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PRODUCTION OF ANISOLE 1

Chapter 1

Introduction

1.1 History

Anisole, or methoxybenzene, is an organic compound with the formula CH3OC6H5. It


is a colorless liquid with a smell reminiscent of anise seed, and in fact many of its derivatives
are found in natural and artificial fragrances. The compound is mainly made synthetically
and is a precursor to other synthetic compounds. It is an ether.

Fig.1.1 Structure of Anisole

1.2 Market Survey

Global anisole market size was USD 39.03 million in 2014 and is expected to witness
significant growth over the next seven years owing to increasing demand in various industries
including cosmetics, pharmaceuticals, and food & beverages. It is also employed as an
intermediate in the manufacturing of various dyes, which is expected to increase its market
share over the forecast period.
Anisole find applications in various sectors including perfumes, pharmaceuticals, and
other application including food & beverages and dyes. Perfume was the largest application
segment in 2014 accounting for over 50% of global revenue and is expected to grow
significantly as a result of high consumption owing to its pleasant and sweet properties.
Robust manufacturing base of cosmetic industry coupled with growing domestic demand in
PRODUCTION OF ANISOLE 2

U.S., China, Germany, Saudi Arabia, Italy, Mexico, Brazil, France and UK is expected to
augment industry growth over the forecast period
Rising need for consumer products such as fragrances and flavors on account of
changing consumer habits along with better living standards is expected to augment the
product demand in emerging economies including India, China, and Brazil. However, raw
material availability will challenge growth over the next seven years.

Anisole is utilized in manufacturing inorganic complexes and nanoparticles, which


include tin oxide, increasing the demand of which is expected to promote market growth over
the forecast period. Increasing application of its derivatives as flavoring agents in animal feed
is likely to contribute to the market growth over the forecast period. However, exposure to the
product above critical limits can cause health problems including throat burning, irritation in
eyes, and foreign taste in mouth.

1.3 Current Demand and Supply Details

The market prices of methanol and phenol (raw materials) are shown in fig.2 and fig.3 as
follows.
PRODUCTION OF ANISOLE 3

Fig.1.2. Market prices of methanol

Fig.1.3 Phenol market rates


PRODUCTION OF ANISOLE 4

Product use in the pharmaceuticals sector is expected to grow at CAGR of over 4.2%
from 2015 to 2022 in light of high growth in China and India on account of favorable FDI
policies. Moreover, growing domestic demand in developing countries due to increasing
health awareness coupled with technological advancement is expected to further drive
pharmaceutical industry, contributing to market growth over the next seven years. The trends
are shown in fig.4.

Fig.1.4. US Anisole market trends (by applications)

1.4 Existing Plant locations in India and Abroad

India:

● Westman Chemicals - Mumbai, Maharashtra


● Sanika Chemicals - Mumbai, Maharashtra
● Sheetal Chemicals - Mumbai, Maharashtra
● Rudolf Atul Chemicals - Aurangabad, Maharashtra
● Harmony Organics - Pune, Maharashtra

International:

● Merck Millipore - Darmstadt, Germany


PRODUCTION OF ANISOLE 5

● Sigma Aldrich - Missouri, USA


● M&U International - Shanghai, China

1.5 Uses

1. Anisole is a solvent used in the synthesis of organic compounds and in large-scale


applications such as the production of perfumes.

2. A novel anisole mixture containing anisole and a mixture of alkyl anisoles and liquid
hydrocarbon fuels containing said novel anisole mixture in an amount sufficient to
increase the octane number of said liquid fuel composition

3. as a flavoring in food
4. In the manufacture other chemicals. Anisole is frequently used in the solid-phase
synthesis of compounds, particularly in the cleavage of compounds from the resin.
5. Anisole is a precursor to perfumes, insect pheromones, and pharmaceuticals and is
extensively employed in industry as intermediates for the synthesis of a variety of
resins, herbicides, insecticides, and other important chemicals.
PRODUCTION OF ANISOLE 6

Chapter 2

Properties

2.1 Property Table

Chemical formula C7H8O

Molar Mass 108.14 g/mol

Density 0.9956 g/cm3

Melting Point −37 °C ( 236 K)

Boiling Point 154 °C (427 K)

Solubility in Water Poor

Solubility in Alcohol/Ether Soluble

Solubility in Acetone Very Soluble

Color Clear Straw Color


Colorless

Odor Sweet, Anise-like


Spicy-Sweet

Taste Sweet

Flash point 52°C (Open Cup)

Vapor Density 3.72 (Air=1)

Vapor Pressure 0.47 kPa (25°C)

Auto - Ignition Temperature 475°C


PRODUCTION OF ANISOLE 7

Decomposition emits acrid fumes

Viscosity 1.52 cP (15°C)


0.77 cP (30°C)

Heat of combustion -3783.12 kJ/mol (25°C)

Heat of vaporization 46.84 kJ/mol (25 °C)

Surface Tension 35.00 dyne/cm (20 °C)


34.15 dyne/cm (30 °C)

Table.2.1 Properties of anisole

2.2 Safety Data

Fig.2.1. Anisole Safety Data

Globally Harmonized System of Classification and Labeling of Chemicals (GHS) categorizes


Anisole as Flammable and Irritant.

Hazard Statements
H226 Flammable liquid and vapour.
H315 Causes skin irritation.
H319 Causes serious eye irritation.
Precautionary Statements
PRODUCTION OF ANISOLE 8

P305 IF IN EYES:
P351 Get immediate medical advice/attention.
P338 Remove contact lenses, if present and easy to do. Continue rinsing.
PRODUCTION OF ANISOLE 9

Chapter 3

Literature Survey

3.1 Manufacturing process of Anisole


The following methods were found to be suitable for industrial production of Anisole from
literature survey.
3.1.1 Williamson ether synthesis
Anisole is generally prepared by the reacting sodium phenoxide with methyl bromide and
related methylating reagents:
C6H5O−Na+ + CH3Br → CH3OC6H5 + NaBr

3.1.2 Preparation as described in patent US2487832


This process relates to the manufacture of anisole and more particularly to processes for the
manufacture of anisole from phenol and dimethyl ether, which processes comprise the steps of
leading phenol and dimethyl ether into a reaction zone and in the reaction zone contacting the
phenol and the dimethyl ether in admixture in the vapor phase with a solid dehydrating
catalyst at a temperature of about 200 to 400 C.
PRODUCTION OF ANISOLE 10

Fig.3.1 Anisole manufacturing process as in patent US2487832.

3.1.3 Preparation as described in patent US2529887

This process relates to the manufacture of anisole, more particularly to continuous


processes in which a methylating agent for phenol is added continuously to a stream of
refortified aqueous sodium phenate maintained in turbulent flow. The stream is heated to form
anisole therein. The anisole is separated and unreacted aqueous sodium phenate is refortified
by adding phenol and an alkaline sodium compound. A stream of the refortified aqueous
sodium phenate is then recycled for admixture with the methylating agent.
PRODUCTION OF ANISOLE 11

Fig.3.2 Anisole manufacturing process as in patent US2529887


PRODUCTION OF ANISOLE 12

3.1.4 Preparation using catalytic vapor phase alkylation of Phenol with


Methanol
Phenol alkylation with methanol, a process that can be accomplished in the liquid- or
vapor-phase mode depending on the methylation conditions, is of the greatest practical
interest for anisole manufacture. The second mode is preferable since it is more economical,
promising, and simpler in the engineering design

3.2 Comparison of alternatives


Alkylation mode is preferable since it is more economical, promising, and simpler in
the engineering design. It is eco friendly compared to other process and the by products that
are produced during the process are easily separable
This method involves the production of anisole by an improved method of alkylating
phenols by reaction in the vapor phase with alcohols in the presence of alumina catalysts
whereby improved selectivity of reaction to monoalkylation products is achieved. It is suitable
to obtain higher yields and conversions to desired monoalkylation products of phenols in this
reaction. The method involves the methylation of alkyl phenols having not more than two
alkyl groups per molecule to the corresponding alkyl phenols having one added methyl group
in a more advantageous manner and provides a unique combination of operating conditions
under which phenols can be more efficiently alkylated by reaction in the vapor phase with
alcohols when using alumina catalysts.
It has been found that by the use of a diluent such as added steam under the proper
combination of reaction conditions, particularly mole ratio of alcohol to phenol and
temperature, optimum yields and conversions of phenols, particularly of alkyl phenols, to
monoalkylation products are obtained when carrying out the reaction in the vapor phase in the
presence of activated alumina catalysts. This was unexpected in view of the fact that steam is
a product of the desired alkylation-hence, its addition would have been predicted to be
disadvantageous because it would retard the reaction and reduce conversion and throughput
without offering any compensating improvement which would have been foreseen. In
practice, however, the addition of substantial amounts of steam, either separately or together
with the reactants, produces the reverse of the expected effects and gives improved yields and
conversions of desirable monoalkylation products.
PRODUCTION OF ANISOLE 13

Chapter 4

Description of the process

The Conventional process for the production of anisole involves the reaction between phenol
and anisole in a catalytic fixed bed reactor with NaX zeolite as catalyst followed a direct
sequence of distillation columns for separation of pure products. Unreacted methanol is
obtained as the top product in the first distillation column followed by water, anisole,
unreacted phenol and cresols, thus the process involves series of distillation units for
separation which results in high investment and high energy requirements. Separation of
phenol from cresol mixture is one of the difficulty faced by the chemical and petrochemical
industries. Thus it is necessary to implement better process alternatives to reduce the energy
requirements. Proper selection of solvent is necessary for azeotropic distillation design to
separate phenol o-cresol mixture. To solve the problem of high energy requirements and
increased number of process equipments, divided wall column arrangement is employed for
the separation of water and anisole from phenol and phenol derivatives mixture. Pressure
swing distillation followed by azeotropic distillation arrangement is made for the separation
of high purity phenol from phenol-cresol mixture.
The process parameters are selected based on the available data as in the tables following:
PRODUCTION OF ANISOLE 14

Table.4.1. Influence of nature of the zeolite catalyst on the yield and composition of alkylation products
(space velocity was 0.5 h-1, phenol to methanol molar ratio was 1:3)

Table.4.2. Influence of the space velocity and the phenol to methanol ratio on the yield and composition of
the alkylation products on the catalyst NaX at 320oC
PRODUCTION OF ANISOLE 15

4.1 Property analysis of the compounds using ASPEN Plus

4.1.1 Azeotrope Search


This aspen tool is used to find azeotropes among selected compounds.
Azeotrope search of the compounds involved in this process i.e., reactants, products and
by-products yielded the following results

Fig.4.1. Azeotrope Search function results from aspen plus.


PRODUCTION OF ANISOLE 16

4.1.2 Distillation Synthesis


1. Phenol and Methanol (Reactants) T-xy diagram
No azeotropes

Fig.4.2 Phenol and Methanol T-xy diagram

2. Methanol (excess reactant) and Water (product) (T-xy diagram):


No azeotropes

Fig.4.3. Methanol and Water T-xy diagram


PRODUCTION OF ANISOLE 17

3. Phenol (reactant) and Water (by-product) T-xy diagram:


Azeotrope formation detected. Solvent may be necessary for complete recovery of
unconverted reactant.

Fig. 4.4 Phenol and Water T-xy diagram

4. Phenol (reactant) and Anisole (product) T-xy diagram


No azeotropes

Fig.4.5. Phenol and Anisole T-xy diagram


PRODUCTION OF ANISOLE 18

5. Methanol (excess reactant) and Anisole (product) T-xy diagram


No azeotropes

Fig.4.6. Methanol and Anisole T-xy diagram

6. Anisole (product) and Water (by-product) T-xy diagram


Azeotrope formation is detected. Hence, a solvent is necessary to extract our product from the
by-product.

Fig.4.7. Anisole and Water T-xy diagram


PRODUCTION OF ANISOLE 19

Toluene can be used as the solvent for extracting water


7. Anisole (product) and Toluene (solvent) T-xy diagram
No Azeotrope formation. Hence, can be used.

Fig.4.8. Anisole and Toluene T-xy diagram

8. Toluene (solvent) and Water (by-product) T-xy diagram:


Strong azeotrope formation. Hence, can be used for extracting by product.

Fig. 4.9. Toluene and Water T-xy diagram


PRODUCTION OF ANISOLE 20

4.2 Flowsheet for the process

Fig.4.10. Flowsheet of the process


PRODUCTION OF ANISOLE 21
PRODUCTION OF ANISOLE 22

Chapter 5

Material Balances

5.1 Overall Mass Balance

Reactions involved in the process :

The selectivity of products are assumed to be

S.No Component/Product Selectivity(%)

1. Anisole 85

2. O-Cresol 3

3. P-Cresol 6

4. 2,4-Xylenol 3
PRODUCTION OF ANISOLE 23

5. 2,6-Xylenol 3

Table.5.1. Selectivity of the products of alkylation reaction of phenol and methanol

Possible Reactions:

Phenol + Methanol --------------→ Anisole + H2O Selectivity: 85%


Phenol + 2Methanol --------------→ Xylenols + 2H2O Selectivity: 5%
Phenol + Methanol --------------→ Cresols + H2O Selectivity: 9%

Desired reaction:
Phenol + Methanol --------------→ Anisole + H2O
[1:9 mass ratio] ↓
~ [1:26 mole ratio] 15 tpd
(required)
Molecular weights:
Phenol + Methanol ---------→ Anisole + H2O + Cresols + Xylenols
94.1112 32.0419 108.1378 18.0153 108.1378 122.1644

Reactants ratio:
Stoichiometric ⇒ phenol:methanol = 1:1
Optimum ⇒ phenol:methanol = 1:9 (by mass)
= (1/9)*(32.0419/94.1112) = 0.0378:1
= 1:26.4342 (by mole)
Limiting reactant: Phenol

Required production of anisole = 15 ton/day = 15*(1000/(24*3600))/0.999 kg/s


= 0.173611/Anisole recovery kg/s
= 0.173611/0.999 kg/s
= 0.173628 kg/s
= 0.173628/108.1378 kmol/s = 0.001606 kmol/s
PRODUCTION OF ANISOLE 24

Stoichiometric requirement of phenol = anisole produced * (MW of phenol/MW of anisole)/


selectivity
= 0.173628*(94.1112/108.1378)/0.85 kg/s
= 0.151107/0.85 kg/s
= 0.177772 kg/s
= 0.001889 kmol/s

Stoichiometric requirement of MeOH =anisole flow rate * (MW of MeOH/MW of anisole)/


selectivity
=0.173628*(32.0419/108.1378)/0.85 kg/s
=0.051451/0.85 kg/s
= 0.06053 kg/s
= 0.001889 kmol/s

Phenol required = stoichiometric requirement/conversion ( ∵ limiting reactant)


= 0.177772/0.5 kg/s
= 0.355554 kg/s
= 0.003778 kmol/s

Methanol required = Phenol mass flow rate*9 ( ∵ optimum ratio - from literature)
= 0.355554*9
= 3.19999 kg/s
= 0.099869 kmol/s

Phenol to be recycled = 0.355554-0.177772 kg/s


= 0.177772 kg/s
= 0.001889 kmol/s

Methanol to be Recycled= 3.19999-0.06053


= 3.13946 kg/s
= 0.097968 kmol/s
PRODUCTION OF ANISOLE 25

Cresols produced = 0.09 * 0.177755 * (108.1378/94.1112)


= 0.018382 kg/s
= 0.00017 kmol/s

Xylenols produced = 0.05 * 0.177755 * (122.1644/94.1112)


= 0.011537 kg/s
= 0.09444e-3 kmol/s

Water produced = (18.0153/94.1112) * 0.177772 * (0.95*1 + 0.05*2)


= 0.035731 kg/s
= 0.001794 kmol/s

Toluene (solvent) to be added to column-2= water produced*92.1384/18.0153


= 0.182747 kg/s = 0.001794 kmol/s

Steam to be added in column-4 = phenol to be recycled*18.0153/94.1112


= 0.03403 kg/s

Toluene to be added in column-5 = (92.1384/18.0153)*0.03403 kg/s


= 0.17404 kg/s = 0.001889 kmol/s
PRODUCTION OF ANISOLE 26

Summary of component flow rates:

S.No Component Flow Rate (Kmol/sec)

1. Anisole 1.60700E-3

2. O-Cresol 5.67750E-5

3. P-Cresol 1.13550E-4

4. 2,4-Xylenol 5.67750E-5

5. 2,6-Xylenol 3.78500E-5

6. Water 1.96658E-3

7. Phenol 1.90427E-3

8. Methanol 0.0963172

Table.5.2. Final flow rates of reactants and products for the production of 15 tpd anisole
PRODUCTION OF ANISOLE 27

5.2 Material balance w.r.t individual unit operations

5.2.1 Reactor
The reactants are sent into the reactor at 310oC
The conversion is assuming to be 0.5, hence the outlet stream consists of unconverted
reactants, the products and by-products formed.

Mass balance equation:


In - Out + Generation = Accumulation
[methanol + phenol ] - [ anisole + (cresols+xylenols+water) + unreacted + unreacted] + 0 = 0
in in formed formed phenol methanol

The catalyst used is a solid catalyst in fixed bed in the reactor, hence there is no loss of
catalyst in the product streams.
PRODUCTION OF ANISOLE 28

5.2.2 Distillation Column-1 (Methanol Column)

The product mixture from reactor first cooled to its saturation temperature and then
enter methanol column where methanol gets separated as the distillate with a purity of 99.9%
and the other products that are residue enters the next distillate column.

Column temperature :342.387K


Column pressure:1 atm
Recovery of methanol:99.9(wt%)
PRODUCTION OF ANISOLE 29

5.2.3 Distillation column-2 (Water column)

The Bottoms mixture form the methanol column is cooled to its saturation temperature
and is feed into the water column. Here a purity of 99.9% of water is recovered and the
residue is sent to the next column.
Water forms azeotropic mixtures with phenol and cresols in the product mix and hence
cannot be separated by simple distillation. The process would have very high energy
requirements. Hence Toluene is used as a solvent for extractive distillation and the
water-toluene heterogenous azeotropic mixture is obtained as the top product.
Being a heterogenous azeotrope, water and toluene are separated by decantation and
toluene is recovered as the top layer. Water can be sent for further treatment.

Column temperature :303.15K


Column pressure:1 atm
Recovery of Water:99.17(wt%)
PRODUCTION OF ANISOLE 30

5.2.4 Distillation Column-3 (Anisole Column)

The Bottom mixture from the water column is sent to the next distillation column to
separate out the next higher Boiling point component, Anisole. The Column is operated at 1
atm pressure with a total condenser and a reboiler where anisole is separated with a purity of
99.9%.

Column temperature :313.15K


Column pressure:1 atm
Recovery of Anisole:99.856(wt%)
PRODUCTION OF ANISOLE 31

5.2.5 Distillation column-4 (Cresol column)

The bottom product from the anisole column is sent to column 4. Separation of Phenol -
o-cresol is one the current separation problem faced in chemical industries to obtain high
purity phenol. It is known that at room temperature and pressure phenol o-cresol form a close
boiling mixture and they both can’t be separated easily to obtain high purity products and they
both form azeotropes with water. From the literature studies it is observed that at 240 torr
pressure only phenol and water forms the minimum boiling azeotrope which can be separated
from o-cresol, later high purity phenol is obtained from the phenol water azeotropic mixture
using toluene as azeotropic agent.
The phenol-water azeotropic mixture is obtained as the top product and
cresols+xylenols are separated as residue.

Column temperature :406.15K


Column pressure:1 atm
Recovery of Phenol+water :99.9(wt%)
PRODUCTION OF ANISOLE 32

5.2.6 Distillation column-5 (Phenol Column)

The residue from anisole column that consists of phenol,cresols and xylenols is cooled and
then enter the phenol column at 1 atm pressure where phenols get separated with purity of
99.9% leaving behind cresols and xylenols as bottom residue. The obtained phenol distillate is
again fed back as recycle.

Column temperature :456.85K


Column pressure:1 atm
Recovery of phenol:99.856(wt%)
PRODUCTION OF ANISOLE 33

Fig.5.1. Overall material balance w.r.t all streams


PRODUCTION OF ANISOLE 34

Chapter 6

Energy Balances

6.1 Calculation of Heats of reactions


6.1.1 Specific heats
Specific heats of all the compounds involved, as extracted from Perry’s Chemical Engineer’s
Hand book, 8ed. are presented in the table below:

Sl.No Compound CP (J/k.mol.K) as a function of Valid Range


Temperature (K)

1 Anisole (150940) + (93.455)T + (0.23602)T2 298.15K - 484.2K

2 m-Cresol (-246700) + (3256.8)T + (-7.4202)T2 285.39K - 400.00K


+ (0.0060467)T3

3 p-Cresol (259980) + (-1112.3)T + (4.9427)T2 + 307.93K - 400.00K


(-0.0054367)T3

4 o-Cresol (-185150) + (3148)T + (-8.0367)T2 + 304.2K - 400.00K


(0.007254)T3

5 Methanol (105800) + (-362.23)T + (0.9379)T2 175.47K - 400.00K

6 Phenol (101720) + (317.61)T 314.06K - 425.00K

7 Water (276370) + (-2090.1)T + (8.125)T2 + 273.16K - 533.15K


(-0.014116)T3 + (9.37 x 10-6)T4

8 Xylenol (15130.7) + (589.228)T + 285.15K - 400.00K


(estimated by Ruzicka (0.39182)T2
Domalski method,
Pg.2-495, Perry, 8e)
PRODUCTION OF ANISOLE 35

9 Toluene (140140) + (-152.3)T + (0.695) T2 178.18K - 500.00K

Table.6.1 Specific heats of reactants and products as a function of temperature.

6.1.2 Estimation of Specific Heat of Xylenol

By Ruzicka - Domalski method


For Xylenol, the values of ni, ai, bi, di are given in table.
CB= Carbon atom in benzene ring.

Sl.No. Group n a b d Temperature


Range (K)

1 (CB)-(C) 2 1.5070 -0.13366 0.011799 180-670

2 O-(H,CB) 1 -7.9768 8.10450 -0.87263 285-400

3 (CB)-(H) 3 2.2609 -0.2500 0.12592 180-670

𝝨niai=1.8199 𝝨nibi=7.08718 𝝨nidi=-0.47127 ~(285-400)

Table.6.2. Ruzicka Domalski method for estimating specific heat of xylenol

The groups identified are: C(benzene ring)-C, C(benzene ring)-H,


O-[H,C(benzene ring)]

(CP/R) = A + B (T/100K) + D(T/100K)2


Where,
A=𝝨niai ; B=𝝨nibi ; D=𝝨nidi
ni = no. of occurences of group i

(CP/R) = 1.8199 + 7.08718(T/100) - 0.471272(T/100)2


PRODUCTION OF ANISOLE 36

CP = R (1.8199 + 7.08718 x 10-2 (T) - 0.471272 x 10-4 (T)2)


=8.314 (1.8199 + 7.08718 x 10-2 (T) - 0.471272 x 10-4 (T)2)

CP = (15130.7) + (589.228)T + (0.39182)T2 (J/k.mol.K)

6.1.3. Latent Heats of vaporization


Of all reactants, products and solvents, at their boiling points are given below

Sl.No Compound ΔHv (J/k.mol)

1 Anisole 4.4*107

2 m-Cresol 4.66 * 107

3 p-Cresol 4.76 * 107

4 o-Cresol 4.49 * 107

5 Methanol 3.76 * 107

6 Phenol 5.88 * 107

7 Water 12.53*107

8 Xylenol 7.56 * 107

9 Toluene 3.73 * 107

Table.6.3 Latent heats of vaporization of reactants and products.

6.1.2 Calculation of Heats of formation at reaction temperature

Heats of formation at 25oC are as follows:

Sl.No. Compound (∆Hf)ideal gas at 25oC (J/k.mol)


PRODUCTION OF ANISOLE 37

1 Anisole -6.79 x 107

2 m-Cresol -13.23 x 107

3 o-Cresol -12.857 x 107

4 p-Cresol -12.535 x 107

5 Methanol -20.094 x 107

6 Phenol -9.6399 x 107

7 Water -24.1814 x 107

8 Xylenol -16.375 x 107

Table.6.4. Heats of formation of reactants and products in gaseous phase at 25oC

Reaction temperature = 320oC = 593.15 K

(∆Hf )593.15= (∆Hf )298.15 +298.15 ∫593.15 Cp dT

Anisole:
593.15
(∆Hf )593.15 = -6.79 x 107 + ∫ (150940) + (93.455)T + (0.23602)T2 dT
298.15

= 370918.1658 J/k.mol
m-Cresol:
593.15
(∆Hf )593.15 = -13.23 x 107 + ∫ (-246700) + (3256.8)T + (-7.4202)T2 + (0.0060467)T3
298.15

dT
= -55675181.49 J/k.mol
PRODUCTION OF ANISOLE 38

p-Cresol:
593.15
(∆Hf )593.15 = -12.535 x 107 + ∫ (259980) + (-1112.3)T + (4.9427)T2 + (-0.0054367)T3
298.15

dT
= -54323931.82 J/k.mol
o-Cresol:
593.15
7
(∆Hf )593.15 = -12.857 x 10 + ∫ (-185150) + (3148)T + (-8.0367)T2 + (0.007254)T3 dT
298.15

= -50853915.7 J/k.mol
Water:
593.15
7
(∆Hf )593.15 = -24.1814 x 10 + ∫ (276370) + (-2090.1)T + (8.125)T2 + (-0.014116)T3
298.15

+ (9.37 x 10-6)T4
dT
= -218485360.9 J/k.mol
Methanol:
593.15
(∆Hf )593.15 = -20.094 x 107 + ∫ (105800) + (-362.23)T + (0.9379)T2 dT
298.15

= -162691453.5 J/k.mol

Phenol:
593.15
(∆Hf )593.15 = -9.6399 x 107 + ∫ (101720) + (317.61)T dT
298.15

= -27521668.75 J/k.mol
Xylenol:
593.15
7
(∆Hf )593.15 = -16.375 x 10 + ∫ (15130.7) + (589.228)T + (0.39182)T2 dT
298.15

= -107878244.3 J/k.mol
PRODUCTION OF ANISOLE 39

6.1.3. Calculation of Heats of Reactions

(∆HR)583K = n[(∆Hf )583K]products - n[(∆Hf )583K]reactants

For reaction 1: {phenol + methanol -----> anisole + water}


[(∆HR )583.15]1 = (370918.1658 x 1 - 218485360.9 x 1) - (-27521668.75 - 162691453.5)
= -2.7901 x 107 J/k.mol
For reaction 2: {phenol + methanol -----> cresol + water}
[(∆HR )583.15]2 =(-52926736.18 x 1 - 218485360.9 x 1) - (-27521668.75 - 162691453.5)
= -8.1199 x 107 J/k.mol

For reaction 3: {phenol + 2methanol -----> xylenol + 2water}


[(∆HR )583.15]3 =(-107878244.3 - 218485360.9 x 2) - (-27521668.75 - 162691453.5 x 2)
= -8.1199 x 107 J/k.mol
PRODUCTION OF ANISOLE 40

6.2 Energy balance around individual unit operations

6.2.1 Preheater:

Q = mCp(∆T)

Q1 = ṁCp(∆T)
= (ṁmethanol ∫Cp (methanol) dT )+ (ṁphenol ∫Cp (phenol) dT)
593.15
= [0.0963172 x ∫ (105800) + (-362.23)T + (0.9379)T2 dT] +
298.15
593.15
[ 1.9042 x 10-3 x ∫ (101720) + (317.61)T dT]
298.15

= +3827245.133 J/s
PRODUCTION OF ANISOLE 41

6.2.2 Reactor:

Heat Produced = [(∆HR)1 x Selectivity of Reaction-1 + (∆HR)2 x Selectivity of Reaction-2


+ (∆HR)3 x Selectivity of Reaction-3 ] x Phenol molar flow rate.

Q2 = [-2.7901 x 107 x 0.85 + -8.1199 x 107 x 0.09 + -8.1199 x 107 x 0.06] x 1.9042 x 10-3
= -74631.311 J/s

6.2.3 Heat Exchanger-1 :


PRODUCTION OF ANISOLE 42

Heat duty (Q3) = Σ [ṁCp(∆T)+ṁλ]


333.15
Q3 =1.607 x 10-3 x[ ∫ (150940) + (93.455)T + (0.23602)T2 dT +4.4 x 107]+
593.15
333.15
0.56775 x 10-4 x[ ∫ (-246700) + (3256.8)T + (-7.4202)T2 + (0.0060467)T3 dT +
593.15

4.66 x 107]
333.15
0.56775 x 10-4 x [ ∫ (259980) + (-1112.3)T + (4.9427)T2 + (-0.0054367)T3 dT+ 4.76
593.15

x 107]
333.15
0.56775 x 10-4 x [ ∫ (-185150) + (3148)T + (-8.0367)T2 + (0.007254)T3 dT + 4.49 x
593.15

107]
333.15
0.098348 x[ ∫ (105800) + (-362.23)T + (0.9379)T2dT + 3.76 x 107]
593.15
333.15
0.00189 x[ ∫ (101720) + (317.61)T dT + 5.88 x 107]
593.15
333.15
1.9665 x 10-3 x[ ∫ (276370) + (-2090.1)T + (8.125)T2 + (-0.014116)T3 + (9.37 x
593.15

10-6)T4 dT + 12.53 x 107]


333.15
9.323 x 10-5 x [ ∫ (15130.7) + (589.228)T + (0.39182)T2 dT +7.56 x 107]
593.15

= 0.00189*(-68877331.25 + 4.4*107) -(100749434.7+3.76*107)* 9.323 * 10-5


-(23327337.45+5.88*107)* 1.9665 * 10-3 - (38374131.71+12.53*107)* 0.098348 -
(77716084.3+4.66*107) * 0.56775 * 10-4 - (71026068.18+4.76*107)* 0.56775 * 10-4 -
(76624818.51+4.49*107)* 0.56775 * 10-4 - (68270918.17+7.56*107 )* 1.607 * 10-3
= -16570336.56 J/s.
PRODUCTION OF ANISOLE 43

6.2.4 Methanol Column:

Top product enthalpy change:


Q4 = Σ ṁCp(∆T) + ṁmethanolλmethanol
337.15
= ṁmethanol ( ∫ (105800) + (-362.23)T + (0.9379)T2 dT +3.76*107)
333.15

= 0.09787 * ( 3334190.234 + 3.76 *107)


= 4006229.1 J/s

Bottom product enthalpy change:


Q5 = Σ ṁCp(∆T)
353.15
= ṁanisole ∫ (150940) + (93.455)T + (0.23602)T2 dT +
333.15
PRODUCTION OF ANISOLE 44

353.15
ṁm-cresol x ∫ (-246700) + (3256.8)T + (-7.4202)T2 + (0.0060467)T3 ,dT+
333.15
353.15
ṁo-cresol x ∫ (259980) + (-1112.3)T + (4.9427)T2 + (-0.0054367)T3 dT+
333.15
353.15
ṁp-cresol x ∫ (-185150) + (3148)T + (-8.0367)T2 + (0.007254)T3 dT+
333.15
353.15
ṁmethanol x ∫ (105800) + (-362.23)T + (0.9379)T2 dT+
333.15
353.15
ṁphenol x ∫ (101720) + (317.61)T dT+
333.15
353.15
ṁwater x ∫ (276370) + (-2090.1)T + (8.125)T2 + (-0.014116)T3 + (9.37 x 10-6)T4 dT+
333.15
353.15
ṁxylenol x ∫ (15130.7) + (589.228)T + (0.39182)T2
333.15

= 11355440.15 * 1.607 x 10-3 + 12948020.35 * 0.56775 x 10-4 + 12874173.61 *


0.56775 * 10-4 +13089709.18 * 0.56775 * 10-4 + 4814621.678 * 0.000278 + 11283233.31 *
0.00189 + 4143234.815 * 1.9665 * 10-3 + 13676479.66 * 9.323 * 10-5
=52543.92 J/s
PRODUCTION OF ANISOLE 45

6.2.5 Water Column:

Top product enthalpy change:

Q6 = Σ ṁ(Cp(∆T)+λ)
345.15
=ṁwater x( ∫ (276370) + (-2090.1)T + (8.125)T2 + (-0.014116)T3 + (9.37 x 10-6)T4
298.15

dT+12.53 *107)
345.15
ṁtoluene( ∫ (140140) + (-152.3)T + (0.695) T2 dT + 3.73*107)
298.15

=(3539078.713+12.53 *107) * 0.001947 + (7669669.388 + 3.73*107)* 0.001977


= 339754.72 J/s

Bottom product enthalpy change:


PRODUCTION OF ANISOLE 46

Q7 = Σ ṁCp(∆T)

428.15
= ṁanisole ∫ (150940) + (93.455)T + (0.23602)T2 dT +
298.15
428.15
ṁm-cresol x ∫ (-246700) + (3256.8)T + (-7.4202)T2 + (0.0060467)T3 ,dT+
298.15
428.15
ṁo-cresol x ∫ (259980) + (-1112.3)T + (4.9427)T2 + (-0.0054367)T3 dT+
298.15
428.15
ṁp-cresol x ∫ (-185150) + (3148)T + (-8.0367)T2 + (0.007254)T3 dT+
298.15
428.15
ṁmethanol x ∫ (105800) + (-362.23)T + (0.9379)T2 dT+
298.15
428.15
ṁphenol x ∫ (101720) + (317.61)T dT+
298.15
428.15
ṁwater x ∫ (276370) + (-2090.1)T + (8.125)T2 + (-0.014116)T3 + (9.37 x 10-6)T4 dT+
298.15
428.15
ṁxylenol x ∫ (15130.7) + (589.228)T + (0.39182)T2 dT+
298.15
428.15
ṁtoluene x ∫ (140140) + (-152.3)T + (0.695) T2 dT
298.15

=28123732.7 x 1.607 x 10-3 + 31961681.19 x 0.56775 x 10-4 + 31996784.78 x 0.56775


x 10-4 +31901886.78 x 0.56775 x 10-4 + 12904496.13 x 0.000278 +28217809.3 x 0.00189 +
9885574.229 x 0.0197 x 10-3 + 36573298.96 x 9.323 x 10-5 + 23070606.36 x 0.000002
=111207.035 J/s
PRODUCTION OF ANISOLE 47

6.2.6 Anisole Column:

Top product enthalpy change:

Q8 = Σ ṁCp(∆T) + ṁanisoleλanisole
425.15
= ṁanisole ∫ (150940) + (93.455)T + (0.23602)T2 dT + 4.4 * 107
298.15

= (27422406.12 + 4.4 * 107) x 0.001604


= 114561.53 J/s
PRODUCTION OF ANISOLE 48

Bottom product enthalpy change:

Q9 = Σ ṁCp(∆T)

473.15
= ṁanisole ∫ (150940) + (93.455)T + (0.23602)T2 dT +
298.15
473.15
ṁm-cresol x ∫ (-246700) + (3256.8)T + (-7.4202)T2 + (0.0060467)T3 ,dT+
298.15
473.15
ṁo-cresol x ∫ (259980) + (-1112.3)T + (4.9427)T2 + (-0.0054367)T3 dT+
298.15
473.15
ṁp-cresol x ∫ (-185150) + (3148)T + (-8.0367)T2 + (0.007254)T3 dT+
298.15
473.15
ṁmethanol x ∫ (105800) + (-362.23)T + (0.9379)T2 dT+
298.15
473.15
ṁphenol x ∫ (101720) + (317.61)T dT+
298.15
473.15
ṁwater x ∫ (276370) + (-2090.1)T + (8.125)T2 + (-0.014116)T3 + (9.37 x 10-6)T4 dT+
298.15
473.15
ṁxylenol x ∫ (15130.7) + (589.228)T + (0.39182)T2 dT+
298.15
473.15
ṁtoluene x ∫ (140140) + (-152.3)T + (0.695) T2 dT
298.15

=38969972.25 x 0.000003 + 4402173.31 x 0.56775 x 10-4 +43900943.45 x 0.56775 x


10-4 + 43851530.74 x 0.56775 x 10-4 + 18898187.38 x 0.000278 +39236101.89 x 0.00189
+13447957.42 x 0.0000197 + 52787039.63 x 9.323 x 10-5 +32645150.83 x 0.000002
= 90010.892 J/s
PRODUCTION OF ANISOLE 49

6.2.7 Cresol Column

Top product enthalpy change:

Q10 = Σ ṁ(Cp(∆T)+λ)
449.15 475.15
= ṁphenol x ( ∫ (101720) + (317.61)T dT + 5.88 * 107) + ṁwater x ( ∫ (276370) +
298.15 298.15

(-2090.1)T + (8.125)T2 + (-0.014116)T3 + (9.37 x 10-6)T4 dT +12.53 * 107)


=(33279641.45+ 5.88 * 107)* 0.00187 + (13609670.03+12.53 * 107)
* 0.001908
= 437228.58 J/s
PRODUCTION OF ANISOLE 50

Bottom product enthalpy change:

Q11 = Σ ṁCp(∆T)

475.15
= ṁanisole ∫ (150940) + (93.455)T + (0.23602)T2 dT +
298.15
475.15
ṁm-cresol x ∫ (-246700) + (3256.8)T + (-7.4202)T2 + (0.0060467)T3 ,dT+
298.15
475.15
ṁo-cresol x ∫ (259980) + (-1112.3)T + (4.9427)T2 + (-0.0054367)T3 dT+
298.15
475.15
ṁp-cresol x ∫ (-185150) + (3148)T + (-8.0367)T2 + (0.007254)T3 dT+
298.15
475.15
ṁmethanol x ∫ (105800) + (-362.23)T + (0.9379)T2 dT+
298.15
475.15
ṁphenol x ∫ (101720) + (317.61)T dT+
298.15
475.15
ṁwater x ∫ (276370) + (-2090.1)T + (8.125)T2 + (-0.014116)T3 + (9.37 x 10-6)T4 dT+
298.15
475.15
ṁxylenol x ∫ (15130.7) + (589.228)T + (0.39182)T2 dT+
298.15
475.15
ṁtoluene x ∫ (140140) + (-152.3)T + (0.695) T2 dT
298.15

=39466598.97 x 0.000003+ 44549932.12 x 0.56775 x 0.0001 +44429447.64 x


0.56775 x 0.0001 + 44399404.84 x 0.56775 x 0.0001 +19187999.32 x 0.000278
+39740731.45 x 0.00002 + 13609670.03 x 0.00000189 + 53552242.75 x 0.00009323 +
33093502.54 x 0.000002
= 18904.643 J/s
PRODUCTION OF ANISOLE 51

6.2.8 Phenol Column

Top product enthalpy change:


Q12 = Σ ṁ(Cp(∆T)+λ)
338.15 338.15
= ṁphenol x ( ∫ (101720) + (317.61)T dT +λ)+ ṁwater x( ∫ (276370) + (-2090.1)T
298.15 298.15
338.15
+ (8.125)T2 + (-0.014116)T3 + (9.37 x 10-6)T4 dT+λ) + ṁtoluene x( ∫ (140140) + (-152.3)T +
298.15

(0.695) T2 dT+λ)
= 0.00002 * (8110704.86+5.88*107) + 0.001908 * (3011224.898+12.53*107) +
0.00189 * (6485036.812+3.73*107)
= 328909.75 J/s
Bottom product enthalpy change: (Reboiler duty)
Q13 = Σ ṁCp(∆T)
455.15
= ṁphenol x ∫ (101720) + (317.61)T dT
298.15

= 0.00185 x 34751605.62
PRODUCTION OF ANISOLE 52

= 64290.4704 J/s
PRODUCTION OF ANISOLE 53

Chapter 7
Design of the equipment

7.1. Design of Tubular Catalytic Packed Bed Reactor

The alkylation reaction occurs at 320oC in gas phase and the catalyst selected viz., NaX
zeolite is a solid catalyst available as pellets. Hence a tubular reactor with catalytic packed
bed is selected as an appropriate reactor design for the process.

7.1.1 Reactor specification design

1. Rate of the reaction


The Rate of the alkylation process is given by

-r = K [C6H5OH].[CH3OH]
Where,
K = 0.00732 [From ISSN 0965-5441, Petroleum Chemistry, 2008,
Vol. 48, No. 5, pp. 389–392. ©Pleiades Publishing, Ltd., 2008.]

CA = CAo (1-x) / (1 + εx)


CB = CBo ((CBo/CAo)-(b/a)xo)

Overall reaction:
Phenol + 7/5 Methanol ----------→ ⅕ Anisole + ⅕ Cresol + ⅕ Xylenol + 7/5 Water
aA + bB ---------→ cC + dD + eE + fF

𝛿 = ((c/a)+(d/a)+(e/a)+(f/a))-((a/a)+(b/a))
=⅕ + ⅕ + ⅕ + 7/5 - 7/5 -1
= -⅖
ε = yA (-⅖)
PRODUCTION OF ANISOLE 54

yA= (-1/10)

ε = (-1/25)

2. Volume of the reactor:

Volume of reactants:
PV=nRT (ideal gas law)
VReactants= nRT/P
= (0.1032*1000*8.314*583.15)/(1.013*105)
= 5.0238 m3

CA= FAo(1-xA)/vo(1+εxA)

Concentration of phenol:
Cph = 3.778(1-x)/5.023(1-(1/25)x)
= 0.752(1-x)/(1-0.04x)

Concentration of methanol:
Cmeth = 99.869(1-x)/5.0238(1-0.04x)
= 19.879(1-x)/(1-0.04x)

Rate of the reaction:


r = K [C6H5OH].[CH3OH] [ K=0.0732 from literature]
= 0.00732 * 19.879 * 0.752 * (1-x)2/(1-0.04x)2

Weight of catalyst:
xA
W/FAo= ∫ dxA/-rA
0
0.5
3.778 (1−0.04x) 2
W = 0.073 *14.98
∫( (1−x)
)
0

= 36.103 kg
PRODUCTION OF ANISOLE 55

Volume of catalyst:
Density of NaX zeolites = 2300 kg/m3

∴ The Volume of catalyst required = 36.103/2300


= 0.015693 m3
Catalyst dimensions:
Pellet diameter = 3mm
Voidage = 55-60%

Assuming voidage be 60%,


⍴ = 2300 kg/m3

Volume of the reactor = VB


Volume of the catalyst = VP

Voidage = 0.6
(VB-VP)/VB = 0.6
1-(VP/VB) = 0.6

(VP/VB)= 0.4
( VB ) = 0.015693/0.4
= 0.039875 m3

∴ The volume of the reactor necessary = 0.039875 m3.

7.1.2. Mechanical Design of Reactor

Dimensions of the Reactor:


Diameter of tube = 1 in = 2.54 x 10-2 m
Length of tube = 16 ft = 4.8768 m
PRODUCTION OF ANISOLE 56

Volume of tube = (π/4)*(2.54 x 10-2)2*(4.8768)


= 2.46985 * 10-3 m3
No. of tubes = (0.059875)/(2.4698*10-3)
= 15.802 = 16 tubes required.

Pitch (square) = 1.25 * OD = 1.25 * 2.54 *10-2 = 0.03175


For square pitch, k1=0.215, n1=2.207
DB = Do*(Nt/k1)1/n1
= 2.54*10-2*(16/0.215)1/(2..207)
= 0.179019

From bundle diameter vs type of head(split ring floating head) graph along fixed tube,
Baffle clearance = 27.4 mm
DS = Shell diameter
DB = Baffle diameter

DS-DB = 27.4 mm
DS = 0.17919+0.0274 m

DS = 0.206419 m
PRODUCTION OF ANISOLE 57

Fig. 7.1. Equipment design drawing of reactor


PRODUCTION OF ANISOLE 58

7.2. Design of Shell and Tube Heat Exchanger


The design for the heat exchanger cooling the product mix being sent into methanol column
for distillation is presented below:

Tube side fluid=products from reactor (Hot fluid)


Shell side fluid= water (cold fluid)

For Co-current flow


T1= entering temperature of hot fluid (583.15K)
T2= leaving temperature of hot fluid (342.382K)
t1= entering temperature of cold fluid (298.15K)
t2= leaving temperature of cold fluid (316.991K)

Use Shell and Tube Heat Exchanger with Triangular Pitch (Counter Current)

ΔT1 = T1 - t2 = 583.15-298.15 = 285 K


ΔT2 = T2 – t1 = 342.387-316.991 K
ΔTLMTD = 107.4063

Q=Heat duty of heat exchanger.


U=overall heat transfer coefficient of heat exchanger.
A= Heat transfer area

Q = U * A * ΔTLMTD * FT = mh * Cph * (T1 – T2)


= mc * Cpc * (t2 – t1)
Q = Hout – Hin
= 1.203*106 J/sec
= 0.08564

R = = 12.7701
PRODUCTION OF ANISOLE 59

From graph R Vs S graph


FT = 0.989

∆Tm = ∆TLMTD * 0.989


= 0.989 * 107.406
= 106.2248

Mean temperature of fluids:


Th = 462.7682K
Tc = = 307.5707K

Let us assume U = 450 W / m2 -K


Q = U * A * ∆TLMTD *FT
A = 25.68m2

Let us use pipes of nominal bore= 0.5 inch (DN 15mm)


d0 = 1 in
di = 0.834 in
Length (L) = 16 ft
Surface area of tube = π * d0* L

Total Number of tubes = 65.8175 tubes


Nearest tube count = 64 tubes

Let us use shell and tube pass triangular pitch


Area of cross-section
Area of one tube cross section = 3.52443*10-4 m2
Number of tubes passes=2
Number of tubes/pass=64/2=32

Tube side velocity = (tube side mass flow rate)/(density*area)


PRODUCTION OF ANISOLE 60

Tube side flow rate (m) = ρ v A


v = 3.504/(823.666*0.01128)=0.3771m/sec

From empirical co-relation


hi = (4200*(1.35+0.02*Tc)*v^0.8)/(di^0.2)
hi =(4200*(1.35+0.02*25*190)*0.3771^0.8)/(21.18^0.2)
hi = 1021.24 W/m2-0c
Db= Bundle diameter
Db = d0* (Nt/K)1/n = 2.54 * 10-2 * (64/0.249)1/2.207

For triangular pitch , two tube passes K=0.249,n=2.207


Db = 0.313 m
Pt =tube pitch
Pt = 1.25 * 2.541.203*106 = 0.026m

Let us use split ring floating head


From graph of bundle diameter vs type of head we get bundle clearance
PRODUCTION OF ANISOLE 61

Fig.7.2. Shell side heat transfer factor vs. Reynolds number

Bundle clearance = 54mm


Ds = Db + clearance
Ds =0.3113+0.054=0.3653m

Baffle spacing (BS) =0.3*Ds=0.3*0.3653=0.10959m


Area for cross flow (As) = = 0.008m2
Equivalent diameter (de)= = 1.10*0.02542*(1.252-0.917 ) = 0.01803m

Mass velocity on shell side (Gs) = mass flow rate (Ws) / area of cross flow (As)
Gs = 24.8489 / 0.01803 = 378.197 Kg/m2-sec
Linear velocity on shell side (us) = Gs/ρ = 378.0197 /995 =0.385m/sec

Re = Gs* de /μ = (385 * 0.01803) / (0.89 * 10-3) = 7799.4


Pr = Cp * μ / K = (4.2 * 1000 * 0.89 * 10-3 / 0.59) = 6.33
PRODUCTION OF ANISOLE 62

Let us assume baffle cut of 25%


From graph of Re vs % baffle cut, we get jf = 3.8*10-3
j Re0.8 * Pr0.33 * (μ/ μw)0.14
= f*

Where (μ/ μw)0.14 = Seider Tate viscosity correction factor = 1 (very less temperature change)
h0 = (3.8 * 10-3 * 77980.8 * 6.330.33 * 0.59) / (18.03 * 10-3) = 827.344 W/m2-0C
hi0 = hi * (di/d0) = (1021.24 * 0.834) = 851.71 W/m2-0C
U = (h0 * hio )/ (ho + hio) =439.28 W/m2-0C

PRESSURE DROP CALCULATIONS


Shell side calculation
ΔPs = (8*jf*Ds*L*ρ*u2) / (2*de*Bs)
ΔPs = (8*3.8*10-3*0.3653*2.5*995*0.37712)/(18.03*10-3*0.10959*2) =3970.614 N/m2 =0.576psi
Tube side calculation
Average viscosity of tube side fluids can be find by formula
μave1/ 3=∑xi* μi1/3
μave = 5.78*10-4 Nsec/m2
ρave = 823.6606 Kg/m3
Tube side Re= (ρave*v*di/ μave) = (823.66*0.3771*21.18*10-3/5.78*10-4) =11381.581
From graph between Re vs L/D ratio jh is found to be = 4*10-3
PRODUCTION OF ANISOLE 63

Fig.7.3. Tube side heat transfer factor vs. Reynolds number

ΔPt = Np*((8*jh*(L/di)* (μ/ μw)-m +2.5)*ρ*u2)/2


For L/di = 192, Re=11381 we get jh = 4*10-3 and ( μ/ μw)=1
ΔPt = 2*((8*4*10-3*192+2.5)*823.15*0.31142)/2 = 6890.15 N/m2 = 0.99psi

Calculation of dirt factor


Rd = (Uc –Ua)/(Uc *Ua)
Where
Uc = calculated overall heat transfer coefficient.
Ua = assumed overall heat transfer coefficient.
Rd = (450-439.18)/(450*439.18) = 5.47*10-4 m2-0C/W

HEAT EXCHANGER SUMMARY


Overall heat transfer coefficient =439.28 W/m2-0C
Area of heat transfer = 25.68 m2
Tube side heat transfer coefficient =1021.24 W/m2-0c
Shell side heat transfer coefficient = 827.344 W/m2-0C
PRODUCTION OF ANISOLE 64

Tube side pressure drop =0.576psi


Shell side pressure drop =0.99psi
Dirt factor = 5.47*10-4 m2-0C/W

Fig. 7.4. Equipment design drawing of heat exchanger


PRODUCTION OF ANISOLE 65
PRODUCTION OF ANISOLE 66

7.3. Design of Distillation Column (Methanol Column)

7.3.1 Preliminary calculations

Light key component: methanol


Basis: One-hour operation.

Calculation of the Vapor pressure by Antoine Equation. Antoine equation is given by


log10P=A-B/(T+C) where temperature is in Kelvin and pressure is in bar.

S.No. Compounds
A B C

1 Water 3.559 643.74 -198.4

Methanol 5.15853 1569.613 -34.846


2

phenol 4.25947 1516.072 -99


3

Anisole 7.32615 1674.45 -80


4

Cresols 7.26723 1670 -94


5

xylenols 7.45107 1874 -64


6
Table.7.1. Antoine Parameters

Components Vapor pressure Vapor pressure Relative Relative


S.No. at at 353K(bottom volatility at volatility at
333K(distillate temperature) in 333K 353K
temperature) bar αij= αij=
Pi/PMethanol Pi/Pmethanol
In bar

1. Water 0.058 0.248 0.074 0.044

2. Methanol 0.78 1.679 1 1

3. Phenol 0.006 0.02 0.008 0.012


PRODUCTION OF ANISOLE 67

4. Anisole 5.102 15.582 6.541 9.281

5. Cresols 1.905 6.594 2.442 3.927

6. Xylenols 3.052 9.261 3.913 5.516

Table.7.2.Vapor pressure of the components at bottom and residue temperature

S.No. Components αavg= (α 375.15K *α436.15K)0.5

1. Water 0.055

2. Methanol 1

3. phenol 0.003

4. Anisole 7.791

5. Cresols 3.097

6. xylenols 4.646

Table.7.3. Average Relative Volatility of Components

Now,
Minimum number of stages required for the given separation are given by Fenske equation
Fenske equation:

log [( 0.997 0.7759


0.037 * 0.00293
)]
N min = log (10.414)
PRODUCTION OF ANISOLE 68

Nmin = 3.786 ≈4
∝lk/hk = 10.414

Minimum reflux ratio is given by Underwood equation,


Underwood equations:

; ∝lk≤≤∝hk

Where = roots of

After solving this equation, we get


θ = 1.1857

Rmin=0.109;
Let R=2Rmin =0.218

Gilliland correlation:

N −N min
N +1 = 0.5586

N = 29.387 ≈30

NR+NS+1 =30
PRODUCTION OF ANISOLE 69

N 14.562*0.166*0.0372
log N R = 0.206log( 54.159 0.793 0.002932
)
S * *
NR
NS = 1.5689

NR = 1.5689 * NS

NR+ NS = 29

NS =17

NR = 12

7.3.2 Optimization of methanol column specifications using ASPEN Plus

RADFAC model is selected for the methanol recovery column.The Flow rates from
Table 3, are used as input feed to the column which is operated at atmospheric conditions. The
variables that can be optimized are reflux ratio, number of feed stages and feed tray
location.The Distillate rate is set as the inlet flow rate of methanol. A total condenser and a
kettle reboiler is used in this process. Optimization is done using Model Analysis tools in
Aspen Plus. The procedure for optimization is as follows:

Reflux Ratio Optimization:

The Number of Stages including condenser and reboiler is kept fixed at any value say 15.
The feed stage is varied keeping the number of stages fixed.Now for each different ratio of
number of stages to feed stage a series of reflux ratio starting from 0.1 is considered. The
process is run and the graph is plotted between reflux ratio and mole fraction of methanol as
shown in Figure 7.5. An optimum reflux ratio of 1.9 is identified.
PRODUCTION OF ANISOLE 70

Fig.7.5. Reflux Ratio vs Mole Fraction of Methanol in the top product.

Feed Tray Location Optimization:

The Reflux ratio is kept fixed at 1.9 and the number of stages is kept fixed at 15.Now the
position of the feed tray is varied and its effect on the mole fraction of methanol is studied and
graph is plotted as shown in figure 7.6. The Number of stages to feed stage ratio of 15:8 is
identified as the optimum ratio.

Fig.7.6. Feed Stage Vs Mole Fraction of Methanol in the top product.


PRODUCTION OF ANISOLE 71

Number of Trays Optimization:

The ratio obtained above is kept constant and the number of trays is varied and its effect on
mole fraction of methanol is studied and graph is plotted as shown in figure 7.7. The optimum
number of trays is obtained as 30. The optimized design parameter and the results are shown
in Table 7.4.

Fig.7.7. Number of Stages Vs Mole fraction of Methanol.

The optimum values obtained for methanol column are listed in table 7.4.

Value Units
Flowrate of Feed Stream 0.1020600 Kmol/sec
Temperature 342.387 K
Pressure 1 Atm
Number of Stages 30 -
Feed Stage 18 -
Operating Pressure 1 Atm
Reflux Ratio 1.9 -
PRODUCTION OF ANISOLE 72

Methanol Purity 99.99985 Wt%


Distillate Rate 0.0963172 Kmol/sec
Reboiler Duty 6637.822 Kw
Condenser Duty -9818.596 Kw
Table.7.4. Optimum Design Parameters and results of Methanol Column.

7.3.3. Design of Enriching Section

Tray Hydraulics:

The design of a sieve plate tower is described below. The equations and correlations are
borrowed from the 6th and 7th editions of Perry’s Chemical Engineers’ Handbook.

1. Tray Spacing, (ts) :

Let ts = 18” = 457 mm. (range 0.15 – 1.0 m).

2. Hole Diameter, (dh):

Let dh = 5 mm. (range 2.5 – 12 mm).

3. Hole Pitch (lp):

Let lp = 3* dh (range 2.5 to 4.0 times dh).

i.e., lp = 3*5 = 15 mm.

4. Tray thickness (tT):

Let tT = 0.6* dh (range 0.4 to 0.7 times dh).

i.e., tT = 0.6*5 = 3 mm.

5. Ratio of hole area to perforated area (Ah/Ap):

Now, for a triangular pitch, we know that,

Ratio of hole area to perforated area (Ah/Ap) = ½ (π/4*dh2)/ [(√3/4) *lp2]

i.e., (Ah/Ap) = 0.90* (dh/lp)2

i.e., (Ah/Ap) = 0.90* (5/15)2


PRODUCTION OF ANISOLE 73

i.e., (Ah/Ap) = 0.1

Thus,

(Ah/Ap) = 0.1

6. Plate Diameter (Dc):

The plate diameter is calculated based on entrainment flooding considerations

L/G {ρg/ρl} 0.5 = 0.00662 ---------- (maximum value)


Now for,
L/G {ρg/ρl} 0.5 = 0.00662 and for a tray spacing of 457mm.

We have,

FLG = L/G( ρ g/ ρ l)0.5

Csb,f = 0.0105+8.127*10-4(TS)0.755exp(-1.463 FLG0.842) where tray spacing is in mm.

Flooding parameter, Csb, flood = 0.0972 m/s

Now,

Unf= Csb, flood * (σ / 20) 0.2 [(ρl - ρg) /ρg]0.5 ---- {eqn. 18.2, page 18.6, 6th edition Perry.}

Unf= gas velocity through the net area at flood, m/s(ft/s)


Csb, flood = capacity parameter, m/s (ft/s, as in fig.18.10)
σ = liquid surface tension, mN/m(dyne/cm.)
ρl = liquid density, kg/m3(lb/ft3)
ρg= gas density, kg/m3(lb/ft3)
Now, we have,
σ = 22.3 dyne/cm.
ρl=792kg/m3.
ρg= 1.11 kg/m3

Unf= 0.0972 * (22.3/20)0.2[(792-1.11)/1.11]0.5

i.e.,Unf= 2.6395m/s.
PRODUCTION OF ANISOLE 74

Let actual velocity

Un=0.8*Unf (80-85% of Unf)

Un=2.12511 m/s

It is desired to design with volumetric flow rate maximum (therefore, actual is less than the
maximum).

Volumetric flow rate of Vapor at the bottom of the Enriching Section= qo

= 0.3175 m3/s
Thus,
Net area available for gas flow (An)

Net area = (Column cross sectional area) - (Down comer area.)

An = Ac - Ad

Thus,

Net Active area, An = qo/ Un = 0.3175/ 2.1251 = 0.1494 m2.

Let Lw / Dc = 0.77 (range 0.6 to 0.85 times Dc ).

Where, Lw = weir length, m

Dc = Column diameter, m

Now,

θc = 2*sin-1(Lw / Dc) = 2*sin-1 (0.77) = 100.70

Now,

Ac=(π /4)*Dc2= 0.785*Dc2 , m2

Ad = [(π/4) * Dc2 * (θc/3600)] - [(Lw/2) * (Dc/2) *cos (θc/2)]

i.e., Ad = [0.785*Dc2 *(100.70/3600)]-[(1/4)* (Lw / Dc) * Dc2 * cos(100.70)]

i.e., Ad = (0.2196* Dc2) - (0.1288* Dc2)

i.e., Ad = 0.0968*Dc2, m2
PRODUCTION OF ANISOLE 75

Since An = Ac -Ad

0.1494 = (0.785*Dc2) - (0.0968* Dc2)

i.e., 0.6882* Dc2 = 0.690

Dc = 0.4659 m

Since Lw / Dc = 0.77,

Lw = 0.77* Dc = 0.77*0.4659 = 0.3587 m.

Therefore, Lw = 0.3587 m.

Now,

Ac = 0.785*0.4689*0.4689 = 0.1703m2

Ad = 0.0968*Dc2 = 0.0968*0.2170 = 0.021 m2

Aa = Ac –2* Ad

i.e., Aa = 0.1703- 2*0.021

Aa= 0.12827 m2

7. Perforated plate area (Ap):

Now,

Lw / Dc = 0.3587/ 0.4659 = 0.7699

θc = 100.73 0

α = 180 0- θc

⇒ α = 79.27 0

Now,

Acz = 2* Lw* (thickness of distribution)

Where, Acz = area of calming zone, m2 (5 to 20% of Ac )

Acz = 2*0.3587* (30×10-3) = 0.021522 m2 -------- (which is 6.76% of Ac)


PRODUCTION OF ANISOLE 76

Also,

Awz= 2*{(π/4)*Dc2*(θc/3600)- (π/4)*(Dc-30*10-3)2*(θc/3600)}

Where, Awz = area of waste periphery, m2 (range 2 to 5% of Ac)

i.e., Awz = 2*{(π/4)*0.46592*(100.730/3600)- (π/4)*(0.4659-30*10-3)2*(100.730/3600)}

i.e., Awz = 0.01188 m2 --------- (which is 3.8% of Ac)

Now,

Ap = Ac - (2*Ad) - Acz - Awz

i.e., Ap = 0.1703- (2*0.021) - 0.021522- 0.01188

Thus, Ap = 0.094898 m2.

8. Total Hole Area (Ah):

Since,

Ah / Ap = 0.1

Ah = 0.1* Ap

i.e., Ah = 0.1*0.094898

Ah = 0.0094898 m2

Thus, Total Hole Area = 0.0094898 m2

Now we know that,

Ah = nh*(π/4)*dh2

Where, nh = number of holes.

nh = (4*Ah)/ (π*dh2) =483.311(Approx)

Therefore, Number of holes = 484


PRODUCTION OF ANISOLE 77

9. Weir Height (hw):

Let hw = 50mm.

10. Weeping Check

The static pressure below the tray should be capable enough to hold the liquid above the tray
so that no liquid sweeps through the holes. All the pressure drops calculated in this section
are represented as mm head of liquid on the plate. This serves as a common basis for
evaluating the pressure drops.

Notations used and their units:

hd= Pressure drop through the dry plate, mm of liquid on the plate

uh = Vapor velocity based on the hole area,m/s


how= Height of liquid over weir, mm of liquid on the plate
hσ = Pressure drop due to bubble formation, mm of liquid
hds= Dynamic seal of liquid, mm of liquid
hl= Pressure drop due to foaming, mm of liquid

hf= Pressure drop due to foaming, actual, mm of liquid Df = Average flow length of the
liquid,m
Rh = Hydraulic radius of liquid flow,m
uf = Velocity of foam,m/s
(NRe) = Reynolds number of flow
f = Friction factor
hhg= Hydraulic gradient, mm of liquid

hda= Loss under down comer apron, mm of liquid Ads =


Area under the down comer apron,m2
c = Down comer clearance, m

hdc= Down comer backup, mm of liquid

Calculations:
PRODUCTION OF ANISOLE 78

Head loss through dry hole

hd= head loss across the dry hole

hd= k1+ [k2* (ρg/ρl) *Uh2] --------- (eqn. 18.6, page 18.9, 6th edition Perry)

Where, Uh=gas velocity through hole area k1, k2 are constants


For sieve plates,

k1 = 0 and

k2= 50.8 /(Cv)2

Where, Cv=discharge coefficient, taken from fig 18.14, page 18.9 6th edition Perry.

Now,
(Ah/Aa) = 0.011803/ 0.12827 =0.07398

Also, tT/dh= 3/5 =0.60

Thus for (Ah/Aa) = 0.07398 and tT/dh=0.60

We have from fig. edition 6th 18.14, page 18.9

Cv =0.72
k2 = 50.8 / 0.722 =97.993

Volumetric flow rate of vapor at top of enriching section

qt = 0.3023m3/s ----(minimum at top)

Volumetric flow rate of Vapor at the bottom of the Enriching Section


qo = 0.3175m3/s. ---- (maximum at bottom)

Velocity through the hole area (Uh):


Now,

Velocity through the hole area at the top = Uh, top = qt/Ah

= 0.3023/0.0094898= 31.855 m/s


PRODUCTION OF ANISOLE 79

Also, Velocity through the hole area at the bottom= Uh, bottom =
qo/Ah

= 0.3175/0.0094898 = 33.4569m/s

Now,

Also,
hd,top = k2[ρg/ρl] (Uh,top)2
= 97.993∗(1.11/792)∗31.8552
hd, top = 139.363 mm clear liquid. -------- (minimum at top)
hd, bottom = k2[ρg/ρl] (Uh,bottom)2

= 97.993*(0.59499/918.52)*49.1232
hd, bottom = 153.73 mm clear liquid ----- (maximum at bottom)

Head loss due to bubble formation


hσ= 409 [σ / ( ρL∗dh)]
where,
σ =Surface tension

dh=Hole diameter, mm

ρl= density of liquid in the section, kg/m3=918.208kg/m3

hσ= 409 [22.3/(792*5)]

hσ= 2.2945 mm clear liquid

Height of liquid crest ones weir

how= 664*Fw[(q/Lw)2/3]

q = liquid flow rate at top,m3/s

=0.003880 m3/min
PRODUCTION OF ANISOLE 80

q=1.0251gal/min.

Lw = weir length = 0.3587m = 1.17683ft


Now,

q’/Lw2.5 = 1.0251/ (1.17683)2.5 = 0.682310

Now for q’/Lw2.5 = 0.682310 and Lw /Dc =0.77

We have from fig.18.16, page 18.11, 6th edition Perry

Fw= correction factor =1.02

Thus, how = 1.02∗664∗ [0.3702/60*0.3587] 2/3

how = 2.031 mm clear liquid.

Now,

(hd + hσ) = 153.73+2.2945 = 156.1245 mm ------ Design value

(hw + how) = 50 + 2.031 = 52.031 mm

For, Ah/Aa = 0.0739 and (hw + how) = 52.031 mm

The minimum value of (hd + hσ) required is calculated from a graph given in Perry,

plotted against Ah/Aa.

i.e., we have from fig. 18.11, page 18.7, 6th edition Perry

(hd + hσ)min = 16.0 mm ------- Theoretical value.

The minimum value as found is 16.0 mm.

Since the design value is greater than the minimum value, there is no problem of weeping.

Downcomer Flooding:

hds =hw + how + (hhg /2) ------- (eqn 18.10, page 18.10, 6th edition Perry)

Where,
PRODUCTION OF ANISOLE 81

hw = weir height, mm

hds = static slot seal (weir height minus height of top of slot above plate floor,

height equivalent clear liquid, mm)

how = height of crest over weir, equivalent clear liquid, mm

hhg = hydraulic gradient across the plate, height of equivalent clear liquid, mm.

Hydraulic gradient, hhg

Let hhg = 0.5 mm.

hds = hw + how + hhg/2

= 50 + 2.301 + 0.5/2 = 52.281 mm.

Now, Fga = Ua ∗ρg0.5

Where Fga = gas-phase kinetic energy factor,

Ua = superficial gas velocity, m/s (ft/s),

ρg = gas density, kg/m3 (lb/ft3)

Here Ua is calculated at the bottom of the section.

Thus, Ua = (Gb/ρg)/ Aa = 0.3175/0.12827= 2.47524 m/s

Thus, Ua = 8.1208 ft/s

ρg = 0.06932 lb/ft3

Therefore, Fga = 8.1208∗(0.06932) 0.5

Fga = 2.1382

Now for Fga = 2.1382, we have from fig. 18.15, page 18.10 6th edition Perry

Aeration factor = β = 0.63

Relative Froth Density = φt = 0.21

Now hl’= β∗hds ---- (eqn. 18.8, page 18.10, 6th edition Perry)
PRODUCTION OF ANISOLE 82

Where, hl’= pressure drop through the aerated mass over and around the disperser,

mm liquid,

hl’= 0.63∗52.281= 33.094 mm.

Now,

hf = hl’/φt ------- (eqn. 18.9, page 18.10, 6th edition Perry)

hf = 33.094/ 0.21 = 157.59 mm.

Average width of liquid flow path, Df = (Dc + Lw)/2

= (0.4659 + 0.3936)/2 = 0.42975 m.

Hydraulic radius of aerated mass Rh = hf * Df /(2*hf + 1000*Df) (from eq. 18.23, page

18.12 6th edition Perry)

Rh = 157.59*0.42975/(2*157.59 + 1000*0.42975)

= 0.0909 m.

Velocity of aerated mass, Uf = 1000*q/ (hl’ * Df )

Volumetric flow rate (liquid at bottom), q = 9.7701*10-5 m3/s.

Uf = 1000* 9.7701*10-5 / (33.094* 0.42975)

= 0.006869 m/s.

Reynolds modulus NRe = Rh * Uf * ρl / μliq

= 0.0909 * 0.006869 * 792 /(4.86 * 10-4)

= 945.090

hhg = 1000* f* Uf2 *Lf/(g * Rh)

f = 0.73 for hw = 1.97” and NRe = 792.461

Lf = 2 * Dc/2 cos(θc/ 2) = 0.8325 m

hhg = 1000* 0.73 *0.0068692*0.8325/(9.81* 0.0909)


PRODUCTION OF ANISOLE 83

= 0.03862 mm.

Head loss over downcomer apron:

hda = 165.2 {q/ Ada}2 ----- (eqn. 18.19, page 18.10, 6th edition Perry)

Where, hda = head loss under the downcomer apron, as millimeters of liquid,

q = liquid flow rate calculated at the bottom of section, m3/s

And Ada = minimum area of flow under the downcomer apron, m2

Now,

q = 9.77∗10-5 m3/s

Take clearance, C = 1” = 25.4 mm

hap = hds - C = 52.281 - 25.4 = 26.881 mm

Ada = Lw * hap = 0.4659∗26.881∗10-3 = 0.0125 m2

hda = 165.2[(9.77* 10-5)/ (0.0106)] 2

hda = 0.01403 mm

Now,

ht = hd + hl`

Here hd and hl’ are calculated at bottom of the enriching section.

Now we have,

hd, bottom = 153.17 mm

hl, bottom = 33.094 mm

ht = hd + hl`

= 153.17+33.094

ht = 186.264 mm
PRODUCTION OF ANISOLE 84

Downcomer Backup:

hdc = ht + hw + how + hda +hhg ---- (eqn 18.3, page 18.7, 6th edition Perry)

ht = total pressure drop across the plate (mm liquid)

= hd + hl`

hdc = height in downcomer, mm liquid,

hw = height of weir at the plate outlet, mm liquid,

how =height of crest over the weir, mm liquid,

hda = head loss due to liquid flow under the downcomer apron, mm liquid,

hhg = liquid gradient across the plate, mm liquid.

hdc = 186.264 +50 +2.031 + 0.01403 + 0.03862

hdc = 238.347 mm.

Let φdc = average relative froth density (ratio of froth density to liquid density)

=0.55

h`dc = hdc / φdc = 238.347/ 0.55

h`dc = 433.33 mm.

which is less than the tray spacing, ts= 457 mm.

Hence no flooding in the enriching section and hence the design calculations are acceptable.

7.3.4. Design of Stripping Section

Tray Hydraulics:

The design of a sieve plate tower is described below. The equations and correlations are
borrowed from the 6th and 7th editions of Perry’s Chemical Engineers’ Handbook.

1. Tray Spacing, (ts) :

Let ts = 18” = 457 mm. (range 0.15 – 1.0 m).


PRODUCTION OF ANISOLE 85

2. Hole Diameter, (dh):

Let dh = 5 mm. (range 2.5 – 12 mm).

3. Hole Pitch (lp):

Let lp = 3* dh (range 2.5 to 4.0 times dh).

i.e., lp = 3*5 = 15 mm.

4. Tray thickness (tT):

Let tT = 0.6* dh (range 0.4 to 0.7 times dh).

i.e., tT = 0.6*5 = 3 mm.

5. Ratio of hole area to perforated area (Ah/Ap):

Now, for a triangular pitch, we know that,

Ratio of hole area to perforated area (Ah/Ap) = ½ (π/4*dh2)/ [(√3/4) *lp2]

i.e., (Ah/Ap) = 0.90* (dh/lp)2

i.e., (Ah/Ap) = 0.90* (5/15)2

i.e., (Ah/Ap) = 0.1

Thus,

(Ah/Ap) = 0.1

6. Plate Diameter (Dc):

The plate diameter is calculated based on entrainment flooding considerations

L/G {ρg/ρl} 0.5 = 0.0679 ---------- (maximum value)

Csb,f = 0.0105+8.127*10-4(TS)0.755exp(-1.463 FLG0.842) where tray spacing


is in mm.

Flooding parameter, Csb, flood = 0.08165 m/s


Now,

Unf = Csb, flood * (σ / 20) 0.2 [(ρl - ρg) / ρg]0.5


PRODUCTION OF ANISOLE 86

---- {eqn. 18.2, page 18.6, 6th edition Perry.}

Where,

Unf = gas velocity through the net area at flood, m/s (ft/s)

Csb, flood = capacity parameter, m/s (ft/s, as in fig.18.10)

σ = liquid surface tension, mN/m (dyne/cm.)

ρl = liquid density, kg/m3 (lb/ft3)

ρg = gas density, kg/m3 (lb/ft3)

Now, we have,

σ = 22.149 dyne/cm.

ρl = 813kg/m3.

ρg = 1.1kg/m3.

Therefore,

Unf = 0.08165*(26.149/20)0.2*[(813-1.11)/ 1.11]0.5

i.e.,Unf = 2.32 m/s

Let,

Actual velocity, Un= 0.8*Unf

i.e., Un = 0.8∗2.32 m/s

i.e., Un = 1.86388 m/s

It is desired to design with volumetric flow rate maximum (therefore, actual is less than the
maximum).

Volumetric flow rate of Vapor at the bottom of the Stripping Section

= qo = 0.3175 m3/s.

Now,
PRODUCTION OF ANISOLE 87

Net area available for gas flow (An)

Net area = (Column cross sectional area) - (Downcomer area.)

An = Ac - Ad

Thus,

Net Active area, An = qo/ Un = 0.3175/1.86388= 0.17034 m2.

Let Lw / Dc = 0.77 (range 0.6 to 0.85 times Dc ).

Where, Lw = weir length, m

Dc = Column diameter, m

Now,

θc = 2*sin-1(Lw / Dc) = 2*sin-1 (0.77) = 100.70

Now,

Ac= (π /4)*Dc2= 0.785*Dc2 , m2

Ad = [(π/4) * Dc2 * (θc/3600)] - [(Lw/2) * (Dc/2) *cos (θc/2)]

i.e., Ad = [0.785*Dc2 *(100.70/3600)]-[(1/4)* (Lw / Dc) * Dc2 * cos(100.70)]

i.e., Ad = (0.2196* Dc2) - (0.1288* Dc2)

i.e., Ad = 0.0968*Dc2, m2

Since An = Ac -Ad

0.17034 = (0.785*Dc2) - (0.0968* Dc2)

i.e., 0.6882* Dc2 = 0.17034

Dc2 = 0.17034/ 0.6882 = 0.5353

Dc = 0.4975 m

Since Lw / Dc = 0.77,

Lw = 0.77* Dc = 0.77*0.4975= 0.3830 m.


PRODUCTION OF ANISOLE 88

Therefore, Lw = 0.3830 m.

Now,

Ac = 0.785*0.3832 = 0.11515 m2

Ad = 0.0968*Dc2 = 0.0968*0.3832= 0.02419 m2

Aa = Ac –2* Ad

i.e., Aa = 0.11515- 2*0.02419⇒ Aa= 0.06677 m2

7. Perforated plate area (Ap):

Now,

Lw / Dc = 0.383/ 0.4975 = 0.77

θc = 100.73 0

α = 180 0- θc

⇒ α = 79.27 0

Now,

Acz = 2* Lw* (thickness of distribution)

Where, Acz = area of calming zone, m2 (5 to 20% of Ac )

Acz = 2*0.383* (30×10-3) = 0.02298 m2 -------- (which is 6.76% of Ac)

Also,

Awz= 2*{(π/4)*Dc2*(θc/3600)- (π/4)*(Dc-30*10-3)2*(θc/3600)}

Where, Awz = area of waste periphery, m2 (range 2 to 5% of Ac)

i.e., Awz = 2*{(π/4)*0.49752*(100.730/3600)- (π/4)*(0.4975-30*10-3)2*(100.730/3600)}

i.e., Awz = 0.0049 m2 --------- (which is 3.8% of Ac)

Now,

Ap = Ac - (2*Ad) - Acz - Awz


PRODUCTION OF ANISOLE 89

i.e., Ap = 0.11515- (2*.02419) – 0.02298 - 0.0049

Thus, Ap = 0.03747 m2.

8. Total Hole Area (Ah):

Since,

Ah / Ap = 0.1

Ah = 0.1* Ap

i.e., Ah = 0.1*0.03747

Ah = 0.003747 m2

Thus, Total Hole Area = 0.003747 m2

Now we know that,

Ah = nh*(π/4)*dh2

Where, nh = number of holes.

nh = (4*Ah)/ (π*dh2) =191(Approx)

Therefore, Number of holes = 191.

9. Weir Height (hw):

Let hw = 50 mm.

10. Weeping Check

All the pressure drops calculated in this section are represented as mm head of

liquid on the plate. This serves as a common basis for evaluating the pressure

drops.

Notations used and their units:

hd = Pressure drop through the dry plate, mm of liquid on the plate

uh = Vapor velocity based on the hole area, m/s


PRODUCTION OF ANISOLE 90

how = Height of liquid over weir, mm of liquid on the plate

hσ = Pressure drop due to bubble formation, mm of liquid

hds= Dynamic seal of liquid, mm of liquid

hl = Pressure drop due to foaming, mm of liquid

hf = Pressure drop due to foaming, actual, mm of liquid

Df = Average flow length of the liquid, m

Rh = Hydraulic radius of liquid flow, m

uf = Velocity of foam, m/s

(NRe) = Reynolds number of flow

f = Friction factor

hhg = Hydraulic gradient, mm of liquid

hda = Loss under downcomer apron, mm of liquid

Ads = Area under the downcomer apron, m2

c = Downcomer clearance, m

hdc = Downcomer backup, mm of liquid

Calculations:

Head loss through dry hole

hd = head loss across the dry hole

hd = k1 + [k2* (ρg/ρl) *Uh2] --------- (eqn. 18.6, page 18.9, 6th edition Perry)

Where, Uh =gas velocity through hole area

k1, k2 are constants

For sieve plates,

k1 = 0 and
PRODUCTION OF ANISOLE 91

k2 = 50.8 / (Cv)2

Where, Cv=discharge coefficient, taken from fig 18.14, page 18.9 6th edition Perry.

Now,

(Ah /Aa) = 0.003747/ 0.06677 = 0.05611

Also, tT/dh = 3/5 = 0.60

Thus for (Ah/Aa) = 0.05611 and tT/dh = 0.60

We have from fig. edition 18.14, page 18.9 6th Perry.

Cv = 0.73

k2 = 50.8 / 0.732 = 95.327

Volumetric flow rate of Vapor at the top of the Stripping Section

=qt = 0.304 m3/s -------- (minimum at top)

Volumetric flow rate of Vapor at the bottom of the Stripping Section

= qo = 0.315 m3/s. ---- (maximum at bottom)

Velocity through the hole area (Uh):

Now,

Velocity through the hole area at the top = Uh, top = qt /Ah

= 0.315/0.003747= 84.1 m/s

Also, Velocity through the hole area at the bottom= Uh, bottom = qo /Ah

= 0.305/0.003747= 81.3 m/s

Now,

hd, top = k2 [ρg/ρl] (Uh,top)2

= 95.327∗ (1.11/815.) ∗81.32

hd, top = 815 mm clear liquid. -------- (minimum at top)


PRODUCTION OF ANISOLE 92

Also,

hd, bottom = k2 [ρg/ρl] (Uh, bottom)2

= 95.327(1.11/815)×24.9672

hd, bottom = 758mm clear liquid ----- (maximum at bottom)

Head Loss Due to Bubble Formation

hσ = 409 [σ / ( ρL∗dh) ]

where σ =surface tension, mN/m (dyne/cm) = 26.059dyne/cm.

dh =Hole diameter, mm

ρl = density of liquid in the section, kg/m3

= 929.167 kg/m3

hσ = 409 [22.5/(815*5)]

hσ= 2.25 mm clear liquid

Height of Liquid Crest over Weir:

how = 664∗Fw [(q/Lw)2/3]

q = liquid flow rate at top, m3/s

= 5569.49/60* (815)

= 0.114 m3/min.

Thus, q’ = 30.1156 gal/min.

Lw = weir length = 0.5633 m

Now,

q’/Lw2.5 = 30.1156/ (1.848)2.5 = 6.485

Now for q’/Lw2.5 = 6.485 and Lw /Dc =0.77

We have from fig.18.16, 6th edition Perry


PRODUCTION OF ANISOLE 93

Fw= correction factor =1.04

Thus, how = 1.04∗664∗ [0.114/60*0.5633] 2/3

how = 15.53 mm clear liquid.

Now,

(hd + hσ) = 96.745 + 2.294= 99.039 mm ------ Design value

(hw + how) = 50 + 15.53= 65.53 mm

For, Ah/Aa = 0.05611 and (hw + how) = 65.03mm

The minimum value of (hd + hσ) required is calculated from a graph given in Perry,

plotted against Ah/Aa.

i.e., we have from fig. 18.11, page 18.7, 6th edition Perry

(hd + hσ)min = 18.0 mm ------- Theoretical value.

The minimum value as found is 18.0 mm.

Since the design value is greater than the minimum value, there is no problem of weeping.

Downcomer Flooding:

hds =hw + how + (hhg /2) ------- (eqn 18.10, page 18.10, 6th edition Perry)

Where,

hw = weir height, mm

hds = static slot seal (weir height minus height of top of slot above plate floor,

height equivalent clear liquid, mm)

how = height of crest over weir, equivalent clear liquid, mm

hhg = hydraulic gradient across the plate, height of equivalent clear liquid, mm.

Hydraulic gradient, hhg

Let
PRODUCTION OF ANISOLE 94

hhg = 0.5 mm.

hds = hw + how + hhg/2

= 50 + 15.53 + 0.5/2 = 65.859 mm.

Now, Fga = Ua ∗ρg0.5

Where Fga = gas-phase kinetic energy factor,

Ua = superficial gas velocity, m/s (ft/s),

ρg = gas density, kg/m3 (lb/ft3)

Here Ua is calculated at the bottom of the section.

Thus, Ua = (Gb/ρg)/ Aa = 3439.49/(3600*1.1* 0.003747) = 2.0824 m/s

Thus, Ua = 6.831 ft/s

ρg = 1.11kg/m3 = 0.0904 lb/ft3

Therefore, Fga = 6.831∗(0.0904) 0.5

Fga = 2.053

Now for Fga = 2.053 we have from fig. 18.15, page 18.10 6th edition Perry

Aeration factor = β = 0.61

Relative Froth Density = φt = 0.22

Now hl’= β∗hds ---- (eqn. 18.8, page 18.10, 6th edition Perry)

Where, hl’= pressure drop through the aerated mass over and around the disperser,

mm liquid,

⇒ hl’= 0.61∗61.859 = 37.733 mm.

Now,

hf = hl’/φt ------- (eqn. 18.9, page 18.10, 6th edition Perry)

⇒ hf = 37.733/ 0.22 = 171.518mm.


PRODUCTION OF ANISOLE 95

Average width of liquid flow path, Df = (Dc + Lw)/2

= (0.4975 + 0.383)/2 = 0.4474 m.

Hydraulic radius of aerated mass Rh = hf * Df /(2*hf + 1000*Df) (from eq. 18.23, page

18.12 6th edition Perry)

Rh = 171.518*0.4975/(2*172.518+ 1000*0.4474)

= 0.107 m.

Velocity of aerated mass, Uf = 1000*q/ (hl’ * Df )

Volumetric flow rate (liquid at bottom), q = 6.4667*10-5 m3/s.

Uf = 1000* 6.4667*10-5/ (42* 0.64745)

= 0.0237 m/s.

Reynolds modulus NRe = Rh * Uf * ρl / μliq

= 0.107 * 0.0237 * 815 /(5.2 * 10-4)

= 3974.53

hhg = 1000* f* Uf2 *Lf/(g * Rh)

f = 0.38 for hw = 1.97” and NRe = 3974.53

Lf = 2 * Dc/2 cos(θc/ 2) = .933 m

hhg = 1000* 0.38 *0.02372*.9333/(9.81* 0.107)

= 0.891 mm.

Head loss over downcomer apron:

hda = 165.2 {q/ Ada}2 ----- (eqn. 18.19, page 18.10, 6th edition Perry)

Where, hda = head loss under the downcomer apron, as millimeters of liquid,

q = liquid flow rate calculated at the bottom of section, m3/s

and Ada = minimum area of flow under the downcomer apron, m2


PRODUCTION OF ANISOLE 96

Now,

q = 6.4667*10-5m3/s

Take clearance, C = 1” = 25.4 mm

hap = hds - C = 65.859- 25.4 = 40.459 mm

Ada = Lw * hap = 0.383∗40.45∗10-3 = 0.015492 m2

hda = 165.2[(6.4667*10-5)/ (0.02448)] 2

hda = 1.1527 mm

Now,

ht = hd + hl`

Here hd and hl’ are calculated at bottom of the stripping section.

Now we have,

ht = hd + hl`

= 96.745+42

ht = 138.745 mm

Downcomer Backup:

hdc = ht + hw + how + hda +hhg ---- (eqn 18.3, page 18.7, 6th edition Perry)

ht = total pressure drop across the plate (mm liquid)

= hd + hl`

hdc = height in downcomer, mm liquid,

hw = height of weir at the plate outlet, mm liquid,

how =height of crest over the weir, mm liquid,

hda = head loss due to liquid flow under the downcomer apron, mm liquid,

hhg = liquid gradient across the plate, mm liquid.


PRODUCTION OF ANISOLE 97

hdc = 138.745 +50 +15.53 + 1.15 + 1.23

hdc = 206.655 mm.

Let φdc = average relative froth density (ratio of froth density to liquid density)

=0.5

h`dc = hdc / φdc = 206.655/ 0.5

h`dc = 413.31 mm.

which is less than the tray spacing, ts= 457 mm.

Hence no flooding in the enriching section and hence the design calculations are acceptable.

Formulas used in calculation of properties:

1 Viscosity:

(i). Average Liquid Viscosity:

(μliq)1/3 = [x1× (μ1)1/3] + [x2 × (μ2)1/3]

2 Diffusivities:

(i). Liquid Phase Diffusivity:

For the case of Organic solutes diffusing in Organic solvents

DAB = (1.173*10-13*(Ɵ*M)0.5*T)/[ ƞB × (VA)0.6] –(Richardson – coulson vol.6)

Where,

Ɵ=constant

M = molecular weight.

T = absolute temperature, 0K,

ƞB = viscosity of solvent B, cP,

VA =molar volume of solute A at its normal boiling temperature, cm3/g-mol.


PRODUCTION OF ANISOLE 98

DAB =mutual diffusivity coefficient of solute A at very low concentration in

solvent B, cm2/s

(ii). Gas Phase Diffusivity:

DAB = 1.013*10-7×T1.75× [(MA+MB)/ (MA×MB)]1/2}/{P×[(∑VA)1/3+ (∑VB)1/3]2

------ (Richardson – coulson vol.6 ).

Where P = Pressure in atmospheres,

T = Temperature in 0K

DAB = Diffusivity, cm2/s

∑VA and ∑VB = summation of atomic diffusion volumes for

Components A and B respectively.

MA and MB = Molecular weights of components A and B respectively.

3. Surface Tension

σ =[Pch *(ρ1-ρg)/M]4 ×10-12 ----- (eqn. 8.23, page 293, Coulson and Richardson

vol.6)

Where,

σ =Surface tension, dyne/cm

Pch =Sugden’s Parachor,

ρ1 = liquid density, kg/m3

ρg = density of saturated vapor, kg/m3

M = Molecular weight

σ , ρ1, ρg are evaluated at system temperature.

σ mix =∑ (xi*σi) where i=1,2,3,……n.

4. Liquid density:
PRODUCTION OF ANISOLE 99

ρ = Pc/ ( R * Tc * Zc[ 1 + ( 1 – Tr)2/7] ) (Coulson and Richardson vol.6)

Where,

Pc = critical pressure = M/(0.34 + (∑ ∆P)2 )

M = Molecular weight.

Tc = Critical temperature = Tb / (0.567 + ∑ ∆T – (∑ ∆T)2 )

Tb = Normal boiling temperature 0K.

Zc = Pc * Vc / (R * Tc)

Vc = critical volume

R = universal gas constant.

5. Gas density:

ρ = P * M /(R * T)

P = pressure

M = Molecular weight.

R = universal gas constant.

T = temperature

2. Overall Efficiency (EOG):

EOG=50.3[αlk/hk *µavg]-0.226 Where α is the relative volatility between the key components and
µavg is the average viscosity of feed in cP.

=50.3[10.414*0.578]-0.226 = 35.75%

Nactual =Nideal / E.O = 11 / 0.3575 = 30.76 ≈ 31

7.3.5 Summary of the Distillation Column:

A) Enriching section
PRODUCTION OF ANISOLE 100

Tray spacing = 457 mm

Column diameter = 0.4659m

Weir length = 0.3936 m

Weir height = 50 mm

Hole diameter = 5 mm

Hole pitch = 15 mm, triangular

Tray thickness = 3 mm

Number of holes = 191

Flooding % = 80%

B) Stripping section

Tray spacing = 457 mm

Column diameter = 0.4979 m

Weir length = 0.5633 m

Weir height = 50 mm

Hole diameter = 5 mm

Hole pitch = 15 mm, triangular

Tray thickness = 3 mm

Number of holes = 191

Flooding % = 80%

7.3.5 Mechanical Design of the distillation Column

a) Shell:

Diameter of the tower =Di =0.4979 m


PRODUCTION OF ANISOLE 101

Working/Operating Pressure = 1 atmosphere =1.03 kg/cm2

Design pressure = 1.1*Operating Pressure = 1.1*1.03 = 1.133 kg/cm2

Working temperature = 333 0K

Design temperature = 350K

Shell material - IS: 2002-1962 Carbon steel (specific gravity 7.7)

Permissible tensile stress (ft) = 95 MN/m2 = 950 kg/cm2

Insulation material - asbestos

Insulation thickness = 2”= 50.8 mm

Density of insulation = 2700 kg/m3

Top disengaging space = 0.3 m

Bottom separator space = 0.4 m

Weir height = 50 mm

Down comer clearance = 1” = 25.4 mm

b) Head - torispherical dished head:

Material - IS: 2002-1962 Carbon steel

Allowable tensile stress = 95 MN/m2 = 950 kg/cm2

c) Support skirt:

Height of support = 1000 mm = 1.0 m

Material - Carbon Steel

d) sieve tray type:

Number of trays = 30

Hole Diameter = 5 mm

Number of holes:
PRODUCTION OF ANISOLE 102

Enriching section = 484

Stripping section = 191

Tray spacing:

Enriching section: 18” = 457 mm

Stripping section: 18” = 457 mm

Thickness = 3 mm

e) Support for tray:

Purlins - Channels and Angles

Material - Carbon Steel

Permissible Stress = 127.5 MN/m2 =1299.7 kg/cm2

1. Shell minimum thickness:

Considering the vessel as an internal pressure vessel.

ts = ((P*Di)/ ((2*ft*J)- P)) + C

where ts = thickness of shell, mm

P = design pressure, kg/cm2

Di = diameter of shell, mm

ft = permissible/allowable tensile stress, kg/cm2

C = Corrosion allowance, mm

J = Joint factor

Considering double welded butt joint with backing strip

J= 85% = 0.85

Thus, ts = ((1.133*497.5)/ ((2*950*0.85)- 1.133)) + 3 = 3.3492 mm


PRODUCTION OF ANISOLE 103

Taking the thickness of the shell = 6 mm (standard)

2. Head Design- Shallow dished and Torispherical head:

Thickness of head = th = (P*Rc*W)/ (2*f*J)

P =internal design pressure, kg/cm2

Rc = crown radius = diameter of shell, mm

W= stress intensification factor or stress concentration factor for torispherical

head,

W= ¼ * (3 + (Rc/Rk)0.5)

Rk = knuckle radius, which is at least 6% of crown radius, mm

Now, Rc = 497.5mm

Rk = 6% of Rc = 0.06*497.5 = 29.85 mm

W= ¼ * (3 + (Rc/Rk)0.5) = ¼ * (3 + (497.5/29.5)0.5) = 0.943649 mm

th = (1.133*731.6*1.7706)/ (2*400*0.85) = 2.1583 mm

Including corrosion allowance take the thickness of head = 5 mm

Weight of Head:

Diameter = O.D + (O.D/24) + (2*sf) + (2*icr/3) --- (eqn. 5.12 Brownell and Young)

Where O.D. = Outer diameter of the dish, inch

icr = inside cover radius, inch

sf = straight flange length, inch

From table 5.7 and 5.8 of Brownell and Young

sf =1”

icr = 1.25”

Also, O.D.= 19.8818”


PRODUCTION OF ANISOLE 104

Diameter = 19.8818+ (19.8818/24) + (2*1)+(10/12)

d = 23.47”

Weight of Head = ((π*d2*t)/4)*(ρ/1728)

=(( π *23.472 *0.19685)/4) * (7700/1728) = 379.19 lb

= 180.16 kg

3. Shell thickness at different heights

At a distance ‘X’m from the top of the shell the stresses are:

3.a Axial Tensile Stress due to Pressure:

fap =(P*Di)/ 4(ts -c) = 1.133*497.5/4(5- 3)= 70.4584 kgf/cm2 .

This is the same throughout the column height.

3.b Circumferential stress

2 * fap = 2*70.4584 = 140.9168 kgf/cm2

3.c Compressive stress due Dead Loads:

3.c.i Compressive stress due to Weight of shell up to a distance ‘X’ meter from top.

fds = weight of shell/cross-section of shell

=(π/4)*(Do2-Di2)*ρs*X/(π /4)* (Do2-Di2)

=weight of shell per unit height X/(π*Dm*(ts-c))

Where Do and Di are external and internal diameter of shell.

ρs = density of shell material, kg/m3

Dm = mean diameter of shell,

ts = thickness of shell,

c = corrosion allowance

Now ρs = 7700 kg/m3 =0.0077 kg/cm3


PRODUCTION OF ANISOLE 105

Fds=ρs* X = (7700*X) kg/m2 = (0.77*X) kg/cm2

The vessel contains manholes, nozzles etc., additional weight may be estimated 20% of

the weight of the shell.

fT,ds = 1.2 * .77*X = 0.924* (X) kg/cm2

3.c.ii Compressive stress due to weight of insulation at a height X meter:

fd(ins) = π *Dins* tins* ρins *X/( π *Dm* (ts - c) )

= weight of insulation per unit height (X)/( π*Dm* (ts - c))

where Dins, tins, ρins are diameter, thickness and density of insulation respectively.

Dm = (Dc+ (Dc+2ts))/2

Assuming asbestos is to be used as insulation material.

ρins = 2700 kg/m3

tins = 2” = 5.08 cm.

Dins =Dc+2ts+2tins = 49.5+ (2*0.5) + (2*5.08) = 60.84 cm.

Dm = (49.5+ (49.5+ (2*0.5)))/2 = 50 cm.

fd(ins) = π *60.84* 5.08*2700*X/( π *50* (0.5 - 0.3))

= 83448.144*X kg/m2

= 83448.144*X kg/cm3

3.c.iii Stress due to the weight of the liquid and tray in the column up to a height X

meter.

fd, liq. = ∑weight of liquid and tray per unit height X/(π*Dm* (ts - c))

The top chamber height is 0.3 m and it does not contain any liquid or tray. Tray

spacing is 457 mm.


PRODUCTION OF ANISOLE 106

Average liquid density in column = 823.5 kg/m3

Liquid and tray weight for X meter

Fliq-tray = [(X-.03)/0.5+1]*(π*Di2/4) ×ρl

= [(X-.03)/0.5+1]*(π*0.4952/4) ×823.5

= [2X + 0.4] * 158.3957 kg

fd (liq) = Fliq-tray *10/ (π*Dm* (ts - c))

= [2X + 0.4] * 158.3957*10/3.14*500* (6 - 3))

= 0.6725*X + 0.133 kg/cm2

3.c.iv Compressive stress due to attachments such as internals, top head, platforms

and ladder up to height X meter.

fd (attch.) =∑weight of attachments per unit height X/( π*Dm* (ts - c))

Now total weight up to height X meter = weight of top head + pipes +ladder, etc.,

Taking the weight of pipes, ladder and platforms as 25 kg/m = 0.25 kg/cm

Total weight up to height X meter = (180.16 +25X) kg

fd (attch.) = (180.6+25X) * 10/ π*500* (5 - 3) = 0.5751 + 0.079617X kg/cm2

Total compressive dead weight stress:

fdx = fds + fins +fd (liq) + fd (attch)

= 0.77X + 8.377X + [0.6725X+0.133] + [0.5751 +0.07961X]

fdx = 10.3946X + 0.7081 kg/cm2

4. Tensile stress due to wind load in self-supporting vessels:

fwx = Mw /Z

Where, Mw = bending moment due to wind load = (wind load* distance)/2

= 0.7*Pw*D*X2/2
PRODUCTION OF ANISOLE 107

Z = modulus for the section for the area of shell ≈ π*Dm2* (ts-c)/4

Thus, fwx =1.4*Pw*X2/ π*Dm* (ts-c)

Now Pw = 25 lb/ft2 --- (from table 9.1 Brownell and Young)

= 37.204 kg/m2

Bending moment due to wind load

Mwx = 0.7*37.204*0.7316*X2/2 = 9.526(X2) kg-m

fwx= 1.4*37.204*X2 /(π*0.5* (5-3) *10-3)/10-4 = 1.658(X2) kg/cm2

5. Stresses due to Seismic load:

fsx = Msx /(π*Dm2* (ts-c)/ 4)

Where, bending moment Msx at a distance X meter is given by

Msx = [C*W*X2/3] * [(3H-X)/H2]

Where, C = seismic coefficient,

W= total weight of column, kg

H = height of column

Total weight of column = W= Cv *π*ρm*Dm*g* (Hv+ (0.8*Dm))*ts*10-3

----- (eqn. 13.75, page 743, Coulson and Richardson 6th volume)

Where W = total weight of column, excluding the internal fittings like plates, N

Cv = a factor to account for the weight of nozzles, man ways, internal

supports, etc.

= 1.5 for distillation column with several man ways, and with plate

support rings or equivalent fittings

Hv = height or length between tangent lines (length of cylindrical section)

g = gravitational acceleration = 9.81 m/s2


PRODUCTION OF ANISOLE 108

t = wall thickness

ρm = density of vessel material, kg/m3

Dm = mean diameter of vessel = Di + (t *10-3) = 0.4975+ (5 *10-3) = 0.5475 m

W=1.5*π*7700*0.7376*9.81*(14.167+(.8*0.7376))*6*10-3 =17255.602N=1757.54 kg.

Weight of plates: ------- (Coulson and Richardson 6th volume)

Plate Area = π *0.52/4 = =0.19625 m2

Weight of each plate = 1.2*0.19625 = 0.2355 kN

Weight of 30 plates = 30*0.2355 = 706.5kg.

Total weight of column = 1757.54 + 706.5 = 2463.9 kg.

Let, C = seismic coefficient = 0.08

Msx = [0.08*2463.9*X2/3] * [((3*13.71)-X)/13.712]

= 65.704X2 * [0.2188-0.00532X] kg-m

fsx = Msx*103/(π*Dm2* (ts-c))/4

=(65.704X2 * [0.2188-0.00523X ])* 103/(π*502* (5-3)/4)

= [1.678X2- 0.0133X3], kg/cm2

On the upwind side:

ft,max = (fwx or fsx) + fap -fdx

Since the chances of, stresses due to wind load and seismic load, to occur together is rare
hence it is assumed that the stresses due to wind load and earthquake load will not occur
simultaneously and hence the maximum value of either is therefore accepted and considered
for evaluation of combined stresses.

Thus,

ft,max = 1.658X2 + 70.4584 - [10.396X + 0.708]-0.85*950

i.e., 1.658X2- 10.3946X + 69.7504 – 807.5 = 0


PRODUCTION OF ANISOLE 109

1.658X2- 10.3946X – 737.7496 =0

=> X = 24.4604 m

On the down side:

fc,max = (fwx or fsx) - fap +fdx

The column height is 5 m, for which the maximum value is

fc,max = 1.658(5)2 – 70.4584 + [10.3946(5) + 0.708]

= -13.799 kg/cm2

this shows that the stress on the downwind side is tensile.

ft,max = 85% of allowable tensile stress.

ft,max = 950 * 0.85 = 807.5kg/cm2.

ft,max = 1.658X2 - 70.4584 + [10.396X + 0.708] = 807.5

Therefore, X = 20.080137 m.

Hence we see that the design value of the column height is more than 5 m, which is the actual
column height. So we conclude that the design is safe and thus the design calculations are
acceptable.

Hence a thickness of 5 mm is taken throughout the length of shell.

Height of the head = Dc/4 = 0.495/4 = 0.12375 m

Skirt support Height = 1.0 m

Total actual height = 14.167 + 1 + 0.12375 = 15.29075 m


PRODUCTION OF ANISOLE 110

Fig. 7.8. (a) Distillation column mechanical design equipment drawings


PRODUCTION OF ANISOLE 111

Fig. 7.8. (b) Distillation column mechanical design equipment drawings


PRODUCTION OF ANISOLE 112

7.4 Optimal design parameters obtained for the distillation


columns

7.4.1. Optimal Design Parameters and Results of Water Column

7.4.2. Optimal Design Parameters and Results of Anisole Column


PRODUCTION OF ANISOLE 113

Chapter 8

Cost Estimation

This unit gives an idea on how to perform cost estimation for a particular plant. In this unit,
total capital cost is estimated along with the total product cost. The first part of the unit deals
with the estimation of total capital investment and the latter part deals with the estimation of
total product cost.

Chemical Engineering Index (CE) or Chemical Engineering Plant Cost Index (CEPCI)
composed of 4 major components – equipment, construction labor, buildings, and engineering
and supervision – the index is employed primarily as a process plant construction index, was
established using a base period of 1957-1959 as 100. The CE Index is updated monthly and it
lags in time by about 3 months. The CE Index was revised in 1982, to account for changes in
labor productivity and, again, in 2002. It is Published in each issue of Chemical Engineering.

Table.8.1. Recent CEPCI data

April 2015 562.9

May 2015 560.5

November 2015 - Final 542.8

December 2015 - Preliminary 537.1

Annual CEPCI for 2015 537.0

8.1 Cost estimation for Reactor


The reactor volume is 0.04 m3 and a simple reactor like this costs about,
20000 US$ = 13,31,960 INR
Cost of catalyst per kg = $ 1.5
PRODUCTION OF ANISOLE 114

One Cycle consumes 36 kg and costs = INR 3597

Total cost of catalyst used in the process = INR 13,12,686

8.2. Cost estimation for Heat Exchangers


We have the following capacities and cost can be calculated by :
Cost 2015 = Cost Base x (Index 2015/ Index Base) x (Capacity 2015 / Capacity Base )α
Capacity exponent factor, α=0.65
In 2004 (Base year) , Similar type of Heat exchangers cost 12000 US$ for 163.32ft2.
CEPCI 2004 = 444.2

Heat Exchanger S No. Surface, m2 Surface, ft2 Cost 2015

1 25 269.1 US$ 19400.00

2 1.5405 16.5818 US$ 3170.00

3 10.1976 109.766 US$ 10830.00

4 1.67 17.975 US$ 3345.00

Total heat exchanger cost , US$ 36745.00

Total heat exchanger cost , INR 24,46,850.00

Table.8.2 Cost estimation of heat exchangers


PRODUCTION OF ANISOLE 115

8.3. Cost estimation for Distillation Columns

The number of trays in the distillation column in the process is 30. For a distillation column
with 4000 trays, the cost was $ 30,000,000 in 1999. The exponent factor is 1. The cost index
for 1999 and 2015 are 390.6 and 537.

Cost of one distillation column = 30,000,000*(30/4000)*(537/390.6)

= $ 309,330

= INR 2,05,95,190

Total Distillation columns’ cost = 5 x 2,05,95,190 = INR 10,29,76,000

8.4. Cost estimation for Total Capital Investment

Assumed percentage of Total


Particular Cost INR
FCI
105422850
Purchased Equipment 25%
21084570
Equipment Installation 5%
21084570
Instrumentation and Controls 5%
12650742
Piping 3%
8433828
Electricals 2%
21084570
Buildings 5%
8433828
Yard improvements 2%
42169140
Service facilities 10%
4216914
Land 1%
42169140
Engineering and Supervision 10%
PRODUCTION OF ANISOLE 116

42169140
Construction expense 10%
8433828
Contractor fee 2%
21084570
Contingency 5%

358437690
Fixed Capital Investment
53765654
Working Capital 15%

412203344
Total Capital Investment
Table.8.3. Total capital investment estimation

8.5 Estimation of Total Production Cost

The total product cost is divided into two parts, the first part is to estimate the manufacturing
expenses and the second one is to estimate the general expenses.

8.5.1.Manufacturing expenses

To estimate the manufacturing expenses one has to estimate, fixed charges, direct production
cost and plant overhead cost.

8.5.1.1 Fixed Charges

Fixed charges are made up of depreciation, local tax, insurance and rent.

Depreciation is calculated by adding yearly depreciation of equipment and buildings. The


yearly depreciation is calculated using straight line method assuming the lifetime for
equipment and buildings to be 20 and 40 years respectively. The salvage value at the end of
the lifetime is assumed to be zero.

1. Depreciation:

Depreciation for buildings = (21084570 – 0)/40 = INR 527115


PRODUCTION OF ANISOLE 117

Depreciation for equipment = (126507420 - 0)/20 = INR 6325371

Total Depreciation = INR 6852486

2. Local taxes:

Local taxes are assumed to be 3 % of FCI

Local Taxes = INR 10753131

3. Insurance:

Insurance constitutes 1 % of FCI

Insurance = INR 3584377

4. Rent:

Rent constitutes 10 % of buildings value

Rent = 0.1*21084570 = INR 2108457

Therefore

Total fixed charges = INR 23298451

8.5.1.2 Direct Production Cost

The direct production costs are made up of of raw material, operating labor, direct
supervisory and clerical staff, utilities, maintenance and repair, operating supplies, laboratory
charges and, patent and royalties

The raw materials used in the process are Methanol and phenol .

Methanol

Cost of methanol = US$ 305 per ton

Mass of methanol used in one year = 1908874.08 kg

Total cost of methanol used in a year = 3,87,74,960 INR


PRODUCTION OF ANISOLE 118

Phenol

Cost of phenol = US$ 1000 per ton = US$ 1 per kg

Mass of Phenol used in one year = 11212751 kg

Total cost of Phenol used in a year = 74,67,46,230 INR

Let the total product cost be X.

Utilities = 15 % of Total Product Cost = 0.15X

Patents and royalties = 2 % of Total Product Cost = 0.02 X

Operating labor = 10 % of Total Product Cost = 0.1 X

Direct supervisory and clerical labor = 10 % of Operating labor = 0.01 X

Laboratory charges = 12 % of Operating labor = 0.012 X

Maintenance and repairs = 5 % of Fixed Capital Investment = INR 17921885

Operating supplies = 1 % of Fixed Capital Investment = INR 3584377

Direct production cost = 0.292 X + 21506262

8.5.1.3 Plant Overhead cost


Plant overhead costs can be calculated as 50-70% of Operating labor, supervision, and
maintenance or 5-15% of total product cost which includes expenses for the following:
general plant upkeep and overhead, payroll overhead, packaging, medical services, safety and
protection, restaurants, recreation, salvage, laboratories, and storage facilities.
Plant overhead cost = 50% of OL, DS & CL, and M & R
= 0.5( 0.1X+0.01X+17921885)
Thus,
Manufacture cost = Direct production cost + Fixed charges + Plant overhead costs.
= 0.292 X + 21506262 + 23298451 + 0.5( 0.1X+0.01X+17921885)
= 0.347 X + 53765656
PRODUCTION OF ANISOLE 119

8.5.2. General Expenses

General expenses include Administrative costs, distribution and selling costs and, research
and development costs

Administrative cost = 40% of operating labor = 0.04 X


Distribution and Selling costs includes costs for sales offices, salesmen, shipping, and
advertising.
Distribution and Selling costs = 5 % of total product cost = 0.05 X
Research and Development costs is about 3% of total product cost.
Research and development costs = 0.03 X
General expenses = Administrative costs + distribution and selling costs + research costs
= 0.04 X + 0.05 X + 0.03 X = 0.12 X

Total Product cost = Manufacture cost + General Expenses


X = (0.347 X + 53765656 ) + (0.12 X)

Total product cost, X = INR 10,08,73,651


PRODUCTION OF ANISOLE 120

Chapter 9

Profitability Analysis

In this unit, the profitability of the production facility is analysed. The parameters used to
assess profitability are rate of return, payback period and break-even analysis. To determine
the above mentioned parameters it is essential to calculate the net profit for the facility
considered in this project.

9.1 Gross Earning/ Income


Wholesale Selling Price of Anisole per kg = Rs 110
Production of Anisole = 15 TPD = 15000 kg/day
Total Income from Anisole sales = Selling price * Quantity of product manufactured
= 110 x 15000 x 365 = 602250000
Gross income = Total Income – Total Product Cost
= ( 602250000 – 6,11,73,763)
Gross Income = Rs. 541076237

Let the Tax rate be 45% of gross income


Tax = 0.45*541076237 = 243484307

Net Profit = Gross income - Taxes = 541076237 - 243484307


Net profit = 297591930

9.2 Rate of Return


Rate of return = (Net profit/ Total Capital Investment) ×100
Rate of Return = (297591930/412203344)×100
Rate of Return = 72.19 %
PRODUCTION OF ANISOLE 121

9.3 Payback Period


It is a measure of time required to pay back the capital investment through the earnings. It is
given by
Payback Period = Depreciable FCI/(Annual Depreciation +Profit)
= 147591990/(6852486+ 297591930)
= 0.484 years

9.4 Break-Even Analysis


From this analysis, we determine the plant capacity at which the operating cost will equal the
revenue from sales. If the plant operates below this capacity then the operation will result in
loss, whilst if it operates above this capacity it will result in a profit. To determine the
break-even point (BEP) we need to estimate the fixed and variable costs involved in the
process.

Fixed cost incurred is the sum of fixed charges, plant overhead and the general expenses.
Therefore fixed cost = Rs 49912282
Variable cost incurred in the process is a result of Direct Production Cost.
Variable cost = 0.292 X + 21506262

= Rs 50961369

This is incurred when the plant is operating at 100% capacity. If the plant were to operate at
y% of this capacity, then the cost incurred is given by
Variable cost at y% capacity =50961369*y
Sales at 100% capacity = Rs 602250000
At y% capacity sales = 602250000*y
At break-even point,
Fixed cost + Variable cost = Revenue from sales
49912282 +50961369*y = 602250000*y
y = 9.05%
Therefore, the break-even point is at 9.05% capacity.
PRODUCTION OF ANISOLE 122
PRODUCTION OF ANISOLE 123

Chapter 10

Plant Layout

A preliminary determination of the plant layout enables consideration of pipe runs and
pressure drops, access for maintenance and repair, access in the event of accidents and spills,
location of the control room and administrative offices. The preliminary plant layout can also
help to identify undesirable and unforeseen problems with the preferred site, and may
necessitate a revision of the site selection.

The proposed plant layout must be considered early in the design work to ensure economical
construction and efficient operation of the completed plant. The plant layout adopted will also
affect the safe operation of the completed plant, and acceptance of the plant (and possibly any
subsequent modification or extension) by the community.

We have chosen Vadinar, Gujarat as a suitable location of this plant due to various factors
meeting the necassary requirements.

10.1 Factors in choosing suitable plant location

There are several major factors that contribute to the operability and economic aspects of a
site location for a plant, which are the primary factor and specific factor.

10.1.1. Primary Factors

1. Availability of Raw Material

A plant with close proximity to the source of the raw material allows a lower cost of
transportation. The cost of shipping raw materials and fuel to the plant site should be
considered along with the cost of transporting the products to market so as to minimize the
total transportation cost as much as possible while balancing that cost against other operating
expenses. A seaport might have to be at a reachable distance from the site location if the raw
material is to be imported.
PRODUCTION OF ANISOLE 124

2. Reasonable land price

The cost of the land depends on the location itself. An ideal land will provide an economical
land price to the total investment cost. It is then vital to choose a suitable land price when
initiating a new plant in order to gain the highest economic and profit value.

3. Proximity to market

The plant should be constructed close to the primary market to minimize transportation costs.
Local demand of product should also be taken into account in selecting a proper plant site. It
would add as an extra point if both the raw material supplier and buyers are at a reachable
distance.

4. Electricity and water

Any chemical plant is in need of large quantities of water supply for cooling and other uses in
the plant. Electricity is needed to run all the machines and equipments. Therefore, sufficient
local water and power supply plants is required to ensure a smooth operation of the plant.

5. Geographical and Weather :

The climate conditions affect the budget and cost operation. It may be necessary to consider
the yearly weather consideration.

10.1.2. Specific Factors

1. Availability of low cost labor and services

Any chemical processing plant should be located where sufficient labor supply is adequately
available. The usual practice is to bring non-local, skilled construction workers and ample
number of local, unskilled workers for training of plant operation. The cost of operation will
reduce if inexpensive manpower for plant operation can be gathered from the surrounding
area.
PRODUCTION OF ANISOLE 125

2. Transport facilities

The construction of the plant should be located close to road network, seaport and airport. All
these major facilities will aid to smooth transportation of the raw feed, product, plant
personnel and plant equipment supplies.

3. Government incentives

To attract investors to place their investment in a state, state governments offer attractive
investments incentives. Some incentives grant partial or total relief from income tax payment
for a specified period, while indirect tax incentives come in the form of exemptions from
import duty, sales tax and excise duty.

4. Waste and effluent disposal facilities

Site location should also take into account the availability of efficient and satisfactory
disposal system. This is to ensure that the factory waste and industrial effluent will have
proper treatment if those are to be treated off-site.

More factors:

Plant layout is often a compromise between a numbers of factors such as :

● The need to keep distances for transfer of materials between plant/storage units to a
minimum to reduce costs and risks
● The geographical limitations of the site
● Interaction with existing or planned facilities on site such as existing roadways, drainage
and utilities routings
● Interaction with other plants on site
● The need for plant operability and maintainability
● The need to locate hazardous materials facilities as far as possible from site boundaries
and people living in the local neighbourhood
● The need to prevent confinement where release of flammable substances may occur
● The need to provide access for emergency services
PRODUCTION OF ANISOLE 126

● The need to provide emergency escape routes for on-site personnel


● The need to provide acceptable working conditions for operators
The most important factors of plant layout as far as safety aspects are concerned are:

● Prevent, limit and/or mitigate escalation of adjacent events (domino)


● Ensure safety within on-site occupied buildings
● Control access of unauthorized personnel
● Facilitate access for emergency services

Many factors must be considered when selecting a suitable site with respect to the marketing
area, raw material supply, transport facilities, availability of labor, availability of utilities,
availability of suitable land, environment impact, etc. All these factors play a significant role
in the choice of the site. The overall site layout is shown.

Several factors have been considered in laying out the site. The process units and ancillary
building should be laid out to give the most economical flow of materials and personnel
around the site. In term of safety, process area is located at enough distance from the place
where there are a lot of personnel.

10.2 Plant Layout Consideration Factors

When laying out the plant, these are the factors that we have considered;

10.2.1. Inherent Safety


The major principle in Inherent Safety is to remove the hazard altogether. The best method in
achieving this is to reduce the inventory of hazardous substances such that a major hazard is
no longer presented. However, this is not often achievable. Other possible methods to achieve
an Inherently Safer design are;

● Intensification to reduce inventories


● Substitution of hazardous substances by less hazardous alternatives
● Simpler systems/processes to reduce potential loss of containment or possibility of
errors causing a hazardous event
PRODUCTION OF ANISOLE 127

10.2.2. Domino Effect


Hazard assessment of site layout is critical to ensure consequences of loss of containment and
chances of escalation are minimized. Domino maybe by fire, explosion (pressure wave and
missiles) or toxic gas cloud causing loss of control of operations in another location.

Fire
There are four ways that fire can spread;

● Direct burning
● Convection
● Radiation
● Conduction
The use of vertical and horizontal compartmentation using fire-resisting walls and floors can
prevent the spread of fire from its origin to the other part of the premises. Protection against
domino by convection, conduction and radiation can be achieved by ensuring that the
distances between plant items are sufficient to prevent overheating of adjacent plants
compromising safety of that plant also. If this is not possible due to other restrictions, other
methods such as firewalls, active or passive fire protection may be considered.

Explosion :

Explosion propagation may be directly by pressure waves or indirectly by missiles. Inherently


safety methods that should be considered are;

● Arranging separation distances such that damage to adjacent plant will not occur even
in the worst case.
● Provision of barriers e.g. blast walls.
● Protecting plant against damage e.g. provision of thicker walls on vessels.
Toxic gas releases
Toxic gas releases may cause domino effects by rendering adjacent plants inoperable and
injuring operators. Prevention of such effects may be affected by provision of automatic
control system using inherently safer principles and a suitable control room.
PRODUCTION OF ANISOLE 128

10.2.3. Reduction of consequences of event on and off site


A plant layout design technique is also applicable to the reduction of the risks from release of
flammable or toxic materials include:

● Locating all high-volume storage of flammable/toxic material well outside process


area
● Locating hazardous plant away from main road
● Siting of plants in the open air to ensure rapid dispersion of minor releases of
flammable gases and vapors and thus prevent concentrations building up which may
lead to flash fires and explosions.
● Provision of ditches, dykes, embankments, sloping terrain to contain and control
releases and limit the safety and environmental effects.
● Hazardous area classification for flammable gases, vapors and dusts to designate areas
where ignition sources should be eliminated.
10.2.4. Positioning of occupied buildings
The distance between occupied buildings and plant buildings will be governed by the need to
reduce the dangers of explosion. Evacuation routes should not be blocked by poor plant
layout, and personnel with more general site responsibilities should be housed in buildings
sited in a non-hazard area near the main entrance. Occupied buildings should not be sited
downwind of hazardous plant areas.

10.2.5. Aggregation / trapping of flammable vapors


To avoid aggregation and trapping of flammable/toxic vapors which could lead to a hazardous
event, buildings should be designed so that all parts of the building are well ventilated by
natural or forced ventilation. Flammable storage should be sited in the open air so that minor
leaks or thermal outbreathing can be dissipated by natural ventilation.
PRODUCTION OF ANISOLE 129

10.3 Site Layout

The site layout can be divided into two parts:

● Non-Process area – area where there is no production activity and has low risk hazards
to workers and process units.

● Process Area - consists of all processing equipments, butadiene is produced.

10.3.1 Non-Process Area


The non-process area usually occupies a smaller fraction of the overall plant site area. All the
facilities in the non-process area should be located in a logical manner that considers site
terrain, accessibility to roads, soil bearing capability and the climate including the wind
direction and other unusual weather condition. This is important to avoid any undesired
incident due to explosion or fire from the process zone will be easily spread to the
non-process area. Taking this into account, the entire process area where the reaction and
separation occurs is surrounded with a buffer zone to ensure that surrounding buildings or
sites are not affected in case of an emergency. Among the buildings or units in the
non-process area are: -

a) Guard Post

Guard posts are located at the entrance of the site in order to ensure that only authorized
personnel gets access into the plant. There are 5 guard posts that are situated at the crucial
entrances in the plant:

● Main entrance guard post – to control the flow in and out of personnel or cars between the
site and public area.
● Emergency entrance guard post – security check for emergencies such as ambulance, fire
engine or other special occasions.
● Process entrance guard post – As shown in the layout, there are two different main
entrances to the plant. The first one is for public entrance where only cars and other small
vehicles are allowed to pass through. The second main entrance is only open to trucks.
This is to avoid congestion and at the same time reduce the hazard of material spillage at
PRODUCTION OF ANISOLE 130

the plant. With two different entrances, the public are less exposed to the danger of
chemicals exposure or accidents with the trucks.

b) Administration Building

The administration block is built adjacent to the main entrance. This is to allow the
administration employees to enter their office without passing through the hazardous process
area. As shown in the plant layout, the administration building is place near to the process
area. This location is most strategic as it is aligned with the process area. This arrangement
allows the employees at the administration building to alert on any mishap at the process area
that is visible from the administration building but far enough to ensure that no accidents from
the processing area can affect the administration block.

c) Cafeteria
Canteen provides meals for the employees and visitors. Canteen is located in the public zone
and far away from the process area to avoid contaminant in food and ensure safety of the
public.

There are other facilities that should be located in the non-process area including surau,
gymnasium, car park and also fire station.

10.3.2 Process Area

Process zone is an area where all processing equipment is allocated and is deemed as a
hazardous area, thus precaution has to be applied at all times. The buildings or units situated
in this process zone are:

● Process zone guard post

● Control Building

● Laboratory

● Wastewater treatment plant


PRODUCTION OF ANISOLE 131

● Plant Area

● Utilities

● Storage area

● Fire assembly points

● Flare area

a) Process zone guard post


This facility is to ensure no unauthorized personnel will be access into the process area by
using a security pass, to record the personnel activity, such as check-in and check-out between
process zone and public zone. The purpose of this process zone guard post is to ensure that all
the personnel will obey to the plant rule and regulations.

b) Control Building :

All the control valves for the whole process area will be controlled and monitored from this
central control building. The control rooms are designed with blast proof construction and
have emergency backup power and air conditioning. In case of emergency occurs in the plant,
control room will be the assembly point in the process area. At least two escape routes for
operators/personnel must be provided from each level in process buildings.

c) Laboratory
Here the quality of the purity of anisole is tested to determine whether it meets the
specifications or not. All the result will be sent to the control room and some adjustments in
controlling will be made, if needed. Thus, the distance between laboratory and control room is
not too far. Laboratory staffs will also perform an analysis regarding waste of the process
before being channeled to nearby environment.

d) Wastewater Treatment Plant

The waste stream from Plant Area will first flow into the Wastewater Treatment plant to
separate the impurities from the water. The impurities will be treated before being recycled
PRODUCTION OF ANISOLE 132

back to the process released to the environment. It is located adjacent to the main process unit
so that the wastewater effluents from the process units can be channeled easily.

e) Plant Area

This area is the major processing unit where the anisole is produced. Safety, economy,
operability and ease of maintenance are considered during the allocation of each equipment
within the area. Adequate spacing between equipment is also considered to minimize the
spread of fire in case it happens. Distances between each unit are also well designed to
prevent any hazards from occurring.

f) Utilities

This unit will supply cooling water, low pressure steam, instrument air and some other
utilities to the main process unit. For this plant, the utilities located near to plant area where
all the process of producing anisole occurs. Its location is perfectly suitable to give the most
economical run of pipe to and from the process unit. The utilities and control building is
situated near to the utilities for easy monitoring.

g) Storage area

This unit stores vessels containing chemical substance, lubricants, and catalyst used for the
process. It also stores chemicals needed for the wastewater treatment plant. It is situated next
to the wastewater treatment plant.

h) Warehouse :

Warehouse stores all the equipment’s spare parts. It is placed near to the workshop to ease the
maintenance job and to conduct hot work.

i) Expansion Site
Ample expansion areas are allocated at the process area for future expansion in case the
management decides to increase production rate or other crucial considerations.

j) Fire assembly points

In case of emergency, the assembly point in the plant for public zone will be located in the
nearest car park area and next to the canteen. For process zone; the assembly point will be
PRODUCTION OF ANISOLE 133

near to the QC Laboratory building and next to the Utilities and Control building for
personnel working there. Once gathered, wait for further instruction from Health, Safety and
Environment personnel or from fire department personnel. There are a total of 5 assembly
points planned at the site.

k) Flare Area

Flare is used to burn all excess gas that is emitted from the process units as well as to burn
some of the waste gas from waste treatment area. The flare is located far from the process
area and administration complex

PROCESS UNIT:

Table below summarizes the layout consideration for process units

Table.10.1 Layout Consideration for Process Unit

PROCESS UNIT LAYOUT CONSIDERATIONS


Process Area ● Located in well ventilated area with leak detector to allow
maximum safety if there is leakage or spillage
● Located as far s possible from ignition sources
Instrumentation ● Instrumentation control cables are routed underground to
prevent any hazards.
● Fireproofing protection should be considered.
● Consider types of fluid, temperatures, pressures and flow
Pipelines
condition
Reactor/Column/Heat ● Isolated from other equipment and from flammable, toxic
Exchanger/Pressure or inert materials.
Vessels ● Consider internal refractory of insulation due to
overheating and rupturing.
PRODUCTION OF ANISOLE 134

Fig.10.1. Plant Layout of anisole Production Plant


PRODUCTION OF ANISOLE 135

Chapter 11

Safety and Environmental Issues

11.1 Exposure Hazards

Workers may be exposed to the organics like anisole, cresols, poly methyl phenols, methanol
and phenol. They should be monitored in a systematic program of medical surveillance that is
intended to prevent occupational injury and disease.
The program should include education of employers and workers about work-related hazards,
placement of workers in jobs that do not jeopardize their safety or health, early detection of
adverse health effects, and referral of workers for diagnosis and treatment. The occurrence of
disease or other work-related adverse health effects should prompt immediate evaluation of
primary preventive measures (e.g., industrial hygiene monitoring, engineering controls, and
personal protective equipment). A medical monitoring program is intended to supplement, not
replace, such measures.
To place workers effectively and to detect and control work-related health effects, medical
evaluations should be performed: before job placement; periodically during the period of
employment; and at the time of job transfer or termination.

11.1.1. Ways Exposure to anisole and first-aid measures

1. INGESTION:
Although ingestion is not thought to produce harmful effects, the material may still be
damaging to the health of the individual following ingestion, especially where pre-existing
organ is damaged or replaced. Limited evidence exists that the substance may cause
irreversible but non-lethal mutagenic effects following a single exposure.
First aid measures: Immediately give a glass of water. Never give anything by mouth to an
unconscious person. Do NOT induce vomiting unless directed to do so by medical personnel.
PRODUCTION OF ANISOLE 136

Loosen tight clothing such as a collar, tie, belt or waistband. Get medical attention if
symptoms appear.

2. EYE CONTACT:
Although the liquid is not thought to be an irritant, direct contact with the eye may produce
transient discomfort characterized by tearing or conjunctival redness (as with windburn).
First aid measures: Check for and remove any contact lenses. In case of contact,
immediately flush eyes with plenty of water for at least 15 minutes occasionally lifting upper
and lower eyelids. Get medical attention.

3. SKIN CONTACT:
Skin contact is not thought to have harmful health effects, however the material may still
produce health damage following entry through wounds, lesions or abrasions. There is some
evidence to suggest that the material may cause moderate inflammation of the skin either
following direct contact or after a delay of some time. Repeated exposure can cause contact
dermatitis which is characterized by redness, swelling and blistering. Open cuts, abraded or
irritated skin should not be exposed to this material. Entry into the blood-stream, through, for
example, cuts, abrasions or lesions, may produce systemic injury with harmful effects.
First aid measures: In case of contact, skin should be immediately flushed with plenty of
water. The irritated skin should be covered with an emollient. Contaminated clothing and
shoes should be removed and washed before reuse. Shoes be thoroughly cleaned before reuse.
Get medical attention. In case of serious skin contact, skin be washed with disinfectant soap
and anti-bacterial cream be applied. Medical attention be sought.

4. INHALATION:
The material is not thought to produce adverse health effects or irritation of the respiratory
tract (as classified using animal models).
Nevertheless, good hygiene practice requires that exposure be kept to a minimum and that
suitable control
measures be used in an occupational setting.Inhalation hazard is increased at higher
PRODUCTION OF ANISOLE 137

temperatures. Limited evidence exists that the substance may cause irreversible but non-lethal
mutagenic effects following a single exposure
First aid measures: If inhaled, victim should be removed to fresh air. If not breathing,
artificial respiration be given. If breathing is difficult, oxygen be given. Get medical attention
if symptoms appear. In case of serious inhalation, Evacuate the victim to a safe area as soon as
possible. Loosen tight clothing such as a collar, tie, belt or waistband. If breathing is difficult,
oxygen be administered. If the victim is not breathing, mouth-to-mouth resuscitation be
performed. Medical attention be sought as soon as possible.

5. LONG TERM EXPOSURE:


Limited evidence suggests that repeated or long-term occupational exposure may produce
cumulative health effects involving organs or biochemical systems. Exposure to the material
may result in a possible risk of irreversible effects. The material may produce mutagenic
effects in man. Long-term exposure to phenol derivatives can cause skin inflammation, loss of
appetite and weight, weakness, muscle aches and pain, liver damage, dark urine, loss of nails,
skin eruptions, diarrhea, nervous disorders with headache, salivation, fainting, discoloration of
the skin and eyes, vertigo and mental disorders, and damage to the liver and kidneys.

11.2. Handling and Storage

11.2.1. Procedure for Handling


Containers, even those that have been emptied, may contain explosive vapours. So cutting,
drilling, grinding, welding or perform similar operations on or near containers should be
strictly avoided..
Clothing wet with material should never be allowed to stay in contact with skin
All personal contact with the material, including inhalation should be avoided.
When risk of overexposure occurs. Protective clothing must be worn.
For flammable liquids and flammable gases, local exhaust ventilation or a process enclosure
ventilation system may be required. Ventilation equipment should be explosion-resistant.
PRODUCTION OF ANISOLE 138

11.2.2. Recommended Storage methods


Glass container.
Packing as supplied by manufacturer. Plastic containers may only be used if approved for
flammable liquid - For low viscosity materials (i) Drums and jerricans must be of the
non-removable head type. (ii) Where a can is to be used as an inner package, the can must
have a screwed enclosure. And for materials with a viscosity of at least 2680 cSt. (23 deg. C)
11.2.3. Storage Requirements
The materials be stored in original containers in approved flammable liquid storage area only
and not store in pits, depressions, basements or areas where vapors may be trapped.
Anisole is not compatible with oxidizing agents such as perchlorates, peroxides, nitrates,
chlorine, bromine, fluorine or strong acids HCl, H2SO4 and HNO3.
Anisole should be stored in tightly closed containers in a cool, well-ventilated area away from
heat or flame.
Sources of ignition such as smoking and open flames are prohibited where anisole is used,
handled or stored in a manner that could create a potential fire or explosion hazard.
Only non-sparking tools and equipment are to be used especially when opening and closing
containers of anisole.

11.3. Potential Hazards and Handling Emergencies

11.3.1 Fire:
Anisole is a combustible liquid. Combustion products include carbon monoxide (CO), carbon
dioxide (CO2), other pyrolysis products typical of burning organic material.
Dry chemical, CO2, water spray or foam extinguishers are to be used in case of any
emergency and personnel shall move upwind.

11.3.2. Spills and Leakage:


Persons without personal protective equipment (PPE) should be immediately evacuated from
the spot until cleanup is complete.
All ignition sources should be removed.
PRODUCTION OF ANISOLE 139

The spilled liquids should be absorbed in vermiculite, dry sand, earth, or a similar material
and be deposited in sealed containers, and the area should be ventilated after the cleanup is
complete.
It is necessary to contain and dispose anisole as a “Hazardous waste” and in accordance with
environmental regulations.
For large spills and fires, fire department shall be called immediately.

11.4. Work Practices and Personnel Safety

11.4.1. Safe Work Practices


Workers whose clothing has been contaminated by anisole should change into clean clothing
promptly.
Contaminated work clothes should be laundered by individuals who have been informed of
the hazards of exposure to anisole.
Eye wash fountains should be provided in the immediate work area for emergency use.
If there is a possibility of skin exposure, emergency shower facilities should be provided.
Eating, drinking or smoking where anisole is handled, processed or stored must be strictly
prohibited since the chemical can be swallowed. Proper hygiene is to be maintained.

11.4.2. Personal Protection


Personal protective equipment inclusive of protective clothing, gloves, footwear, helmet,
goggles and respirators if necessary must be used.

1. RESPIRATOR
Type A Filter of sufficient capacity. (AS/NZS 1716 & 1715, EN 1432000 & 1492001, ANSI
Z88 or national equivalent)
2. EYE
Safety glasses with side shields.
Chemical goggles.
3. HANDS/FEET
Wear chemical protective gloves, eg. PVC.
PRODUCTION OF ANISOLE 140

Suitability and durability of glove type is dependent on usage. Important factors in the
selection of gloves include
•Frequency and duration of contact,
•Chemical resistance of glove material,
•Glove thickness and
•Dexterity
(Select gloves tested to a relevant standard (e.g. Europe EN 374, US F739, AS/NZS 2161.1 or
national equivalent).
When prolonged or frequently repeated contact may occur, a glove with a protection class of 5
or higher (breakthrough time greater than 240 minutes according to EN 374, AS/NZS
2161.10.1 or national equivalent) is recommended.
When only brief contact is expected, a glove with a protection class of 3 or higher
(breakthrough time greater than 60 minutes according to EN 374, AS/NZS 2161.10.1 or
national equivalent) is recommended.
Contaminated gloves should be replaced.
Gloves must only be worn on clean hands. After using gloves, hands should be washed and
dried thoroughly.
Application of a non-perfumed moisturiser is recommended.
4. OTHER
•Overalls.
•PVC Apron.
•Some plastic personal protective equipment (PPE) (e.g. gloves, aprons, overshoes) are not
recommended as they may produce static electricity. For large scale or continuous use wear
tight-weave non-static clothing (no metallic fasteners, cuffs or pockets),
•Non sparking safety footwear.

11.5. Pollution Prevention

No gaseous emissions are produced in the process. Proper operation and process control has
to be maintained to reduce vent emissions from the reactor and distillation columns.
PRODUCTION OF ANISOLE 141

The sources of waste generation in the process are:


Wastewater generated in distillation columns containing products and solvent residues.
The water can be contaminated with toluene, anisole, phenol, cresols or xylenols since most
of the chemicals involved form azeotropes with water.
The poly-methyl phenols i.e., cresols, xylenols etc. generated as residue in the last column.

The water shall either be treated and reused for steam generation or disposed according to
environmental regulations of the government concerned.
The residue is mostly o-cresol and can be sold for good prices to other processing industries
or disposed only in closed and sealed bins or containers, since they are flammable.
Waste could also be generated from the raw material purges, that can be minimized by
increasing the efficiency of the process and proper maintenance and operations.
The process being a complete hydrocarbon system, all safety measures applicable in a
petroleum industry are applicable.
PRODUCTION OF ANISOLE 142

Chapter 12

References

1. Google Patents, “Process for preparing anisole - US 2487832 A”


www.google.com/patents/US2487832

2. Google Patents, “Process for the preparation of anisole - US 2529887 A”


www.google.com/patents/US2529887

3. G.N. Kirichenko, V.I. Glazunova, A.V. Balaev, U.M. Dzhemilev, Catalytic Vapor-Phase
Alkylation of Phenol with Methanol, published in Neftekhimiya, 2008, Vol. 48, No. 5, pp.
386–389

4. Sigma Aldrich, “ Product Catalog - 123226 SIGMA-ALDRICH Anisole”


http://www.sigmaaldrich.com/catalog/product/sial/123226

5. Pubchem - Open Chemistry Database. “Compound Summary for CID 7519”


http://pubchem.ncbi.nlm.nih.gov/compound/anisole#section=Experimental-Properties

6. Sigma Aldrich, “ Globally Harmonized system - GHS”


http://www.sigmaaldrich.com/safety-center/globally-harmonized.html

7. United Nations Economic Commission for Europe (UNECE), “Globally Harmonized


System”
http://www.unece.org/fileadmin/DAM/trans/danger/publi/ghs/ghs_rev02/English/07e_annex3.
pdf

8. Sax, N.I. Dangerous Properties of Industrial Materials. 5th ed. New York: Van Nostrand
Rheinhold, 1979., p. 381
PRODUCTION OF ANISOLE 143

9. Furia, T.E. (ed.). CRC Handbook of Food Additives. 2nd ed. Volume 2. Boca Raton,
Florida: CRC Press, Inc., 1980., p. 258

10. Gerhartz, W. (exec ed.). Ullmann's Encyclopedia of Industrial Chemistry. 5th ed.Vol A1:
Deerfield Beach, FL: VCH Publishers, 1985 to Present., p. VA19 355

11. Budavari, S. (ed.). The Merck Index - Encyclopedia of Chemicals, Drugs and Biologicals.
Rahway, NJ: Merck and Co., Inc., 1989., p. 106

12. Ambrose D et al; J Chem Therm 8: 165-78 (1976)

13. Fire Protection Guide to Hazardous Materials. 12 ed. Quincy, MA: National Fire
Protection Association, 1997., p. 325-16

14. Riddick, J.A., W.B. Bunger, Sakano T.K. Techniques of Chemistry 4th ed., Volume II.
Organic Solvents. New York, NY: John Wiley and Sons., 1985., p. 317

15. NIST properties


anisole
http://webbook.nist.gov/cgi/cbook.cgi?ID=C100663&Mask=1#Thermo-Gas
methanol
http://webbook.nist.gov/cgi/cbook.cgi?ID=67-56-1
phenol
http://webbook.nist.gov/cgi/cbook.cgi?ID=108-95-2
water
http://webbook.nist.gov/cgi/cbook.cgi?ID=7732-18-5

16. , Robert H. Perry, Perry's Chemical Engineers' Handbook, 8th edition.