Nagpur. MAnufacture of Acetic Anhydride

Manufacture of acetic anhydride
1. Introduction :-
Acetic anhydride also known as ethanoic anhydride or

methyl carboxylic anhydride is a colourless liquid, very similar to acetic acid in its
pungent, acrid odour, viscosity, density & refractive index. It does not occur
naturally & was 1st synthesized by C.F.Gerhardt in 1852 by the reaction of benzoil
chloride & molten potassium acetate. Today it is one of the most important organic
intermediates & is widely used in both research & industry.
About 40% of the acetic anhydride produced throughout

the world is used for the production of Vinyl acetate monomer(VAM) which is
used for the production of downstream products such as adhesives, textiles, and
paints.
Apart from this acetic anhydride has many other utilities

such as in the manufacture of “Aspirin” an important medicine, in the production
of acetanilide which is used as a starting material in the manufacture of some
sulpha drugs, it is also useful in manufacture of perfumes, herbicides, acetyl
peroxide bleach & plasticizers.
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Production of acetic anhydride (in kt) :-

Country 1961 1971 1974 1979 1980 1981 1982 1989 1990 1996 2001
United 571 686 741 - - 567 481 778 830 1000 1160
States
Germany 32 47 74 91 85 77 76 108 112 - -
Japan 33 96 115 114 150 145 144 205 1160 - -
Major producers in India :-

Sr. No. Manufacturer Capacity(TPA)
1 VAM Organics Ltd, 33000
2 Andhra sugars Ltd, Andhra. 3058
3 Ashok Brothers, Mumbai 6600
4 IOL chemicals & pharmaceuticals Ltd, 12000

Punjab
5 Vasantdada Shetkari SSK 3000
6 Trichy distillers & chemicals Ltd, Trichy 2,100

7 R L G Group of industries, Gujrat 10000
8 Naran Lala Private Ltd, Gujrat -
9 FISCHER Chemic Ltd, Chennai -
10 Mysore Acetate & chemicals Ltd., Mysore 6000
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Markets :-
Vinyl Acetate Monomer (VAM) :-
It is the largest consumer of acetic anhydride and constitutes nearly 40% of the
demand. VAM is usually used in the downstream products such as adhesives,
textiles, and paints.
Drugs/ Pharma :-
Drugs and pharmaceuticals constitute 18% of the total production. It is used in the
manufacturing of Aspirin. About 0.8 tons of anhydride is required to produce 1 ton
of Aspirin. This constitutes 3% of the total production. Manufacturing 0.9 ton of
Paracetamol requires 1 ton of acetic anhydride and it constitutes 9% of the total
demand. Vitamins constitute nearly 1% of the total demand and intermediates like
MCA account for 5% of total demand.
Cellulose acetate :-
These account for nearly 9 % of the total demand for anhydride. Cellulose acetate.
is used in the downstream products such as cigarette filters. About 1 ton of
anhydride is required to produce 1 ton of the cellulose acetate.
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Dyes and pigments :-

This constitutes about 18% of the total production.
Capacity structure :-
VAM organics is the largest producer with an installed capacity of 33,000 ton per
annum. Ashok organic, Mysore acetate and IOL have smaller capacities. The total
installed capacity is around 62,000 ton per annum whereas the demand hovers
around 42000 ton per annum. Most of the consumption is captive.
Demand and pricing :-

Demand has seen a steady rise, but the capacity utilization has been around
65-70%. The main reason for the slow growth has been the plant change-overs
where anhydride capacity can be used for acetic acid production.
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The prices are dependent on the prices of the raw

material namely acetic acid. The import duty for acetic anhydride was reduced
from 65% in 1994-95 to 40% in 1996-97. Unlike acetic acid domestic prices were
pegged slightly lower than the landed costs. All the major manufacturers of acetic
anhydride also manufacture acetic acid. Hence the sizeable difference between
international and domestic prices of acetic acid allows the producers to peg the
prices of acetic anhydride just below the landed cost.
Outlook
The demand is expected around 55000 tonnes this year. However, with the
reducing of import duty the flexibility of the local manufacturers will be eroded.
The declining international prices of acetic acid have resulted in the reduction of
the prices of the anhydride. This has resulted in the reduction of the
competitiveness among domestic producers.
Import :-
Market estimated at Rs. 90 crs. Import not high - around 3%
Price :-
Historical (1994 - 1999): 45 Rs./kg , Current: 50 Rs/kg.
L.I.T. Nagpur
1.1 Historical background :-
The oldest process for making acetic anhydride is

based on the conversion of sodium acetate with the excess of an inorganic chloride
such as thionyl chloride, sulfuryl chloride or phosphoryl chloride. In this process
half of the sodium acetate is converted to acetyl chloride, which then reacts with
the remaining sodium acetate to form acetic anhydride as follows:-
CH3COONa + X-Cl → CH3COCl + X-ONa
CH3COONa + CH3COCL → (CH3CO)2O + NaCl
Where, X= SOCl, SO2Cl, POCL2
A further development, the conversion of acetic acid
with phosgene in the presence of aluminium chloride, has the advantage that it
allows continous operation.
2CH3COOH + COCl2 → (CH3CO)2O + 2HCl + CO2
Two other methods also were used in the past:
The cleavage of ethylidene diacetate to form
acetaldehyde and acetic anhydride in the presence of acid catalyst such as zinc
chloride & the second method is by the reaction of vinyl acetate with acetic acid on
palladium to form acetaldehude and acetic anhydride. None of these processes is
having any industrial importance.
Today, acetic anhydride is made mostly by either the
ketene process or the oxidation of acetaldehyde. Production by another process, the
carbonylation of methyl acetate (Halcon process ) was begun in 1983. In western
Europe, 77% of the acetic anhydride is made by the ketene processand rest 23% by
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the oxidation of acetaldehyde. In United States 25% of the acetic anhydride is

made by the Halcon Process & the rest 75% by the ketene process.
1.2. Physical Properties of Raw Material:-
Acetic Acid :-
 Auto-ignition temperature (°C) 565

 Boiling point at 760mm Hg (°C) 118.1
 Colour colourless
 Critical pressure, (atm) 57.2
 Critical temperature, (°C) 321.6
 Molecular Weight 60.0530
 Heat of Combustion (Kcal/mole) -208.7
 Heat of Formation (Kcal/mole) -116.2
 Heat of Fusion (cal/g) 44.7
 Heat of Vapourisation (cal/g) 96.8
 Heat of Solution at 18°C (Kcal/mole) 0.375
 Refractive index 1.3718
 Specific Heat at 0°C (cal/g) 0.468
 Surface Tension at 20°C in air, (dyne/cm) 27.6
 Taste acrid
 Viscosity (cp)
At 20°C 1.18
At 40°C 0.82
 Specific Gravity 1.049
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1.3. Physical Properties Of The Product :-
Acetic Anhydride :-
Property Vapour Liquid
 Molecular Weight 102.090 102.090

 Melting Point (°C) - -73
 Normal Boiling Point (°C) - 139
 Specific Gravity 3.52 1.084
 Coefficient of expansion (20°C) - 0.00112
 Critical Temperature (°C) - 326 -
 Critical Pressure (atm) - 43 -
 Critical Volume (cc/g-mol) - 290 -
 Surface Tension (dyne/cm, 20°C) air - 33
 Viscosity (cp, 20°C) 0.008 0.91
 Specific Heat (cal/g °C) 0.23 0.434
 Heat of Fusion (cal/g) - 24.6
 Heat of Vapourisation (at NBP, cal/g) - 93
 ΔHf° (cal/g) at 25°C -1347.8 -1460.9
 ΔGf°(cal/g) at 25°C -1116.0 -1144.8

 Heat of Hydrolysis (cal/g) at 25°C - 136.9
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1.4. Chemical Properties Of Acetic Anhydride :-
 On chlorination it produces chloro-acetyl chloride. In addition small quantities

of dichloro-acetyl chloride, acetyl chloride, chloro-acetic acid & HCl are
formed.
(CH3CO)2O + Cl2 → Cl-CH2COCl + CH3COOH

Acetic anhydride chloro-acetyl Acetic acid
chloride
 On reaction with hydrogen chloride under pressure it gives acetyl chloride.
(CH3CO)2O + HCl → CH3OCl + CH3COOH

Acetic anhydride acetyl chloride Acetic acid
 It undergoes hydrolysis slowly with water but rapidly hydrolysed with alkali to
form acetic acid.
(CH3CO)2O + H2 O → 2CH3COOH
Acetic anhydride Acetic acid
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 On reaction with acetaldehyde it forms ethylidene di-acetate.
(CH3CO)2O + CH3CHO → CH3CH(OCOCH3)2

Acetic anhydride Acetaldehyde Ethylidene di-acetate
1.5. Storage & Transportation :-
For storage & transportation of pure acetic

anhydride tanks made of aluminium, stainless ste.6el ( 18% Cr, 8% Ni & 2% Mo )
or poly-ethylene are generally used. Although glass or enamel containers also may
be employed. Iron is highly resistant to acetic anhydride, provided moisture is
excluded. Hence it is possible to use iron in the production & workup in certain
instances for example in pumps & tanks.
1.6. Health & Safety Aspects :-
Acetic anhydride penetrates the skin

quickly and painfully forming burns and blisters that are slow to heal. Anhydride is
especially dangerous to the delicate tissues of the eyes, ears, nose & mouth. The
threshold value for eyes is 0.36 mg/m3. When handling acetic anhydride, rubber
gloves that are free of pinholes are recommended for the hands, as well as plastic
goggles for the eyes, and Face-marks to cover the face and ears.
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Acetic acid is dangerous in combination with various

oxidizing substances and strong acids. Chromium trioxide and anhydride react
violently to burn, thermal decomposition of nitric acid in acetic acid is accelerated
by the presence of anhydride.
1.7. Applications :-
 The biggest use of acetic anhydride is in the manufacture of cellulose

acetates( about 86% of world production ). Acetates produced include cellulose
acetate, cellulose di-acetate, cellulose tri-acetate, cellulose acetate propionate &
cellulose butyrate. The remaining 14% is consumed in various miscellaneous
uses which are as given below.
 It is used in the production of polymethyl-acylamide or hard foam, acetic
anhydride is used for binding ammonia that is liberated on conversion of two

amide groups to an imide group.
 It is used in dyeing industry, where acetic anhydride is used chiefly in mixtures
with nitric acid as a nitrating agent. Here the solvent and dehydrating properties
of acetic anhydride are used.
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 It is used in the manufacture of various organic intermediates such as chloro-
acetyl chloride, di-acetyl peroxide, higher carboxylic anhydrides, acetates and

boron tri-fluoride complex.
 It is used in the manufacture of certain pharmaceutical products such as acetyl

salicylic acid(aspirin), p-acetyl amino phenol, acetanilide, acetophenacetin,
theophyllin, sulfamides, a number of hormones & vitamins.
 It is used in the detergent industry for the production of cold-bleaching

activators such as tetra-acetyl-ethylene diamine.
 It is used in the manufacture of explosives, particularly hexogen production.
 It is used in the manufacture of acetylated plastic auxiliaries such as glycerol

tri-acetate acetyl tri-butyl citrate & acetyl ricinolate.
 It is used in the food industry, mainly in the acetylation of animal & plant fats
in order to obtain the desired solubilities, in the production of acetostearin, in
the edible packing materials & to clarify plant oils.
 It is used in the manufacture of flavours & fragrances.
 It is used n metallography, etching & polishing of metals and in semiconductor

manufacture.
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 Small % of acetic anhydride in acetic acid or cold water solutions are used as
powerful fungicides & herbicides.
2. Different Routes Of Manufacture :-
(a) Acetaldehyde oxidation :-
Acetaldehyde oxidation for the production of acetic

anhydride co-produces acetic acid. The reaction conditions are about 60ºC at 1atm
pressure and 70ºC at 6atm. Oxygen or air is employed for the oxidation purpose in
the presence of cobalt acetate catalyst promoted by copper acetate. The reactions
taking place are :-
CH3CHO + O2 → CH3COOOH
Acetaldehyde peracetic acid
CH3COOOH + CH3CHO → (CH3CO)2O + H2 O

Peracetic acid Acetic acid Acetic anhydride
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(CH3CO)2O + H2 O → 2CH3COOH
The last reaction is to be minimized if acetic

anhydride yield is to be maximum. Overall selectivity of acetaldehyde plus the
acetic acid is maintained at 95-98% while the weight ratio of overall yields can be
from 0.5-9 (anhydride to acid ). The higher ratios require a vapor product from the
reactor to rid the product mixture of the catalyst quickly. An azeotropic solvent,
such as ethyl acetate also enhances water vaporization from the reaction zone. Heat
of reaction is adequate to vaporize the product and unconverted acetaldehyde, but a
high recycle of low oxygen content off-gas is required for stripping because of the
low vapor pressure of the reaction products.
(b) Methyl Acetate Carbonylation :-
Acetic anhydride can be made by the carbonylation

of methyl acetate. Methanol acetylation is an essential 1st step in anhydride
manufacture by carbonylation, the reactions taking place are :-
CH3COOH + CH3OH → CH 3COOCH3 + H2O , ∆H= -4.89

KJ/mol
Acetic acid Methanol Methyl acetate
CH3COOCH3 + CO → (CH3CO)2O , ∆H= -94.8 KJ/mol

Methyl acetate Acetic anhydride
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The catalyst stream for the methyl acetate carbonylation

process involves rhodium chloride tri-hydrate, methyl iodide, chromium metal
powder and alumina support or nickel carbonyl complex with tri-phenyl
phosphine, methyl iodide and chromium hexa-carbonyl. In another, the alumina
catalyst support is treated with an organosilicon compound having either a terminal
organophosphine or similar ligands and rhodium or a similar noble metal. Such a
catalyst enabled methyl acetate carbonylation at 200ºC under 20 MPa pressure.
Conversion is 42.8% with the 97.5% selectivity. In anhydride purification, iodide
purification is of considerable significance, potassium acetate is employed for this
purpose. Because of the presence of iodide in the reaction system, titanium is the
most suitable material of construction.
(c) Ketene processes :-
(i) Acetone Cracking :-
Acetic anhydride can be manufactured by

acetone cracking. In this process acetone is 1st cracked to ketene and in the next
step ketene reacts with acetic acid to form acetic anhydride. The 1st step of the
reaction is carried out in a pyrolysis heater at about 700ºC and 1.5 atm pressure.
The reaction goes to achieve 20-25% of acetone and 70-75% selectivity to ketene.
The reaction taking place are :-
CH3-CO-CH3 → CH2=CO + CH4

Acetone Ketene Methane
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CH2=CO + CH3COOH → (CH3CO)2O + H20

Ketene Acetic acid Acetic anhydride
Quenching of the high-temperature reaction by

evaporating an injected mixture of acetic acid and acetic anhydride preceeds
cooling and ketene absorption by acetic acid. At the available pressure, chilling is
unnecessary, however both excess acetone and ketene must be absorbed from a
relatively large volume of gas. Water formed inside the reaction leads to some
hydrolysis of acetic anhydride. Water wash of the vent gas recovers acetic acid
vapor and recycle acetone.
(ii) Acetic Acid Dehydration :-
Acetic anhydride can be

manufactured by the thermal decomposition of acetic acid. The 1st step of the
reaction is the dehydration of acetic acid at pressures of about 15-20 KPa and
temperature of about 700ºC to form ketene, the 2nd step involves the reaction of
ketene with acetic acid to form acetic anhydride at a temperature of about 50ºC.
The reactions taking place are :-
CH3COOH → CH2=CO + H2 0 , ∆H=147 KJ/mol

Acetic acid Ketene
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CH2=CO + CH3COOH → (CH3CO)2 , ∆H= -63 KJ/mol

Ketene Acetic acid Acetic anhydride
Tri-ethyl phosphate is commonly used as a

dehydration catalyst for the water formed in the 1st step. It is neutralized in the exit
gases with ammonia. Aqueous 30% ammonia is employed as a solvent in the
second step because water facilitates the reaction, and the small amount of water
introduced is not significanr overall. Nickel-free alloys for example, ferrochrome
alloy, chrome-aluminium steel, are needed for the acetic acid pyrolysis tubes,
because nickel promotes the formation of soot and coke, and reacts with carbon
monoxide yielding a highly toxic metal carbonyl. Conventional operating
conditions furnish 85-88% conversion, selectivity to ketene is 90-95%.
3. Process Selection :-
(a) Acetone process :-
It can be used only when acetone is relatively

expensive, but the major disadvantages are that methane is formed during the
process which is very harmful and extra measures are to be taken to remove it.
Coke formation at the severe conditions is more of a problem than with acetic
acid dehydration process, also low conversion demands more heater duty for
the ketene produced.
(b) Acetaldehyde oxidation :-
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Acetic anhydride formed during the process may

undergo hydrolysis to form acetic acid according to the reaction :-
(CH3CO)2 + H2O → 2CH3COOH

This reaction is to be minimized in order to achieve

the maximum yield of acetic anhydride. Also acetaldehyde is to be manufactured
1st because it is not available directly, this makes the process uneconomical & the
cost of the production increases.
(c) Methyl Acetate Carbonylation :-
Catalyst recovery is the major operating problem

because rhodium is very costly metal & every trace must be recovered, otherwise it
may lead to a major economic loss. Hence additional process would be required for
the recovery of the catalyst which makes the process a bit expensive. Also the
process is still in a developing phase and only 15% of the acetic anhydride
produced in the world is being manufactured using this process.
(d) Acetic Acid Dehydration :-
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Ketene reacts readily with acetic acid to produce

acetic anhydride hence the process is economically and practically more viable this
is the why about 85% of the acetic anhydride produced in the world is being
manufactured by this process. Also the raw material required is only acetic acid
which is readily available which makes the process more economical.
Thus from above considerations it is clear that the

acetic acid process is the one which is generally employed because it is
economically and practically more viable. Thus acetic acid process is being
selected taking in to account its advantages than the other processes of
manufacture.
4. Process Description :-
(i) Principle :-
Production of acetic anhydride from

acetic acid comprises of two steps :-
(a) Pyrolysis of acetic acid to form ketene.

(b) Reaction of ketene obtained with acetic acid
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The first conversion which is highly endothermic is

carried out in vapor phase at high temperature at about 700ºC, and at reduced
pressure about 10-20 KPa, very short residence time in the neighborhood of 1
sec, and the presence of catalyst, serve to limit the formation of by products.The
catalyst system employed for dehydration are usually organic phosphates (tri-
ethyl, tri-cresyl, di-methyl ammonium, pyridium phosphates, etc.) which are
added directly and continuously in to the gas feed stream, at the rate of 0.2-
0.5% weight.
The addition of water in small concentrations(10%
weight) to the acetic acid offers similar advantage to those procured in steam
cracking. In particular it slows down the formation of coke. The addition of
small amounts of ammonia (< 1000 ppm) exerts an indirect inhibiting effect on
the polymerization of ketene. If these precautions are taken then once-through
conversion is about 85-90% and the molar yield 90-95%.
The second conversion, which is exothermic, can

be can be carried out in the absence of catalyst, by absorption in acetic acid,
between 45-55ºC, at reduced pressure 7-25 KPa. Higher temperatures and
pressures facilitate the dimerisation of ketene to di-ketene, whose boiling point is
127.4ºC which is fairly close to that of anhydride. Less than 2% weight is generally
formed, so that the yield of operation, with respect to both acid and ketene is about
95-98 molar percent.
(ii) Industrial Manufacture :-
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The industrial manufacture of acetic anhydride

using acetic acid consists of four main sections :-
(a) Acetic acid pyrolysis

(b) Ketene absorption
(c) Acetic acid purification.
(d) Recovery of unconverted acetic acid.
The first step which is the pyrolysis of acetic acid

involves the thermal decomposition of acetic acid preheated to about 110ºC and
containing continuous additions of triethyl phosphate catalyst, which contains
nickel and facilitate the complete cracking of the reactants and products, as well
as the formation of coke, it is preferable to use high-chromium steels as the tube
material, or alloys of chromium (23%), aluminium (1.5%), and silicon (1.5%).
If not, coking can be slowed down by the addition of carbon-di-sulfide to the
feed.
The reactor effluents, available at about 700ºC, first

receive an inline injection of ammonia to neutralize the catalyst. They are then
cooled rapidly to 0ºC in a series of heat exchangers. The liquid obtained by
condensation and containing about 35% weight acetic acid is sent to the
recovery section.
Ketene absorption takes place on the off gases, with

a countercurrent of acetic acid, collecting about 95% of the available ketene.
The unit operates at around 45-55ºC and the pressure of about 5-15 KPa
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absolute. The liquid leaving the absorption stage contains more than 90% acetic
anhydride. It is sent to the purification system.
Purification takes place by distillation in a series of
two distillation columns, the first column separates acetic acid from the top
which is sent to the recovery section and acetic anhydride of about 99% purity
from the bottom, the heavier components are collected at the bottom of the final
fractionation.
The recovered acetic acid ( unconverted acetic acid)
is reconcentrated in a distillation column which removes water from the top and
acetic acid of 95% purity at the bottom.
5. Thermodynamics :-
Thermodynamic properties of raw materials &
product are as given below :-
(i) Acetic Acid :-
Property A B C D
Specific -18.944 1.0971 2.8921 ×10-3 2.9275 ×10-6
Heat(Cp), J/mol
K
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∆Hf (KJ/mol) -44.988 -0.00983 2.46×10-6 -
∆G (KJ/mol) -47.916 0 5.04×10-6 -
(ii) Ketene :-
Property A B C D
∆Hf (KJ/mol) -44.988 -0.00983 2.46×10-6 -
∆G (KJ/mol) -47.916 0 5.04×10-6 -
(iii) Water :-
Property A B C D
Specific 92.053 -3.9953×10-2 -2.1103×10-4 5.3469×10-7
Heat(Cp), J/mol
K
∆Hf (KJ/mol) -238.41 -0.01226 2.77×10-6 -
Also, ∆G at 298K for Water = 238.59 Kj/hr
(iv) Acetic Anhydride :-
Property A B C D
Specific 71.831 8.8879 ×10-1 -2.6534 ×10-3 3.3501 ×10-6
Heat(Cp), J/mol
K
∆Hf (KJ/mol) -44.988 -0.00983 2.46×10-6 -
∆G (KJ/mol) -47.916 0 5.04×10-6 -
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Reaction 1 :-
CH3COOH → CH2=CO + H2 O
Acetic acid Ketene
a) Heat of Reaction :-
Ketene :-
∆H0 = A + BT + CT2 (KJ/mol)
∆H0 = -44.988 – 0.00983×T + 2.46×10-6×T2
Therefore. at 298K
∆H0298 = -44.988 – 0.00983×298 + 2.46×10-6×2982

= -74.063 KJ/mol
And, at 700 ºC that is at 973K
∆H0973 = -44.988 – 0.00983×973 + 2.46×10-6×9732

= -51.23 KJ/mol
Acetic acid :-
∆H0 = -422.584 – 4.8354×10-4×T + 2.46×10-6×T2
Therefore. at 298K
∆H0298 = -422.584 – 4.8354×10-4×298 + 2.3337×10-5×2982

= -434.84 KJ/mol
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And at 973K
∆H0973 = -422.584 – 4.8354×10-4×973 + 2.3337×10-5×9732

= -408.3 KJ/mol
Water :-
∆H0 = -238.41 – 0.01226×T + 2.77×10-6×T2

Therefore. at 298K
∆H0298 = -238.41 – 0.01226×298 + 2.77×10-6×2982

= - 241.8 KJ/mol
And at 973K
∆H0973 = -238.41 – 0.01226×973 + 2.77×10-6×9732

= -246.4 KJ/mol
Therefore, At 298K
∆H0reaction = ∑ H products – ∑ H reactants

= ( ∆H0ketene + ∆H0water ) – (∆H0acetic acid )
= (-74.063-241.8) – (-434.84)
= 118.977 KJ/mol
And at 973K
= ( ∆H0ketene + ∆H0water ) – (∆H0acetic acid )
= (-51.23-246.4) – (-408.3)
= 110.09 KJ/mol
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(b) Feasibility of Reaction :-
Ketene :-
∆G0 = A + BT + CT2 (KJ/mol)
∆G0 = -47.916 + 0×T + 5.04×10-6×T2

Therefore, At 298K
∆G0298 = -47.916 + 0×298 + 5.04×10-6×2982

= -47.47 KJ/mol
Acetic acid :-
∆G0 = -435.963 + 1.9346×10-1×T + 1.6362×10-5×T2

Therefore, At 298K
∆G0298 = -435.963 + 1.9346×10-1×298 + 1.6362×10-5×2982

= -365.69 KJ/mol
Water :-
For water ∆G0298 = -238.59
Thus,
∆G0reaction = ∑ ∆G products – ∑ ∆G reactants
= ( ∆G0ketene + ∆G0water ) – (∆G0acetic acid )
Therefore, at 298K
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∆G0298 = (-47.47-238.59) – (-365.69)
= 79.63 KJ/mol
Since, ∆G is positive, the reaction is not feasible at 298K.
Now, ∆G0298 = -RT ln K
ln K1 = (-79.63×1000)/(8.314 × 298)
= -32.14
Therefore, K298 = 1.1×10-14
Now,
dlnK ΔH o
=
dT RT
Therefore, ln(K2/K1) = (-∆H0298 /R) × [(1/T2)-(1/T1)]
ln(K2/K1) = (-118.977×1000/ 8.314) × [(1/973)-(1/298)]
= 33.314
Therefore, (K2/K1) = 2.938 × 1014

K2 = 3.232
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∆G0973 = - RT (ln K2)
= -8.314 × 973 × ln 3.232
= -26.15 KJ/mol
Since, ∆G0973 is negative, the reaction is feasible at 973K
Reaction 2 :-
CH3COOH + CH2=CO → (CH3CO)2

Acetic acid Ketene Acetic Anhydride
(a) Heat of Reaction :-
Ketene :-
∆H0 = -44.988 – 0.00983×T + 2.46×10-6×T2
Therefore, at 50 ºC that is at 323K
∆H0323 = -44.988 – 0.00983×323 + 2.46×10-6×3232

= -47.9 KJ/mol
Acetic acid :-
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∆H0 = -422.584 – 4.8354×10-4×T + 2.46×10-6×T2
Therefore, at 323K
∆H0323 = -422.584 – 4.8354×10-4×323 + 2.3337×10-5×3232

= -420.23 KJ/mol
Acetic Anhydride :-
∆H0 = -554.715 – 8.4124×10-2×T + 4.3618×10-5×T2

Therefore, at 323K
∆H0323 = -554.715 – 8.4124×10-2×323 + 4.3618×10-5×3232
= -577.615 KJ/mol
And at 323K
= (∆H0acetic anhydride ) – ( ∆H0ketene + ∆H0acetic acid )
= (-577.615) – (-47.9 – 420.23)
= -109.485 KJ/mol
(b) Feasibility of Reaction :-
Ketene :-
L.I.T. Nagpur
∆G0 = -47.916 + 0×T + 5.04×10-6×T2

Therefore, At 323K
∆G0323 = -47.916 + 0×323 + 5.04×10-6×3232

= -47.39 KJ/mol
Acetic acid :-
∆G0 = -435.963 + 1.9346×10-1×T + 1.6362×10-5×T2

Therefore, At 323K
∆G0323 = -435.963 + 1.9346×10-1×323 + 1.6362×10-5×3232

= -371.75 KJ/mol
Acetic Anhydride :-
∆G0 = -578.076 + 3.3162 ×10-1×T + 2.5188 ×10-5×T2

Therefore, at 323K
∆G0323 = -578.076 + 3.3162 ×10-1×323 + 2.5188 ×10-5×3232
= -468.334 KJ/mol
L.I.T. Nagpur
Thus,
∆G0reaction = ∑ ∆G products – ∑ ∆G reactants
= ∆G0acetic anhydride – ( ∆G0ketene + ∆G0acetic acid )
Hence, at 323K
∆G0323 = -468.334 – (–47.39–371.75)
= –49.194 KJ/mol
Since, ∆G0323 is negative, the reaction is feasible at 323K
Now, ∆G0323 = -RT ln K
ln K = (-∆G0323) / (RT)
= (49.194 × 1000)/ (8.314 × 323)
= 18.32
Therefore, K = 9.032 × 107
L.I.T. Nagpur
6. Material Balance :-
Plant capacity = 50 tonnes/day
= (50 × 1000)/ 24
= 2083.33 Kg/ hr
Therefore, Acetic Anhydride to be produced = 2083.33 Kg/hr
Considering 5% overall loss
Hence, acetic Anhydride to be produced actually = 1.05 × 2083.33

= 2187.5 Kg/hr
Molecular weight of Acetic Anhydride = 102
Therefore, Acetic Anhydride to be produced = 2187.5/102
= 21.446 Kmol/hr
The main reaction is :-

% Yield based on ketene required is = acetic anhydride formed/ ketene required
0.9 = 21.446/ketene required
Therefore, ketene required = 21.446/0.9 = 23.83 Kmol/hr
L.I.T. Nagpur
% yield base on acetic acid required = acetic anhydride formed / acetic acid
required
Therefore, acetic acid required = 21.446/0.85
= 25.23 Kmol/h
The first reaction taking place is :-
CH3COOH → CH2=CO + H2O

Acetic acid Ketene
Ketene to be produced = 23.83 Kmol/hr
Hence, water produced = 23.83 Kmol/hr
% yield based on acetic acid required = 0.9 = ketene formed / acetic acid required
Therefore, Acetic acid required = 23.83/ 0.9 = 26.478 Kmol/hr
% conversion based on acetic acid = 0.88 = acetic acid required / acetic acid fed
Therefore, acetic acid to be fed = 26.478/0.88 = 30.1637 Kmol/hr
33% excess of acetic acid is taken :-
0.33 = (fed-reacted)/fed
Therefore, total acetic acid to be fed = (25.23 + 26.478) / 0.77
= 77.18 Kmol/hr
L.I.T. Nagpur
(i) Pyrolysis Heater :-
Acetic acid input = 30.1637 Kmol/hr
Acetic acid reacted = 26.478 Kmol/hr
Hence, acetic acid remaining = 30.1637-26.478
= 3.6857 Kmol/hr
1.5% of the unreacted acetic acid gets converted in to flue gases
Therefore, flue gases produced = 0.015 × 3.6857
= 0.0553 Kmol/hr
Acetic acid remaining = 3.6857 – 0.0553 = 3.6304
Component Input (Kmol/hr) Output (Kmol/hr)

Acetic acid 30.1637 3.6304
Water - 23.83
Ketene - 23.83
Flue gases - 0.0553
L.I.T. Nagpur
Considering overall 0.1% loss of ketene, 0.5% loss of acetic acid & 0.2% loss of
water in condenser, cooler & chiller.
(ii) Separator :-
3% water goes from the top :-
Therefore, water in the upstream = 23.83 × 0.03 = 0.715 Kmol/ hr
And, water in the downstream = 23.83 – 0.715 = 23.782 Kmol/hr
1% ketene goes in the downstream :-
Hence, ketene in the downstream = 0.01 × 23.86 = 0.2383 Kmol/hr
And, ketene in upstream = 23.806 – 0.2383 = 23.59 Kmol/hr
The bottom product contains 35% by weight acetic acid
Hence, acetic acid in the bottom product = 0.35 × 3.612 = 1.2565 Kmol/hr
And, acetic acid in the top product = 0.65 × 3.612 = 2.3478 Kmol/hr
Component Input Output (Kmol/hr) Output (Kmol/hr)

(Kmol/hr) ( Upstream ) ( downstream )
Acetic acid 3.612 2.3478 0.2383
L.I.T. Nagpur
Water 23.782 0.715 1.2565
Ketene 23.806 23.59 23.115
Flue gases 0.055 0.055 -
(iii) Ketene Absorber :-
Total acetic acid fed = 2.3478 + 47.09 = 49.44 (Kmol/hr)
Acetic acid required = 25.23(Kmol/hr)
Hence, acetic acid remaining = 49.44 – 25.23 = 24.21(Kmol/hr)
95% acetic anhydride is produced
Hence, acetic anhydride formed = 0.95 × 23.59 = 22.41 Kmol/hr
12% acetic anhydride goes from the top
Hence, acetic anhydride in the top product = 0.12 × 22.41 = 2.6892 Kmol/hr
And, acetic anhydride in the bottom product = 0.88 × 22.41 = 19.7208
Total acetic acid fed = 2.3478 + 47.09 = 49.44 (Kmol/hr)
Acetic acid required = 25.23(Kmol/hr)
Hence, acetic acid remaining = 49.44 – 25.23 = 24.21(Kmol/hr)
80% acetic acid goes from the top
Hence, acetic acid in top product = 24.21 × 0.8 = 19.368 Kmol/hr
And, in the bottom product = 0.2 × 24.21 = 4.842 Kmol/hr
L.I.T. Nagpur
0.4 % water goes from the bottom
Hence, water in the bottom product = 0.004 × 0.715 = 0.00286 Kmol/hr
Component Input Output Output (Kmol/hr)

(Kmol/hr) (Kmol/hr) ( downstream )
( Upstream )
Acetic acid 49.44 19.368 4.842
Water 0.715 12.816 0.00286
Ketene 23.59 1.18 -
Flue gases 0.055 0.055 -
Acetic anhydride - 2.6892 19.368
(iv) Tail gas scrubber :-
2% Water goes from the top :-
Hence, Water in the top product = 0.02 × 0.712 = 0.01424 Kmol/hr
1% acetic anhydride goes from the top
Hence, acetic anhydride in the top product = 0.01 × 2.6892 = 0.0268 Kmol/hr
0.5% acetic acid goes from the top
Hence, acetic acid in the top product = 0.05 × 19.368 = 0.097 Kmol/hr
L.I.T. Nagpur
Component Input(Kmol/hr) Output (Kmol/hr) Output (Kmol/hr)

( Upstream ) ( downstream )
Acetic acid 19.368 0.097 19.271
Water 0.712 0.01424 0.698
Ketene 1.18 1.18 -
Flue gases 0.055 0.055 -
Acetic 2.6892 0.0268 2.6623
anhydride
(v) Jet Condensor :-
Considering 0.2% loss of Acetic acid, 0.1% loss of acetic anhydride and 0.5% loss
of
water in jet condenser :-
Component Input (Kmol/hr) Output (Kmol/hr) Output (Kmol/hr)

(Upstream) (Downstream)
Acetic acid 0.097 - 0.0968
L.I.T. Nagpur
Water 0.01424 - 0.01417

Ketene 1.18 1.18 -
Flue gases 0.055 0.055 -
Acetic 0.0268 - 0.02677
anhydride
(vi) Acetic acid column :-
Input Feed (F):
1) Acetic acid (CH3COOH) = 20.632 Kmol/hr
2) Water (H2O) = 23.827 Kmol/hr
Total feed to the distillation column = 20.632 + 23.827
= 44.459 Kmol/hr
Mole fraction of components in the feed :-
Xf1 (CH3COOH) = 20.632/44.459 = 0.464
Xf2 (H2O) = 23.827/44.459 = 0.536
Top Product (D) :-
Mole fraction of components in the top product :-
L.I.T. Nagpur
Xd1 (CH3CO0H) = 0.1
Xd2 (H2O) = 0.9
Bottom Product (W):
Mole fraction of components in the bottom product :-
Xw1 (CH3COOH) = 0.95
Xw2 (H2O) = 0.05
Taking overall material balance :-
F= D + W
Putting the values in above equation :-
44.459 = D + W --------------------------------------------- (1)
Now, taking component balance :-
F Xf= D Xd +W Xw
For Water :-
44.459 ×0.536 = D × 0.9 + W × 0.05
23.827 = 0.9 D + 0.05 W -------------------------------- (2)
Solving equations 1 & 2, we get :-
Top product (D) = 24 Kmol/hr
Bottom product (W) = 20.45 Kmol/hr
L.I.T. Nagpur
Hence, acetic acid in the top product = 0.1 × 24 = 2.4 Kmol/hr
And, Water in the top product = 0.9 × 24 = 21.6 Kmol/hr
Acetic acid in the bottoms product = 0.95 × 20.45 = 19.4275 Kmol/hr
Water in the bottoms product = 0.95 × 20.45 = 1.0225 Kmol/hr
Reflux Ratio = 2.25 ( calculated below )
Hence, Ln = 2.25 × D = 2.25 × 24 = 54 Kmol/hr
(vii) Acetic anhydride column :-
Input Feed (F):
1) Acetic acid = 4.842 Kmol/hr
2) Acetic anhydride = 19.7208 Kmol/hr
= 24.563 Kmol/hr
Xf1 (CH3COOH) = 4.842/24.563 = 0.197
Xf2 (Acetic anhydride) = 19.7203/24.563 = 0.803
Top Product (D) :-
L.I.T. Nagpur
Xd1 (CH3CO0H) = 0.9
Xd2 (Acetic anhydride) = 0.1
Bottom Product (W):
Xw2 (Acetic anhydride) = 0.99
F= D + W
24.563 = D + W --------------------------------------------- (1)
F Xf= D Xd +W Xw
For Acetic acid :-
24.563 ×0.197 = D × 0.9 + W × 0.01
4.842 = 0.9 D + 0.01 W -------------------------------- (2)
Top product (D) = 5.164 Kmol/hr
L.I.T. Nagpur
Hence, acetic acid in the top product = 0.9 × 5.164 = 4.6476 Kmol/hr = 278.856
Kg/hr
And, Acetic anhydride in the top product =0.1 × 5.164 = 0.5164 Kmol/hr =
52.6728 Kg/hr
Acetic acid in the bottoms product = 0.01 × 19.398 = 0.194 Kmol/hr = 11.64 Kg/hr
Acetic anhydride in the bottoms product = 0.99 × 19.398 = 19.2 Kmol/hr = 1958.4
Kg/hr
7. Energy Balance :-
Component Specific heat (J/mol K) Latent Heat of Vaporization

( cal/g)
Acetic Acid -18.944–1.0971×T + 2.8921×10-6×T2 96.8
Acetic 78.831 – 8.8879×10-1T+ 2.6534×10-6T2 93
Anhydride
(i) Pyrolysis Reactor :-
Reaction Temperature = 700ºC
Temperature of acetic acid entering = 110 ºC
Taking enthalpy balance around the pyrolysis Reactor :-
Heat to be supplied by the fuel gas = Heat required to raise the temperature of
acetic
L.I.T. Nagpur
acid
+
Heat required for the decomposition of acetic

acid to form ketene.
That is, ∆Hf (theoretical) = Q1 + Q2

Tenter
Q1 = n × ∫ CpdT
Tref
973
= 30.1637× ∫ (−18.944 + 1.0971× T + 2.8921× 10− 3 × T 2 )dT
383
= 12.9 × 106 KJ/hr
Q2 = Heat of reaction × amount of acetic acid cracked
= 110.09 × 103 × 30.1637
= 3.32 × 106
Therefore, ∆Hf (theoretical) = Q1 + Q2
= (12.9 + 3.32) × 106
= 16.22 × 106 KJ/hr
But, efficiency of the furnace = 0.65
Therefore, heat to be supplied actually = ∆Hf (theoretical) /0.65
= 16.22 × 106/0.65
= 24.954 × 106 KJ/hr
(ii) Waste Heat Boiler :-
L.I.T. Nagpur
Texit
Heat removed = nacetic acid × ∫ CpdT

Tenter
773
= 3.6304× ∫ (− 18.944 + 1.0971× T + 2.8921× 10 × T )dT

−3 2
973
= - 685.341 × 103 KJ/hr
Heat lost = Heat gained by the cooling medium (water)
Inlet temperature of water = 25ºC
Outlet temperature of water = 210ºC
Cooling water flowrate = ?
Heat gained = mwater × Cpwater × ∆T
mwater = 685.341 × 103/[4.184 × (483-298)]
= 885.4 Kg/hr
(iii) Cooler :-
Texit

Tenter
473
= 3.6304× ∫ (− 18.944 + 1.0971× T + 2.8921× 10 × T )dT

−3 2
773
= - 726.226 × 103 KJ/hr
L.I.T. Nagpur
Heat lost = Heat gained by the cooling medium (water)
Inlet temperature of water = 25ºC
Outlet temperature of water = 195ºC
Cooling water flowrate = ?
Heat gained = mwater × Cpwater × ∆T
mwater = 726.226 × 103/[4.184 × (468-298)]
= 1021.012 Kg/hr
(iv) Chiller :-
Texit

Tenter
273
= 3.6304× ∫ (− 18.944 + 1.0971× T + 2.8921× 10 × T )dT

−3 2
473
= -283.495 × 103 KJ/hr
Heat lost = Heat gained by the cooling medium (ammonia)
Inlet temperature of ammonia = -33ºC
Outlet temperature of ammonia = 50ºC
ammonia flowrate = ?
Heat gained = mammonia × Cpammonia × ∆T
mammonia = 283.495 × 103/[2.114 × (323-298)]
= 1615.7 Kg/hr
L.I.T. Nagpur
(iv) Ktene Absorber :-
The reaction taking place in the ketene absorber is :-

Above reaction is exothermic and the amount of heat released = -109.485 KJ/mol
This is the amount of heat released when one mole of acetic anhydride is formed.
Hence, for the formation of 22.41 Kmol acetic anhydride, the amount of heat
released wil be :-
∆H = -109.485 × 1000 × 22.41
= -2453.56 × 103 KJ/hr
The negative sign shows that the heat is released,
that is the reaction is exothermic.
L.I.T. Nagpur
(v) Acetic Acid Column :-
Temperature of feed = 382K
Temperature of distillate = 373K
Temperature of the bottoms product = 392K
Reference Temperature = 273K
Heat in feed (F×HF) = Heat in acetic acid + Heat in water
Texit Texit
= nacetic acid × ∫ CpdT

Tenter
+ nwater × ∫ CpdT
Tenter
382
= 20.632 × ∫ (− 18.944 + 1.0971× T + 2.8921× 10− 3 × T 2 )dT

273
+
382
23.827 × ∫ (92.053 − 3.9953× 10− 2 T − 2.1103× 10− 4 T 2 )dT
273
= 765.31 × 103 + 239.075 × 103
= 1004.385 × 103 KJ/hr
Heat in Distillate (D×Hd) = Heat in acetic acid + Heat in water
L.I.T. Nagpur
Texit Texit

Tenter
Tenter
373
= 2.4 × ∫ (−18.944 + 1.0971× T + 2.8921× 10− 3 × T 2 )dT

273
+
373
21.6 × ∫ (92.053 − 3.9953× 10− 2 T − 2.1103× 10− 4 T 2 )dT
273
(D×Hd) = 80.50 × 103 + 198.834 × 103

= 279.334 × 103 KJ/hr
Heat in bottoms (WHW) = Heat in acetic acid + Heat in water
Texit Texit

Tenter
Tenter
392
= 19.4275× ∫ (− 18.944 + 1.0971× T + 2.8921× 10 × T )dT

−3 2
273
+
392
1.0225× ∫ (92.053 − 3.9953× 10− 2 T − 2.1103× 10− 4 T 2 )dT
273
= 799.542 × 103 + 11.32 × 103

= 810.862 × 103 KJ/hr
L.I.T. Nagpur
Average Latent heat ( Lavg ) = Lacetic acid × Xacetic acid + Lwater × Xwater
= 18 × 2200 × 0.9 + 60 × 96.8 × 4.184 × 0.1
= 38.07 × 103 KJ/Kmol
Condenser duty ( Qc ) = Vn × Lavg
= 78 × 38.07 × 103
= 2969.46 × 103 KJ/hr
Taking overall Heat balance on distillation column :-
Heat in Feed (FHF) + Reboiler duty (Qr) = Heat in distillate (DHd)+Heat in

bottoms(WHW)
+
Condenser duty (Qc)
Hence, (Qr) = (DHd) + (WHW) + (Qc) - (FHF)
= ( 279.334 + 810.682 + 2969.46 – 1004.385 ) × 103
= 3055.091 × 103 KJ/hr
Therefore, quantity of steam required = (Qr) / Lsteam

= 3055.091 / 2200
= 1388.67 Kg/hr
(v) Acetic anhydride column :-
Temperature of feed = 403K
L.I.T. Nagpur
Temperature of distillate = 392K
Temperature of the bottoms product = 413K
Reference Temperature = 273K
Heat in feed (F×HF) = Heat in acetic acid + Heat in acetic anhydride
Texit Texit

Tenter
+ nanhydride × ∫ CpdT
Tenter
403
= 4.842× ∫ (− 18.944 + 1.0971× T + 2.8921× 10− 3 × T 2 )dT

273
+
403
19.7208× ∫ (71.831+ 8.8879× 10−1 T − 2.6534× 10−3 T 2 )dT
273
= 221.491 × 103 + 202.099 × 103
= 423.59 × 103 KJ/hr
Heat in Distillate (D×Hd) = Heat in acetic acid + Heat in anhydride
Texit Texit

Tenter
Tenter
L.I.T. Nagpur
392
= 4.6476× ∫ (− 18.944 + 1.0971× T + 2.8921× 10− 3 × T 2 )dT

273
+
392
0.5164× ∫ (71.831+ 8.8879× 10−1 T − 2.6534× 10− 3 T 2 )dT
273
(D×Hd) = 191.272 × 103 + 4.844 × 103

= 196.117 × 103 KJ/hr
Heat in bottoms (WHW) = Heat in acetic acid + Heat in anhydride
Texit Texit

Tenter
Tenter
413
= 0.194× ∫ (− 18.944 + 1.0971× T + 2.8921× 10 × T )dT

−3 2
273
+
413
19.2 × ∫ (71.831+ 8.8879× 10−1 T − 2.6534× 10−3 T 2 )dT
273
= 9.704 × 103 + 211.942 × 103

= 221.647 × 103 KJ/hr
Average Latent heat ( Lavg ) = Lacetic acid × Xacetic acid + Lanhydride × Xanhydride
= 60 × 96.8 × 4.184 × 0.9 + 102 × 93 × 4.184 × 0.1
L.I.T. Nagpur
= 25.84 × 103 KJ/Kmol
Condenser duty ( Qc ) = Vn × Lavg
= 24.227 × 25.84 × 103

= 626.025 × 103 KJ/hr
Taking overall Heat balance on distillation column :-
Heat in Feed (FHF) + Reboiler duty (Qr) = Heat in distillate (DHd)+Heat in

bottoms(WHW)
+
Condenser duty (Qc)
Hence, (Qr) = (DHd) + (WHW) + (Qc) - (FHF)
= ( 196.117 + 221.647 + 626.025 – 423.59 ) × 103
= 620.199 × 103 KJ/hr
Therefore, quantity of steam required = (Qr) / Lsteam

= 621.199 / 2200
= 281.91 Kg/hr
L.I.T. Nagpur
8. Equipment Design :-
(i) Acetic Anhydride column :-
Input Feed (F):
2) Acetic anhydride = 19.7208 Kmol/hr
= 24.563 Kmol/hr
Xf1 (CH3COOH) = 4.842/24.563 = 0.197
Xf2 (Acetic anhydride) = 19.7203/24.563 = 0.803
Top Product (D) :-
Xd1 (CH3CO0H) = 0.9
Xd2 (Acetic anhydride) = 0.1
L.I.T. Nagpur
Bottom Product (W):
Xw2 (Acetic anhydride) = 0.99
F= D + W
24.563 = D + W --------------------------------------------- (1)
F Xf= D Xd +W Xw
For Acetic acid :-
24.563 ×0.197 = D × 0.9 + W × 0.01
4.842 = 0.9 D + 0.01 W -------------------------------- (2)
Top product (D) = 5.164 Kmol/hr
Hence, acetic acid in the top product = 0.9 × 5.164 = 4.6476 Kmol/hr = 278.856
Kg/hr
And, Acetic anhydride in the top product =0.1 × 5.164 = 0.5164 Kmol/hr =
L.I.T. Nagpur
52.6728 Kg/hr
Acetic acid in the bottoms product = 0.01 × 19.398 = 0.194 Kmol/hr = 11.64 Kg/hr
Acetic anhydride in the bottoms product = 0.99 × 19.398 = 19.2 Kmol/hr = 1958.4
Kg/hr
Boiling point of acetic acid = 118 ºC
Hence, acetic acid is more volatile component ( MVC)
Acetic acid- acetic anhydride (x-y data) :-
x 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
y 0.225 0.41 0.56 0.66 0.735 0.795 0.85 0.9 0.94 1.0
ya = α xa/ 1+( α-1)xa
substitute, y = 0.225 & x= 0.1
we get, α = 2.613
from graph :-
(xd/R+1)min = 0.26
(0.9/R+1)min = 0.26
Therefore, Rmin = 2.461
But, Ropt = 1.5 Rmin
Therefore, Ropt. = 1.5 × 2.461 = 3.6915
R = Ln/ D
L.I.T. Nagpur
Hence, Ln = 3.6915 × 5.164 = 19.063 Kmol/hr
Or, D = 52.6728 + 278.856 = 331.53 Kg/hr
Therefore, Ln = 1223.842 Kg/hr
Vn = Ln + D = 19.063 + 5.164 = 24.227 Kmol/hr
0r, Vn = 1223.842 + 331.53 = 1555.372 Kg/hr
Lm = Ln + F = 19.063 + 24.563 = 43.626 Kmol/hr
Or, Lm = 1223.842 + (19.7208 × 102 + 4.842 × 60 ) = 3525.88 Kg/hr
Vm = Lm – W = 3525.88 – (11.64 + 1958.4 ) = 1555.84 Kg/hr
Or, Vm = 43.626- 19.398 = 24.228 Kmol/hr
Therefore, equation of upper operating line :-
R x
yn = x n +1 + d
R +1 R +1
3.6915 0.9
yn = x n +1 +
4.6915 4.6915
Therefore, yn = 0.7868 xn+1 + 0.192
Hence, y-intercept = 0.192 & slope = 0.7868
Equation of lower operating line (LOL) :-
LM Wx w
y m +1 = xM −
VM VM
L.I.T. Nagpur
43.626 19.398 × 0.01

∴ y m +1 = xm −
24.228 24.228
∴ y m +1 = 1.8 x m − 0.7926
Therefore, number of theoretical plates = 14 -1=13 (from graph)

One plate is deducted for reboiler
Efficiency of the column = 62%
Therefore actual no. of plates required = 13/0.62 = 23 plates
Feed plate = 6/0.62 = 10th plate.
For atmospheric columns generally, tray spacing = 0.457m
Therefore, height of the distillation column = (N+1) × 0.457
= 24 × 0.457 = 10.968m=11m
Take 100 mm of water as the pressure drop per plate in the column.
Therefore, column pressure drop = 100 × 10−3 × 1000 × 9.81× 23
= 20601 Pa = 20.601 KPa.
Therefore, Top pressure = 101.325 KPa.
Bottom pressure = 101.325 + 20.601= 127.926 KPa.
At the bottom of the distiilation column vapor density can be calculated as follows;
L.I.T. Nagpur
P × M avg
( ρ v ) bottom =
RT
127.926 × (60 × 0.9 + 102 × 0.1) × 273

∴ ( ρ v ) bottom =
101.325 × 22.414 × 392
∴ ( ρ v ) bottom = 1.995 Kg / m 3 .
The density of liquid at the bottom of the column can be calculated by multiplying
the density of each component with the mole fraction.
( ρ l ) top = 1084 × 0.99 + 1049 × 0.01
∴ ( ρ l ) top = 1083.65Kg / m 3 .
At the top of the distiilation column vapor density can be calculated as follows;
P × M avg
( ρ v ) top =
RT
101.325 × (60 × 0.01 + 102 × 0.99) × 273

∴ ( ρ v ) top =
101.325 × 22.414 × 413
∴ ( ρ v ) top = 3.782 Kg / m 3 .
L.I.T. Nagpur
The density of liquid at the bottom of the column can be calculated by multiplying
the density of each component with the mole fraction.
( ρ l ) top = 1084 × 0.1 + 1049 × 0.9
∴ ( ρ l ) top = 1052.5 Kg / m 3 .
Calculation of Parachor value (P) :-
Ptop = 134.16 × 0.9 + 228.2 × 0.1 = 143.56

Pbottom = 134.16 × 0.01 + 228.2 × 0.99 = 227.26
Surface tension :-
4
 P × ( ρ L − ρV ) 
σ top =  × 10 −12
 M 
4
143.56 × (1052.5 − 1.995 ) 
∴ σ top =  × 10
−12
 (60 × 0.9 + 102 × 0.1) 
∴ σ top = 30.45dyne / cm = 0.03045 N / m
Similarly :-
L.I.T. Nagpur
4
 P × ( ρ L − ρV ) 
σ bottom =  × 10 −12
 M 
∴ σ top = 0.03406 N / m
Liquid-vapor flowrate factor FLV is given by :-
Ln ρV
∴ FLV (top ) =
Vn ρL
19.063 1.995
= = 0.0342.
24.227 1052.5
ρV
L
FLV ( bottom ) = m ρL
Vm
= 0.1063
tray spacing = 0.457 m.

From graph in RC-6 page-568 we get;
L.I.T. Nagpur
Bottom k1 = 0.086, Top k1 = 0.096
For liquid surface tension (0.02 N/m) take K1 as it is otherwise:-
0 .2
 σ 
K 1 (bottom ) = 0.086
 0.02 
= 0.1067
0 .2
 σ 
K 1 (TOP ) = 0.096
 0.02 
= 0.0935
Maximum velocity at top and bottom can be calculated as follows;

ρ L − ρV 1083.65 − 3.782
Bottom: u f = k1 = 0.1067 = 1.8m / s.
ρV 3.782
ρ L − ρV 1052.5 − 1.995
Top: u f = k1 = 0.0935 = 2.145m / s.
ρV 1.995
Now we will design the column for 70% flooding, therefore the velocities will be
given by;
Bottom: uf = 1.8 × 0.7 = 1.26 m/s.
Top: uf = 2.145 × 1.5015 m/s.
Maximum volumetric flow rate of vapor can be calculated as follows:
L.I.T. Nagpur
Lm × M 1555.372
Bottom Q = = = 0.1143m 3 / s.
ρ V × 3600 3.782 × 3600
1555.372
Top Q = = 0.2165m 3 / s.
1.995 × 3600
Now area at the bottom and at the top of the tower can be calculated as follows:
Q 0.1143
Net area(An) bottom = = = 0.0907m 2 .
uv 1.26
Q 0.2165
Net area(An) top = = = 0.144m 2 .
u v 1.5015
Now let us take 15% of the area as the downcomer area,

Ad = 0.15AT
But, AT = An + Ad
Therefore, An/0.15 = AT
L.I.T. Nagpur
0.0907
Therefore, Bottom area = = 0.1067 m 2 .
0.85
0.144
Top area = = 0.1694m 2 .
0.85
π
× di .
2
Now, area =
4
Column diameter can be calculated as follows;

0.1067 × 4
Bottom = = 0.3685m
π
.
0.144 × 4
Top = = 0.4644m.
π
Take 0.4644 m as inside diameter of the column.
Liquid Flow Pattern :-
Now, maximum volumetric flowrate at the bottom
L.I.T. Nagpur
3525.88
= = 9.04 × 10 − 4 m 3 / sec .
1083.65 × 3600
Provisional Plate Design :-
Column diameter Dc = 0.4644 m.

π
Area of column, Ac = × 0.4644 2 = 0.0.1694m 2 .
4
Now area of downcomer is 15% of the area of the column.
Ad = 0.15 × Ac = 0.02541m 2 .
Also Net area is given by, An = Ac − Ad = 0.1694 − 0.02541 = 0.144m 2 .

Active area, Aa = Ac − 2 Ad = 0.1694 − 2 × 0.02541 = 0.11858m 2 .
Take hole area as 10% of active area.
Therefore Ah = 0.1×0.11858 = 0.011858 m2.
Iw
For 15% downcomer area, from graph of (Ad/Ac) ×100 Vs
Dc
Iw
For, (Ad/Ac) = 0.15, = 0.82
Dc
Therefore Length of the weir, Iw = 0.82 × O.4644 = 0.38 m.
Take weir height as 50 mm.
Plate thickness = 5mm
Hole diameter = 5mm
Check Weeping :-
Maximum liquid rate,
L.I.T. Nagpur
3525.88
LW = = O.9794kg / sec .
3600
At 70% turndown the liquid rate is,
= 0.7 × 0.9794 = 0.6856 kg/sec.
The height of the liquid crest over the weir can be estimated using the Francis weir
formula. For a segmental downcomer this can be written as:
Lw 2 / 3
how = 750( )
ρ Llw
Where, lw = weir length, m,
how = weir crest, mm liquid,
Lw = liquid flow-rate, kg/s.
At the maximum flow rate of liquid the liquid crest over the weir can be calculated
using the maximum liquid flow rate calculated above, while for the conditions at
minimum flowrate are assumed to be the 70% turndown conditions.
0.9794
Maximum how = 750( ) 2 / 3 = 13.31 mm.
1083.65 × 0.38
0.6856
Minimum how = 750( ) 2 / 3 = 10.53 mm.
1083.65 × 0.38
At minimum rate, hw + how = 50 + 10.53 = 60.53 mm.

From graph of K2 Vs (hw + how), K2 = 30.3
Where, K2 is a constant dependent on the depth of the clear liquid on the plate.
The minimum design vapour velocity is given by
,
L.I.T. Nagpur
[ K 2 − 0.9(25.4 − d h )]
uh =
ρV
Where, uh = minimum vapour velocity through the holes(based on the
hole area), m/s,
dh = hole diameter, mm,
K2 = a constant, dependent on the depth of clear liquid on the plate
30.4 − 0.9(25.4 − 5)
uh = = 6.14m / sec .
3.782
Actual minimum vapour velocity is given by,

Actual uh = Minimum vapour rate/Ah
0.7 × 0.1143
uh = = 6.747 m / sec .
0.011858
This is well above the weeping velocity(minimum vapor velocity), therefore the
design is acceptable.
Plate Pressure Drop :-
Maximum vapour velocity through the holes is given by,
Vmax 0.1143
u h (max) = = = 9.64m / sec .
hole area 0.011858
For (plate thickness)/(hole dia) = 1, from graph of (Ah/Aa)×100 Vs Co

For, (Ah/Aa)= 0.1;
L.I.T. Nagpur
Co = 0.84
The pressure drop through the dry plate can be estimated using expressions derived
for flow through orifices.
u h 2 ρV
hD = 51[ ]
Co ρ L
9.64 2 3.782
= 51[ ] × = 23.44mm. ……..(bottom)
0.84 1083.65
Residual Head :-
12.5 × 10 3
hr =
ρL
= 11.53 mm.
Total Head :-
ht = hD + (hw + how ) + hr
L.I.T. Nagpur
= 23.44 + (50 + 10.53) + 11.53 = 95.5mm. of H 2 O
This is less than the assumed per plate pressure drop of 100 mm, thus the design is
acceptable.
Downcomer Liquid Backup :-
The height above the bottom edge of the apron is calculated as follows:
hap = hw − 10 = 50 − 10 = 40mm.
Thus the clearance area under the apron is given by,
Aap = haplw = 0.04×0.38 = 0.0152 m2.
This is less than the area of the downcomer Ad.
Thus use Aap in the equation given below :-
Head loss in the downcomer can be estimated by the following equation:
Lwd 2
hdc = 166[ ]
ρ L Am
Where, Am = Ad or Aap whichever is smaller.

Lwd = liquid flowrate in the downcomer.
0.9794
∴ hdc = 166[ ]2 = 0.586m
1083.65 × 0.0152
L.I.T. Nagpur
In terms of clear liquid, the downcomer backup is given by;
hb = (hw + how ) + ht + hdc
= 50 + 10.53 + 95.5+ 0.586 = 156.616 mm.
= 0.156 m.
Now tray spacing + weir height = 0.38 + 0.05 = 0.43 m.

1
hb 〈 × 0.43
2
Therefore he tray spacing is within acceptable limits.
Downcomer Residence Time :-
The residence time of the liquid over the downcomer is given by;
Ad hbc ρ L 0.02541 × 0.156 × 1083.65

tr = = = 4.386 sec .
Lwd 0.9794
This is greater than 3 seconds therefore it is acceptable.
Entrainment :-
L.I.T. Nagpur
The entrainment can be estimated by the following realationships which give

entrainment as a function of percentage flooding.
max imun bottom vapor. flowrate 0.1143

uv = = = 0.79375m / sec .
An 0.144
uv 0.79375
% flooding = = × 100 = 62.996%
u f (bottom ) 1.26
Therefore from graph of FLV Vs % flooding.

(fractional entrainment), ψ = 0.015 , this is less than 0.1, therefore it is acceptable.
Trial Layout :-
0.38m 0.4644m
Number Of Holes :-
L.I.T. Nagpur
Area of one hole,

π
A1 = × d 2 = 1.964 × 10 −5 m 2 / hole
4
Number of holes,
Ah 0.011858
N= = = 604.23 ≈ 605 holes.
A1 1.964 × 10 −5
MECHANICAL DESIGN
Design of shell :-
Taking material of construction as Stainless Steel
Maximum allowable stress f = 1420 kg/cm2
Operating pressure = 101.325 KN/m2 = 101325/(9.81 x 10000)
= 1.033 Kg/cm2
Design pressure is 10% excess of operating pressure = 1.033 x 1.1
= 1.1363 kg/cm2
Thickness of shell (ts) = (P x Di)/(2fJ –P)
= (1.1363 x 46.44)/(2 x 1420 x 0.85 – 1.1363)
= 0.218 mm
Taking allowance = 3 mm
Shell thickness = 3.218
Use thickness of 3.5 mm
Therefore, Outer diameter of the column (Do) = Di + 2t
= 0.4714m
Design of heads :-
Elliptical heads are used
L.I.T. Nagpur
th = (P DiV)/(2fJ)
Where,
Di = internal diameter of the column
P = design pressure = 1.1363 kg/cm2
th = thickness of head
J = welded joint efficiency = 0.85

V = stress intensity factor
And, V = (2 + k2)/6
k = ratio of major axis to minor axis = 2:1 =2
Therefore, V = 1
th = (1.1363 x 46.44 x 1) / (2x1420 x0.85)
=0.0218 cm
= 0.218 mm
Taking allowance = 3 mm
Thickness of head = 3.218 mm

Therefore, use thickness of 3.5mm
Design of gasket and bolt size :-
Gaskets are used for making leak proof joint between two surfaces
Gasket: Asbestos with suitable binder (3mm thick)
Gasket factor m = 2.0
Minimum design sitting stress for asbestos with suitable binder (3 mm
L.I.T. Nagpur
thick) is
Ya = 112 kg / cm2
Go/Gi = [(Ya – Pi x m)/(Ya – Pi (m + 1))]0.5

= [(112 – 1.1363 x 2)/(112 – 1.1363(2+1)] 0.5
= 1.010
Gi = 46.44 + 2 x 0.0816
= 46.6 cm
Go = 1.010 x 46.6
= 47.07 cm
Mean gasket diameter G = (Go + Gi)/2
= 46.835 cm
Basic gasket sitting width
bo = ( Go - Gi )/4
= 0.1175 cm
= 1.2 mm
Taking it as 1 mm.
Effective gasket sitting width as bo is less than 6.3 mm
b = bo
b = 1.2 mm
Force acting on bolt under atmospheric condition

Wm1 = 3.14 x b x G x Ya
= 3.14 x 0.12 x 46.835 x 112
= 1977.514 kg
L.I.T. Nagpur
Force acting on the bolt under operating condition

Wm2 = 3.14 x 2b x G x m x Pi + 3.14 x G2 x Pi / 4
= 3.14 x 2 x0.12 x 46,835 x2 x1.1363 + 3.14 x 46.8352 x 1.1363 / 4
= 2037.85 kg
Maximum bolting area :-
Bolting material is rolled carbon steel.

Am1 = Wm1 / fa
Am2 = Wm2 / fb
Where,
fa = allowable stress for bolt material under atmospheric Conditions = 545 kg / cm2
fb = allowable stress for bolt material under operating condition = 545 kg / cm2
Am1 = 1977.514/545
= 3.628 cm2
Am2 = 2037.85/545
= 3.74 cm2
Therefore, minimum bolting area is taken as 3.74 cm2
No. of bolts = mean diameter of gasket/2.5
= 46.835/2.5
= 18.734
Since the total no. of bolts must be a multiple of 4
No. of bolts = 20
If Am is the area of one bolt then,
L.I.T. Nagpur
Am x 20 = 3.74
Am = 0.187 cm2
Therefore, 3.142 x db2 /4 = 0.187

db = 0.487 cm
Diameter of bolt = 0.487 cm
Pitch circle diameter = outside diameter of gasket + 2xdiameter of bolt + 1.2

= Go + 2 x db + 1.2
= 47.07 + 2 x 0.487 + 1.2
= 49.244 cm
Bolt spacing = (3.14 x pitch circle diameter)/no. of bolts

= 3.14 x 49.244 / 20
= 7.73 cm
Flange design :-
Outside diameter of the flange = Pitch circle diameter + 2 x diameter of bolt

= 49.244 + 2 x o.487
= 50.218 cm
Thickness of the flange tf = G x (Pi/kf)0.5
Where, k = 1/[0.3 + (1.5 x Wm x Hg) /(HxG)]

G = diameter of the gasket load reaction or mean diameter of gasket
L.I.T. Nagpur
Wm = maximum bolt load = 53678.106 kg

Hg = radial distance from gasket load reaction to the bolt circle
= (pitch circle diameter – G)/2
= (49.244 – 46.835)/2
= 1.2045 cm
H = hydrostatic end force

= (3.14 x G2 x Pi)/4
= (3.14 x 46.8352x 1.1363)/4
= 1956.6 Kg
k = 1/[0.3 +(1.5 x 53678.106 x 1.2045)/(1956.6x 46.835)]

= 0.736
tf = 46.835 x (1.1363/0.736x1420)0.5
= 1.544 cm
Design of skirt support :-
The stresses due to vessel dead weights, wind load and seismic load
are taken into account while the column is designed to withstand
maximum values of tensile or compressive stresses.
The stresses are:
L.I.T. Nagpur
1. Due to dead weight
fd = W/(3.14 x Dsk x tsk)
Dsk = outside diameter of skirt support
tsk = thickness of skirt support
W = total weight of the vessel including attachments
Weight of shell can be calculated as :-
lnW = 0.694 + 0.882 lnB
B = {[(L/D) + 1.82] P D3}/(25600 + 1.2P) + 20L
Where W = weight of column without internals (kg)
D = diameter of column (inches)
D = 0.4644 m = 18.283 inches

P = design pressure (Psig)
= 1.1363 kg / cm2 = (14.7 x 1.1363)/1.1 = 15.185 Psig
L = column height of cylindrical shell and heads (inches)
L = 10.968 m = 431.81 inches
Therefore, B = 7638.05 kg
W = 5323.42 kg
Weight of the contents = volume of contents x Avg density
L.I.T. Nagpur
= [(3.14 x 0.46442 x 10.968) x (0.803 x 1084 + 0.197 x 1049)]/4

= 1790.295 kg
Assume, Weight of accessories = 200 kg
∑W = 1790.295 + 200 + 5323.42

= 7313.715 kg
Dsk = Gi = 46.6 cm
fd = ∑W/(3.14 x Dsk x tsk)
= 7313.715/(3.14 x 46.6 x tsk
= 49.98 / tsk kg/cm2
2. Due to wind load
PLW = K1 x K2 X P x H x Do
Where K1 = coeff depending on shape factor = 0.7
K2 = 1
P = wind pressure = 152 kg/m2 (assuming)

Do = 0.4714 m
H = 10.968 + 2 = 12.968 m
L.I.T. Nagpur
PLW = K1 x K2 x P x H x Do
= 0.7 x 1 x 152 x 0.4714 x 12.968
= 581.67 kg
The bending moment due to wind at the base of skirt is
Mw = PLW x H/2
= 581.67x 12.968/2
= 3372.813 kg-m
fw = Mw / Z
= 3372.813/[(3.14 D2sk tsk)/4]
= 19785.67/tsk kg / m2
= 0.528138/tsk kg /cm2
2. Due to seismic load
fs = 4 Mw / (3.14 D2o tsk)

but, Mw = (2 x C x H x W)/3
therefore, fs = (2 x 4 x C x H x W)/(3 x 3.14 D2o tsk)

Where, C = seismic coefficient = 0.8
H = 10.968 + 2 = 12.968 m
W = 7313.715 kg; Do = 0.4714 m
fs = (2 x4 x 0.8 x 12.968 x 7313.715)/(3 x 3.14 x 0.4714 3 x tsk)

= 25.932/tsk kg/cm2
L.I.T. Nagpur
Maximum tensile stress at the bottom of the skirt

= fd - (fw or fs)
= (49.98-25.932)/tsk
= 20.048/tsk kg/ cm2
Permissible tensile stress = 1420 kg/ cm2

tsk = 20.048 / 1420
= 0.0169 cm
= 0.169 mm
fc (max) = (49.98/tsk) + (25.932/tsk)

= 75.912/tsk kg/ cm2
fc (permissible ) = yield point stress / 3

= 2000 / 3
= 666 kg/ cm2
tsk = 75.912/ 666

= 0.114 cm
= 1.14 mm
L.I.T. Nagpur
Therefore, thickness of 2 mm is used.
2. Acetic acid column :-
Input Feed (F):
2) water = 23.827 Kmol/hr
= 44.459 Kmol/hr
Xf1 (CH3COOH) = 20.632/44.459 = 0.464
Xf2 (water) = 23.827/44.459 = 0.803
L.I.T. Nagpur
Top Product (D) :-
Xd1 (water) = 0.9
Xd2 (CH3CO0H) = 0.1
Bottom Product (W):
Xw2 (water) = 0.05
F= D + W
44.459 = D + W --------------------------------------------- (1)
F Xf= D Xd +W Xw
For Acetic acid :-
44.459 × 0.464 = D × 0.1 + W × 0.95
20.632 = 0.1 D + 0.95 W -------------------------------- (2)
L.I.T. Nagpur
Top product (D) = 24 Kmol/hr
Hence, acetic acid in the top product = 0.1 × 24 = 2.4 Kmol/hr = 144 Kg/hr
And, water in the top product =0.9 × 24 = 21.6 Kmol/hr = 388.8 Kg/hr
Acetic acid in the bottoms product = 0.95 × 20.45 = 19.4275 Kmol/hr = 1165.65
Kg/hr
water in the bottoms product = 0.05 × 20.45 = 1.0225 Kmol/hr = 18.405 Kg/hr
Boiling point of water = 100 ºC
Hence, water is more volatile component ( MVC)
Water-Acetic acid (x-y data) :-
x 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
y 0.173 0.32 0.447 0.557 0.654 0.74 0.815 0.883 0.944 1.0
ya = α xa/ 1+( α-1)xa
substitute, y = 0.173 & x= 0.1
we get, α = 1.89
from graph :-
(xd/R+1)min = 0.36
(0.9/R+1)min = 0.36
Therefore, Rmin = 1.5
L.I.T. Nagpur
But, Ropt = 1.5 Rmin
Therefore, Ropt. = 1.5 × 1.5 = 2.25
R = Ln/ D
Hence, Ln = 2.25 × 24 = 54 Kmol/hr
Vn = Ln + D = 54 + 24 = 78 Kmol/hr
Lm = Ln + F = 54 + 44.459 = 98.459 Kmol/hr
Vm = 98.459 – 20.45 = 78.009 Kmol/hr
Therefore, equation of upper operating line :-
R x
yn = x n +1 + d
R +1 R +1
2.25 0.9
yn = x n +1 +
3.25 3.25
Therefore, yn = 0.692 xn+1 + 0.277
Hence, y-intercept = 0.277 & slope = 0.692
Equation of lower operating line (LOL) :-
LM Wx
y m +1 = xM − w
VM VM
L.I.T. Nagpur
98.459 20.45 × 0.05

∴ y m +1 = xm −
78.009 78.009
∴ y m +1 = 1.262x m − 0.013
Therefore, number of theoretical plates = 14 -1=13 (from graph)
One plate is deducted for reboiler
Efficiency of the column = 65%
Therefore actual no. of plates required = 13/0.65 = 20 plates
Feed plate = 6/0.65 = 10th plate.
9. Material of Construction :-
Acetic acid, ketene & acetic anhydride require a

suitable material to be used to avoid any corrosion and spoiling of the product.
Aluminium though can be used throughout the
process except in the hot zones of pyrolysis where stainless steel is used. Stainless
steel 316 and copper are best suitable material that can be used in the process
equipment. Stainless steel for process equipment has an additional advantage over
copper of causing less discolourization and moreover for pure acetic anhydride
L.I.T. Nagpur
condenser silver coils are used. In general stainless steel of composition 33%
chromium, 1.5% aluminium, 1.5% silicon is used.
For storage & transportation of pure acetic
anhydride tanks made of aluminium, stainless steel ( 18% Cr, 8% Ni & 2% Mo ) or
poly-ethylene are generally used. Although glass or enamel containers also may be
employed. Iron is highly resistant to acetic anhydride, provided moisture is
excluded. Hence it is possible to use iron in the production & workup in certain
instances for example in pumps & tanks.
Nickel is avoided in the alloys for a high
temperature applications, since it is reported to accelerate the coking on heater tube
walls unless pacified periodically by special pretreatment or injection of sulfur
compounds.
Cost Estimation & Economics :-
Determining Purchased Equipment cost(PEC) :-
Acetic Anhydride column :-
Internal diameter of the column = Di = 0.4644 m

External diameter of the column = Do = 0.4644 m
Volume of the distillation column = volume of the cylindrical shell
L.I.T. Nagpur
+
volume of elliptical heads
Therefore, V =
(
π DO − DI
2 2
) +
πD 3
= 3.14 ×
( 0.4744 2 − 0.4644 2 ) + 3.14 × 0.46443
4 12 4 12
= 0.118 m
Density of stainless steel = 8000 kg/m3
Hence, weight of the material used for the column = 8000 × 0.118
= 944 kg
Considering the weight of the accessories to be = 150 kg
Hence, total weight of the material used for the column = 1094 kg
Cost of stainless steel = 192 Rs/kg
Cost index of 2004 = 432
Cost index of 2006 = 606.5
L.I.T. Nagpur
Therefore, the cost of the material for the column = (606.5 × 192 × 1094)/432
= 294893.778/- Rs
Cost of fabrication = 50% of the cost of material
Hence, the total cost of the column = 1.5 × 294893.778
= 442340.67 /- Rs.
Considering the cost of accessories i.e. condenser and reboiler to be = 2lakh
Hence, total cost of the column along with the accessories = 642340.67 /- Rs.
Sr. No. Equipment Quantity Cost

1 Acetic acid column 1 622000
2 Waste heat boiler 1 320000
3 Cooler 1 370000
4 Chiller 1 420000
5 Separator 1 325000
6 Ketene absorber 1 678000
7 Tale gas scrubber 1 288000
8 Vacuum jet 1 301000
9 Storage tanks 2 1022000
10 Pyrolysis heater 1 1522000
Total PEC = 642340.67 + 622000 + 320000 + 370000 + 420000 + 325000 +

678000 + 288000 + 301000 + 1022000 + 1522000
Therefore, PEC = 6510340.67 Rs.
L.I.T. Nagpur
For a fluid processing plant the following quantities must be added to the PEC to
get the physical plant cost or the PPC.
Installation charges = 50% of PEC.
= 3255170.335
Piping = 70% of PEC = 4557238.469
Instrumentation = 20% of PEC = 1302068.134
Electrical 10% of PEC = 651034.067
Site development = 5% of PEC = 325517.0335
Buildings and land cost = 1 Crore.
Therefore total Physical plant costs (PPC) = 26601368.71 .
Design and engg. = 30% of PPC = 7980410.613
Contractor’s fees = 5% of PPC = 1330068.436
Contingency = 10% of PPC = 2660136.871
Total indirect costs = 56250000.
Fixed capital investment(FCI) = Total direct costs + Total indirect costs
= 26601368.71 + 11970615.92
= 38571984.63
Working capital(WC) = 40% of FCI
= 15428793.85
Total Capital investment(TCI) = FCI + WC = 50400000
L.I.T. Nagpur
Production Costs :-
 FIXED CHARGES
Depreciation is 10% on machinery and equipment and 3% on buildings.

Depreciation = 0.1 × FCI + 0.03 × Buildings.
= 0.1 × 38571984.63 + 0.03 × 10000000
= 4157198.463
Local taxes = 4% of FCI = 1542879.385
Insurance = 1% of FCI = 385719.8463
Therefore total fixed charges = Depreciation + Local taxes + Insurance
= 6085797.694
 DIRECT PRODUCTION COSTS
Total product charges (TPC):

Fixed charges = 10% of TPC.
Therefore TPC = 60857976.94
Cost of raw material = 25 × 60 × 51 × 24 × 300
= 550800000
Operating labour = 15% of TPC = 9128696.541
Supervisory control and clerical labour = 25% of operating labour
= 2282174.135
L.I.T. Nagpur
Utilities = 20% of TPC = 12171595.39

Maintenance = 10% of FCI = 3857198.463
Operating supplies = 1% of FCI = 385719.8463
Patents and royalties = 5% of TPC = 3042898.847
Plant overheads cost = 15% of TCI = 8100116.772
Manufacture Cost = 650626376.9
 GENERAL EXPENSES
Administrative expenses = 6% of TPC = 3651478.616

Distribution and selling costs = 15% of TPC = 9128696.991
Research & development cost = 5% of TPC = 3042898.8
Financing = 10 % of TCI = 5400077.848
General Expenses = 21223152.26
Therefore, Total production cost(TPC) = Manufacture Cost

+
General Expenses
= 650626376.9 + 21223152.26
= 671849529.2
L.I.T. Nagpur
Selling price = Rs 56 per kg.

Total income = 50 × 19.2 × 102 × 24 × 300 = 705024000
Total profit = Total income − TPC = 3.32 Crore
Tax on income = 40% of total profit = 1.328 Crore.
Net profit = 1.992 Crore.
Dividend = 10% of Net profit = 0.1992 Crore.
Tax on dividend = 10% = 0.01992 Crore.
Therefore total dividend = 0.21912 Crore.
Profit = 1.77288 Crore.
Net Pr ofit 1.77288

Rate Of Return = = × 100 = 35.17%
Total Investment 50400000
Pay Back Period = 1/0.3517 = 2.85 YEARS = 35 MONTHS
L.I.T. Nagpur
Process Control & Instrumentation :-
Digital feedback control of pyrolysis heater :-
The direct digital feedback control of pyroysis

heater is shown in the figure. The temperature inside the pyrolysis heater is
measured by the thermocouple and the signal is sampled using a sampler switch.
The discrete time signal in the analog form is converted in to digital signal by
analog to digital converter. The electronic error detector generates the error which
is the difference between the measured value and the set point. The generated error
is minimized by the digital feedback controller monitored by computer. The output
command signal from the digital feedback controller is converted into analog from
by digital to analog converter. The hold element is used to convert the discrete time
analog signal into the continuous analog signal. Electro-pneumatic transducer is
used to convert the electric signal in to pneumatic signal. The output from the
electro-pneumatic transducer acts on the diaphragm actuator of the pneumatic
control valve which in turn regulates the flowrate of the fuel gas in order to
maintain the temperature inside the pyrolysis heater at a desired value. The signals
are transmitted through the transmission lines. The flowrate of fuel gas is the
manipulated variable.
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Digital Feedforward control of distillation column :-
The direct digital feedforward control of distillation

column is shown in the figure. The two principal disturbances inlet flowrate and
inlet composition are measured and the signals are samples using the sampler
switch. The discrete time signal is converted in to digital form by analog to digital
converter.The electronic comparator generates the errors which are nothing but the
difference between the set points or the desired values and the corresponding
measured values. The generated errors are minimized by the digital feedforward
controller monitored by computer. The output command signals from the computer
are in the digital form and converted in to analog signals using digital to analog
converters. The discrete time signals are converted in to the continuous analog
signal using hold elements. The electro-pneumatic transducers are used to convert
the electric signal in to pneumatic signal.
The pneumatic signal from the electro-pneumatic
transducer in the transmission line used for the inlet feed composition
measurement acts on the diaphragm actuator of the pneumatic control valve which
L.I.T. Nagpur
in turn regulates the steam pressure in the reboiler. The pneumatic signal from the
electro-pneumatic transducer in the transmission line used for inlet feed flowrate
measurement acts on the diaphragm actuator of the pneumatic control valve which
in turn regulates the reflux ratio. The signals are carried through the transmission
lines. The steam pressure in the reboiler and the reflux ratio are the manipulated
variables.
SCADA Configuration :-
The SCADA system configuration consist of

following control units.
1) Supervisory control station

2) PLC & RTU
3) Computer network segment.
The process information such as temperature,

flowrate, composition etc. are communicated between the process plant and PLC’s
of control system.
Sr. No. Control Equipment Sensor

1 Pyrolysis heater Thermocouple
2 Cooler Thermocouple
3 Separator Composition measurement
4 Ketene absorber Thermocouple & Composition measurement
5 Acetic acid column Flowmeter & Composition measurement
6 Acetic anhydride column Flowmeter & Composition measurement
L.I.T. Nagpur
Plant Location & Layout :-
The location of the plant can have a crucial effect on

the profitability of a project, and the scope for future expansion. Many factors must
be considered when selecting a suitable site, the principal factors to consider are:
1. Location, with respect to the marketing area.
2. Raw material supply.
3. Transport facilities.
4. Availability of labour.
5. Availability of utilities: water, fuel, power.
6. Availability of suitable land.
7. Environmental impact, and effluent disposal.
8. Local community considerations.
9. Climate.
10. Political and strategic considerations.
Marketing Area :-
Acetic anhydride is widely used in the production
of dyes as an intermediate. Hence, it is necessary to locate the plant near to dye
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factories. From this prospective Mumbai is the ideal place for acetic anhydride
plant since many dye factories are located close to Mumbai.
Raw Materials :-
The raw material for the plant is acetic acid. As Most
of the acetic acid is produced from petroleum, hence it can be obtained very easily
from the refineries. Hence it is advised that the site of the plant should be nearer to
the refineries, so that the transportation cost is reduced. From this prospective
Mumbai or any place nearer to Mumbai is the most suitable region for the plant.
Transport :-
The transport of materials and products to and from the
plant will be an overriding consideration in site selection. If practicable, a site
should be selected that is close to at least two major forms of transport: road, rail,
waterway (canal or river), or a sea port. Road transport is being increasingly used,
and is suitable for local distribution from a central warehouse. Rail transport will
be cheaper for the long-distance transport of bulk chemicals. Air transport is
convenient and efficient for the movement of personnel and essential equipment
and supplies, and the proximity of the site to a major airport should be considered.
All these facilities of transport are very easily available in a place like Mumbai,
L.I.T. Nagpur
hence from the prospective transportation facilities Mumbai is the ideal place for
the project.
Availability Of Labour :-
Labour will be needed for construction of the plant
and its operation. Skilled construction workers will usually be brought in from
outside the site area, but there should be an adequate pool of unskilled labour
available locally; and labour suitable for training to operate the plant. Skilled
tradesmen will be needed for plant maintenance. Local trade union customs and
restrictive practices will have to be considered when assessing the availability and
suitability of the local labour for recruitment and training.
Utilities (services)
Chemical processes invariably require large
quantities of water for cooling and general process use, and the plant must be
located near a source of water of suitable quality. Process water may be drawn
from a river, from wells, or purchased from a local authority. At some sites, the
cooling water required can be taken from a river or lake, or from the sea; at other
locations cooling towers will be needed.
L.I.T. Nagpur
Electrical power will be needed at all sites. A

competitively priced fuel must be available on site for steam and power generation.
Environmental impact, and Effluent disposal :-

All industrial processes produce waste products, and
full consideration must be given to the difficulties and cost of their disposal. The
disposal of toxic and harmful effluents will be covered by local regulations, and
the appropriate authorities must be consulted during the initial site survey to
determine the standards that must be met. An environmental impact assessment
should be made for each new project, or major modification or addition to an
existing process.
Local Community Considerations :-

The proposed plant must fit in with and be
acceptable to the local community. Full consideration must be given to the safe
location of the plant so that it does not impose a significant additional risk to the
community. On a new site, the local community must be able to provide adequate
facilities for the plant personnel: schools, banks, housing, and recreational and
cultural facilities
L.I.T. Nagpur
Land (site considerations)

Sufficient suitable land must be available for the
proposed plant and for future expansion. The land should ideally be flat, well
drained and have suitable load-bearing characteristics. A full site evaluation should
be made to determine the need for piling or other special foundations.
Climate :-
Adverse climatic conditions at a site will increase
costs. Abnormally low temperatures will require the provision of additional
insulation and special heating for equipment and pipe runs. Stronger structures will
be needed at locations subject to high winds (cyclone/hurricane areas) or
earthquakes.
Political and strategic Considerations :-

Capital grants, tax concessions, and other inducements
are often given by governments to direct new investment to preferred locations;
such as areas of high unemployment. The availability of such grants can be the
overriding consideration in site selection.
L.I.T. Nagpur
GENERAL PLANT LAYOUT FOR A CHEMICAL INDUSTRY:
Maintain
Future
-ance Storage
Building
Expa- Building
Main Plant
nsion gg
Scrap
Research Yard
and
Develo-
pment
Centre
Sec-
Quality Fire Medical
Control urity
Station Centre
Laboratory
Cooling
Control towers
ETP
Room
Tank Yard
Power Wash and Utilities
Changing
Station Room Genera-
L.I.T. Nagpur tion
Sec- Garden
urity
Training Administration
Parking
Centre Building
Space
Canteen
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Nagpur. MAnufacture of Acetic Anhydride

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Nagpur. MAnufacture of Acetic Anhydride

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Manufacture of acetic anhydride

Acetic anhydride also known as ethanoic anhydride or

About 40% of the acetic anhydride produced throughout

Apart from this acetic anhydride has many other utilities

Production of acetic anhydride (in kt) :-

Major producers in India :-

2 Andhra sugars Ltd, Andhra. 3058

3 Ashok Brothers, Mumbai 6600

4 IOL chemicals & pharmaceuticals Ltd, 12000

6 Trichy distillers & chemicals Ltd, Trichy 2,100

8 Naran Lala Private Ltd, Gujrat -

9 FISCHER Chemic Ltd, Chennai -

10 Mysore Acetate & chemicals Ltd., Mysore 6000

Dyes and pigments :-

Demand and pricing :-

The prices are dependent on the prices of the raw

1.1 Historical background :-

The oldest process for making acetic anhydride is

the oxidation of acetaldehyde. In United States 25% of the acetic anhydride is

1.2. Physical Properties of Raw Material:-

 Auto-ignition temperature (°C) 565

1.3. Physical Properties Of The Product :-

Property Vapour Liquid

 Molecular Weight 102.090 102.090

 ΔGf°(cal/g) at 25°C -1116.0 -1144.8

1.4. Chemical Properties Of Acetic Anhydride :-

 On chlorination it produces chloro-acetyl chloride. In addition small quantities

(CH3CO)2O + Cl2 → Cl-CH2COCl + CH3COOH

 On reaction with hydrogen chloride under pressure it gives acetyl chloride.

(CH3CO)2O + HCl → CH3OCl + CH3COOH

form acetic acid.

 On reaction with acetaldehyde it forms ethylidene di-acetate.

(CH3CO)2O + CH3CHO → CH3CH(OCOCH3)2

1.5. Storage & Transportation :-

For storage & transportation of pure acetic

1.6. Health & Safety Aspects :-

Acetic anhydride penetrates the skin

Acetic acid is dangerous in combination with various

 The biggest use of acetic anhydride is in the manufacture of cellulose

 It is used in the production of polymethyl-acylamide or hard foam, acetic

anhydride is used for binding ammonia that is liberated on conversion of two

 It is used in dyeing industry, where acetic anhydride is used chiefly in mixtures

 It is used in the manufacture of various organic intermediates such as chloro-

acetyl chloride, di-acetyl peroxide, higher carboxylic anhydrides, acetates and

 It is used in the manufacture of certain pharmaceutical products such as acetyl

 It is used in the detergent industry for the production of cold-bleaching

 It is used in the manufacture of explosives, particularly hexogen production.

 It is used in the manufacture of acetylated plastic auxiliaries such as glycerol

 It is used in the manufacture of flavours & fragrances.

 It is used n metallography, etching & polishing of metals and in semiconductor

2. Different Routes Of Manufacture :-

(a) Acetaldehyde oxidation :-

Acetaldehyde oxidation for the production of acetic

CH3COOOH + CH3CHO → (CH3CO)2O + H2 O

The last reaction is to be minimized if acetic

(b) Methyl Acetate Carbonylation :-

Acetic anhydride can be made by the carbonylation

CH3COOH + CH3OH → CH 3COOCH3 + H2O , ∆H= -4.89

CH3COOCH3 + CO → (CH3CO)2O , ∆H= -94.8 KJ/mol

The catalyst stream for the methyl acetate carbonylation

(c) Ketene processes :-

(i) Acetone Cracking :-