CH3I 750 100

K CH3COOH 915.33 84
CH3COOCH3 114.16 10
H2O 20.08 2
CH3I 45.5 4

Catalyst = 2250 ppm & promoter = 2300 ppm

TOTAL MASS IN = 6565 Kg/hr

MATERIAL COMING OUT:
Stream Component Mass Mass
(Kg/hr) %

F CO 37 .2
CO2 364 89
CH4 1 8.9
H2 7 1.8
E CH3COOH 3694.1 60
CH3COOCH3 1256.5 20
H2O 103.4 2
CH3I 795.5 13
CO 15.7 0.3
CO2 270 4.4
CH4 21.21 0.3

Catalyst = 2250 ppm & promoter = 2300 ppm

TOTAL MASS OUT = 6565 Kg/hr

According to the law of conservation of mass

MASS GOING IN = MASS COMING OUT

6565 = 6565 Kg/hr

Thus verified
MATERIAL BALANCE AROUND SEPARATOR

E
H

MATERIAL GOING IN:

Stream Component Mass %

E CH3COOH 60
CH3COOCH3 20
H2O 2
CH3I 13
CO 0.3
CO2 4.4
CH4 0.3

TOTAL 100

Catalyst = 2250 ppm & promoter = 2300 ppm

TOTAL MASS IN = 6156.46 Kg/hr

 MATERIAL COMING OUT:
Stream Component Mass %

G CO 5.12
CO2 87.97
CH4 6.91
TOTAL 100

Total = 306.9 Kg/hr

Stream Components Mass %

H CH3COOH 63.15
CH3COOCH3 21.48
H2O 1.77
CH3I 13.60

TOTAL 100

Catalyst = 2250 ppm & promoter = 2300 ppm

Total = 5849.5 Kg/hr

TOTAL MASS OUT = 6156.46 Kg/hr

According to the law of conservation of mass

MASS GOING IN = MASS COMING OUT
6156.46 Kg/hr = 6156.46 Kg/hr
MATERIAL BALANCE AROUND THE FLASH TANK

MATERIAL GOING IN:

Stream Component Mass %

J CH3COOH 63.15
CH3COOC 21.48
H3 1.77
H2O 13.60
CH3I

TOTAL 100

Catalyst = 2250 ppm & promoter = 2300 ppm

Total = 5849.5 Kg/hr

TOTAL MASS IN = 5849.5 Kg/hr

MATERIAL COMING OUT:
Stream Component Mass %

K CH3COOH 84
CH3COOC 10
H3 2
H2O 4
CH3I

TOTAL 100

Catalyst = 2250 ppm & promoter = 2300 ppm

Total = 1095.06 Kg/hr

Stream Component Mass %

L CH3COOH 58.4
CH3COOCH3 24.0
H2O 1.8
CH3I 15.8

TOTAL 100

Total = 4754.5 Kg/hr

TOTAL MASS OUT = 5849.5 Kg/hr
According to the law of conservation of mass
MASS GOING IN = MASS COMING OUT

5849.5 Kg/hr = 5849.5 Kg/hr

MATERIAL BALANCE AROUND THE DISTILLATION
COLUMN
N

M
MATERIAL GOING IN:
Stream Component Mass %

L CH3COOH 58.4
CH3COOCH3 24.0
H2O 1.8
CH3I 15.8

TOTAL 100

TOTAL MASS IN = 4754.5 Kg/hr

 MATERIAL COMING OUT:
Stream Component Mass %

N CH3COOH 0.04
CH3COOCH3 58.05
H2O 3.81
CH3I 38.11

TOTAL 100

Total = 1968.07 Kg/hr

Stream Component Mass %

M CH3COOH 99.7
H2O 0.30

TOTAL 100
Total = 2786.42 Kg/hr

TOTAL MASS OUT = 4754.5 Kg/hr

According to the law of conservation of mass

MASS GOING IN = MASS COMING OUT

4754.5 Kg/hr = 4754.5 Kg/hr

MATERIAL BALANCE AROUND DECANTER

MATERIAL GOING IN:

Stream Component Mass %

N CH3COOH 0.04
CH3COOCH3 58.05
H2O 3.81
CH3I 38.11

TOTAL 100

Total = 1968.07 Kg/hr

TOTAL MASS IN = 1968.07 Kg/hr

 MATERIAL COMING OUT:
Stream Component Mass %

O CH3I 100

TOTAL 100

Total = 750 Kg/hr

Stream Component Mass %

P CH3COOH 0.06
CH3COOCH3 93.79
H2O 6.15

TOTAL 100
Total = 1218.07 Kg/hr

TOTAL MASS OUT = 1968.07 Kg/hr

According to the law of conservation of mass

MASS GOING IN = MASS COMING OUT

1968.07 Kg/hr = 1968.07 Kg/hr

OVERALL MATERIAL BALANCE AROUND THE PLANT

MATERIAL GOING IN:

STREAM COMPONENT MASS
(Kg/hr)
C CH3OH 2470

A CO 2250

TOTAL 4720

MATERIAL COMING OUT:

STREAM COMPON MASS Weigh
ENT ( Kg/hr) t%
E CO 1.008 .2
CO2 363.96 89.1
CH4 36.42 1.8
H2 7.204 8.9
TOTAL 408.6 100
G CO 15.7 5
CO2 270.0 88
CH4 21.2 7
TOTAL 306.9 100
P H2o 74.94 6.2
CH3COOC 1142.36 93.8
H3 0.75 0.01
TOTAL CH3COOH 1218.1 100
M CH3COOH 2778 99.7
H2O 8.42 0.3
TOTAL 2786.42 100
TOTAL 4720

SO THE LAW OF CONSERVATION OF MASS IS VERIFIED.

THAT IS
TOTAL MASS IN = TOTAL MASS OUT
4720 Kg/hr = 4720 Kg /hr
ENERGY BALANCE
ENERGY BALANCE AROUND THE REACTOR

O F

1
E
D
2
B

ENERGY GOING IN:

Stream Component Energy
( KJ/hr)

D CH3OH 18844

B CO 432506

O CH3I 4380

K CH3COOH 204686
CH3COOCH3
H2O
CH3I

1 Dowtherm Q 34463298

TOTAL ENERGY IN: 35123714 KJ/hr

ENERGY COMING OUT:
Stream Component Energy
(KJ/hr)

F CO 205296
CO2
CH4
H2

E CH3COOH 2678755
CH3COOCH3
H2O
CH3I
CO
CO2
CH4
2 Dowtherm Q 32239663

TOTAL ENERGY OUT: 35123714 KJ/hr

ENERGY BALANCE AROUND THE SEPARATOR

E H

ENERGY GOING IN:

Stream Component Energy (KJ/hr)

E CH3COOH 2678755
CH3COOCH3
H2O
CH3I
CO
CO2
CH4

TOTAL ENERGY IN: 2678755 KJ/hr

ENERGY COMING OUT:

Stream Component Energy ( KJ/hr)

G CO 139821.45
CO2
CH4

Stream Components Energy (KJ/hr)

H CH3COOH 2538933.788
CH3COOCH3
H2O
CH3I

TOTAL ENERGY OUT: 2678755 KJ/hr

ENERGY BALANCE AROUND THE HEAT
EXCHANGER

4 3

H I

ENERGY GOING IN:

Stream Components Energy (KJ/hr)

H CH3COOH 2538933.788
CH3COOCH3
H2O
CH3I

Stream Components Energy (KJ/hr)

3 Dowtherm Q 112204.12

TOTAL ENERGY IN: 2651137.91 KJ/hr

ENERGY COMING OUT:

Stream Components Energy
(KJ/hr)

I CH3COOH 1336266.82
CH3COOCH3
H2O
CH3I
Stream Components Energy (KJ/hr)

4 Dowtherm Q 1314871.09

TOTAL ENERGY OUT: 2651137.91 KJ/hr

ENERGY BALANC AROUND THE FLASH TANK:

ENERGY GOING IN:

Stream Component Energy
(KJ/hr)

J CH3COOH 1336266.8
CH3COOC
H3
H2O
CH3I

TOTAL ENERGY IN: 1336266.8 KJ/hr

ENERGY COMING OUT:
Stream Component Energy
(KJ/hr)
K CH3COOH 204686
CH3COOC
H3
H2O
CH3I

Stream Component Energy (KJ/hr)

L CH3COOH 1131580.7
CH3COOCH3
H2O
CH3I

TOTAL ENERGY OUT: 1336266.8 KJ/hr

ENERGY BALANCE AROUND THE DISTILLATION
COLUMN:
N
8

7
N’
N’’’ N’’
10
N’’’’
L 9

6
12
5
M 11 M’

ENERGY GOING IN:

Stream Component Energy
(KJ/hr)
L CH3COOH 1131580.7
CH3COOCH
3
H2O
CH3I
Stream Component Energy
(KJ/hr)

7 Cooling 2788767.981
water

Stream Component Energy

(KJ/hr)

9 Cooling 28004
water

Stream Component Energy

(KJ/hr)

11 Cooling 97495.0
water

Stream Component Energy

(KJ/hr)

5 Steam 6469834.25

TOTAL ENERGY IN: 10515681.93 KJ/hr

ENEGRY COMING OUT:
Stream Component Energy
(KJ/hr)

8 Cooling 8360969.1
water

Stream Component Energy

(KJ/hr)

10 Cooling 139884.1
water

Stream Component Energy

(KJ/hr)

12 Cooling 584620.2
water

Stream Component Energy

(KJ/hr)

6 Steam 1298533.96
Stream Component Energy
(KJ/hr)

N’’’’ CH3COOH 31381

CH3COOCH3
H2O
CH3I

Stream Component Energy

(KJ/hr)

M’ CH3COOH 100292.6
H2O

TOTAL ENERGY OUT: 10515681.93 KJ/hr

ENERGY BALANCE AROUND THE DECANTER
P

N’’’’

O
ENERGY GOING IN:

Stream Component Energy

(KJ/hr)

N’’’’ CH3COOH 31381

CH3COOCH3
H2O
CH3I

TOTAL ENERGY IN: 31381 KJ/hr

ENERGY COMING OUT:
Stream Component Energy
(KJ/hr)

O CH3I 4380

Stream Component Energy

(KJ/hr)

P CH3COOH 27001
CH3COOCH3
H2O

TOTAL ENERGY OUT: 31381 KJ/hr

 OVERALL BALANCE AROUND THE PLANT:

ENERGY IN:
Stream Component Energy Utility flowrate
(KJ /hr) ( Kg / hr )

B CO 432506 --

D CH3OH 18844 --

1 Dowtherm Q 34463298 100678

3 Dowthern Q 112204 13437.6

5 Steam 6469834 2378.7

7 Cooling water 2788768 133370

9 Cooling water 28004 1339

11 Cooling water 97495 4663

TOTAL ENERGY IN = 44410953 KJ/hr

ENERGY OUT:
Stream Components Energy (KJ/hr) Utility Flowrate (Kg/hr)
F •CO 205296 --
•CO2
•CH4
•H2
G • CO 139821 --
•CO2
•CH4
2 Dowtherm Q 32239663 100678

4 Dowtherm Q 1314871 13438

6 Steam 1298534 2379

8 Cooling Water 8360969 133370
p • CH3COOCH3 27001 --
• H2O
• CH3COOH
M’ • CH3COOH 100293 --
• H2O
10 Cooling water 139884 1339
12 Cooling water 584620 4663

TOTAL ENERGY OUT = 44410953 KJ/hr

Thus law of conservation of energy is verified. That is

Energy going in at steady state = Energy coming out at

steady state

44410953 KJ/hr = 44410953 KJ/hr

REACTOR DESIGN
REACTOR DEFINITION:

Reactors or more precisely speaking chemical reactors are vessels

designed to contain chemical reactions.

TYPES OF GAS LIQUID REACTORS:

Following are the four main types of gas liquid reactors.

• Gas liquid continuous stirred tank reactor

• Bubble column
• Packed column
• Plate column
REACTOR SELECTION:

The selection of the gas liquid reactor to be used is as follows.

Reasons for selecting gas liquid continuous stirred tank reactor:

o Excellent gas and liquid mixing.

o High mass transfer occurs.

o High heat transfer occurs.

o Good temperature control.

o Gas spends more time in liquid phase due to stirring this facilitates
reaction in liquid phase.

o Stirring greatly decreases the probability of coalescence of bubbles.

o Very less pressure drop.

o High liquid hold up.

Reasons for not selecting Bubble Column:

o Non negligible pressure drop because the column is usually high.

o Less mass transfer as compared to stirred tank reactor.

o Less heat transfer as compared to stirred tank reactor.

 o There is more probability of coalescence of bubbles in thus type of
reactor.

o Less efficient gas liquid mixing as compared to stirred tank reactor

o Problem of foaming can occur.

Reasons for not selecting Plate Column:

o Relatively high capital investment.

o Less liquid holdup.

o Flooding can occur.

o Less efficient mass transfer as compared to stirred tank reactors

Reasons for not selecting Packed Column:

o Poor heat transfer.

o High pressure drop.

o Less efficient heat transfer as compared to mechanically stirred tank

reactor.

o Cost is more than as compared to mechanically stirred tank reactor.

I
 IMPELLER SELECTION:

There are two main types of impellers.

1. Axial flow impellers

2. Radial flow impellers

Axial flow impellers:

The impellers that generate currents parallel to the shaft of the impeller
are called axial flow impellers.

Radial flow impellers:

The impellers that generate currents which flow tangentially or radially

from the impeller blade are termed as radial flow impellers.

There are three main categories of impellers for low to moderate viscosity
systems.

1. Propellers
2. High efficiency impellers
3. Turbines

As the system of this process is of low to moderate viscosity, so we will

have to choose from the categories described above.

1. Propellers:

A propeller is an axial flow high speed impeller for low viscosity liquids.
Small propellers turn at about 1150 to 1750 rpm. And larger ones turn at
bout 400 to 800 rpm. The direction of rotation is usually chosen to force
the liquid downward, and the flow currents leaving the impeller continue
until deflected by the floor of the vessel.As described above these are
recommended for low viscosity liquids, but are not recommended for gas
dispersion in liquid. Also note that they are only axial flow.
So they are ruled out from the selection.

2. High efficiency impellers:

They are designed to provide more uniform axial flow and better mixing.
These impellers are widely used for low to moderate viscosity liquids, but
are not recommended for very viscous liquids or for gas dispersion. So
they are also eliminated from the selection.

3. Turbines:

These push the liquid radially and tangentially. The currents they generate
travel towards the vessel wall and than flow either upward or downward.
Main types of turbines are shown below.

simple straight blade turbine pitched blade turbine

 disk turbine Concave blade CD-6 impeller
Out of these only disk turbine and concave blade CD-6 impeller are used
for gas dispersion. So the selection is to be made among them. Following
is the selection between these two types of turbine impellers.

• Disk turbine is useful for gas-liquid dispersion. But efficiency is not

high.

• Concave blade CD-6 disk turbine impellers are highly efficient. It is

different from simple disk turbine in the manner that its blade are in a
concave shape which cup the gas and disperse it more efficiently than
simple disk turbine.

• Concave blade CD-6 impeller show enhanced mass transfer for the same
power/volume & superficial gas velocity than simple disk turbine.

• There are two processes in gas dispersion which continuously oppose

each other, that is dispersion and coalescence. CD-6 impeller decrease
the probability of coalescence to a large extent by decreasing the
probability of bubbles existing in the same portion of volume.

• Also Concave blade CD-6 disk turbine impellers are quite economical

• Concave blade CD-6 disk turbine impellers are being widely used in
industries which require gas dispersion in liquid.

Based upon all only these points Concave Blade CD-6 Impellers are
selected.
SELECTION OF HEATING MEDIUM:

As the reactions occurring in the reactor are overall endothermic

therefore there is a need of a heating medium. Dowtherm Q
(transfer fluid contains a mixture of diphenylethane and alkylated
aromatics) has been selected as the heating medium. Because of
the following reasons.

1. Compared to hot oils, it exhibits better thermal stability,

particularly at the upper end of hot oils' use range, and
significantly better low-temperature pumpability.

2. Does not corrodes the reactor jacket.

3. Highly efficient.

4. Suitable working temperature range.

5. Considered as economical in the thermal fluid family.

GAS LIQUID CONTINUOUS STIRRED TANK
REACTOR
DESIGN STEPS:

 Calculate gas holdup.

 Subtract the gas holdup from 1 to get liquid holdup.

 Calculate the volume occupied by the liquid using overall residence

time.

 As liquid holdup is volume occupied by the liquid divided by total

volume. From this calculate the total volume of reactor.

 Give allowance of headspace to this total reactor volume

 Assume a value of superficial gas velocity.

 Divide the volumetric flowrate of entering gas with superficial gas

velocity. To get area of reactor.

 From this area calculate the diameter of the reactor.

 Divide the volume of rector by area of reactor to get the height of

reactor.

 Now the ratio of height of rector to diameter of reactor should be equal

to 1. This provides the right value of superficial gas velocity.

 Now calculate the internal dimensions using standard shape factors.

 Calculation of power absorbed by the impeller requires first the

determination of power absorbed if only liquid phase is present
 For this purpose determine Reynolds number against this Reynolds
number see the value of power number.

 From this power number determine the value of power absorbed by the
impeller.

 Now determination of aeration number is done. Against this aeration

number see the ratio of power absorbed by the liquid to the power
absorbed by the gas.

 This ratio is than used to calculate the power absorbed in the gas liquid
mixing.

 This is than followed by the calculation of gas and liquid holdup.

 Than bubble diameter and sparger type is determined.

REACTOR JACKET DESIGN STEPS:

 Gather all the standard suitable jacket specifications.

 Calculate the inside heat transfer coefficient.

 Calculate the outside heat transfer coefficient.

 Calculate the overall heat transfer coefficient and compare it with

standard values.

 Determine the pressure drop in the reactor jacket.

DESIGN CALCULATIONS:

• Step 1 :
Reactor Volume calculations

 GAS HOLDUP(ЄG)

ЄG = 0.25(QVGNR2/σ)0.45

( Ref : Hassan and Robinson (1997) )

QVG = Volumetric flowrate of gas entering = 0.031m3/s

NR = Rotational speed = 150 rpm = 2.5 rps
σ = Surface tension = 0.07 N/m

ЄG = 0.40

 LIQUID HOLDUP (ЄL):

ЄL = 1 – ЄG

So putting the values e get

ЄL = 0.60
  VOLUME:

ЄL = VL/VT
Where
VL = volume occupied by liquid = Flowrate of liquid entering multiplied
(QL) multiplied by overall residence time(tr).
As residence time(tr) is as follows

tr = 1 hr = 60 minutes = 3600 seconds

So

VL = QL * tr = 0.00087 * 3600 = 3 m3

VT = Total reactor volume =?

Putting the values in the above equation we get

VT = 5.2 m3

According to the book “Chemical Process Equipment Design And

Economics by H.Silla (2003)

 If Volume < 1.9 m3 than 15 % allowance is must

 If volume > 1.9 m3 than 10 % allowance is must

Because VT > 1.9 m3. So with allowance of 10 %

Total Reactor Volume = VR = 6 m3

• Step 2:
 Diameter and Height Calculation

 SUPERFICIAL GAS VELOCITY(VSG):

Assume a superficial gas velocity

VSG = 0.01 m/s

 AREA (A):

A = QVG / VSG

Putting the values we get.

A = 3 m2
 DIAMETER(DR ):

A = (π/4) DR2

From this equation we calculate diameter.

DR = 2.00 m

 HEIGHT(HR):

H R = VR / A

Putting the values we get.

HR = 2.00 m

Optimum HR / DR ratio of a gas liquid CSTR is 1. Reference : book

Chemical Reactors by Tremobuze and Euzen. And also in my case
 HR / DR = 1

• Step 3 :

Internal Dimension calculations

According to the book “CHEMICAL REACTORS” by

Trembouze and Euzen we have.
 Distance from the bottom of rector to the bottom of impeller = H1
= DR/3 = 0.67m
 Height of the impeller blade = H3 = DR/5 = 0.13 m
 Width of the impeller blade = L3 = DR/4 = 0.17m
 Diameter of the impeller = DA = DR/3 = 0.67 m
 Width of the baffles = DR/12 = 0.17 m

 Step 4 :

Power absorbed by the impeller

 First let us calculate the power absorbed by the liquid stream only
= PL

 Reynolds number = Re = (ρL*NR*DA2)/µL

Nomenclature
 ρL = Average liquid density = 1103 Kg/m3
 µL = Average liquid viscosity = 0.00065 Kg/m.s
 NR = Rotational speed of impeller = 150 rpm = 2.5 rps

Substituting the values we get

Re = 1882356
 Now against this Reynolds number, Power number from figure 4.20
book “Chemical Reactors” by Trembouze and Euzen is.

NP = 6.5

Now as power number is

NP = PL / (ρL*NR3*DA5)

Substituting the values and calculating PL

PL = 4.0 hp/m3

Aeration number = NQG = QVG / ( NR*DA3)

Putting the values we get

NQG = 0.042

Now from figure 4.21 page # 276 book “chemical reactors“

We have against this NQG ratio PLG/PL equal to

PLG/PL = 0.58

PLG = 2.5 hp / m3

• Step 7:
Liquid holdup

LH = 3.14 m3

• Step 8:
Gas holdup

GH = 2.07 m3
 • Step 9:

Sparger calculations and selection

For this first we will have to calculate bubble diameter

According to Jiang et al (1995) bubble diameter is given as below.

dB2 = 8.8 * ((VSG*µL/σ)-0.04) * ((ρL* σ3)/gµL4) -0.12) * ((ρL/ρG) 0.22) * (σ/g ρL)

Where

dB = bubble diameter

Substituting the values we get

dB = 3 mm

According to data given by Trembouze et al if bubble diameter

comes this small than sintered metal sparger is used.

Selected Sparger: Sintered metal sparger

• Step 10:

Reactor jacket calculations

Jacket Specifications
 • Jacket type = Spiral baffle jacket
• Height of jacket = 1.36 m
• Spacing between reactor and jacket = 75 mm = 0.075m
• Pitch = 200 mm= 0.2 m
• Tenetring = 200 oC = 473 K
• Tleaving = 190 oC = 463 K

• Calculation of overall heat transfer coefficient:

 Heat transfer coefficient at the outside wall of the reactor:

Using the following equation to calculate the heat transfer coefficient at

the outside wall of reactor (from Chemical Engineering by Coulson and
Richardson volume 6).

Nu = C * Re 0.8 * Pr 0.33

Where
Re = Reynolds number
Pr = Prandtl number

C = constant = 0.023 (Reference: Chemical Engineering by Coulson and

Richardson volume 6)

Re = (ρ * v * de) / µ eq (E)

Where

ρ = density of Dowtherm Q = 833.1 Kg/m3

v = Velocity with which dowtherm is moving in jacket = 8.7 m/s
de= hydraulic mean diameter = 0.109 m
µ = viscosity of dowtherm = 0.000323 Pa.s

Substituting the values in equation E

We get

Re = 2440250

And

Pr = Cp * µ / Kf eq (F)

Where
Cp = Specific heat = 2.193 KJ/Kg .K
Kf = Thermal conductivity = 0.0974 W/m. K

Substituting the values in equation F we get

Pr = 7.3

Substituting all these values in eq (D)

Nu = 5702

As
Nu = ho de / Kf eq ( G )

Equating the value of Nusselt number in the equation above we get

ho = 5091 W / m2 .C

 Heat transfer coefficient at the inside wall of reactor

Nu = 1.10 * Re .62 * Pr .33

Re = Reynolds number = ρ * NR * DA 2/ µ = 1882356

Pr = Prandtl number = Cp µ / K = 11

Nu = 18646.3
From definition of Nusselt number we have

hi = 1448.30 W/m2.oC

 OVERALL HEAT TRANSFER COEFFICIENT:

1/U = (1/hi) + (1/ho) + (Xw/K)

Where
Xw = wall thickness=.01 m
K = Thermal conductivity = 22 W/m. oC

U = 760 W/m2 oC

Also from Chemical Engineering by Coulson and Richardson Volume 6

Figure 12.1 page # 639 U is between 750-1000 W/m2.oC

• Calculation of pressure drop:

From equation # 12.18 chemical engineering by Coulson and

Richardson Volume 6 it is given as.

ΔP = 8*Jf*(L/de)*ρ*v2/2
Where
Jf = friction factor

Putting the values we get

ΔP = 17412 Pa
= 0.2 atm
= 2.5 psi
MECHANICAL DESIGN OF REACTOR

• Step 1:
Design Pressure
 Pdesign = Poperating + 0.075Poperating + Phydrostatic

Pdesign = 29.2 atmospheres = 2958.7 K Pa

• Step 2:
Design Temperature

Tdesign = 509 K

• Step 3:
Material Selection

Following factors must be considered in selecting a suitable material of

construction for the reactor.

1. Mechanical properties
2. Corrosion resistance
3. Availability
4. Cost

Selection:
The selected material is Zirconium (Zircadyne 702). The reasons
for selection are as follows.

a) The criteria of selection that overrides all others from chemical

engineering point of view is corrosion. And whenever hot acids
especially acetic acid because of its high corrosivity is present than
Zirconium is used.
b) It has great mechanical properties
c) It is now easily available
d) Its cost is not very high. It is very similar in price with high Nickel
steel.
 Selected Material = Zirconium (Zircadyne 702)

• Step 4:
Design Stress (f)

f = 369300000 N/m2
= 369.3 N/mm2

• Step 5:
Wall thickness

e = PiDi/ (2*f-Pi)

Where
e = minimum wall thickness
Pi= internal pressure
Di=internal diameter

Substituting the values in the above equation we get

e = 0.008 m
= 8 mm

Giving 2mm corrosion allowance we get

efinal = 10 mm
= 0.001 m

• Step 6:
Head thickness

Ellipsoidal head is chosen

ehead=PiDi/ (2*J*f-0.2*Pi)
 J = joint factor = 1
Substituting the values in the above equation we get
ehead = 8mm
= 0.008 m

Observe the similarity between the values of wall thickness and head
thickness. This indicates that the choice of ellipsoidal head is correct.

• Step 7:
Weight of vessel:

It is given as

Wv = CvπρmDmg(Hv+0.8Dm) t

Where

Wv = Weight of vessel
Cv = A factor to account for manways, internal support etc. = 1.08
Hv = Length of cylindrical section = 2 m
g = Acceleration due to gravity = 9.8m/s
ρm = Density of material of construction
Dm = Mean diameter of the vessel = Di + e = 2.01 m

After giving 2 mm corrosion allowance it becomes

ehead = 10mm

Substituting the values in the above equation we get

Wv = 15081.4 N

• Step 8:
Direct Stress
It is due to the weight of the vessel and its contents

σw = W/π* (Di + t)*t

Substituting the values we get

σw = 1428335 N / m2
= 1.4 N/mm2
• Step 9:
Principal stresses

σ 1 = (1/2)*(σh+σz+sqrt((σh-σz)^2+4ĩ^2))= longitudinal
σ 2 = (1/2)*(σh+σz-sqrt((σh-σz)^2+4ĩ^2))=circumferential
σ 3 = 0.5(P)=radial

Where
ĩ = Torsional shear stress is very small and is usually neglected
σz=Total longitudinal stress = σL + σw = 147 N / mm2

Substituting the values in the above equations we get

σ1=292 N/mm2
σ2=147 N/mm2
σ3= 1.48N/mm2

Step 10:
Vessel support

The method used to support a vessel depends on the size, shape and weight
of the vessel; the design temperature and pressure; the vessel location and
arrangement; and the internal and external fittings and attachments.

There are basically three types of support for vessels.

1. Saddle support
 2. Skirt support
3. Bracket or lug support

1. Saddle Support:
These are used for horizontal vessels. As the reactor is
not a horizontal vessel in this case, so this choice is ruled out.

2. Skirt Support:
These are used for tall vertical columns. As the H/D ration
of reactor is 1 therefore it cannot be supported for this type of support.

3. Bracket Support:
These are used for all types of vessels. Therefore as the
above two types of supports are not suitable for the reactor, so this type of
support must e chosen.

Thus the selected support is BRACKET SUPPORT.

GAS LIQUID CONTINOUOUS STIRRED TANK REACTOR

MECHANICAL DIAGRAM SHOWING DIMENSIONS:
 10 mm

2.01 m
Ellipsoidal
head

2m Weight =
0.17 m 15081.4 N

0.67 m
1.36 m
Bracket
Support

2m
0.13 m

SPECIFICATION SHEET
Equipment Name Gas Liquid continuous stirred tank
reactor
Mode Of Operation Continuous
Operating Pressure 2735.7 KPa
Operating Temperature 463 K
Volume 6 m3
Height 2m
Diameter 2m
Area 3 m2
Superficial gas velocity 0.01 m / s
Power absorbed 2 hp/m3
Liquid Holdup 3.14 m3
Gas Holdup 2.07 m3
Bubble diameter 3 mm
Sparger type Sintered metal sparger
Jacket type Spiral baffled sparger
Overall heat transfer coefficient 760 W/m2.oC
Jacket pressure drop 17412 Pa
Design pressure 2958.7 K Pa
Design temperature 509 K
Material of construction Zirconium (Zircadyne 702)
Design stress 369.3 N / mm2
Wall thickness 10 mm
Head type Ellipsoidal
Head thickness 10 mm
Weight of vessel 15081.4 N
Support type Bracket support
FLASH TANK DESIGN
Introduction
If we say that Chemical Engineering is nothing but the combination of art and science to

design and control the separation equipment, it won’t be a lie. In a chemical industry,

more than the 70% of total capital investment is incurred on separation and purification

equipment. These stats might highlight the importance of separation equipment in

chemical industry.

Defining the problem:-

In Cativa Process, one of the product streams is coming out from the

reactor. This stream contains the Acetic Acid; which is our sole product, and the Iridium

Catalyst Complex. We have to maintain some liquid level in the reactor as well so that

we might use this liquid as the solvent for the incoming feed stream. The catalyst has to

be recycled back to reactor for further utilization. So we need equipment that might

separate out the product (not essentially all of it) and recycle back some fraction of

Acetic Acid along with the catalyst. A little amount of water should also be maintained in

the reactor as this is the requirement of the technology (Cativa Process) we are using. So

up till now, we have successfully defined our problem. Let’s look for a solution to it.

Looking for the solution:-

Now there are a number of equipments that are available to us for this

purpose. We need to have a look at the physical conditions of the stream. All the

components are in liquid state at 110 oC and 27 atm pressure.

We need to recycle some of the Acetic Acid and the catalyst back to reactor. Both of

these are required to be there for further conversion. The feed mixture is in homogenous

phase. This makes our choice quite simple. We can eliminate the possibility of a phase

separator. One thing that must be kept in mind is that the solution has to be economical

and quite effective. If we have a look at various industries; we find that most industries

generate a second phase from this feed and recycle successfully some of the desired

components in liquid state. This is quite an energy efficient process. Now let’s have a

look at the possible choices that we have at our hand.

Possible Choices Available:-

We have our feed in liquid state in which catalyst is homogenously

dissolved. We want some of the Acetic Acid, little amount of water and the catalyst

recycled back to reactor. We’ll make use of equipment that can generate the vapor phase

without expenditure of much of external energy and then successfully recycle the desired

components back to reactor. One choice looks obvious. It’s the Flash Drum. There are

other possible alternatives available to us, likewise Knockout Drum, Horizontal Flash

Drum or the spherical one. All have their own characteristics and are used in specific

situations. We’ll make use of Vertical Flash Drum.

Construction of a Flash Drum:-
When feed is flashed in a Flash Drum, vapor and liquid mixture is

generated. As this mixture enters the drum, the surface area is increased, due to which

pressure drop is generated. Right at eh entrance of the feed, there’s a splash plate in the

drum. This splash plate directs the vapor and liquid flow downwards. This way the effect

of gravity is enhanced. The liquid settles down at the bottom while the vapors with little

momentum, change their path and rise up the vessel. At the top of the vessel, there’s a

mist eliminator. Actually when vapors rise up the vessel, small liquid droplets also

accompany them. The phenomenon of splashing is avoided by the use of splash plate. So

our splash plate is serving two major purposes. First it helps us to avoid the splashing of
liquid. Secondly, it directs the vapor liquid mixture downwards which in turn enhances

the effect of gravity. Due to this effect, liquid is separated out of vapor. One thing should

be kept in mind is that most of the impaction process takes place at the splash plate. So it

has to be mechanically sound so that it can handle all the impact. Now there are two

kinds of mist eliminators.

 Vane type Mist Eliminator

 Mesh Eliminators

Vane type mist eliminator consists of metallic plates arranged closely to each other.

Vapors with small liquid droplets rise. The plates are arranged in such a manner that they

provide a zigzag path to the incoming vapor and liquid droplets. Droplets due to inertia

and large momentum strike the plates and are captured at the surface while the vapors

change their path accordingly and escape the eliminator. The phenomenon is referred to

as Impaction and the size increase of droplets is called as Coalescence. Hence vapors are

collected at the top of the vessel. A vane type mist eliminator is shown in the following

figure.
Now in mesh mist eliminators, a metallic or plastic wire mesh with a diameter ranging

0.006 to 0.011 in is used. The phenomenon is the same; impaction on the wire and then

captured. Mist escapes the wire while droplets are captured at the surface where they

coalesce and fall down as large drops. A mesh mist eliminator is shown in the following

figure:
There’s a radial vane vortex breaker shown at the bottom of the vessel. The purpose of

this vortex breaker is to avoid the phenomenon of Vortex Formation. There are a couple

of causes that induce the vortex formation in the drum. The first one is the earth’s
rotational speed. Due to the earth’s rotational speed, anticlockwise vortex is observed in

Northern Hemisphere while a clockwise motion is observed in Southern Hemisphere.

Second reason is the introduction of feed in the vessel tangentially. Whenever feed is

entered tangentially, vortexes are formed. Third reason is the vapors. Whenever there’s a

two phase mixture and they differ in their velocity; then the fluid with lesser velocity and

high density would start the rotational motion (Vortex Formation). In our case, we are

handling a vapor-liquid mixture. Vapors are at a higher speed in the vessel while the

liquid are a bit slower due to the impaction with the splash plate. So the vapors would

induce the vortex to the liquid. The formation of vortexes brings some disadvantages to

the system. Our system with vortex formed, experiences:

 Loss of valuable vapors

 Downstream equipment damage

 Loss of flow

 Erroneous liquid level readings resulting in poor control

 Vibrations caused by unsteady two phase flow.

The formation of vortexes is shown in the following figure:

To avoid the vortex formation, we should avoid the usage of a tangential feed line.

Secondly, we can use a vortex breaker to get rid of vortexes. Following types of vortex

breaker are usually used in the industry:

 Flat plate vortex breaker

 Crosses

 Radial vane or gratings

We are using a Radial Vane Vortex Breaker. A vortex breaker is stationary and it doesn’t

move. If it starts the motion with the vortex then it wouldn’t break the vortex rather it

would just weaken it. To break the vortex and get rid of it, we’ll have to fix the vortex

breaker and make it stationary.

Why use Vertical Flash Drum?

 Let’s carry out the process of elimination to justify our choice. We can

simply rub aside the choice of Knockout Drum as it is used wherever there’s gas in the

feed stream. In our stream there are no gases. We have only liquid phase. So we will not

go for the Knockout Drum. Now we are left with Horizontal, Spherical and Vertical Flash

Drums. Horizontal Drums are used when we have to handle a large liquid flow rate. But

in our case we’ll see that the liquid flow rates wouldn’t be that huge. Instead we’ll have

to deal with a high amount of vapor flow rate. Also Walas carried out a survey and in his

book “Chemical Process Equipment Selection and Design” writes that out of every ten

chemical industries; seven are making use of Vertical Flash Drums. The choice is made

due to the economy and the ease with which we can handle the flow rates. A design

engineer is required to start designing a Vertical Flash Drum by default and then after the

design is complete we have a look at the L/D (length to Diameter Ratio) to decide which

configuration to use. So we’ll follow the same procedure. We’ll design a Vertical Flash

Tank and then would analyze the L/D ratio obtained to determine which configuration to

use. Just remember one rule of thumb; for large liquid flow rates, we’ll use Horizontal

Flash Drum and for small liquid flow rate, you’ll go for a vertical configuration. You can

start designing any one of these and then the final decision would rest upon the L/D ratio

of the drum. So don’t bother. Just start your computer software and begin designing any

configuration. Let’s start the design of Vertical Flash Drum. Before the process of

designing, we’ll see what exactly flashing is.

Throttling:-
When a fluid (liquid or a liq/vapor mixture) at high temperature and high

pressure experiences sudden reduction in pressure, then some of the liquid is vaporized
and the phenomenon is referred to as Throttling. During the process the temperature of

the feed stream doesn’t change that much and in such a case the process is called as

Adiabatic Flashing. Actually for an ideal gas or a fluid behaving likewise an ideal gas,

there’s no temperature drop. But in real fluids, little temperature drops have been

observed. These temperature drops are due to the Joule-Thomson Effect and the frictional

loss. Since there’s no appreciable change in the kinetic and potential energy; and also

there’s no shaft work or heat transferred, therefore the eq:

Δ (H + u2/2 + gz) = Q + Ws reduces to ΔH = 0.

We know that the enthalpy depends upon the temperature of fluids. Since

there’s no change in enthalpy so theoretically there will be no change in the temperature

of the fluid stream. Usually for real fluids, a very little temperature drop is observed. In

our case, the feed is at 110 oC and the pressure is 27 atm. We’ll suddenly reduce the

pressure of the liquid stream and this would ultimately generate a vapor phase without the

expenditure of any external energy. There will be ignorable temperature drop. All the

beauty of equipment lies in this phenomenon. We are generating a second phase without

expanding any external energy. But we know that energy is always conserved. We have

generated the vapors on the expense of the pressure of the incoming feed So although the

process of throttling makes us lose some of the energy contents of the feed stream, yet we

get more benefits. Now the problem comes out to be the selection of the valve.

Selection of Valve:-
No ordinary valve would be used for this purpose. We need such a valve

that would handle a feed stream with such a high temperature and pressure and allow it to

expand suddenly. The valve would allow only one sided flow of the stream. There are a
number of options open to us. Globe Valve, Gate Valve, Butterfly Valve, Ball Valve etc

are all at our disposal. But none of these is manufactured for the purpose of throttling. As

we look for the best choice, we come to know that there’s a valve that is manufactured

keeping in mind the sole idea of throttling. This is Lever sealed Plug Cock. The valve

operates up to a temperature of 260 oC. It has plastic lining that makes it corrosion

resistant. It has a tapered plug that is moved by a lever. The plug contains perforations

just like a ball valve. As the feed stream passes through it, pressure drops from 27 atm to

1.4 atm. The temperature change is negligible. So after getting flashed, vapors are

generated. The temperature of the stream remains more or less the same.

Determination of Flash Temperature:-

To determine the Flash temperature, we’ll have to determine the Dew

Point and the Bubble Point Temperatures. To calculate the Bubble Point Temperature, we

assume that all of our feed is saturated liquid. We assume a temperature and at that

temperature, the K value for the component is determined. Then by multiplying this K

value with the liquid weight fraction, we get the vapor fractions. The sum of these

fractions should be unity in order to have the correct Bubble Point Temperature. So we

see that it’s a hit-and-trial method. Similarly, we assume a temperature and at that

temperature we determine the K value for the component. Then we assume that all of our

feed is saturated vapor. So dividing these fractions with the K values, we get liquid

fractions; whose sum should be unity. If the sum of liquid fractions is unity then our

assumed Dew Point is correct. Taking the arithmetic average of this Bubble Point and

Dew Point Temperatures, we get the Flash Temperature. K values for Iodomethane and

Acetic Acid has been determined directly from the Himmelblau Software. The equation
that this software uses is V.P = A- {B/(T + C)} Here A,B and C are empirical constants

while T is the assumed temperature. By dividing this Vapor Pressure (V.P) by the total

pressure, we get the K value. K values for Water and Methyl Acetate have been

determined by using the empirical relation given in Perry’s Chemical Engineering

Handbook. The relation is:

V.P = exp [C1+C2/T + (C3*lnT) + (C4*TC5)] * 9.869233E-06 atm

Here C1, C2, C3, C4 and C5 all are empirical constants and there value is given in

Chemical Engineer’s Handbook by Perry. The Vapor Pressure thus obtained is divided by

the total pressure to get the K value at the assumed temperature. The process of

calculating Bubble Point and the Dew Point Temperature is given below:

Compound Xi K at 101 oC K*Xi

Acetic Acid 0.632 0.416 0.263

Methyl Acetate 0.215 2.673 0.574

Iodomethane 0.018 3.682 0.065

Water 0.136 0.736 0.100

1.000 1.002

This employs that our Bubble Point Temperature is 101 oC.

Compound Yi K at 119 oC Yi/K

Acetic Acid 0.632 0.739 0.855
Methyl Acetate 0.215 4.163 0.052
Iodomethane 0.018 5.469 0.003
Water 0.136 1.348 0.101
1.000 1.011

This determines our Dew Point Temperature which comes out to be 119 oC. Now:

Flash Temperature = (101 + 119)/2

= 110 oC
Determining the Vapor and Liquid Flows:-
Determination of Vapors going out and the liquid draining the drum is a

result of some lethal calculations. These calculations are explained over here. First we

make a material balance for a single component. It yields:

Fxfi = Vyi + Lxi ………….Eq. I

From Henry’s Law, we have: xi = yi /K

Putting this value in Eq.I, we get:

Fxfi = Vyi + L (yi/K)……….Eq. II

 yi = Fxfi / (V + L/K)

Since F = V + L which employs that V = F – L, therefore;

yi = Fxfi / (F- L + L/K)

yi = xfi / {1 – L/F (1 – 1/K)}

Also from Eq. II, we can write that

yiV = Fxfi / (1 + L/VK)………..Eq. III

Which employs that: yi = (Fxfi / V) / (1 + L/KV)……..Eq. IV

Now after determining yi’s, we can calculate xi’s by using the K values from the

expression: yi = Ki xi where Ki is determined by using the relation Ki = V.P/P

V.P stands for Vapor Pressure at the specified Flash Temperature.

Eq. III can be written in the form as:

i=c i=c

Σi=1 (yi V) = Σi=1 {Fxfi / (1 + L/KV)}……..Eq. V

Procedure to be followed for Flash Calculations:-

 So simplifying all the procedure, we come to know that if we are to

calculate V, L, yi’s and xi’s then we’ll have to follow these steps:

1. Assume V.

2. Calculate L = F – V

3. Calculate L / V

4. Look up for K values at Flash Temperature and Total Vessel Pressure

5. Substitute values in;

i=c

V = Σi=1 {Fxfi / (1 + L/KV)}

If equality is obtained between the assumed V and the calculated V, then the assumed

value is satisfactory.

6. Calculate yi’s from Eq. IV

7. Calculate xi’s from yi = Ki xi

Now using this procedure the values of V, L, yi’s and xi’s have been calculated for the

Flash Drum. The calculations are given below.

Getting started with Design of Flash Drum:-
Since our calculations are based upon an hour of operation, so we have the

following amount of vapor and liquid flow rates;

FL = 1480.196 kg/hr pL = 961.55 kg/m3

Fv = 4664.308 kg/hr pv = 2.654 kg/m3

Vapor liquid separation factor, which is equal to (F L/Fv) / (pv/pL) ½; comes out to be 0.017.

Using the graph, we notice that the Vapor Velocity Factor is equal to 0.35 m/sec.

Maximum design vapor velocity is obtained by multiplying the vapor velocity factor with

{(pL – pv)/ pL} 0.5. The value of velocity comes out to be

Uv = Kv* {(pL – pv)/pL} 0.5

Uv = 6.653 m/sec

If we divide the vapor mass flow rate by the density, we get the volumetric flow rate. So

VL = 0.488 m3/sec
Dividing volumetric flow rate by the vapor velocity, we get the minimum cross sectional

area of the drum. Hence

Amin = VL/Uv

Amin = 0.073 m2

From this minimum cross sectional area, we can calculate the minimum diameter for the

vessel. The minimum diameter is:

Dmin = 0.306 m

Actual internal diameter is obtained by adding 6in to this minimum diameter. Therefore

D = 0.458 m

For a vertical Flash Drum the surge time is in the range of 4 to 7 min and that for a

horizontal vessel, it ranges between 7 to 12 min. Flash Drum used in Cativa Process has a

surge time of 5 min. So multiplying this time with the liquid volumetric flow rate, we get

the liquid volume held in the flash drum.

Liquid Volume = VL * 300

Liquid Volume = 0.128 m3

Since the vessel is cylindrical, therefore its volume is equal to 3.145*(radius) 2*height.

Using this relation, we can determine the liquid height in the vessel. The liquid height

comes out to be:

Liquid Height = 0.779 m

Now both H. Silla and Coulson have suggested the following formula for determining the

vapor height in the vessel. This formula is:

Vapor Height = 1.5* D + 0.4

Vapor Height = 1.087 m

Now by adding the liquid and vapor heights, we can determine the total internal height of

the vessel. Thus

Total Height = 1.866 m

The L/D ratio for the Flash Drum comes out to be 4.072 which is a satisfactory value.

This ratio actually determines the type of vessel. It tells us that whether we should go for

a horizontal vessel or a vertical one. If the value of L/D ratio is between 3 and 5, then a

vertical flash drum is used. If its value exceeds 5, then a horizontal vessel should be

employed.

Material of construction:-
Though material of construction is the part of mechanical design of the

equipment but we can predict about it. Since we are dealing with acidic, corrosive fluid;

therefore we’ll have to look for a material that is corrosion resistant. We come across two

important choices that are corrosion resistant as well as economical. The flash drum can

either be manufactured from Stainless Steel or we may make use of Aluminium. We can

use either of the materials. Both have good mechanical strength, quite resistant to

corrosion and are also cheap. Most of the heat transfer equipment in industry is made up

from Aluminium Alloys. We are not that concerned with the heat transfer over here, so

stainless steel is recommended as the priority material of construction.

DESIGN OF DISTILLATION COLUMN
Introduction:
The separation of liquid mixtures
into their various components is one of
the major operations in the process
industries, and distillation, the most
widely used method of achieving this
end, is the key operations in any oil
refinery. In processing the demand for
purer products, coupled with the need
for greater efficiency, has promoted
continues research into techniques of
distillation. This process of getting pure
products is accomplished by partial
vaporization and subsequent
condensation.
Distillation:
“Process in which a liquid or vapour
mixture of two or more substances is separated
into its component fractions of desired purity, by
the application and removal of heat”

TYPES OF DISTILLATION COLUMNS;

There are basically two types of distillation columns used
in industries.

 Batch columns
 Continuous columns
There selection criteria depends upon total number of
stages and reflux ratio. As it is shown that when a large
number of plates are used, then continuous distillation has
the lowest reflux requirements and hence operating costs. If
a smaller number of plates are used and high purity product
is not required, then batch distillation is probably more
attractive.

Batch Columns:
In batch distillation the more volatile
component is evaporated from the still which therefore
becomes progressively richer in the less volatile
constituent. Distillation is continued, either until the residue
of the still contains a material with an acceptably low
content of the volatile material, or until the distillate is no
longer sufficiently pure in respect of volatile content. In
batch operation, the feed to the column is introduced batch-
wise. That is, the column is charged with a 'batch' and then
the distillation process is carried out. When the desired task
is achieved, a next batch of feed is introduced. Most
distillation processes operate in a continuous fashion, but
there is a growing interest in batch distillation, particularly
in the food, pharmaceutical, and biotechnology industries.
The advantage of this separation process is that the
distillation unit can be used repeatedly, after cleaning, to
separate a variety of products. The unit generally is quite
simple, but because concentration are continuously
changing, the process becomes more difficult to control.

Continuous Distillation:
In contrast to batch columns, a
continuous feed is given to the column. No interruptions
occur unless there is a problem with the column or
surrounding process units. They are capable of handling
high throughputs and are the more common used. I will put
light only on this type of distillation column.

CHOICE BETWEEN PLATE AND

PACKED COLUMN

The choice between use of tray column or a packed column

for a given mass transfer operation should, theoretically, be
based on a detail cost analysis for the two types of
contactors. However, the decision can be made on the basis
of a qualitative analysis of relative advantages and
disadvantages, eliminating the need for a detailed cost
comparison.
Which are:
(1) Because of liquid dispersion difficulties in
packed columns, the design of tray column is
considerably more reliable.
(2) Tray columns can be designed to handle wide
ranges liquid rates without flooding.
(3) If the operation involves liquids that contain
dispersed solids, use of a tray column is preferred
 because the plates are more accessible for
cleaning.
(4) For non-foaming systems the plate column is
preferred.
(5) If periodic cleaning is required, man holes will
be provided for cleaning. In packed columns
packing must be removed before cleaning.
(6) For large column heights, weight of the packed
column is more than plate column.
(7) Design information for plate column is more readily
available and more reliable than that for packed
column.
(8) Inter stage cooling can be provided to remove heat
of reaction or solution in plate column.
(9) When temperature change is involved, packing may
be damaged.
(10) Random-packed columns generally are not
designed with diameters larger than 1.5 m, and
diameters of commercial tray column are seldom
less than 0.67m.
 As my system is non foaming and diameter calculated is
larger than 1.5m so I am going to use tray column.
Also as average temperature calculated for my
distillation column is higher that is approximately equal
to 98oc. So I prefer Tray column.

PLATE CONTACTORS:
Cross flow plate are the
most commonly used plate contactor in distillation. In
which liquid flows downward and vapours flow upward.
The liquid move from plate to plate via down comer. A
certain level of liquid is maintained on the plates by weir.
Other types of plate are used which have no down comer
(non-cross flow) the liquid showering down the column
through large opening in the plates (called shower plates).
Used when low pressure drop is required.
Three basic types of cross flow trays used are
(1) Sieve Plate (Perforated Plate)
(2) Bubble Cap Plates
(3) Valve plates (floating cap plates)
I prefer sieve plate because:
 (1) Their fundamentals are well established, entailing
low risk.
(2) The trays are low in cost relative to many other types of
trays.
(3) They can easily handle wide variations in flow rates.
(4) They are lighter in weight. It is easier and cheaper to
install.
(5) Pressure drop is low as compared to bubble cap trays.
(6) Peak efficiency is generally high.
(7) Maintenance cost is reduced due to the ease of cleaning.

Man Way
Label.Diagram
Calming
Down comer zone
And weir

Plate
support ring

Major Beam
Real picture of Sieve Tray

Factors Affecting Selection of Trays:

 Relative Cost of plate will depend upon material of

construction used.

For mild steel, the ratio of cost between plates is

Sieve plate : valve plate : bubble-cap plate

3.0 : 1.5 : 1.0
  There is little difference in Capacity Rating of the
three types (the column diameter required for a given
flow rate).
Sieve tray > valve tray > bubble-cap tray
 Operating Range means the range of liquid and
vapour flow rates which must be above the weeping
conditions and below the flooding conditions.
Operating range flexibility comparison is.
Bubble cape tray > Valve tray > Sieve tray

Sieve plate depends on the vapours flow through the

holes to hold the liquid on the plate, and cannot operate at
very low vapour flow rates. But with good design, sieve
plate gives satisfactory operating range.

 The Plate pressure drop will depends on the

detailed design of plate but, in general, sieve plate
gives the lowest pressure drop, followed by valves,
with bubble-caps giving the highest.

Operation of Typical distillation Column:

The
operation of typical distillation column may by
followed by figure. The column consists of a
cylindrical structure divided into sections by a series
of perforated trays which permit the upward flow of
vapour. The liquid reflux flows across each tray, over
a weir and down a down comer to the tray below.
The vapour rising from the top tray passes to
condenser and then through an accumulator or
reflux drum and a reflux divider, where part is
withdrawn as the overhead product D and the
remainder is returned to the top tray as reflux R.
In the bottom there is reboiler which is used to give
heat to the system. Liquid from the bottom of
distillation column is fed to the reboiler which
vaporises the in coming liquid. These vapours in turn
move towards the bottom plate interact with the
liquid over that plate. Due to which partial
condensation of vapours occur. Also partial
vaporization of liquid occurs too. That is less volatile
component condensed first and more volatile
component vaporizes first. This phenomenon occurs
on each plate. Causing enrichment on each plate.

A schematic of a typical distillation unit with a single

feed and two product streams is shown below.
FACTORS AFFECTING DISTILLATION
COLUMN OPERATION

Vapour Flow Conditions

Adverse vapour flow conditions can cause:

 Foaming
 Entrainment
 Weeping/dumping
 Flooding

 Foaming

Foaming refers to the expansion of liquid due to passage of

vapour or gas. Although it provides high interfacial liquid-
vapour contact, excessive foaming often leads to liquid
build-up on trays. In some cases, foaming may be so bad
that the foam mixes with liquid on the tray above. Whether
foaming will occur depends primarily on physical
properties of the liquid mixtures, but is sometimes due to
tray designs and condition. Whatever the cause, separation
efficiency is always reduced.

 Entrainment

Entrainment refers to the liquid carried by vapour up to the

tray above and is again caused by high vapour flow rates. It
is detrimental because tray efficiency is reduced: lower
volatile material is carried to a plate holding liquid of
higher volatility. It could also contaminate high purity
distillate. Excessive entrainment can lead to flooding.

 Weeping/Dumping

This phenomenon is caused by low vapour flow. The

pressure exerted by the vapour is insufficient to hold up the
liquid on the tray. Therefore, liquid starts to leak through
perforations. Excessive weeping will lead to dumping. That
is the liquid on all trays will crash (dump) through to the
base of the column (via a domino effect) and the column
will have to be re-started. Weeping is indicated by a sharp
pressure drop in the column and reduced separation
efficiency.

 Flooding

Flooding is brought about by excessive vapour flow,

causing liquid to be entrained in the vapour up the column.
The increased pressure from excessive vapour also backs
up the liquid in the down comer, causing an increase in
liquid hold-up on the plate above.  Depending on the
degree of flooding, the maximum capacity of the column
may be severely reduced. Flooding is detected by sharp
increases in column differential pressure and significant
decrease in separation efficiency.

Reflux Conditions:
Minimum trays are required under
total reflux conditions, i.e. there is no withdrawal of
distillate. On the other hand, as reflux is decreased, more
and more trays are required.
Feed Conditions:
The state of the feed mixture and feed
composition affects the operating lines and hence the
number of stages required for separation. It also affects the
location of feed tray.

State of Trays:
Remember that the actual number of
trays required for a particular separation duty is determined
by the efficiency of the plate. Thus, any factors that cause a
decrease in tray efficiency will also change the
performance of the column. Tray efficiencies are affected
by fouling, wear and tear and corrosion, and the rates at
which these occur depends on the properties of the liquids
being processed. Thus appropriate materials should be
specified for tray construction.

Column Diameter:
Vapour flow velocity is dependent
on column diameter. Weeping determines the minimum
vapour flow required while flooding determines the
maximum vapour flow allowed, hence column capacity.
Thus, if the column diameter is not sized properly, the
column will not perform well.

DESIGNING STEPS OF DISTILLATION

COLUMN

 Calculation of Minimum number of stages.Nmin

 Calculation of Minimum Reflux Ratio Rm.

 Calculation of Actual Reflux Ratio.

 Calculation of theoretical number of stages.

 Calculation of actual number of stages.

 Calculation of diameter of the column.

 Calculation of weeping point.

 Calculation of pressure drop.

 Calculation of thickness of the shell.

  Calculation of the height of the column.

Condenser

REFLUX DRUM

PUMP

(1) Methyl Iodide = 0.212

(2) Acetic Acid = 0.0005
(3)Methyl Acetate = 0.62
FEED (4) Water = 0.167

(1) Methyl Iodide = 0.074

(2) Acetic Acid = 0.65
(3)Methyl Acetate = 0.215
(4) Water = 0.065
 Reboiler

(1)Acetic Acid = 0.99

Process Design: (2)Water = 0.01

Using Vapors Liquid Equilibrium Data

Temperature of feed = 119 o C
Temperature of top product =71 o C
Temperature of bottom product = 118 o C
From Material Balance:
Feed Bottom Top
Component Fraction Fraction Fraction
xf xb xd
 (1) Methyl Iodide 0.074 0 0.212

(2) Acetic Acid 0.65 0.99 0.0005

(3)Methyl Acetate 0.215 0 0.62

(4) Water 0.065 0.01 0.167

Heavy Key Component = Acetic Acid

Light Key Component = Water
Calculation of Minimum no. of Plates:
The minimum no. of stages Nmin is obtained from Fenske
relation which is,

Nmin = LN[(xLK/xHK)D(xHK /xLK)B]

LN (αLK/HK) average

To find average geometric relative volatility of light key to

heavy key:

 Lk / Hk  avg   Lk / Hk  D  Lk / Hk  B 0.5
 Average geometric relative volatility = 1.53
So,

Nmin = 24 (reboiler is excluded)

Calculation of Minimum Reflux Ratio Rm:

Using Underwood equation,

α A xfA α B xfB
 1 q
αA  θ αB  θ
As feed is entering as saturated vapors so, q = 0
By trial,  = 1.68,
Using equation of minimum reflux ratio,
α A xDA α B xDB
  Rm 1
αA  θ αB  θ
Putting all values we get,
Rm = 4.154
Actual Reflux Ratio:
The rule of thumb is:
R = (1.2 ------- 1.5) R min
R = 1.5 R min
R = 6.23

Theoretical no. of Plates:

Gilliland related the number of
equilibrium stages and the minimum reflux ratio and the no. of
equilibrium stages with a plot that was transformed by Eduljee
into the relation;

N  N min   
0.566
 0.751   R  Rmin
N 1 R  1 
  

From which the theoretical no. of stages to be,

N= 39

Calculation of actual number of stages:

Overall Tray Efficiency:
Using O'Connell's Correlation overall tray efficiency can
calculated using average viscosity and relative volatility
evaluated at average temperature.
Eduljee has expressed the O' Connell graphical method to a
mathematical relation,

  
Eo  51  32.5log  avg . avg 
  
α avg =average relative volatility of light key component = 1.75
μ avg = molar average liquid viscosity of feed evaluated at average
temperature of column

Average temperature of column = (118+71)/2 = 95 oC

Feed viscosity at average temperature = avg = 0.3850
mNs/m2
So,
Eo = 56.60%
So,
No. of actual trays = 39/0.566 = 68

Location of feed Plate:

The Kirk bride method is used to
determine the ratio of trays above and below the feed point.


   x LK  B 
2

log N   .206 log  B  x  
D
  HK
 
 x HK  D  
 NB  
D x LK 
From which,
Number of Plates above the feed tray = ND = 47
Number of Plates below the feed tray = NB = 21

Determination of the Column Diameter:

Top Conditions Bottom Conditions

Ln =155.13 Kgmol/hr Lm = 226.8 Kgmol/hr
Vn = 180.02 Kgmol/hr Vm = 180.02 Kgmol/h r
T = 71 0C T = 118 0C
ρV = 3.469 Kg/m3 ρV = 1.87 Kg/m3
ρL = 1123.93 Kg/m3 ρL = 938.85 Kg/m3

Because liquid flow rates are greater at top so based upon

bottom liquid flow rates.

Flow Parameter:
0.5
L  ρ v 
FLV   n  
 Vn  ρ L 

FLV = Liquid Vapor Factor = 0.0562

Capacity Parameter:
Assumed tray spacing = 18 inch (0.5 m)
From Fig (15-5) Plant Design and Economics for
Chemical Engineering, sieve tray flooding capacity,
Csb = 0.0760 m/Sec
Surface tension of Mixture = σ = 18.35 dynes/Cm
0.2 0.5
   l  v 
V nf  C sb    
 20   v 

Vnf=1.6740 m/sec
Assume 90% of flooding then
Vn=0.9Vnf
So, actual vapor velocity,
Vn=1.507 m/sec
Net column area used in separation is An =mv/Vn
Volumetric flow rate of vapors = mv
mv = (mass vapor flow rate /(3600) vapor density)
mv = 2.1184m3/sec
Now, net area = mv/Vn = 1.4061m2
Assume that downcommers occupies 15%of cross sectional
Area (Ac) of column thus:
Ac = A n + A d
Where, Ad = downcommer area
Ac = An + 0.15(Ac)
Ac = An / 0.85
Ac=1.6542 m2
So Diameter of Column Is
Ac =π/4D2
D = (4Ac/π)
D = 1.4513 meter = 5ft (based upon bottom conditions)

Liquid flow arrangement:

In order to find liquid flow arrangement first find maximum
liquid volumetric flow rate
So liquid flow rate =
(Liquid mass rate)/ (3600) (Liquid density)
Max Liquid Rate Is At the bottom of column so using "L m"
values
So Maximum liquid flow rate = 0.0050m3/sec
So from fig11.28 cross flow single pass plate is selected
Provisional Plate Design:
Column Diameter Dc= 1.4513 m
Column Cross-sectional Area(Ac)= 1.6542 m2
Down comer area Ad = 0.15Ac = 0.2481 m2
Net Area (An) = Ac - Ad =1.406 m2
Active area Aa=Ac-2Ad = 1.1580 m2
Hole area Ah take 10% Aa = 0.1 × 1.1580 = 0.0462 m2
Weir length
Ad / Ac = 0.248 / 1.654 = 0.15
(From figure 11.31 volume 6) Coulson and Richardson’s
Lw / dc = 0.80
Lw = 1.452*0.80
= 0.733 m
Weir length should be 60 to 85% of column diameter
which is satisfactory
Take weir height, hw = 50 mm
Hole diameter, dh = 5 mm
Plate thickness = 5 mm
Check Weeping:
 K 2  0.9 25.4  d h 
U  min  
 v  1 / 2

where Umin is the minimum design vapor velocity.

The vapor velocity at weeping point is the minmum velocity
for the stable operation.
In order to have K2 value from fig11.30 we have to 1st find
how(depth of the crest of liquid over the weir)
Where how is calculated by following formula:

how=750{[Lm/lw*ρ]2/3}

Maximum liquid rate Lm = 4.73 kg/sec

Minimum Liquid Rate At 70% turn down ratio = 3.3Kg/sec
At Maximum rate ( how)= 19.95 mm Liquid
At Minimum rate (how) = 15.72 mm Liquid
hw + how = 50 + 15.7245 = 66 mm Liquid
From fig 11.30, Coulson and Richardson Vol.6
K2 = 30.50
So,
U (min) = 8.89 m/sec
Now maximum volumetric flow rate (vapors)
Base = 2.12 m3/sec
Top = 1.14 m3/sec
At 70% turn down ratio
Actual minimum vapor velocity =minimum vapor rate / Ah
= 12.81 m/sec
 So minimum vapor rate will be well above the weep
point.

Plate Pressure Drop (P.D):

Consist of dry plate P.D (orifice loss), P.D due to static head of
liquid and residual P.D (bubbles formation result in energy loss
+ froth formed in operating plates)
Dry Plate Drop:
Max. Vapor velocity through holes (Uh) = Max Volumetric
Flow Rate / Hole Area = 18.30 m/sec
Perforated area Ap (active area) = 1.158 m2
Ah/Ap = 0.100
From fig. 11.34(for plate thickness/hole diameter) = 1.00
We get, Co = 0.840
2
Uˆ h   V
hd  51 
 C o   L
This equation is derived for orifice meter P.D
hd= 48.1 mm Liquid
Residual Head (hr):
hr = (12.5*103 / ρL)
= 13.312 mm Liquid
So,
ht  hd  (hw  how )  hr
Total pressure drop = 48.1 + (50 + 19.95) + 13.32
ht = 131.35 mm liquid
Total column pressure drop Pa, (N/m2) = (9.81*10-3) htρLN
= 82771.6 Pa
Down comer Liquid Backup:
Caused by P.D over the plate and resistance to flow in the
downcomer it self.
hb = (hw+ how) + ht + hdc
where hdc is equal to to head loss in downcomer.
The main resistance to flow in downcomer will be caused by
constriction in the downcomer outlet, and head loss in the
down comer can be estimated using the equation given as,
2
 l 
hdc  166 wd 
  L Aap 

where Lwd is the liquid flowrate in downcomer, kg/sec

and Aap is the clearance area under the downcomer, m2

Aap =hapLw
Where hap the height of bottom edge of apron above the plate.
hap = hw – (5 to 10 mm)
hap = 40.00 mm
so,
Area under apron “Aap” = .0464 m2
As this is less than area of downcomer Ad so using A ap values
in above formula.
So,
hdc = 1.95 mm
As a result,
hb = 203.24 mm
= 0.203 m
hb < ½ (Tray spacing + weir height)
0.203 < 0.25
So tray spacing is acceptable

Check Residence Time:

Sufficient residence time should be allowed in the downcomer
for the entrained vapors to disengage from liquid stream to
prevent aerated liquid being carried under the downcomer.
tr =Ad hbc ρL/L(max)
 tr = 10.02 sec
It should be > 3 sec. so, result is satisfactory

Check Entrainment:
(un) actual velocity (based on net area) = (maximum volumetric
flow rate at base Vm / net area An)
(un) actual velocity = 1.51 m/sec
Velocity at flooding condition Uf = 1.67 m/sec
So Percent flooding =un/uf = 0.90 = 90%
Liquid flow factor FLV = 0.0562
From fig. 11.29 Coulson vol.6 fractional entrainment ψ can be
found out.
Fractional entrainment (ψ) = 0.0750
Well below the upper limit of (ψ) which is 0.1. Below this the
effect of entrainment on efficiency is small.

No of Holes:
Area of 1 Hole = (π/4) Dhole2 = 0.0000196 m2
Area of N Holes = 0.1158 m2
So,
Number OF Holes = 5900
Height of Distillation Column:

Height of column Hc= (Nact-1) Hs+ ∆H

No. of plates = 68
Tray spacing Hs = 0.50 m
∆H= (1-1.5% of total height) for liquid hold up and vapor
disengagement
∆H=0.55 m
Total thickness of trays = 0.005*68 = 0.34 m
So,
Height of column = (68-1)*.50+ 0.55+0.34
= 35 meters
Chemical Process Control

Introduction
A chemical plant is an arrangement of processing
units (reactors, heat exchanger, pumps, distillation column,
absorber, evaporators, tanks, etc), integrated with one
another in a systematic manner. The plant’s overall
objective is to convert certain raw materials into desired
products using available sources of energy, in the most
economical way.
During its operation, a chemical plant must satisfy several
requirement imposed by its designers and general technical,
economic, and social conditions in the presence of ever-
changing external influences (disturbances). Among such
requirements are the following:-

(1) Safety:
The safe operation of a chemical process is a
primary requirements foe the well-being of the people in
the plant. Thus the operating pressures, temperatures,
concentrations of chemicals, and so on, should always be
within allowable limits.

(2) Production specifications:

A plant should produce the desired
amounts and quality of the final products. For example,
we may require the production of 2 million pounds of
ethylene per day, of 99% purity. Therefore, a control
system is needed to ensure that the production level (2
million pounds per day) and purity specifications (99.5%
ethylene) are satisfied.

(3) Environmental regulations:

Various federal and state laws may
specify that the temperatures, concentrations of chemicals,
and flow rates of the effluent from a plant be within certain
limits. Such regulations exist, for example, on the amounts
of SO2 that a plant can reject to the atmosphere, and on the
quality of water returned to a river or a lake.
(4) Operational constraints:
The various types of equipment used in a
chemical plant have constraints inherent to their operation.
Such constraints should be satisfied throughout the
operation of plant. Foe example, pumps should maintain a
certain net positive suction heads; distillation columns
should not flooded; the temperature in a catalytic reactor
should not exceed an upper limit since the catalyst will be
destroyed.

(5) Economics:
The operation of plant must confirm with the
market conditions, that is, the availability of raw material
and the demand of final products. Thus it is required that
the operating conditions are controlled at given optimum
levels of minimum operating cost, maximum profit, and so
on.
All the requirements listed above dictate the need for the
continuous monitoring of the operation of chemical plant
and external intervention (control) to guarantee the
satisfaction of operational objectives. This is accomplished
of a rational arrangement of equipment (measuring devices,
valves, controllers, computers) and human intervention
(plant designers, plant operators), which together constitute
control system.

Control Over Continuous Stir Tank Reactor:

Temperature Control:
 For temperature control we employed
cascade control configuration. In a cascade control
configuration we have one manipulated variable and more
than one measurement.

The reaction is endothermic and heat is supplied by

dowtherm, which flows in the jacket around the tank. The
control objective is to keep the temperature of the reacting
mixture, T, constant at the desired value. Possible
disturbances to the reactor include the feed temperature T f.
and the dowtherm temperature Th. The only manipulated
variable is the dowtherm flow rate Fh.

Configuration:

We control the reaction temperature by measuring T h and

taking control action before its effect has been felt by the
reacting mixture. Thus if Th goes down, increase the flow
rate of dowtherm to give the same amount of heat.
Decrease the flow rate when Th increases. Disturbances
arising within the secondary loop are corrected by the
secondary controller before they can affect the value of the
primary controlled output.

Control Over Heat Exchanger:

The control objective
is to keep the exit temperature at 110 oC for our shell and
tube heat exchanger.
The possible disturbances are:

(1) Offset of temperature value from its desired value

of 110oC.
(2) Variation in temperature of dowtherm used as a
coolant media.

Control over Distillation Column:

Cascade
control is usually employed to regulate the temperature
(and consequently the concentration) at the bottom or top
of a distillation column.