A Project Report

On

“Design a plant to manufacture of styrene

from ethyl benzene for a capacity of 50

tons/day”

Submitted by

Dharmesh B. Lad

(Roll No: 12 / M12 / 257)

Registration no: M/III/ 18/31

Guided by

Manish k Bidawat

LAM NO:54004

Reliance industries Ltd.

 Self Declaration

CERTIFICATE

This is to certify that the project report is prepared on the topic

“Design a plant to manufacture of styrene from ethyl

benzene for a capacity of 50 tons/day” for the submission

of partial fulfilment part-III home paper of Indian institute

of Chemical engineers Associate membership examination

March 2018, the work carried out by myself and is not

copied from anywhere.

Prepared by Guided by

Dharmesh B Lad Manish k Bidawat

(Roll No: 12 / M12 / 257) LAM NO:54004

Registration no: M/III/ 18/31 Reliance industries Ltd.

 TABLE OF CONTENTS

Chapter

1. Literature survey

2. Detailed process description with flow sheet.

3. Material balance

4. Energy balance

5. Design of distillation column.

6. Instrumentation and process control in the process plant.

7. Plant layout

8. Safety and Pollution abetment aspects.

9. Cost estimation of the Plant

10. References
CHAPTER 1 LITERATURE SURVEY

1.1 INTRODUCTION:-

Styrene is an unsaturated aromatic monomer, which polymerizes to

give polystyrene. Though, it was discovered in 1786, its commercial

production and application were developed in nineteen thirties.

Styrene is a naturally occurring substance that has been known

since the time of Greek civilization. It occurs naturally in many

foods and beverages, such as milk, beer, coffee, strawberries, olives

and various nuts. Styrene has been approved by FDA to be used as

food additive to present flavour in foods such as baked goods,

frozen dairy products, soft candy, gelatines and puddings. This is

not harmful because styrene is present in such low dosages that it is

metabolized and excreted by the body, preventing any build up if

fatty tissues and any organs. Other name of styrene is phenylethene,

vinyl benzene, phenyl ethylene, styrol, cinnamene.

1.2 DEMAND OF PRODUCT:-

Styrene is, understandably, in great demand. With amongst so

wide a variety of fields in the marketplace, it comes as no

surprise that styrene production raises into the billions of

pounds when looking at global consumption. Post world war

period witnessed a boom in styrene demand due to its

application in manufacturing of synthetic rubber. This lead to a

dramatic increase in its capacity and with the world’s growing

need for automobile parts, fiberglass, rubber and insulation,

along with the general uses mentioned earlier, the demand of

styrene has risen to an estimated 11.39 billion pounds. The

predicted demand for styrene in the year 1999 is an estimated

14 billion pounds, an increase of about 19% in the span of two

years.

1.3 INDIAN INDUSTRY STATUS

In India, styrene manufacture started in 1963, simultaneously

by M/s Polychem Limited and M/S Synthetic and Chemicals

Limited (SACL). Plants were setup in collaboration with Dow

Chemicals of U.S.A and Hulls of Germany, respectively. In

1973, one more unit, M/s Hindustan Polymers (HP),

 Commenced production in collaboration with M/s Universal

Oil Products of U.S.A. AD The Three units use molasses based

distilled alcohol to manufacture EB. EB is manufactured by

Liquid phase alkylation process using promoted aluminium

chloride catalyst complex. Styrene is manufactured by catalytic

dehydrogenation of Ethyl benzene.

1.4 INTERNATIONAL INDUSTRY STATUS:-

The Current global capacity is distributed among more than 75

units. Total capacity, considering both, those existing and

those under construction is estimated around 17 million TPA;

with USA having about 4.5 – 5 TPA capacity. USA represents

about 30% of the total capacity, followed by west Europe,

Japan and Korea. Average global capacity utilization is in the

range of 70-75%.

1.5 Styrene Properties & Uses:-

Mol formula = C6H5CHCH2

Molar Mass = 104.15 g/mol

Boiling point = 145.15 0 C

Freezing Point = -30.6 0 C

Appearance = colourless oily liquid

 Density at 200C = 906kg/m3

Critical Density = 297 Kg/m3

Critical pressure = 3.83MPa

Critical temperature = 362.1 0 C

Critical volume= 3.37mL/g

Heat of combustion at constant P = -4263 MJ/mol

Flammable limits in air = 1.1-6.1 vol%

Flash point = 31.1 0 C

Auto ignition point =490 0 C

Solubility in water = 310mg/l at 25 0 C

Chemical Structure

1.6 USES:-

Its main use is in the manufacture of polymers, copolymers and

reinforced plastics, particularly polystyrene which accounts for

over 50% of the total production of styrene. When it is linked

together in long chains, or polystyrene, it is used in production

of polystyrene plastics and resins, such as in insulation or in the

fabrication of fiberglass boats and rubber.

It is versatile monomer extensively used for the manufacture of

plastics, including crystalline polystyrene, rubber-modified

impact polystyrene, expandable polystyrene, acrylonitrile-

butadiene-styrene copolymer (ABS), styrene-acrylonitrile resins

(SAN), acrylonitrile-butadiene latex, styrene-butadiene rubber

Styrene-Butadiene Rubber (qv) (SBR), and unsaturated

polyester resins.
 CHAPTER-2 PROCESS DESCRIPTION

2.1 HISTORY AND DEVELOPMENT:-

Styrene was first isolated inc1786 from liquidambar with steam

distillation on the laboratory scale. It was not until 1925 that

commercial production of styrene commenced. In 1938 Dow

Chemical began using cracking of Ethylbenzene with zinc oxide as

the catalyst. Although the catalysts used today are different, the basic

reaction pathway is so efficient that is still used catalyst.

In present time there are following types of process in use-

2.0 Ethylbenzene dehydrogenation process (EBD process)

3.0 Styrene Monomer production (Dow Process)

4.0 Oxidative dehydrogenation of ethylbenzene with carbon

dioxide.

5.0 Air Oxidation ethylbenzene to form ethylbenzene peroxide and

propylene to propylene peroxide.

2.2 BRIEF DESCRIPTION OF DIFFERENT PROCESSES

2.2.1 EBD PROCESS

The majority of industrial production of styrene follows from the

dehydrogenation of ethyl benzene. This process involves the catalytic

reaction of ethyl benzene. Fresh Ethylbenzene is mixed with a

recycle stream and vaporized. Steam is then added before feeding the

effluent into a train of 2 of 4 reactors. This process involves a highly

endothermic reaction carried out in the vapour phase over a solid

catalyst. Steam is used to provide heat for the reaction, to prevent

excessive coking or carbon formation, to shift equilibrium of the

reversible reaction towards the products, and to clean the catalyst of

any carbon that does form. The reactors are run adiabatically in

multiple reactors with steam added before each stage with typical

yields of 88-94%.

Crude Styrene from the reactors is then fed into a distillation train.

Because of the possibility of polymerization of the styrene during

distillation, small residence time, avoidance of high temperature, and

addition of inhibitor are necessary.

Some companies use the oxidation of ethylbenzene as an alternative

to dehydrogenation. This reaction path produces water as a by-

products as opposed to hydrogen and is therefore an exothermic

reaction 5% of styrene is produced by oxidation. Present day

reactions are usually run at 600 to 650 0C with a constant time of

about 1 second between feedstock and the catalyst. Pressure is

maintained as low as possible with atmospheric and vacuum

reactions. Feed ratios of steam to ethylbenzene are typically between

10 and 15. A yield of 90% is typical with 65% conversion on a per

pass basis. The distillation train is run at low pressures in order to

maintain low temperatures and avoid polymerization. The

temperature of the reaction train can be lowered when newer catalyst

are utilized. For example, zeolite catalysts such as ZSM-5 can have

reaction conditions of 1.4 to 2.7 Mpa and 370 0C.

2.2.2 DOW PROCESS

This is another process for the production of the styrene monomer. In

this process, the energy needed for the reaction is supplied by

superheated steam (at about 700 0C) that is injected into a vertically

mounted fixed bed catalytic reactor with vaporized ethylbenzene.

The catalyst is iron oxide based and contains Cr2O3 and a potassium
compound (KOH or K2CO3) which act as reaction promoters.

Typically, 2.5-3 kg steam is required for each kilogram of

Ethylbenzene to ensure sufficiently high temperatures throughout the

reactor. The superheated steam supplies the necessary reaction

temperature of 550-620 0C. Throughout the reactor. Ethylbenzene

conversion is typically 60-65%. Styrene selectivity is greater than

90%. The significant by-products are toluene, benzene and hydrogen.

After the reaction, the products are cooled rapidly (perhaps even

quenched) to prevent polymerization. The product stream

(containing styrene, toluene, benzene and unreacted Ethylbenzene) is

fractionally condensed after the hydrogen is flashed from the stream.

The hydrogen from the reaction is used as fuel to heat the steam

(boiler fuel). After adding polymerization inhibitor (usually a

phenol), the styrene is vacuum distilled in a series of four columns

(often packed column) to reach the required 99.8% purity. The

separation is difficult due to the similar boiling points of styrene and

Ethylbenzene. Typical capacity per plant ranges from 70,000 to

100,000 metric tonnes per year in each reactor and most plants

contain multiple reactors or units.

2.2.3 OXIDATIVE DEHYDROGENATION OF EB WITH CO2:-

This process is under research. In this process, a fluidized bed reactor

is used in place of fixed bed reactor. Heat of reaction is produced by

the help of control oxidation of methane and hydrogen. In this

process the conversion is achieved vary high but control of this

process is very critical due high temperature up to 1100 0C.

2.2.4 AIR OXIDATION OF ETHYL BENZENE:-

Styrene manufacture by dehydrogenation of Ethylbenzene is simple

in concept and has the virtue of being a single –product technology,

an important consideration for a product of such enormous volume.

This route is used for nearly 90% of the word wide styrene

production. The rest is obtained from the coproduction of propylene

oxide (PO) and styrene (SM). The PO-SM route is complex and

capital-intensive in comparison to dehydrogenation of Ethylbenzene,

but it still can be very attractive. However, its use is limited by the

mismatch between the demands for styrene and propylene oxide. The

global demand for propylene oxide is only 2/10 of that of styrene by

weight, while the ratio of propylene oxide to styrene from PO-SM

route more than 4:10. The propylene oxide from PO-SM must also

compete with that obtained from other routes. Consequently, the

propylene oxide market dictates the PO-SM capacity that can be

profitably installed, and the larger-volume styrene is thus reduced to

the status of a by-product. As such, this styrene can be priced

elastically and profitably at the same time. The PO-SM operators are

thus the envy of the styrene industry when propylene oxide is in light

their position becomes less enviable. The PO-SM processes, unlike

some of the dehydrogenation processes are not available for

licensing.

2. REACTION CHEMISTRY:
 Step I : Ethyl benzene to Ethylbenzene hydroperoxide
OH
O

O2
Catalyst

Ethylbenzene Ethylbenzene hydropeoxide

Mol.Wt.:106.16 Mol.Wt:138.16

Step II : Ethylbenzene hydroperoxide to 1-phenylethanol

OH
O HO

+ O
Ethylbenzene hydropeoxide Prop-1-ene 1-phenylethan-1-ol
Mol.Wt:138.16 Mol.Wt:42.08 Mol.Wt:122.16
 Step III : 1-phenylethanol to Styrene
HO

Al2O3

1-phenylethan-1-ol Styrene
Mol.Wt:122.16 Mol.Wt:104.15

Raw materials and Process:

2.1 Step I: Ethyl benzene to Ethyl benzene hydro peroxide

Qty
Sr Density Purity Mol Molar
Name of Materials Moles used
No g/ml (%) Wt Ratio
(g)

1 Ethylbenzene 0.866 98.00 106.17 0.799 1.00 86.60

2 Isobutane hydro peroxide - 70.00 91.13 0.036 0.045 4.69
3 Barium oxide - 99.00 153.33 0.0006 0.0007 0.09
4 Oxygen 0.00143 - 16.00 1.609 2.013 25.74
5 Carbon dioxide 1.98 - 44.00 0.82 1.02 36.00
Raw material specification :
1.Ethyle benzene
M wt 106.17
C8H10
Appearance : colourless liquid
B P : 136 degree C
Purity : 98 %
2.Isobutane hydro peroxide
C4H10O2
M wt 90.12
Appearance : colourless liquid
B P : 96.2 degree C
Density: 0 .93 g/ml
Storage Temp : 2-8 degree C
3.Barium oxide
M wt 153.32
Apperance : White Solid
4.Tert Butanol
M wt 74.12
Appearance : colourless liquid
B P : 82-83 degree C
Density: 0 .775 g/ml
Purity : 99 %
 5. Osmium Tetroxide
M wt 254.23
Appearance : White volatile solid
M P : 40.25 degree C
Density: 0 .775 g/ml

Process:
Arranged 300 ml glass assembly in a constant temperature bath equipped with gas bubble tube, dip
tube for sampling and magnetic stirrer.
Charged Ethyl benzene (86.6 g), Isobutane hydro peroxide (4.69 g, 70%) and finely powdered Barium
oxide in to the assembly respectively.
Bubbled oxygen gas at the rate of 100ml/min and the pressure of 140 Psi to the above reaction
mixture. Start the stirrer and heat the reaction mixture to the 135° to 140°C. Maintain the
temperature for 3.0 to 4.0 Hrs. Check the sample for the conversion of Ethyl benzene hydro peroxide
by Iodometric titration. Also check the sample on Gas Chromatography.
If reaction is completed then proceed for the next step, if not then continue the process until the
complete conversion of Ethyl benzene.
Obtained Ethylbenzene hydro peroxide is purified by preparing it’s sodium salt and then acidified
with carbon dioxide to get purity up to 99.4% (by GC) and yield up to 86% (based on Ethyl benzene).
2.2 Step II: Ethyl benzene hydro peroxide to 1-Phenyl ethanol

Qty
Sr Density Purity Mol Molar
Name of Materials Moles used
No g/ml (%) Wt Ratio
(g)

Ethylbenzene hydro peroxide

1 1.089 26.50 138.16 0.691 1.00 360.00
solution
2 t-Butanol 0.781 - 74.12 6.382 9.242 473.00

3 Osmium tetroxide in t-Butanol 0.81 2.50 254.23 0.0030 0.0044 31.00

4 Tetraethyl ammonium hydroxide 1.015 10.00 91.15 0.050 0.073 46.00

5 Propylene 1.81 - 42.08 1.45 2.10 61.00

6 Ethanol 0.789 99.00 46.00 13.26 19.20 610.00

Process:

Arranged 300 ml thick wall glass assembly equipped with magnetic stirrer, charge tube and thermo
couple. Charge t-Butanol (473 g), Osmium tetroxide in t-Butanol (31g, 2.5 %). Tetraethyl ammonium
hydroxide (46 g, 10% Aq Solution). Started stirring and cooled the solution to 0°C. Add Ethyl benzene
hydro peroxide solution the above cooled reaction mass and sealed the reactor.

Charge Propylene (61g) through the charge tube. The exotherm observed up to 13°C and also the
pressure raised up to 80 Psi. Maintain the reaction at 0°C for 6 hrs. Allow the reaction mass to reach
the room temperature (25° to 30°C) and maintain for 12-15 hrs. Distilled off the solvent.

Add Ethanol (610 g) to the obtained residue and filter the slurry to get salt (85 g) and filtrate (1495
g, Contain 1-Phenyl ethanol).

Analysis of filtrate shows the 1-Phenyl ethanol (67%) and Acetophenon (33%) and the yield is 58%
(on the base of Ethyl benzene hydro peroxide).

2.3 Step III: 1-Phenyl ethanol to Styrene

 Qty
Sr Density Purity Mol Molar
Name of Materials Moles used
No g/ml (%) Wt Ratio
(g)

Alpha methyl benzyl alcohol

1 1.012 67.00 122.16 8.199 1.00 1495.00
solution

2 Aluminium oxide(Alumina) 3.95 - 101.96 1.559 0.190 159.00

Process:
Arranged 300 ml thick wall glass assembly equipped with magnetic stirrer, charge tube and thermo
couple. Charged the filtrate (1495 g) obtained in Step II in it. Added powdered Alumina (159 g) and
started stirring. Heated to 265°C and maintained for 5-6 hrs.
Analysis of the sample shows the selectivity to the Styrene is 98%. Reaction mixture cooled to room
temperature and the Organic and Aqueous layers were separated.
The fractional distillation of Organic layer gives the Styrene (811.7 g). The GC analysis shows the
purity >99% and the yield is 95%.

Step I: Ethyl benzene to Ethyl benzene hydro peroxide

Ethyl benzene (86.6 g)
Isobutane Hydro Reaction
Peroxide (4.6 g, 70%)
Barium Oxide (0.09 g) 25° to 30°C

Reaction
Oxygen (100 ml/min)
135° to 140°C
3 to 4 Hr

Sodium Hydroxide
(232 g, 15 %)
Purification
Carbon dioxide (36 g)

Output
Ethyl benzene hydro
peroxide (360 g, 26.5 %)

Step II: Ethyl benzene hydro peroxide to 1-Phenyl ethanol

T-Butanol (431 g) Ethylbenzene hydro
Osmium tetroxide in peroxide(360 g)
T-Butanol (31 g, 2.5 %)
Tetraethyl ammonium Reaction
Hydroxide (46 g, 10%)
25° to 30°C

Reaction
0°C
Propylene (61 g)
5 to 6 Hr

Ethanol (610 g)

Salt: 85 g
Distillation & Filtration

Output
1-Phenyl ethanol in filtrate
(1495 g, 67 %)

Step III: 1-Phenyl ethanol to Styrene

1-Phenyl ethanol in
Filtrate (1495 g, 67%) Reaction

Alumina (159 g) 25° to 30°C

Reaction
265°C
5 to 6 Hr

Layer Separation
[Organic layer: 1623 g] Aq layer: 30.5 g

Distillation
(Rec. Ethanol = 737.4 g)

Output
Styrene (811.7 g)

RAW MATERIAL REQUIRED FOR 50MT .

Step - I : Ethylbenzene to Ethylbenzene hydro peroxide
Qty Qty for Qty for
Sr Density Purity Mol Molar
Name of Materials Moles used 1 MT 50 MT
No g/ml (%) Wt Ratio
(Kg) (Kg) (Tonne)
1 Ethylbenzene 0.866 98.00 106.17 0.799 1.00 86.60 893.06 44.65
Isobutane hydro
2 - 91.13 0.036 0.045 4.69 48.37 2.42
peroxide 70.00
3 Barium oxide - 99.00 153.33 0.0006 0.0007 0.09 0.90 0.04
4 Oxygen 0.00143 - 16.00 1.609 2.013 25.74 265.44 13.27
5 Carbon dioxide 1.98 - 44.00 0.82 1.02 36.00 371.25 18.56

Yield actual (Kg) 96.97

112.7
Yield theoretical (Kg)
5
Yield efficiency (%) 86.00

Step - II : Ethylbenzene hydroperoxide to Alpha methyl benzylalcohol

Qty Qty for Qty for
Sr Density Purity Mol Molar
Name of Materials Moles used 1 MT 50 MT
No g/ml (%) Wt Ratio
(Kg) (Kg) (Tonne)
Ethylbenzene 360.0
1 1.089 138.16 0.691 1.00 7360.46 368.02
hydroperoxide solution 26.50 0
473.0
2 t-Butanol 0.781 74.12 6.382 9.242 9670.82 483.54
- 0
Osmium tetroxide in t-
3 0.81 254.23 0.0030 0.0044 31.00 633.82 31.69
Butanol 2.50
Tetraethyl ammonium
4 1.015 91.15 0.050 0.073 46.00 940.50 47.03
hydroxide 10.00
5 Propylene 1.81 - 42.08 1.45 2.10 61.00 1247.19 62.36
610.0 12471.8
6 0.789 99.00 623.59
Ethanol 46.00 13.26 19.20 0 9

Yield actual (Kg) 48.91

Yield theoretical (Kg) 84.33
Yield efficiency (%) 58.00
Step - III : Alpha methyl benzyl alcohol to Styrene
Qty Qty for Qty for
Sr Density Purity Mol Molar
Name of Materials Moles used 1 MT 50 MT
No g/ml (%) Wt Ratio
(Kg) (Kg) (Tonne)
Alpha methyl 1495.
1 1.012 67.00 122.16 8.199 1.00 1841.81 92.09
benzylalcohol solution 00
Aluminium 159.0
2 3.95 101.96 1.559 0.190 195.89 9.79
oxide(Alumina) - 0

811.7
Yield actual (Kg) 0
854.4
Yield theoretical (Kg)
0
Yield efficiency (%) 95.00
Styrene Flow Sheet
 CHAPTER-3 MATERIAL BALANCE

The basis of the feed stream is 6.17MT/hr of Ethylbenzene. The

assumptions of the following condition at the reactor in order to produce
about 50MT/day of styrene:-

1) Fractional conversion of the Ethylbenzene to styrene and benzene is

about 37.5% of the feed,

2) The selectivity of styrene over benzene to be 90%,

3) Fractional conversion of Ethylbenzene to toluene is about 14% of
the Ethylbenzene balance of the main reaction,

4) The total conversion of Ethylbenzene is about 83.75%.

6.17 MT/Hr
6.17 MT/Hr
REACTOR
1.0 Ethylbenzene 0.1625 Ethylbenzene
0.3375 Styrene
0.25 Hydrogen gas
0.0375 Ethylene
0.0375 Benzene
0.0875 Toluene
0.0875 Methane

Fig 1: The Composition of the Components at Main Reactor

Streams.
 Table 1. Mass Flow rate and composition of the component present at
reactor
Input Output
Component Mass Composition Component Mass Composition
flow flow
rate rate
(Mt/hr) (Mt/hr)
Ethylbenzene 6.17 1.0 Ethylbenzene 1.002625 0.1625
Styrene 2.082375 0.3375
Hydrogen 1.5425 0.25
Ethylene 0.231375 0.0375
Benzene 0.231375 0.0375
Toluene 0.539875 0.0875
Methane 0.539875 0.0875
Total 6.17 1.0 6.17 1.0

Since the production of styrene under high temperature using steam

technology where the steam was first mix with the ethyl benzene before fed
to the reactor, there are presence of water (H2O) molecule at the effluent
stream, however since the molecule does not take part in the reaction and
considered inert, it is negligible in the calculation.

The effluent of the reactor is then, fed to three-phase separator to remove

the by-product gaseous and most of the water present in the effluent
mixture. The efficiency of the separator is assumed to be 80%. Thus, about
 80% of the by-product gases is removed while waste water is assumed to be
completely removed.

1.851 MT / hr
0.667 Hydrogen
0.1 Ethylene
0.233 Methane

6.17 MT/hr THREE-PHASE 4.319 MT /hr

SEPARATOR
0.1625 Ethylbenzene 0.2321 Ethylbenzene
0.3375 Styrene 0.4821 Styrene
0.25 Hydrogen gas 0.0714 Hydrogen gas
0.0375 Ethylene 0.0107 Ethylene
0.0375 Benzene 0.0536 Benzene
0.0875 Toluene 0.1250 Toluene
0.0875 Methane Waste water (inert) 0.0250 Methane

Fig2: The Composition of The Components on Three phase

separator Streams
 Table 2. Mass Flowrate and composition of the component present at three
phase Reactor
Input to 3 phase Output to flash Tank Output Vapor Split
Reactor
Component Mass Composition Mass Composition Mass Composition
flow flowrate flowrate
rate (Mt/hr) (Mt/hr)
(Mt/hr)
Ethylbenzene 1.002625 0.1625 0.0997689 0.231
Styrene 2.082375 0.3375 0.20821899 0.4821
Hydrogen 1.5425 0.225 0.03083766 0.0714 1.234431919 0.6667
Ethylene 0.231375 0.0375 0.00462133 0.0107 0.18515553 0.1000
Benzene 0.231375 0.0375 0.02314984 0.0536
Toluene 0.539875 0.0875 0.0539875 0.1250
Methane 0.539875 0.0875 0.0107975 0.0250 0.431967851 0.2333
Total 6.17 1.00 0.4313 1.00 1.85155 1.00

The effluent of the three-phase reactor is then fed to flash tank, where

all the remaining vapour split is assumed to be completely removed.

Therefore, hydrogen gas, ethylene and methane is no longer presence

in the output stream of the flash tank.

The organic liquid split (composition of ethylbenzene, styrene,

benzene and toluene) is the separated using distillation columns

where separation using the differences in boiling point is considered.

The organic liquid split fed to the primary distillation column and

the component with lower boing point (Benzene-Toluene) goes to

the overhead output stream while the higher boiling point to the

bottom output stream (Ethylbenzene-Styrene).

Assumptions on the primary distillation column are as follow: -

1) 98 wt% of Benzene from feed stream presence at the overhead

product stream,

2) 95 wt% of Toluene from feed stream presence at the overhead

product stream,

3) 98 wt% of Styrene from feed stream presence at the bottom

product stream,

4) 95 wt% of Ethylbenzene from feed stream presence at the bottom

product stream.
 0.77MT/hr
0.0603 Ethylbenzene
0.0501 Styrene
0.2727 Benzene
0.6169 Toluene
3.85MT/hr PRIMARY
DISTILLATION
3.08 MT/hr
COLUMN
0.3149 Ethylbenzene
0.0089 Toluene
0.260 Ethylbenzene
0.540 Styrene
0.060 Benzene
0.140 Toluene
Fig 3: The Composition of the Components on the Primary

Distillation Column Streams

Table 3 - The Mass Flow Rate and Composition of the Component

Present At the Primary Distillation Column
Input Overhead output Bottom Output
Component Mass Composition Mass Composition Mass Composition
flow flowrate flowrate
rate (Mt/hr) (Mt/hr)
(Mt/hr)
Ethylbenzene 1.001 0.260 0.046431 0.0603 0.969892 0.3149
Styrene 2.079 0.540 0.038577 0.0501 2.078076 0.6747
Benzene 0.231 0.060 0.209979 0.2727 0.00462 0.0015
Toluene 0.539 0.140 0.475013 0.6169 0.027412 0.0089
Total 3.85 1.00 0.77 1.00 3.08 1.00

0.23MT/hr
Benzene

0.77MT/hr
SECONDARY
0.3 Benzene DISTILLATION
COLUMN
0.7 Toluene 0.539 MT/hr
Toluene

Fig 4: The Composition of the Components on the Secondary

Distillation Column Streams

Table 4 – The Mass Flow Rate and Composition of the

Component Present At the Secondary Distillation Column

Input Overhead output Bottom Output

Component Mass Composition Mass Composition Mass Composition
flow flowrate flowrate
rate (Mt/hr) (Mt/hr)
(Mt/hr)
Benzene 0.231 0.3 0.231 1.0
Toluene 0.539 0.7 0.539 1.0
Total 0.77 1.00 0.231 1.0 0.539 1.0

1MT/hr
Ethylbenzene

3.08MT/hr
TERNARY
0.325 Ethylbenzene DISTILLATION
COLUMN
0.675 Styrene 2.08 MT/hr
Styrene

Fig 5: The Composition of the Components on the Ternary

Distillation Column Streams

Table 5 – The Mass Flow Rate and Composition of the

Component Present At the Ternary Distillation Column

Input Overhead output Bottom Output

Component Mass Composition Mass Composition Mass Composition
flow flowrate flowrate
rate (Mt/hr) (Mt/hr)
(Mt/hr)
Ethylbenzene 1.001 0.325 1 1.0
Styrene 2.079 0.675 2.08 1.0
Total 3.08 1.00 1 1.0 2.08 1.0
Real production will not give the complete separation of the mixture

at the distillation column since efficiency of 100% is impossible to be

achieved. For example, at the secondary distillation column, traces of

benzene could still be found in the bottom product stream.

CHAPTER-4 ENERGY BALANCE

Required temperatures are specified; for example, a reactor outlet

Temperature of 600°C is needed. The temperature and energy requirements for

the heating and cooling loads are matched as closely as possible.

Styrene reactors typically operate adiabatically (no heat is added), causing the

Temperature to drop as the endothermic reaction proceeds. The reactor-inlet

Temperature required to achieve the specified outlet temperature is calculated

From a reactor energy balance,

Enthalpy of products = enthalpy of reactants - Heat of reaction

Enthalpies of reactants and products are expressed with respect to a reference

Temperature of 25°C, and the heat of reaction is available at 25°C:

[m*C*(600-25)],= [m*C*(T-25)],-m*AH,

Where m is the mass flow rate (kg/h), C is the heat capacity (kcal/kg-C), m *

ΔH, is the total heat of reaction (kcal/h), and subscripts p and r denote

products and Reactants, respectively. The reactant and product mass flow rates

are both 6170.0 kg/h from the earlier mass balances. Using 0.53 kcal / kg C

for the heat capacity of both products and reactants, Heat of reaction of

Styrene from ethylbenzene is Heat of reaction ΔHr = 140,000 kJ/kg mol

(Perry’s Chemical engg Handbook, seventh edition page 23-14), 669760

Kcal/hr as the total heat of reaction (styrene flow rate * heat of reaction for

styrene),

Steam Requirement,
6.17 x 1000x 0.53 (660-25) + 6.17 x 1000 x 174 = 3150093.5 kcal /hr

Steam Required = 3150093.5 / (1010) = 3119 kg/hr

Heat Exchanger Heat balance

The ethyl benzene feed needs to be heated and the reactor effluent cooled.

Heat exchange between them is feasible and desirable. Setting an approach

Temperature for a counter current exchanger (temperature difference between

Heated feed and reactor effluent) at l0OC, fixes the heated feed temperature at

590°C. An energy balance for the heated feed and steam mixture establishes

the required steam temperature:

[m*C*(T- 660)]s + [m*C*(590 - 660)]EB = 0, subscripts s is steam and

EB is ethylbenzene.

Using C, = 0.5s, CEB = 0.6 kcal/kg C, and the flow rates calculated above gives

3119 x 0.5 (T-660) + 6.17 x 1000 x 0.6 (590-660)

T (of superheated steam) = 826°C

An energy balance around the feed-effluent heat exchanger,

[m*C*(600 - T)]effluent = [m*C*(590 - 60)]feed

T = 422°C as the outlet temperature of the effluent

The reactor effluent must reach about 40°C for condensation. Thus,
Further cooling is required, by cooling water or other process loads. Heating

and cooling for the distillation columns represent such possible loads

Cooling water required,

Steam required is 5 times of ethyl benzene for styrene production,

6.17 x 1000 x .53 x 5 ( 422-40) = 62445891 kg/hr

Energy balance around Primary column

In primary column mainly top product is toluene, hence

3.85 x 1000 x 0.6x (110-25) + 0.77 x 1000 x 0.6 = 196812 kcal/hr

Steam Required = 196816 / 530 = 371 kg/hr

Cooling Water required = 196812 / (m cp ΔT)

= 40000 kg/hr

Energy balance around Secondary column

In primary column mainly top product is Benzene, hence

0.77 x 1000 x 0.6x (80-25) + 0.23 x 1000 x 80 = 43810 kcal/hr

Steam Required = 43810 / 530 = 82.66 kg/hr

Cooling Water required = 43810 / (m cp ΔT)

= 8762 kg/hr

Energy balance around Tertiary column

In primary column mainly top product is Ethyl Benzene, hence

3.08 x 1000 x 0.6x (136-25) + 1 x 1000 x 80 = 285128 kcal/hr

Steam Required = 285128 / 530 = 538 kg/hr

Cooling Water required = 285128 / (m cp ΔT)

= 57025 kg/hr

CHAPTER-5 DESIGN OF DISTILLATION COLUMN

STYRENE DISTILLATION COLUMN

In styrene column only styrene and ethyl benzene are entered at

saturated state. Reflux ratio 8 is considered, Equilibrium data

obtained by the help of Antoine’s equation and Raoult’s law as

follows- Ethylbenzene is the more volatile component.

Antoine equations, Ethylbenzene, In P0 = 9.386- 3279.47/ (T-59.95)

Styrene In P0 = 9.386 – 3328.57 / (T-63.72)

P bar, T Kelvin

Material balance, basis 20 kmol feed:

at 85 per cent recovery, styrene in bottoms = 20 x 0.85 = 17.0 kmol

at 99.5 per cent purity, ethyl benzene in bottoms = 17/99.5 x 0.5 =

0.085 kmol Ethylbenzene in the tops = 20-0.085 = 19.915 kmol

styrene in tops = 20 — 17.0 = 3.0 kmol

mol fraction ethylbenzene in tops = 19.915 / (19.915+3.0) =0.869

zf = 0.5, xb = 0.005, xd = 0.87

Column bottom temperature, from Antoine equation for styrene

In (0.2) = 9.386- 3279.47/ (T-59.95)

T = 366 K, 93.3 0C
At 93.3°C, vapour pressure of Ethylbenzene.

Styrene In P0 = 9.386 – 3328.57 / (T-63.72)

P0= 0.27 bar

Relative Volatility = P0 ethylbenzene / P0 Styrene

α = 0.27/0.2 =1.35

The relative volatility will change as the compositions and (particularly for a

vacuum column) the pressure changes up the column. The column pressures

cannot be estimated until the number of stages is known; so as a first trial the

relative volatility will be taken as constant, at the value determined by the

bottom pressure.

Rectifying section

S= 8/1+8 = 0.89

b = 0.869 / (8+1) = 0.09655

S (α -1) x2 + [S+ b (α-1)]-α] x +b = 0

0.89 (1.35-1) x2 + [0.89 +0.0965(1.35-1)]-1.35] x +0.09655 = 0

x = 0.290

X*0 = 0.87 -0.29 = 0.58

Xn =0.50 – 0.29 = 0.21

c = 1 + (1.35—1) 0.29 = 1.10

β = 0.89 x 1.1 (1.35-1) / (1.35-0.89 x 1.12) = 1.255

N = log [x0*(1-βxn) / x0*(1-βx0)] / log (α/sc2)

β = sc (α-1) / (α-sc2)

N= log [0.58 (1-1.255 x 0.21) / 0.58(1-1.255x.58)] / log

(1.35/0.891.12)

N= log 7.473 / log 1.254 = 8.8 ~ 9 stages

N = number of stages required to effect the separation represented by the

concentration

Change from

x* to x%;x* = (x - k) and *J > x*

c=l + (a-l)k

s — slope of the operating line between x* and *Q,

a = relative volatility, assumed constant over x* to XQ.

Stripping section, feed taken as at its bubble point

S = 8 x 0.5 +0.87-(8+1)0.005 / (8+1) (0.5-0.005) = 1.084

b = (0.5-0.87) 0.005 / (8+1) (0.5-0.005) = -4.15 x10-4 (essentially zero)

1.084 (1.35-1) k2 + [1.084 - 4.15 x 10 -4 (1.35-1)-1.35] k -4.15 x 10 -4

k = 0.702

xo* = 0.5-0.702 = -0.202

xn* = 0.005-0.702 = -0.697

c = 1+ (1.35-1)0.702 =1.246

β = 1.084 x 1.246 (1.35-1) / (1.35-1.084 x1.2462) = -1.42

N = log [ -0.202 (1-0.697 x 1.42)] / [-0.697 (1-0.202 x1.42) ] / log

(1.35 /1.084 x 1.2462)

N = log [4.17 x 10-3] / log 0.8 = 24.6 , say 25

Column Diameter, Vapour flow rate is the principal factor that

determines the column diameter. Souder’s and Brown Equation,

Lowenstein (1961) is used to estimate the allowable superficial

vapour velocity and hence the column area and diameter

UV = (-0.171 lt2 + (-0.27 lt-0.047) (ρL –ρv / ρv) 0.5

u = maximum allowable vapour velocity, based on the gross (total)

column cross sectional area, m/s

lt = plate spacing, m (range 0.5 – 1.5)

Assumption,

1) Plate spacing, lt = 0.45m

2) Liquid density, pl = 909 kg/mL at 25⁰C

3) Vapour density, pv = 1.45 kg/mL

Therefore, substitute the assumption value, uv = 0.9975

Dc = √4vw/πp vuv

Dc = 0.975 m ~ 1.0 mt

MINOR EQUIPMENT DESIGN

Condenser
(Process Design)

The condenser to be designed over here is been placed after the reactor in
the process. The stream coming out of the reactor contains steam as well
as some non-condensable gases (like hydrogen) and organic vapours.

The gas out of the reactor is passed through the vaporizer where the gas

temperature falls from 600 to 454oC. Even at this temperature, the load on

the condenser is very high, so to make the process more economical a

boiler is positioned in between the vaporizer and condenser in order to

recover the waste heat from the flue gas stream.

Therefore, after the super heat recovery the stream is entering the reactor

at its normal boiling point temperature. The condenser is operated under

atmospheric pressure. Hence, the normal boiling point of the mixture is

calculated 90oC.

To perform the given operation the load is very high for a single

condenser, so to avoid overloading of the condenser two condenser of

identical performance are put in series.

HOT GAS IN (1000C) CONDENSATE OUT (90OC)

Condenser

HOT WATER OUT (45OC) COLD WATER IN (25OC)

• Hot condensing gases enters at 100oC temperature and leaves at

90oC (I.e., effective boiling condensing gases)

• Cold fluid enters at 25oC and leaves at 40oC.

INITIAL CALCULATION:

Average latent heat of condensation of the condensing vapour = 1299.24

kJ/kg

Total mass of the condensing vapour feed into each condenser=9.27 kg/s.

Specific heat of water at 300C =4.184 kJ/kg

Mass of process water required= 9.27*1299.24/

(4.184*(45-25)) kg/s. = 190.68 kg/s
Assuming counter current operation ∆Tln
= 57.170C Assuming U heat transfer
coefficient = 800 W/m2K

A = Q / (∆Tln) = 261.65
m2. Assuming, length of
pipe is 12 ft.

Tube for the heat transfer purpose is

selected: Tube OD = ¾”, 12 BWG

∴OD: ID= 1.41:1

∴ the total no of tube is calculated= Nt = 1204

From Perry, for 1-2 STHE TEMA P for ¾ in. OD on 1-

inch ∆lar pitch Nt = 1378 for Shell diameter = 1.067 m.

U corrected = 700 W/m2K

FILM COEFFICIENT

Shell side - Condensate

The heat transfer coefficient for the shell side given as:

hs = 1.51*[k3*ρ2*g/µ2]1/3 *Nre-1/3

Reynolds number ( NRe )= 4*Γ/µ

Where, Γ= W/(N1/3*L)
W= condensation rate

N= total no of tubes

L= length of each tubes

∴, Γ= 0.02062

Again, µ= 0.347 cp

N.B., all the properties been evaluated at the condensate average

temperature.i.e, at 75.62oC.

Therefore, the Reynolds no is calculated= 237.72

Properties are evaluated at 75.62oC.

K = Thermal conductivity = 0.398 w/m.K.

µ = Viscosity = 0.347 x 10-3 cp.

ρ = Density = 892 kg/m3.

hs= 3897 W/m2.K.

TUBE SIDE
Nre= v*ρ*d/µ

ρ = 994 kg/m3

Therefore, velocity of the fluid on the tube

side=1.948 m/s diameter of each tube= 13.51
mm Reynolds’s number (NRe) = 33438

k = 0.61 W/mK

µ = 0.78 cp

cp = 4.184 KJ/kgK

Prandtl number (NPr) = 5.35

For turbulent condition Dittos Bolter equation.

h i d e
= 0.023 (NRe )0.8 ( NPr )0.33 ( φ )0.14

φ = µl/µw

∴,φ= 1.0, since the liquid used is water.

hi = 5996 W/m2K

Calculated Ud = 926.61 W/m2K assuming hd = 1892 W/m2K

 ∴, Ud > Ucorrected

∴ Design is okay.

PRESSURE DROP CALCULATION

SHELL SIDE
Let us assume, no of baffles (B)=0

as = 0.9683 m2

Gs = 9.57 kg/m2s.

de = 18.29 mm

NRe = 21887

From Perry graph of f v/s/ NRe on log log sheet

f = 0.2452

+
2f (N 1)D G
b s s
x 0.5 = 1.369 kPa.(KERN’s
∆Ps = method)
gρg de

Since the shell side pressure drop is less than 14 kPa , the design is
satisfactory.

TUBE SIDE
NRe = 33438

F = 0.0791 ( NRe )-1/4 = 0.00584

∆Pl = 4*f*L*v2*ρl/2di = 11.82 kPa

∆Pe = 2.5*v2*ρl/2 = 4.700kPa

∆PTotal = 2*(∆Pl + ∆Pe )= 33.04 kPa.

which is very less than permissible value (70 kPa), therefore design is
satisfies all the necessary condition.
MECHANICAL DESIGN OF DISTILLATION COLUMN (REF:
BROWNELL & YOUNG, CH: 10)

a) SPECIFICATION:

1. inside diameter : 4.65 m ( design with the maximum dia for

safety)

2. height of disengaging section: 40 cm

3. design pressure: 50 mmHg

4. (since the vessel operated under vacuum, subjected to

external pressure)external pressure: 0.965 kgf/cm2
5. design pressure: 1.033 kgf/cm2
6. design temperature: 70oC

7. shell material: carbon steel(sp. Gr.=7.7) (IS:2002-1962,

GRADE I)

8. permissible tensile stress: 950 kgf/cm2

9. insulation material: asbestos

10. density of insulation: 2700 kg/m3

11. insulation thickness: 50 mm

12. tray spacing: 500 mm

13. down comer plate material: stainless steel(sp. Gr.: 7.8)

SHELL THICKNESS CALCULATION:

Let the thickness of the shell= 10 mm

Using stiffener channels of C-60, 18x4, of CSA=18 in2

Wt =51.9 lb/ft

At a distance of 500 mm, (below each tray)

∴, Do = 4.67 m

L = 0.5 m

∴, L/Do = 0.11

&, Do/t = 467 ∴, B= 12000

∴, p allowable= B/( 14.22*( Do/t)), t= 5.71 mm ≈ 6 mm

Which, suggest the thickness is allowable under the operating condition.

Therefore, allowing corrosion correction, thickness choose= 12 mm

HEAD:

Design for torrispherical head.

The head is under external pressure.

Let, th = 10 mm

Rc = Do = 4.67 m

∴, Rc/(100*th) = 4.67

∴, B= 4000

∴,pallowable= B/(14.22*Rc/th), ∴, th= 17.15 mm(> 10 mm)

Hence, 10 mm thickness is not satisfactory.

Further, iteration suggest the design thickness with a

The approximate weight of the head is calculated= 3000 kg

CHECK FOR SHELL THICKNESS:

Material specification:

Carbon steel (sp. Gr. =7.7) (IS: 2002-1962, GRADE I)

Tensile strength (R20) = 37 kgf/mm2

Yield stress (E20) = 0.55R20

Since, the vessel operated under vacuum, compressive axial stress:

 fap= pd/(4*(ts-c)) = 120.6 kgf/cm2

i) Dead wt calculation:

Total dead load can be calculated as:

∑W = head wt+ liquid wt(X)+ wt of the attachment(X)

head wt= 3000 kg

liquid hold up in each tray= ρl*( Aa*hl + Ad*hdc)

= 571 kg ≈ 600 kg

wt of attachment per plate= 1100 kg (approx.)

∴,∑W= (3000+ 3400X) kg

Where, X is the distance in meter from the top tangent.

Further, the wt. of the insulation and shell also exerts a compressive stress:

π*di*X*t*ρs + π/4*(D0,ins 2
– d02)*X*ρins = 3126.8X kg
∴, total compressive stress on the shell due to dead wt:
fdsx= ∑W/(π*di*(ts-c)) = (2.055+4.47X) kg/cm2

ii) Wind pressure calculation:

Wind load: Pw = 0.0025 Vw2

Where, Pw= wind pr on the column (lb/ft2)

Vw= wind velocity in miles per hour

Let the design wind velocity= 90 mi/hr

Pw = 20.25 lb/ft2 = 98.67 kg/m2

∴Moment at a distance X from the top tangent:

Mwx= ½*Pw*X2*deff = 235.35X2 kg-m

Where, deff= effective outer diameter of the vessel including insulation=

4.77 m

∴, fwx= tensile stress on the upwind side

 = Mwx/(π*ro2*(ts-c)) = 0.1386 kg/cm2

STRESS BALANCE FOR THE UPWIND SIDE:

Ft,max = fwx- fdsx- fap

Where, Ft,max= 50% of the maximum

allowable stress = 475 kg/cm2

There for upwind side solution gives: X= 69.1 m (>14m)

STRESS BALANCE FOR THE DOWNWIND SIDE

FC,max = fwx+ fdsx+ fap

Where, FC,max= maximum allowable compressive stress.

=1/3* yield stress

=1/3* 20.25 kgf/mm2

Therefore, the solution to the quadratic equation:

X= 49.27 m (> 14m)

 N.B. the wind moment on the downwind side act as a compressive force
on the tower. Since, the thickness of 12 mm with corrosion allowance is
enough to with stand the load

of the tower of 14 m height, the thickness of the shell is maintained 12 mm

throughout the entire tower length.

SKIRT SUPPORT DESIGN:

Let, we assume skirt material: carbon steel;

IS:2002-1962,GRADE1

Yield stress= 20.35 kgf/mm2

Allowable compressive stress: 9660.31 lb/in2

We design for cylindrical skirt support.

Moreover, it is been attached to the shell at a height of 50 cm from the

bottom tangent. Skirt height selected= 2.0 m

Where, the tangent to tangent distance= 13.5 m

Let, t= thickness of the skirt.

For, X= 13.5 m

Fwb= 24599/t
 Further for seismic load: fsb= 8CWH/(πr2t)

Where, for safe design, C=0.1

W= weight of the tower = 20300 lb

&, r= 92 in

∴, fsb= 3226/t

Again, fdb = stress due to dead load at

the bottom = 35.12/t

Therefore the force balance at the bottom of the tower gives: ft,max=( fwb
or fsb) - fdb (upwind side)

fc,max=( fwb or fsb) + fdb (downwind side)

since, fwb > fsb , for safe design we will consider fwb in consideration.

Therefore, the minimum allowable thickness calculated= 2.3 in = 58 mm

SKIRT BEARING PLATE:

η= ES/EC

where, Es= modulus of steel

Ec= modulus of concrete

Let, η= 10.

∴, let, fs= 20000 psi

fc= 1200 psi (from table: 10.1, BROWNELL & YOUNG)

∴, k= = 0.375

1 + fs/(η fc)

Let, width of the bearing plate, t3= 1 ft

kd + t3

∴, fc,max = fc,bolt circle * ( )

2kd

Where, d=
184 in
fc,bolt= 1104 psi

Again (from table 10.2, BROWNELL & YOUNG)

At k= 0.375 Cc= 1.7025

Ct= 2.2785

Z= 0.4215

J= 0.7835

∴, t1= A/πd; A= bolt area

let assume the circle in which 24 bolts of 21/2 in diameter.

∴, area per bolt = 3.72 sq in

∴, t1= 0.154 in

∴, Ft = fs*t1*r*Ct

⇒ 30700 =
fs*0.154*92*2.2785 ⇒ fs=
951 psi

∴, Fc= Ft+ W = 51000 lb.

Again t2= 11.846 in

Fc = (t2 + ηt1)*r*fc*Cc ⇒ fc = 24.324 psi

∴,k= 0.2036

thus iterating with new values finally we get,

k= 0.269

Cc= 1.340

Ct= 2.571

Z= 0.450

J= 0.778

∴, the max compressive stress in bolt & concrete

fs,compression= η*fc = 305.8 psi

Where, fc,max induced= 34.286 psi

This is a safe value.

Therefore, the thickness of the bearing plate,

⇒ t4 = l*√( 3*fc,max/fallowable) = 1

in where, l= outer radius of

bearing plate
 CHAPTER-6 INSTRUMENTATION AND PROCESS CONTROL

IN THE PROCESS PLANT

The primary objective of a designer when specifying instrumentation and

Controls are:

1. Safe plant operation.

2. To keep the process variables within known safe operating limits.

3. To detect dangerous situations as they develop and to provide alarms

And automatic shut-down systems.

4. To provide interlocks and alarms to prevent dangerous operating

Procedures.

5. Production rate: To achieve the design product output.

6. Product quality: To maintain the product composition within the specified

quality standards.

7. Cost: To operate at the lowest production cost

Processes may be controlled more precisely to give more uniform and higher

Quality products by the applications of automatic control often leading to

higher profits. Automatic control is also beneficial in certain remote,

hazardous or routine operations for manual control an operator periodically

measures the temperature; If this temperature is below the desired value the

operator increases the steam flow by opening the valve slightly. For automatic
control, a temperature sensitive device is used to produce a signal proportional

to the measured temperature. This signal is fed to a controller which compares

it with a preset desired value, or set point. If the difference exists the controller

changes the opening of the steam control valve to correct the temperature.

CONTROL VALVE:

The control valve contains a pneumatic device that moves the valve stem as

the pressure on a spring loaded diaphragm changes. The stem positions a plug

in the orifice of the valve body. As the pressure increases the plug moves

downward and restricts the flow of fluid through the valve. This action is

referred to as Air to close. The valve may be constructed to have air to open

action. Most commercial valves move from fully open to fully closed as the

valve top pressure changes from 3 to 15 psi.

In general the flow rate of fluid through the valve depends upon the upstream

and downstream fluid pressures and the size of the opening through the valve.

The plug and seat can be shaped so that the various relationships between the

stem position and size of opening are obtained.

CONTROLLER:

The control hardware required to control the temperature of a stream leaving

at heat exchanger. This hardware available from manufacturers of such

equipment consist of the following components listed along with their

respective conversions:

1. Transducer (Temperature to current)

2. Controller-recorder (Current to current)

3. Converter (current to pressure)

4. Control valve (pressure to flow rate)

DISTILLATION COLUMNS:

The control of continuous distillation columns to give products of constant

Composition is one of the more difficult problems in process control. To begin

with, it is very difficult to obtain accurate continuous measurements of the

composition of nearly pure streams. The usual practice has been to control the

temperature from one end of the column where the temperature changes are

easily measured. A constant composition at some intermediate plate does not

assure a constant composition at the top or bottom plate. Instruments such as

IR analyzers refract meters or chromatographs have been used for direct

control of product purity in a few recent installations. At present the analytical

systems are less reliable than temperature systems, but they will certainly be

more widely used in the future.

The dynamic analysis of distillation columns is difficult because of the counter

flow of vapor and liquid, which introduces a special type of composition

interaction between the stages and because of the nonlinear equilibrium

relationship, which makes the gain of each stage different. The eqns for a series

of thermal capacities of interacting pneumatic stages apply though the

solutions for counter flow heat exchangers may be of some help in predicting

the response of distillation columns. In addition to composition lags there are

also lags in the flow of vapor and liquid through a large column and the lags

have a large effect on the control system performance.

CONTROL OF PRODUCT COMPOSITION:

By controlling the distillate flow rate the overhead composition XD can

Generally be kept constant in spite of changes in the feed composition.

However the concentration of the bottom product XB does change as the feed

composition changes. If the feed plate is correctly located for a normal feed a

shift in feed composition means that the feed is now introduced too high or too

low in the column which tends to decrease the separation that is achieved. The

separation can be increased by using a higher vapor rate and a higher reflux

rate. Therefore both XD and XB can be controlled by varying D/F and V/F
independently. Although the control of both the product composition has a

potential advantage over single product control, it has received little attention

in the literature. The trouble comes from the interaction between the control

loops and the lags between the changes in flow rates at one column and effects

at the other.

CONTROL OF BATCH REACTOR:

The changes in temperature and concentration with time for a perfectly mixed

batch reactor are the same as for an ideal tubular reactor. Therefore the curves

can be used to predict safe operating conditions for the batch reactors.

Batch reactors can be controlled at an otherwise unstable point by

automatically adjusting the jacket temperature to make the rate change of heat

transfer with temperature to make the rate of change of heat transfer with

temperature to make the rate of change of heat transfer greater than it would be

done for continuous reactors. The reactor can be stabilized by using just

proportional control, provided that the reactor can be a major lag in the control

system. To put it in another way the reactor can be stabilized if the

temperature changes fairly slowly compared with the rate at which the jacket

temperature can be changed.

Extremely fast reactions are sometimes carried out in semi batch fashion to
Prevent runaway temperatures. One reagent is added continuously to a cooled

reactor containing the other reagent or catalyst and the addition rate is

controlled to maintain a given batch temperature or a given heat removal rate.

For self operation the temp should be high enough to ensure a lower

concentration of the added reactant.

CHAPTER-7 PROCESS PLANT LAYOUT

Plant layout (including the details of equipment arrangement)

serves as a starting point for many of the specialized design

functions such as civil engineering and piping designer, it will

also influence every other design function, including process

design. Because of its influence on all other work, the plant

layout along with process design is one of the most important

factors in determining the sources of failure of the project.

The layout asset the project engineer in coordinating the work

of various designers far by allotting space for equipment and

facilities so mechanical engineers can do their work

simultaneous without interference. The development of layout

also permits the orientation of those nozzles and vessels and

heat exchangers so the designs of these items can be finalized

before piping design has advanced very far.

Factors to be considered in plant layout

During the development of layout and the process design the

project engineer should be consider the needs for plant

expansion. Shelter is required whenever there is need to protect

operator equipment form whether, and very elaborate buildings

may be required necessary to maintain a special atmosphere

such as in the packing rooms of some pharmaceutical plants. In

large size of continuous process plants, less and fewer shelters

are being provided as the equipment becomes larger and more

reliable and as the techniques for remote surveillance and

control becomes better developed. It must be remembered that

if shelter is provided, it may be necessary to provide

exceptionally ventilation in order to prevent the accumulation

of hazardous vapours etc. maintenance requirements can be

the most important factor in arrangement of equipment for

some plants. Some equipment’s such as complex machinery

and heat exchangers in severely corrosive and severe fouling

services may require frequent maintenance. At the very last

such equipment requires easy access and it should paid

attention for easy escape and isolation of equipment’s. One or

more escapes to be provided for emergency situation. Project

engineer should assure that sufficient space is kept clear to

permit increase in size of equipment or even for adding more

equipment’s in the plant.

1) A process flow sheet

2) Every item of major equipment and its size

3) Materials of construction of equipment and piping if these

will introduce special support for other layout problems.

4) Those factors having a significant effect on piping design

such as

I. Operating pressure and temperature

II. Flow quantity

III. The nature of flowing fuel example vapour liquid

slurry paste etc.

5) Drawing for mechanical equipment showing.

I. Vertical dimensions

II. Space required to be left clear for maintenance.

III. Location of connection.

6) Hazards of materials handled as they affect requirements

for:
 I. Separation of equipment’s.

II. Ventilation

III. The water or other barriers.

7) An area plan that shown neighbouring features that may

influence the layout such as;

I. Steam , water and sewage disposal

II. Raw material and products storage at pipelines.

III. Sources of atmosphere pollution

8) Load bearing ability of the soil and substrate condition.

9) Atmosphere condition with regard to;

I. Extremes of weather which may make it desirable to

provide shelter, a production for equipment or

operation.

10) Prevailing wind direction if there are items such as intake

or exhaust stack or furnaces, that should be located up or

down wind of the remain of the plant.

11) Preferred operating and maintenance practices as they

affect.
I. Extremes of weather which may make it desirable to

provide shelter, a production for equipment or

operation.

II. Raw material and product storage at pipelines.

III. Sources of atmosphere pollution that may affect the

process or the operation.

CHAPTER 8. SAFETY AND POLLUTION ABETMENT ASPECTS

Styrene is mildly toxic and inflammable, and it can polymerize violently

under specific conditions. However, none of the hazard associate with

styrene is severe, and it is considered a relatively safe organic chemical

when handled according to appropriate safe guards.

Styrene has an odor threshold of .05-.15 ppmv. Both liquid and vapour

irritate the eye and respiratory system, and high vapour concentration

results in depression of central nervous system.

Irritation of eye and respiratory tract occurs at 400-500 ppmv, but does not

result in permanent injury. Test animals for one hr serious systematic

effects can tolerate concentration up to 2500 ppmv. Exposure for 30-40

min to a conc. of 10000 ppmv may be fatal.

Styrene is low in oral toxicity. Contact with eyes is painful, but results in

transient damage. Short term contact with skin, do not cause irritation;

however prolonged contact may cause swelling, blistering. However,

styrene as it is commonly store and transported contains TBC, which is

skin sensitizer. Styrene monomer is flammable and can form explosive

mixture with air at atmospheric ambient condition. It is generally

suggested to store & handle styrene below or at atmospheric temp.

Polymerization of styrene is an exothermic reaction and proceeds slowly

at room temperature. Thus, there is potential for a runaway

polymerization reaction, which may results in an accelerating evolution

of styrene vapour that may cause fire or rupture in the confining vessel.

The polymerization reaction is generally been prevented by adding TBC

inhibitor.

Effective inhibition of polymerization by TBC occurs in presence of

dissolved oxygen, and so storage in an atmosphere-permeable tank is

preferred, where inert gas blanketing of the stored material is to be done.

Periodic air addition is recommended to maintain the presence of

dissolved oxygen.

For the areas, where, average temperature is over 27o C, additional

refrigeration is required.

MEASURES:

• The efficiency of the, condenser should must be properly

justified, so that there be minimum loss of styrene in the

atmosphere.
• The reactor is generally made adiabatic, and the reaction is

endothermic. The heat of reaction is generally supplied by adding

steam at 800o C. This steam is then condensed and separated as

an aqueous solution, saturated with different organic chemical.

To maintain the proper industrial economy, this condensate must

be treated and recycled back at maximum possible limit.

• The heavy end from the final column, contain styrene polymers

and some styrene derivatives, which have good economical

values. However, disposal of this heavy end causes problem. So

by adopting proper separation method it is desired to separate

those components of high economical values.

• In order to prevent the chance polymerization, final treatments

are generally carried out under reduced temperature and low

pressure.
• HAZARD AND RISK ASSESSMENT

Study Parameter Deviations Causes Consequences Action

Mode required

Distillation Flow No Loss of feed Schedule

Columns Plugging into the inspection

or distillation and do

blockage column maintenance

in Decrease in regularly on

pipeline production the pipeline.

Broken rate Install

pipeline automatic

Valve valve

is closed Clean the

pipeline

Install

automatic

valve

Regular

maintenance
 Less Of Backflow of

Leakage some feed

in the material

pipeline Low product

Less rate

amount

of

opening

valve

More Of Valve Flooding

Failure to into

closed distillation

column

Level High Blockage Install high

at the Overpressure level alarm

output of reflux drum

pipe Liquid flow

back to
 distillation

column

Low Pipe Level

particle decreases Scheduling

clogged Backflow of inspection

and material Install valve

leakage

Temperature Low Failure of Will affect the Install

heat production temperature

exchanger rate alarm sensor

High Failure as Off

column 1 specification Scheduling

feed product inspection

heater Install

temperature

sensor
Safety

The reaction feed and effluent are concerns for the safety of the plant

design. The ethyl benzene and styrene flow streams pose health and

flammability safety risks with a rating of two and three on the safety

diamond. Styrene poses a reactivity risk with a rating of two on the

safety diamond. All of the reactor effluent components, with the

exception of water, are flammable at standard conditions. Additional

fire safety equipment needs to be implemented to prevent a plant fire.

The 3-phase separator poses an immediate flame risk since it operates

at 40 atm. The organic liquid split experiences a large pressure drop

from the pressure relief valve into the flash tank. Arrester elements

are recommended to prevent ignition of potential leaks during the

high pressure drop. The 3-phase separator should be placed in an

area where no people or processes can be harmed, or within a

reinforced concrete enclosure as another layer of safety precaution.

The reactor and the distillation column operate at low pressures (1- 2

atm). However, the reaction is in the vapour phase, so pressure relief

valves should be in place to vent in the case of pressure build ups.

 CHAPTER-9 COST ESTIMATION OF THE PLANT

ESTIMATION OF THE TOTAL CAPITAL INVESTMENT

The total capital investment “I” involves the following:

A. The fixed capital investment in the process area, IF.

B. The capital investment in the auxiliary services, IA.

C. The capital investment as working capital, IW.

i.e., I=IF+IA+IW

A.FIXED CAPITAL INVESTMENT IN THE PROCESS AREA, IF.

This investment in all processing equipment within the processing area.

Fixed capital investment in the process area, IF=Direct plant cost+ Indirect

plan cost.

The approximate delivered cost of major equipment’s used in the

Proposed--manufacturing plant is furnished below:

Sr no Equipment Units Cost in Total Cost in

lakhs/unit lakhs
(x 10 6) (x 10 6)

1 Furnace 1 5 5

2 Reactor 1 8 8

3 Heat exchanger 1 1 1
4 Condenser 4 0.25 1

5 Distillation column 3 2 6

6 Settling drum 1 1 1

7 Steam super heater 1 10 10

8 Reboiler 3 1.1 3.3

Total 35.3

Direct Cost Factor

Sr no Items Direct cost factor

1 Delivered Cost of major equipment’s 100

2 Equipment’s Installation 15

3 Insulation 15

4 Instrumentation 15

5 Piping 75

6 Land & Building 30

7 Foundation 10

8 Electrical 15

9 Cleanup 5

Total Direct Cost Factor 280

Direct plant cost = (Delivered cost of major equipment’s) X (Total direct cost

Factor)/100

Direct plant cost = (3.5368*10 7 *280)/100

= 9.903*107 lakhs

Indirect cost factor

Sr no Item Indirect cost factor

1 Overhead contract etc. 30

2 Engineering fees 13

3 Contingency 13

Total indirect cost factor 56

Indirect plant cost = (Direct plant cost)(Total indirect cost factor)/100

= (9.903*107 *56)/100

= 5.54576*107 lakhs

Fixed capital investment in the process area, IF = Direct plant cost+ Indirect

plant cost

= (9.903*107 +5.5476*10 7)

= 1.544876*10 8 lakhs
B. THE CAPITAL INVESTMENT IN THE AUXILLARY SERVICES, IA.

Such items as steam generators, fuel stations and fire protection facilities are

commonly stationed outside the process area and serve the system under

Consideration.

Sr .No Items Auxiliary services cost

factor

1 Auxiliary buildings 5

2 Water supply 2

3 Electric Main Sub station 1.5

4 Process waste system 1

5 Raw material storage 1

6 Fire protection system 0.7

7 Roads 0.5

8 Sanitary and waste disposal 0.2

9 Communication 0.2

10 Yard and fence lighting 0.2

Total 12.3

Capital investment in the auxiliary services = (Fixed capital investment in the

process Area) (Auxiliary services cost factor)/100

= (1.544876*10 8 *12.3)/100
=1.9002*10 7 lakhs

Installed cost = Fixed capital investment in the process area+ Capital

= 1.54486*10 8+1.9002*10 7

= 1.734895*10 8 lakhs

C.THE CAPITAL INVESTMENT AS WORKING CAPITAL, IW.

This the capital invested in the form of cash to meet day-to-day operational

Expenses, Inventories of raw materials and products. The working capital may

be assumed as 15% of the total capital investment made in the plant (1).

Capital investment as working capital, IW = (1.734895*108 *15)/85

= 3.061581*107 lakhs

Total capital investment, I = IF+IW

= 1.544876*108 +1.9002*107 +3.06158*107

= 2.041054*108 lakhs
ESTIMATION OF MANUFACTURING COST:

The manufacturing cost may be divided into three items as follows:

A. Cost proportional to total investment

B. Cost proportional to production rate

C. Cost proportional to labor requirement

A. COST PROPORTIONAL TO TOTAL INVESTMENT:

This includes the factors, which are independent of production rate and

Proportional to the fixed investments such as

- Maintenance-labor and material

- Property taxes

- Insurance

- Safety expenses

- Protection, security and first aid

- General services, laboratory

- Administrative services

For this purpose we shall charge 15% of the installed cost of the plant

= (1.734895*108 *15)/100

=2.60234*107 lakhs
B. COST TO PRODUCTION RATE:

The factors proportional to product rate are

- Raw material costs

- Utilities cost –power, fuel, water, Steam, etc.

- Maintenance cost

- Chemical, ware house, shipping expenses

Assuming that the cost proportional rate is nearly 60% of total capital

Investment,

Cost proportional to production rate= (Total investment*60)/100

=2.041054*10 8 *0.6

=1.224632*108 lakhs

C. COST PROPROTIONAL TO LABOUR REQUIREMENT:

The cost proportional to labor requirement might amount to 10% of total

Manufacturing cost.

Cost proportional to labor requirement

= (2.60234*107 +1.224632*108 )(0.1)/0.9

=1.649847*107 lakhs

Therefore, the manufacturing cost

= (2.60234*10 7+1.224632*10 8+1.649847*10 7)

=1.64985071*10 8lakhs
SALES PRICE OF PRODUCT

Market price of styrene = Rs.70/kg

Production rate = 14400TPA

Total sales income = 70 x 50 x 1000 x 30 x 12

= 1.26 x 10 8 lakhs

PROFITABILITY ANALYSIS

A. DEPRICIATION:

According to sinking fund method:

R= (V-VS) I / (1+I) n

R = Uniform annual payments made at the end of each year

V = Installed cost of the plant

VS = Salvage value of the plant after n years

N = life period (assumed to be 15 years)

I = Annual interest rate (taken as 15%)

R = (1.734895 x 108 x 0.15)/ (1+0.15)15-1

= 3.64623 x 106 lakhs

B. GROSS PROFIT:

Gross profit = Total sales income – manufacturing cost

= 1.26 x 108 -1.64985071*108

= 5.9014929*10 7 lakhs
C. NET PROFIT:

It is defined as the annual return on the investment made after deducting

Depreciation and taxes. Tax rate is assumed to be 40%.

Net profit = Gross profit-Depreciation-(Gross profit*Tax rate)

= 5.901493*10 7-3064623*10 6-5.901493*10 7*0.4

= 3.17627274*10 7 lakhs

D. ANNUAL RATE OF RETURN

Rate of return = (100*Net profit/Installed cost)

= (100*3.17627274*10 7)/1.734895*10 8

= 18.308%

E. PAYOUT PERIOD

Payout period = Depreciable fixed investment/ ((profit) +(depreciation))

= (1.734895*10 8)/3.s7627274*107+3.64623*10 6

= 4.899 years
11. NOMECLATURE
NOMENCLATURE:

A Heat transfer area

Cp Specific heat

D Diameter

F Feed flow rate

H Enthalpy

f Friction factor

ID Inner diameter

J Jouls

K Temperature measurement Kelvin

k Thermal conductivity.

L Length

M Mass flow

Nt Number of tubes

Nre Reynolds number

OD Outer diameter

P pressure

Q Heat flow
T Temperature

U Overall heat transfer co officient

V velocity

µ Viscosity

ρ Density

∆P Pressure difference

∆T Temperature difference

Npr Prendlt number

11.0 REFERENCES:

1. PLANT DESIGN AND ECONOMICS FOR CHEMICAL

ENGINEERS, Max S. Peters Klaus D. Timmerhaus, Fourth Edition,

McGraw-Hill, Inc, 1991.

2. Encyclopedia of Chemical Technology, by kirk-othmer 5th Edition, John

Wiley, New York

3. Austin , G.T. Shreve’s Chemical Process Industries, 5th Edition

McGraw- Hill,1986

4. Charles E.Dryden , Outlines of Chemical Technology for 21st Century,

Third edition , NEW YORK PRESS,1997.

5. Process Plant: A handbook for inherently Safer Design, by Trevor

Akletz, Taylor & Francis, 1998.

6. Coulson and Richardson, Chemical engineering Volume 6, Chemical

Engineering Design, R.K. Sinnot, IV edition,2005.

7. Patat F.; Kirchner, K.: “ Praktikum der technischemChemie” (in

German), 4th Edition, page 237-244, de Gruyter, Berlin 1986.

8. Ullmann’s Encyclopedia of industrial chemistry , 5th Edition, Vol. A25,

Chapter “ Styrene”, page 329-344, VCH , Weinheim 1994.