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 United 1961 571 1971 686 47 96 1974 741 74 115 1979 91 114 1980 85 150 1981 567 77 145 1982 481 76 144 1989 778 108 205 1990 830 112 1160 1996 1000 2001 1160 -
States Germany 32 Japan 33
Major producers in India :Sr. No. 1 2 3 4 5 6 7 8 9 10 Manufacturer VAM Organics Ltd, Andhra sugars Ltd, Andhra. Ashok Brothers, Mumbai IOL chemicals & pharmaceuticals Ltd, Punjab Vasantdada Shetkari SSK Trichy distillers & chemicals Ltd, Trichy R L G Group of industries, Gujrat Naran Lala Private Ltd, Gujrat FISCHER Chemic Ltd, Chennai Capacity(TPA) 33000 3058 6600 12000 3000 2,100 10000 -
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.
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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 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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Two other methods also were used in the past:
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) Boiling point at 760mm Hg (C)
565 118.1 colourless 57.2 321.6 60.0530 -208.7 -116.2 44.7 96.8 0.375 1.3718 0.468 27.6 acrid 1.18 0.82 1.049
Colour Critical pressure, (atm)

Critical temperature, (C)
Molecular Weight
Heat of Combustion (Kcal/mole) Heat of Formation (Kcal/mole) Heat of Fusion (cal/g)
Heat of Vapourisation (cal/g)

Heat of Solution at 18C (Kcal/mole)
Refractive index Specific Heat at 0C (cal/g) Surface Tension at 20C in air, (dyne/cm)
Taste
Viscosity (cp) At 20C At 40C

Specific Gravity
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1.3.
Physical Properties Of The Product :-
Acetic Anhydride :Property Molecular Weight Melting Point (C) Normal Boiling Point (C) Specific Gravity Coefficient of expansion (20C) Critical Temperature (C) Critical Pressure (atm) Critical Volume (cc/g-mol) Surface Tension (dyne/cm, 20C) air Viscosity (cp, 20C) Specific Heat (cal/g C) Heat of Fusion (cal/g) Heat of Vapourisation (at NBP, cal/g) Hf (cal/g) at 25C Gf(cal/g) at 25C Heat of Hydrolysis (cal/g) at 25C Vapour 102.090 3.52 0.008 0.23 -1347.8 -1116.0 326 43 290 Liquid 102.090 -73 139 1.084 0.00112 33 0.91 0.434 24.6 93 -1460.9 -1144.8 136.9
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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 Acetic anhydride + Cl2 Cl-CH2COCl chloro-acetyl chloride
On reaction with hydrogen chloride under pressure it gives acetyl chloride.
+ CH3COOH Acetic acid
(CH3CO)2O Acetic anhydride
HCl
CH3OCl acetyl chloride
It undergoes hydrolysis slowly with water but rapidly hydrolysed with alkali to
form acetic acid. (CH3CO)2O Acetic anhydride + H2 O 2CH3COOH Acetic acid
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On reaction with acetaldehyde it forms ethylidene di-acetate. (CH3CO)2O Acetic anhydride + CH3CHO CH3CH(OCOCH3)2 Ethylidene di-acetate
Acetaldehyde
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 60C at 1atm pressure and 70C 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 Acetaldehyde CH3COOOH Peracetic acid + CH3CHO Acetic acid + O2 CH3COOOH peracetic acid (CH3CO)2O + H2 O
Acetic anhydride
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(CH3CO)2O Acetic anhydride
H2 O
2CH3COOH Acetic acid
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 KJ/mol Acetic acid Methanol Methyl acetate (CH3CO)2O , H= -94.8 KJ/mol + CH3OH CH 3COOCH3 + H2O , H= -4.89
CH3COOCH3 + CO 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 200C 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 700C 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 Acetone CH2=CO Ketene + CH4 Methane
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CH2=CO Ketene
(CH3CO)2O + Acetic anhydride
H20
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 700C to form ketene, the 2nd step involves the reaction of ketene with acetic acid to form acetic anhydride at a temperature of about 50C. The reactions taking place are :CH3COOH Acetic acid CH2=CO + H2 0 , Ketene H=147 KJ/mol
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CH2=CO Ketene
CH3COOH Acetic acid
(CH3CO)2 ,
H= -63 KJ/mol
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.
(a)
Process Selection :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 Acetic acid 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.
Acetic anhydride
(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.
(i)
Process Description :Principle :Production of acetic anhydride from
acetic acid comprises of two steps :(a) (b) Pyrolysis of acetic acid to form ketene. 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 700C, 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 (triethyl, tri-cresyl, di-methyl ammonium, pyridium phosphates, etc.) which are added directly and continuously in to the gas feed stream, at the rate of 0.20.5% 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 45-55C, at reduced pressure 7-25 KPa. Higher temperatures and pressures facilitate the dimerisation of ketene to di-ketene, whose boiling point is 127.4C 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) (b) (c) (d)
Acetic acid pyrolysis Ketene absorption Acetic acid purification. 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 110C 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 700C, first receive an inline injection of ammonia to neutralize the catalyst. They are then cooled rapidly to 0C 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 45-55C 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 :A B 1.0971 C 2.8921 10-3 D 2.9275 10-6
Property
Specific -18.944 Heat(Cp), J/mol K
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Hf (KJ/mol) G (KJ/mol)
-44.988 -47.916
-0.00983 0
2.4610-6 5.0410-6
(ii)
Ketene :A -44.988 -47.916 B -0.00983 0 C 2.4610-6 5.0410-6 D -
Property Hf (KJ/mol) G (KJ/mol)
(iii)
Water :A B -3.995310-2 -0.01226 C -2.110310-4 2.7710-6 D 5.346910-7 -
Property
Specific 92.053 Heat(Cp), J/mol K Hf (KJ/mol) -238.41
Also, G at 298K for Water = 238.59 Kj/hr
(iv)
Acetic Anhydride :A B 8.8879 10-1 -0.00983 0 C -2.6534 10-3 2.4610-6 5.0410-6 D 3.3501 10-6 -
Property
Specific 71.831 Heat(Cp), J/mol K Hf (KJ/mol) -44.988 G (KJ/mol) -47.916
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Reaction 1 :CH3COOH Acetic acid

a)
CH2=CO + Ketene
H2 O
Heat of Reaction :-
Ketene :-
H0 = A + BT + CT2 (KJ/mol) H0 = -44.988 0.00983T + 2.4610-6T2 Therefore. at 298K H0298 = -44.988 0.00983298 + 2.4610-62982 = -74.063 KJ/mol And, at 700 C that is at 973K H0973 = -44.988 0.00983973 + 2.4610-69732 = -51.23 KJ/mol
Acetic acid :-
H0 = A + BT + CT2 (KJ/mol) H0 = -422.584 4.835410-4T + 2.4610-6T2 Therefore. at 298K H0298 = -422.584 4.835410-4298 + 2.333710-52982 = -434.84 KJ/mol
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And at 973K H0973 = -422.584 4.835410-4973 + 2.333710-59732 = -408.3 KJ/mol

Water :-
H0 = A + BT + CT2 (KJ/mol) H0 = -238.41 0.01226T + 2.7710-6T2 Therefore. at 298K H0298 = -238.41 0.01226298 + 2.7710-62982 = - 241.8 KJ/mol And at 973K H0973 = -238.41 0.01226973 + 2.7710-69732 = -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 H0reaction = H products H reactants = ( 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 + 0T + 5.0410-6T2 Therefore, At 298K G0298 = -47.916 + 0298 + 5.0410-62982 = -47.47 KJ/mol
Acetic acid :-
G0 = A + BT + CT2 (KJ/mol) G0 = -435.963 + 1.934610-1T + 1.636210-5T2 Therefore, At 298K G0298 = -435.963 + 1.934610-1298 + 1.636210-52982 = -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 = (-79.631000)/(8.314 298) = -32.14 Therefore, K298 = 1.110-14 Now,
dlnK H o = dT RT
Therefore, ln(K2/K1) = (-H0298 /R) [(1/T2)-(1/T1)] ln(K2/K1) = (-118.9771000/ 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 Acetic acid Ketene (CH3CO)2 Acetic Anhydride
(a)
Heat of Reaction :-
Ketene :-
H0 = A + BT + CT2 (KJ/mol) H0 = -44.988 0.00983T + 2.4610-6T2 Therefore, at 50 C that is at 323K H0323 = -44.988 0.00983323 + 2.4610-63232 = -47.9 KJ/mol
Acetic acid :-
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H0 = A + BT + CT2 (KJ/mol) H0 = -422.584 4.835410-4T + 2.4610-6T2 Therefore, at 323K H0323 = -422.584 4.835410-4323 + 2.333710-53232 = -420.23 KJ/mol
Acetic Anhydride :-
H0 = A + BT + CT2 (KJ/mol) H0 = -554.715 8.412410-2T + 4.361810-5T2 Therefore, at 323K H0323 = -554.715 8.412410-2323 + 4.361810-53232 = -577.615 KJ/mol And at 323K H0reaction = H products H reactants = (H0acetic anhydride ) ( H0ketene + H0acetic acid ) = (-577.615) (-47.9 420.23) = -109.485 KJ/mol
(b) Feasibility of Reaction :Ketene :-
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G0 = A + BT + CT2 (KJ/mol) G0 = -47.916 + 0T + 5.0410-6T2 Therefore, At 323K G0323 = -47.916 + 0323 + 5.0410-63232 = -47.39 KJ/mol
Acetic acid :-
G0 = A + BT + CT2 (KJ/mol) G0 = -435.963 + 1.934610-1T + 1.636210-5T2 Therefore, At 323K G0323 = -435.963 + 1.934610-1323 + 1.636210-53232 = -371.75 KJ/mol
Acetic Anhydride :-
G0 = A + BT + CT2 (KJ/mol) G0 = -578.076 + 3.3162 10-1T + 2.5188 10-5T2 Therefore, at 323K G0323 = -578.076 + 3.3162 10-1323 + 2.5188 10-53232 = -468.334 KJ/mol
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Thus, G0reaction = G products G reactants = G0acetic anhydride ( G0ketene + G0acetic acid ) Hence, at 323K G0323 = -468.334 (47.39371.75) = 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
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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 :CH3COOH + CH2=CO Acetic acid Ketene (CH3CO)2 Acetic Anhydride
% 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
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% 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 Acetic acid CH2=CO Ketene + H2O
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
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(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 Acetic acid Water Ketene Flue gases Input (Kmol/hr) 30.1637 Output (Kmol/hr) 3.6304 23.83 23.83 0.0553
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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 Acetic acid Input (Kmol/hr) 3.612 Output (Kmol/hr) ( Upstream ) 2.3478 Output (Kmol/hr) ( downstream ) 0.2383
L.I.T. Nagpur
Water Ketene Flue gases
23.782 23.806 0.055
0.715 23.59 0.055
1.2565 23.115 -
(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 Acetic acid Water Ketene Flue gases

Acetic anhydride
Input (Kmol/hr) 49.44 0.715 23.59 0.055

-
Output (Kmol/hr) ( Upstream ) 19.368 12.816 1.18 0.055

2.6892
Output (Kmol/hr) ( downstream ) 4.842 0.00286 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 Acetic acid Water Ketene Flue gases Acetic anhydride
Input(Kmol/hr) Output (Kmol/hr) ( Upstream ) 19.368 0.097 0.712 1.18 0.055 2.6892 0.01424 1.18 0.055 0.0268
Output (Kmol/hr) ( downstream ) 19.271 0.698 2.6623
(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 Acetic acid Input (Kmol/hr) 0.097 Output (Kmol/hr) (Upstream) Output (Kmol/hr) (Downstream) 0.0968
L.I.T. Nagpur
Water Ketene Flue gases Acetic anhydride
0.01424 1.18 0.055 0.0268
1.18 0.055 -
0.01417 0.02677
(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 Total feed to the distillation column = 4.842 + 19.7208 = 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
Mole fraction of components in the top product :Xd1 (CH3CO0H) = 0.9 Xd2 (Acetic anhydride) = 0.1
Bottom Product (W):
Mole fraction of components in the bottom product :Xw1 (CH3COOH) = 0.01 Xw2 (Acetic anhydride) = 0.99

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) Solving equations 1 & 2, we get :Top product (D) = 5.164 Kmol/hr
L.I.T. Nagpur
Bottom product (W) = 19.398 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 = 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 :Specific heat (J/mol K) Latent Heat of Vaporization ( cal/g)
Component
Acetic Acid -18.9441.0971T + 2.892110-6T2 Acetic Anhydride (i) 78.831 8.887910-1T+ 2.653410-6T2
96.8 93
Pyrolysis Reactor :-
Reaction Temperature = 700C Temperature of acetic acid entering = 110 C

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)
Tenter
Q1
Q2
Q1 = n
Tref
CpdT
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
Tenter
CpdT
3 2 = 3.6304 ( 18.944 + 1.0971 T + 2.8921 10 T )dT 973
773
= - 685.341 103 KJ/hr Heat lost = Heat gained by the cooling medium (water)
Inlet temperature of water = 25C Outlet temperature of water = 210C Cooling water flowrate = ? Heat gained = mwater Cpwater T mwater = 685.341 103/[4.184 (483-298)] = 885.4 Kg/hr (iii) Cooler :Texit
Tenter
CpdT
3 2 = 3.6304 ( 18.944 + 1.0971 T + 2.8921 10 T )dT 773
473
= - 726.226 103 KJ/hr
L.I.T. Nagpur
Heat lost = Heat gained by the cooling medium (water) Inlet temperature of water = 25C Outlet temperature of water = 195C Cooling water flowrate = ? Heat gained = mwater Cpwater T mwater = 726.226 103/[4.184 (468-298)] = 1021.012 Kg/hr (iv) Chiller :Texit

273
Tenter
CpdT
3 2 = 3.6304 ( 18.944 + 1.0971 T + 2.8921 10 T )dT 473
= -283.495 103 KJ/hr Heat lost = Heat gained by the cooling medium (ammonia) Inlet temperature of ammonia = -33C Outlet temperature of ammonia = 50C 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 :CH3COOH + CH2=CO Acetic acid Ketene (CH3CO)2 Acetic Anhydride
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 (FHF) = Heat in acetic acid + Heat in water

Texit
= nacetic acid
Tenter 382
CpdT
Texit
+ nwater
Tenter
CpdT
20.632 ( 18.944 + 1.0971 T + 2.8921 10 3 T 2 )dT

273
23.827 (92.053 3.9953 10 2 T 2.1103 10 4 T 2 )dT

273
382
= =
765.31 103 + 239.075 103
1004.385 103 KJ/hr
Heat in Distillate (DHd) = Heat in acetic acid + Heat in water
L.I.T. Nagpur
Texit
= nacetic acid
Tenter
CpdT
Texit
nwater
Tenter
CpdT
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
373
(DHd)
= =
80.50 103 + 198.834 103 279.334 103 KJ/hr
Heat in bottoms (WHW) = Heat in acetic acid + Heat in water

Texit
nacetic acid
392
Tenter
CpdT
Texit
+ nwater
Tenter
CpdT
3 2 = 19.4275 ( 18.944 + 1.0971 T + 2.8921 10 T )dT 273
1.0225 (92.053 3.9953 10 2 T 2.1103 10 4 T 2 )dT

273
392
= =
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 (FHF) = Heat in acetic acid + Heat in acetic anhydride

Texit
= nacetic acid
Tenter 403
CpdT
Texit
+ nanhydride
Tenter
CpdT
4.842 ( 18.944 + 1.0971 T + 2.8921 10 3 T 2 )dT

273
19.7208 (71.831+ 8.8879 101 T 2.6534 103 T 2 )dT

273
403
= =
221.491 103 + 202.099 103 423.59 103 KJ/hr
Heat in Distillate (DHd) = Heat in acetic acid + Heat in anhydride
Texit
= nacetic acid
Tenter
CpdT
Texit
nanhydride
Tenter
CpdT
L.I.T. Nagpur
4.6476 ( 18.944 + 1.0971 T + 2.8921 10 3 T 2 )dT

273
392
0.5164 (71.831+ 8.8879 101 T 2.6534 10 3 T 2 )dT

273
392
(DHd)
= 191.272 103 + 4.844 103 = 196.117 103 KJ/hr
Heat in bottoms (WHW) = Heat in acetic acid + Heat in anhydride

Texit
nacetic acid
413
Tenter
CpdT
Texit
+ nanhydride
Tenter
CpdT
3 2 = 0.194 ( 18.944 + 1.0971 T + 2.8921 10 T )dT 273
19.2 (71.831+ 8.8879 101 T 2.6534 103 T 2 )dT

273
413
= =
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 :Acetic Anhydride column :-
(i)
Input Feed (F):
1) Acetic acid = 4.842 Kmol/hr 2) Acetic anhydride = 19.7208 Kmol/hr Total feed to the distillation column = 4.842 + 19.7208 = 24.563 Kmol/hr
Xf1 (CH3COOH) = 4.842/24.563 = 0.197 Xf2 (Acetic anhydride) = 19.7203/24.563 = 0.803

Top Product (D) :-
Mole fraction of components in the top product :Xd1 (CH3CO0H) = 0.9 Xd2 (Acetic anhydride) = 0.1
L.I.T. Nagpur
Bottom Product (W):
Mole fraction of components in the bottom product :Xw1 (CH3COOH) = 0.01 Xw2 (Acetic anhydride) = 0.99

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) Solving equations 1 & 2, we get :Top product (D) = 5.164 Kmol/hr Bottom product (W) = 19.398 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 C Boiling point of acetic acid = 139 C Hence, acetic acid is more volatile component ( MVC) Acetic acid- acetic anhydride (x-y data) :x y 0.1 0.2 0.225 0.41 0.3 0.56 0.4 0.66 0.5 0.6 0.7 0.735 0.795 0.85 0.8 0.9 0.9 0.94 1.0 1.0
ya = xa/ 1+( -1)xa substitute, y = 0.225 & x= 0.1 we get, = 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 :-
yn =
x R x n +1 + d R +1 R +1
0.9 3.6915 x n +1 + 4.6915 4.6915
yn =
Therefore, yn = 0.7868 xn+1 + 0.192 Hence, y-intercept = 0.192 & slope = 0.7868 Equation of lower operating line (LOL) :-
y m +1 =
Wx w LM xM VM VM
L.I.T. Nagpur
y m +1 =
19.398 0.01 43.626 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 = 100 103 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;
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( v ) bottom =
P M avg RT 127.926 (60 0.9 + 102 0.1) 273 101.325 22.414 392
( v ) bottom =
( 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.
( l ) top = 1084 0.99 + 1049 0.01 ( l ) top = 1083.65Kg / m 3 .
At the top of the distiilation column vapor density can be calculated as follows;
( v ) top = P M avg RT 101.325 (60 0.01 + 102 0.99) 273 101.325 22.414 413
( v ) top =
( 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.
( l ) top = 1084 0.1 + 1049 0.9 ( 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 : top
P ( L V ) 12 = 10 M 143.56 (1052.5 1.995 ) 12 = 10 (60 0.9 + 102 0.1)
4 4
top
top = 30.45dyne / cm = 0.03045 N / m
Similarly :L.I.T. Nagpur
bottom
P ( L V ) 12 = 10 M
top = 0.03406 N / m
Liquid-vapor flowrate factor FLV is given by :-
FLV (top ) =
Ln Vn
V L
19.063 1.995 = 0.0342. 24.227 1052.5
FLV ( bottom ) = 0.1063
L = m Vm
V L
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
K 1 (bottom )
= 0.086 0.02
= 0.1067
0 .2
K 1 (TOP )
= 0.096 0.02
= 0.0935
Maximum velocity at top and bottom can be calculated as follows; Bottom: u f = k1

L V 1083.65 3.782 = 0.1067 = 1.8m / s. V 3.782
Top: u f = k1
L V 1052.5 1.995 = 0.0935 = 2.145m / s. V 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
Bottom Q =
Lm M 1555.372 = = 0.1143m 3 / s. V 3600 3.782 3600
Top Q =
1555.372 = 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 = = 0.0907m 2 . uv 1.26
Net area(An) bottom =
Net area(An) top =
Q 0.2165 = = 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
Therefore, Bottom area =
0.0907 = 0.1067 m 2 . 0.85
Top area =
0.144 = 0.1694m 2 . 0.85
Now, area =
2 di . 4
Column diameter can be calculated as follows;

Bottom = . Top = 0.144 4 = 0.4644m. 0.1067 4 = 0.3685m
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. 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 = 0.10.11858 = 0.011858 m2.
For 15% downcomer area, from graph of (Ad/Ac) 100 Vs
Iw Dc
For, (Ad/Ac) = 0.15,
Iw = 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
LW =
3525.88 = 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:
how = 750(
Where,
Lw 2 / 3 ) Llw
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. Maximum how = 750(
0.9794 ) 2 / 3 = 13.31 mm. 1083.65 0.38
Minimum how = 750(
0.6856 ) 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
uh =
Where,
[ K 2 0.9(25.4 d h )] V
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) 3.782
uh =
= 6.14m / sec .
Actual minimum vapour velocity is given by, Actual uh = Minimum vapour rate/Ah
0.7 0.1143 = 6.747 m / sec . 0.011858
uh =
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 = = 9.64m / sec . hole area 0.011858
u h (max) =
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.
hD = 51[
u h 2 V ] Co L
= 51[
9.64 2 3.782 ] = 23.44mm. ..(bottom) 0.84 1083.65
Residual Head :-
12.5 10 3 hr = L
= 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 = 0.040.38 = 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:
hdc = 166[
Lwd 2 ] L Am
Where, Am = Ad or Aap whichever is smaller. Lwd = liquid flowrate in the downcomer.
hdc = 166[
0.9794 ]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 L 0.02541 0.156 1083.65 = = 4.386 sec . Lwd 0.9794
tr =
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 = = 0.79375m / sec . An 0.144
uv =
% flooding =
uv u f (bottom )
0.79375 100 = 62.996% 1.26
Therefore from graph of FLV Vs % flooding. (fractional entrainment), = 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,
A1 =
Number of holes,
N=
d 2 = 1.964 10 5 m 2 / hole 4
Ah 0.011858 = = 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 Where,
= (P DiV)/(2fJ)
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 Am2 = 1977.514/545 = 3.628 cm2 = 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):
1) Acetic acid = 20.632 Kmol/hr 2) water = 23.827 Kmol/hr Total feed to the distillation column = 20.632 + 23.827 = 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) :-
Mole fraction of components in the top product :Xd1 (water) = 0.9 Xd2 (CH3CO0H) = 0.1
Bottom Product (W):
Mole fraction of components in the bottom product :Xw1 (CH3COOH) = 0.95 Xw2 (water) = 0.05

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) Solving equations 1 & 2, we get :-
L.I.T. Nagpur
Top product (D) = 24 Kmol/hr Bottom product (W) = 20.45 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 acetic acid = 118 C Boiling point of water = 100 C Hence, water is more volatile component ( MVC) Water-Acetic acid (x-y data) :x y 0.1 0.2 0.173 0.32 0.3 0.4 0.5 0.6 0.447 0.557 0.654 0.74 0.7 0.8 0.9 1.0 0.815 0.883 0.944 1.0
ya = xa/ 1+( -1)xa substitute, y = 0.173 & x= 0.1 we get, = 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 :-
yn =
x R x n +1 + d R +1 R +1
0.9 2.25 x n +1 + 3.25 3.25
yn =
Therefore, yn = 0.692 xn+1 + 0.277 Hence, y-intercept = 0.277 & slope = 0.692 Equation of lower operating line (LOL) :y m +1 = Wx LM xM w VM VM
L.I.T. Nagpur
y m +1 =
20.45 0.05 98.459 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 =
DO DI
2
D 3 ( 0.4744 2 0.4644 2 ) + 3.14 0.46443 = 3.14 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. 1 2 3 4 5 6 7 8 9 10
Equipment Acetic acid column Waste heat boiler Cooler Chiller Separator Ketene absorber Tale gas scrubber Vacuum jet Storage tanks Pyrolysis heater
Quantity 1 1 1 1 1 1 1 1 2 1
Cost 622000 320000 370000 420000 325000 678000 288000 301000 1022000 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 Contractors 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 = 100 = 35.17% Total Investment 50400000
Rate Of Return =
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.
L.I.T. Nagpur
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 PLCs of control system. Sr. No. 1 2 3 4 5 6 Control Equipment Pyrolysis heater Cooler Separator Ketene absorber Acetic acid column Acetic anhydride column Sensor Thermocouple Thermocouple Composition measurement Thermocouple & Composition measurement Flowmeter & Composition measurement 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
L.I.T. Nagpur
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 -ance Building
Future Expansion
Storage
Main Plant
Building
Research and Development Centre Quality Control Laboratory
Scrap Yard
gg
Fire Station
Medical Centre
Security Cooling towers
ETP
Control Room Tank Yard
Power Station Security
Wash and Changing
Utilities Genera-
Room L.I.T. Nagpur Garden
tion
Parking Space
Training Centre
Administration Building
Canteen
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Acetic Anhydride

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Acetic Anhydride

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Manufacture of acetic anhydride

Manufacture of acetic anhydride

States Germany 32 Japan 33

Mysore Acetate & chemicals Ltd., Mysore 6000

Manufacture of acetic anhydride

Manufacture of acetic anhydride

Manufacture of acetic anhydride

Import :Market estimated at Rs. 90 crs. Import not high - around 3%

Price :Historical (1994 - 1999): 45 Rs./kg , Current: 50 Rs/kg.

Manufacture of acetic anhydride

Two other methods also were used in the past:

Manufacture of acetic anhydride

Colour Critical pressure, (atm)

Heat of Vapourisation (cal/g)

Viscosity (cp) At 20C At 40C

Manufacture of acetic anhydride

Physical Properties Of The Product :-

Manufacture of acetic anhydride

+ CH3COOH Acetic acid

(CH3CO)2O Acetic anhydride

CH3OCl acetyl chloride

+ CH3COOH Acetic acid

form acetic acid. (CH3CO)2O Acetic anhydride + H2 O 2CH3COOH Acetic acid

Manufacture of acetic anhydride

Health & Safety Aspects :Acetic anhydride penetrates the skin

Manufacture of acetic anhydride

Manufacture of acetic anhydride

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

Manufacture of acetic anhydride

Different Routes Of Manufacture :-

Manufacture of acetic anhydride

(CH3CO)2O Acetic anhydride

2CH3COOH Acetic acid

CH3COOCH3 + CO Methyl acetate

Manufacture of acetic anhydride

(c) Ketene processes :(i) Acetone Cracking :-

Manufacture of acetic anhydride

+ CH3COOH Acetic acid

(CH3CO)2O + Acetic anhydride

Acetic Acid Dehydration :-

Manufacture of acetic anhydride

CH3COOH Acetic acid