Professional Documents
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Acetic Anhydride
Acetic Anhydride
L.I.T. Nagpur
1961
571
States
Germany 32
Japan
33
1971
686
1974
741
1979
-
1980
-
1981
567
1982
481
1989
778
1990
830
1996
1000
2001
1160
47
96
74
115
91
114
85
150
77
145
76
144
108
205
112
1160
Manufacturer
Capacity(TPA)
33000
L.I.T. Nagpur
3058
6600
12000
3000
2,100
10000
6000
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.
L.I.T. Nagpur
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.
L.I.T. Nagpur
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.
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
L.I.T. Nagpur
565
118.1
Colour
colourless
57.2
321.6
Molecular Weight
60.0530
-208.7
-116.2
44.7
96.8
0.375
Refractive index
1.3718
0.468
27.6
Taste
acrid
Viscosity (cp)
At 20C
1.18
L.I.T. Nagpur
At 40C
0.82
Specific Gravity
1.3.
1.049
Vapour
Liquid
Molecular Weight
102.090
102.090
-73
139
Specific Gravity
3.52
1.084
0.00112
326
43
290
33
0.008
0.91
0.23
0.434
24.6
93
Hf (cal/g) at 25C
-1347.8
-1460.9
L.I.T. Nagpur
Gf(cal/g) at 25C
-1116.0
-1144.8
136.9
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
Acetic anhydride
Cl-CH2COCl
+ CH3COOH
chloro-acetyl
Acetic acid
chloride
On reaction with hydrogen chloride under pressure it gives acetyl chloride.
(CH3CO)2O
Acetic anhydride
HCl
CH3OCl
acetyl chloride
+ CH3COOH
Acetic acid
It undergoes hydrolysis slowly with water but rapidly hydrolysed with alkali to
form acetic acid.
L.I.T. Nagpur
(CH3CO)2O
H2 O
2CH3COOH
Acetic anhydride
Acetic acid
CH3CHO
CH3CH(OCOCH3)2
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/m 3. When handling acetic anhydride, rubber
L.I.T. Nagpur
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.
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.
L.I.T. Nagpur
It is used in the manufacture of various organic intermediates such as chloroacetyl 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.
Small % of acetic anhydride in acetic acid or cold water solutions are used as
powerful fungicides & herbicides.
2.
O2
Acetaldehyde
CH3COOOH
Peracetic acid
CH3COOOH
peracetic acid
CH3CHO
Acetic acid
L.I.T. Nagpur
(CH3CO)2O
+ H2 O
Acetic anhydride
(CH3CO)2O
H2 O
2CH3COOH
Acetic anhydride
Acetic acid
The last reaction is to be minimized if acetic
(b) Methyl Acetate Carbonylation :Acetic anhydride can be made by the carbonylation
of methyl acetate. Methanol acetylation is an essential 1 st step in anhydride
manufacture by carbonylation, the reactions taking place are :CH3COOH
CH 3OH
CH 3COOCH3
H 2O , H= -4.89
KJ/mol
Acetic acid
Methanol
CH3COOCH3 + CO
Methyl acetate
Methyl acetate
(CH3CO)2O ,
H= -94.8 KJ/mol
Acetic anhydride
L.I.T. Nagpur
Acetone Cracking :-
CH2=CO
Ketene
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CH4
Methane
CH2=CO
Ketene
+ CH3COOH
(CH3CO)2O +
Acetic acid
H20
Acetic anhydride
Quenching of the high-temperature reaction by
(ii)
CH2=CO
H2 0 ,
Ketene
L.I.T. Nagpur
H=147 KJ/mol
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.
Process Selection :-
(a)
(b)
Acetaldehyde oxidation :-
L.I.T. Nagpur
H2O
2CH3COOH
Acetic anhydride
Acetic acid
This reaction is to be minimized in order to achieve
(c)
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)
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4.
Process Description :-
(i)
(b)
L.I.T. Nagpur
Industrial Manufacture :-
L.I.T. Nagpur
(b)
Ketene absorption
(c)
(d)
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.
L.I.T. Nagpur
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.
Acetic Acid :-
Property
Specific
-18.944
Heat(Cp), J/mol
K
1.0971
2.8921 10-3
2.9275 10-6
L.I.T. Nagpur
Hf (KJ/mol)
-44.988
-0.00983
2.4610-6
G (KJ/mol)
-47.916
5.0410-6
Property
Hf (KJ/mol)
-44.988
-0.00983
2.4610-6
G (KJ/mol)
-47.916
5.0410-6
-3.995310-2
-2.110310-4
5.346910-7
-0.01226
2.7710-6
Specific
71.831
Heat(Cp), J/mol
K
Hf (KJ/mol)
-44.988
8.8879 10-1
-2.6534 10-3
3.3501 10-6
-0.00983
2.4610-6
G (KJ/mol)
5.0410-6
(ii)
(iii)
Ketene :-
Water :-
Property
Specific
92.053
Heat(Cp), J/mol
K
Hf (KJ/mol)
-238.41
(iv)
Acetic Anhydride :-
Property
-47.916
L.I.T. Nagpur
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
L.I.T. Nagpur
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
L.I.T. Nagpur
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 :-
L.I.T. Nagpur
G0298
= (-47.47-238.59) (-365.69)
= 79.63 KJ/mol
dT
RT
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(a)
(CH3CO)2
Acetic Anhydride
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 :-
L.I.T. Nagpur
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
L.I.T. Nagpur
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
L.I.T. Nagpur
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
L.I.T. Nagpur
6.
Material Balance :-
(CH3CO)2
Acetic Anhydride
% 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
L.I.T. Nagpur
(i)
Pyrolysis Heater :-
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
Acetic acid
Input
(Kmol/hr)
3.612
Output (Kmol/hr)
( Upstream )
2.3478
L.I.T. Nagpur
Output (Kmol/hr)
( downstream )
0.2383
Water
23.782
0.715
1.2565
Ketene
23.806
23.59
23.115
Flue gases
0.055
0.055
(iii)
Ketene Absorber :-
Component
Input
(Kmol/hr)
Output (Kmol/hr)
( downstream )
49.44
Output
(Kmol/hr)
( Upstream )
19.368
Acetic acid
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)
4.842
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
Output (Kmol/hr)
( downstream )
19.271
Water
0.712
0.01424
0.698
Ketene
1.18
1.18
Flue gases
0.055
0.055
Acetic
anhydride
2.6892
0.0268
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
Input (Kmol/hr)
Acetic acid
0.097
Output (Kmol/hr)
(Upstream)
-
L.I.T. Nagpur
Output (Kmol/hr)
(Downstream)
0.0968
Water
0.01424
0.01417
Ketene
1.18
1.18
Flue gases
0.055
0.055
Acetic
anhydride
0.0268
0.02677
(vi)
L.I.T. Nagpur
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
L.I.T. Nagpur
F= D + W
Putting the values in above equation :24.563 = D + W --------------------------------------------- (1)
Now, taking component balance :-
F Xf= D Xd +W Xw
For Acetic acid :-
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
Acetic Acid
-18.9441.0971T + 2.892110-6T2
96.8
Acetic
Anhydride
93
(i)
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 =
CpdT
Tref
973
30.1637
T 2 ) dT
383
Heat removed =
nacetic acid
CpdT
Tenter
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773
3.6304
T 2 )dT
973
Cooler :Texit
CpdT
Tenter
473
3
2
= 3.6304 (18.944 1.0971 T 2.8921 10 T )dT
773
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Chiller :Texit
CpdT
Tenter
273
3
2
= 3.6304 (18.944 1.0971 T 2.8921 10 T )dT
473
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(iv)
Ktene Absorber :-
(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.
= nacetic acid
CpdT
+ nwater
Tenter
Texit
CpdT
Tenter
382
20.632
T 2 )dT
273
+
382
23.827
(92.053 3.9953 10
T 2.1103 10 4 T 2 )dT
273
=
=
= nacetic acid
Texit
CpdT
Tenter
373
2 .4
Texit
nwater
CpdT
Tenter
273
L.I.T. Nagpur
T 2 )dT
+
373
21.6
(92.053 3.9953 10
T 2.1103 10 4 T 2 )dT
273
(DHd)
=
=
Texit
nacetic acid
CpdT
+ nwater
Tenter
Texit
CpdT
Tenter
392
19.4275
T 2 )dT
273
+
392
1.0225
(92.053 3.9953 10
T 2.1103 10 4 T 2 )dT
273
=
=
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
L.I.T. Nagpur
(v)
L.I.T. Nagpur
Texit
CpdT
Texit
+ nanhydride
Tenter
CpdT
Tenter
403
4.842
T 2 )dT
273
+
403
19.7208
(71.831 8.8879 10
T 2.6534 10 3 T 2 ) dT
273
= nacetic acid
Texit
CpdT
Texit
nanhydride
Tenter
392
4.6476
CpdT
Tenter
T 2 )dT
273
+
392
0.5164
(71.831 8.8879 10
273
L.I.T. Nagpur
T 2.6534 10 3 T 2 ) dT
(DHd)
Texit
nacetic acid
CpdT
+ nanhydride
Tenter
CpdT
Tenter
413
Texit
0.194
T 2 ) dT
273
+
413
19.2
(71.831 8.8879 10
T 2.6534 10 3 T 2 )dT
273
=
=
Average Latent heat ( Lavg ) = Lacetic acid Xacetic acid + Lanhydride Xanhydride
= 60 96.8 4.184 0.9 + 102 93 4.184 0.1
= 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 :-
L.I.T. Nagpur
8.
Equipment Design :-
(i)
L.I.T. Nagpur
F= D + W
Putting the values in above equation :24.563 = D + W --------------------------------------------- (1)
L.I.T. Nagpur
F Xf= D Xd +W Xw
For Acetic acid :-
L.I.T. Nagpur
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
L.I.T. Nagpur
0.9
0.94
1.0
1.0
x
R
x n 1 d
R 1
R 1
yn
0.9
3.6915
x n 1
4.6915
4.6915
Wx w
LM
xM
VM
VM
y m 1
19.398 0.01
43.626
xm
24.228
24.228
y m 1 1.8 x m 0.7926
P M avg
( v ) bottom
RT
127.926 (60 0.9 102 0.1) 273
101.325 22.414 392
( 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 1083.65 Kg / m 3 .
L.I.T. Nagpur
At the top of the distiilation column vapor density can be calculated as follows;
( v ) top
P M avg
( v ) top
RT
101.325 (60 0.01 102 0.99) 273
101.325 22.414 413
( v ) top 3.782 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 0.1 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 :-
L.I.T. Nagpur
top
10 12
top
10 12
Similarly : P ( L V )
bottom
10 12
top 0.03406 N / m
FLV ( top )
19.063
24.227
Ln
Vn
V
L
1.995
0.0342.
1052.5
L.I.T. Nagpur
V
Lm
L
FLV (bottom )
Vm
0.1063
tray spacing = 0.457 m.
From graph in RC-6 page-568 we get;
Bottom k1 = 0.086, Top k1 = 0.096
For liquid surface tension (0.02 N/m) take K1 as it is otherwise:-
K 1 ( bottom ) 0.086
0.2
0.02
0.1067
K 1 (TOP ) 0.096
0.2
0.02
0.0935
Top: u f k1
L V
1083.65 3.782
0.1067
1.8m / s.
V
3.782
L V
1052.5 1.995
0.0935
2.145m / s.
V
1.995
L.I.T. Nagpur
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 M
1555.372
3
m
Bottom Q = 3600 3.782 3600 0.1143m / s.
V
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
0.0907 m 2 .
uv
1.26
0.2165
0.144m 2 .
1.5015
L.I.T. Nagpur
Top area
0.0907
0.1067 m 2 .
0.85
0.144
0.1694m 2 .
0.85
Now, area =
2
di .
4
0.1067 4
0.3685m
.
Top
0.144 4
0.4644m.
L.I.T. Nagpur
3525.88
9.04 10 4 m 3 / sec .
1083.65 3600
Ac
0.4644 2 0.0.1694m 2 .
4
w
For, (Ad/Ac) = 0.15, D 0.82
c
L.I.T. Nagpur
LW
3525.88
O.9794kg / sec .
3600
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
0.9794
750(
)2/3
1083.65 0.38
= 13.31 mm.
Minimum how
0.6856
750(
)2/3
1083.65 0.38
= 10.53 mm.
L.I.T. Nagpur
uh
Where,
[ K 2 0.9(25.4 d h )]
V
uh
30.4 0.9(25.4 5)
3.782
6.14m / sec .
uh
0.7 0.1143
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,
u h (max)
Vmax
0.1143
9.64 m / sec .
hole area 0.011858
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 :-
hr
12.5 10 3
L
= 11.53 mm.
Total Head :ht hD (hw how ) hr
L.I.T. Nagpur
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.
hdc 166[
Lwd 2
]
L Am
hdc 166[
0.9794
]2 0.586m
1083.65 0.0152
L.I.T. Nagpur
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;
tr
4.386 sec .
Lwd
0.9794
uv
0.79375m / sec .
An
0.144
L.I.T. Nagpur
0.79375
100 62.996%
% flooding = u
1.26
f ( bottom )
0.015 ,
Trial Layout :-
0.38m
0.4644m
d 2 1.964 10 5 m 2 / hole
4
Number of holes,
L.I.T. Nagpur
Ah
0.011858
604.23 605
A1 1.964 10 5
holes.
MECHANICAL DESIGN
= (P DiV)/(2fJ)
Where,
Di = internal diameter of the column
P = design pressure = 1.1363 kg/cm2
th = thickness of head
L.I.T. Nagpur
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
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
L.I.T. Nagpur
= 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
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
L.I.T. Nagpur
= 1977.514/545
= 3.628 cm2
Am2
= 2037.85/545
= 3.74 cm2
L.I.T. Nagpur
L.I.T. Nagpur
L.I.T. Nagpur
Dsk = Gi = 46.6 cm
fd
L.I.T. Nagpur
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
Maximum tensile stress at the bottom of the skirt
= fd - (fw or fs)
= (49.98-25.932)/tsk
= 20.048/tsk kg/ cm2
L.I.T. Nagpur
L.I.T. Nagpur
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 Acetic acid :-
L.I.T. Nagpur
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
L.I.T. Nagpur
0.7
0.8
0.9
1.0
0.815 0.883 0.944 1.0
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
x
R
x n 1 d
R 1
R 1
yn
0.9
2.25
x n 1
3.25
3.25
Wx w
LM
xM
VM
VM
y m 1
20.45 0.05
98.459
xm
78.009
78.009
y m 1 1.262 x m 0.013
L.I.T. Nagpur
9.
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
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.
L.I.T. Nagpur
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
+
volume of elliptical heads
2
2
3
2
2
3
Therefore, V = DO DI D 3.14 0.4744 0.4644 3.14 0.4644
12
= 0.118 m
L.I.T. Nagpur
12
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
L.I.T. Nagpur
= 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
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
L.I.T. Nagpur
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L.I.T. Nagpur
L.I.T. Nagpur
Rate Of Return =
Net Pr ofit
1.77288
100 35.17%
Total Investment 50400000
L.I.T. Nagpur
SCADA Configuration :-
L.I.T. Nagpur
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
Raw Materials :-
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L.I.T. Nagpur
L.I.T. Nagpur
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
L.I.T. Nagpur
Maintain
-ance
Building
Future
Expa-
Storage
Building
Main Plant
nsion
gg
Scrap
Yard
Research
and
Development
Centre
Quality
Control
Laboratory
ETP
Fire
Station
Medical
Centre
Security
Cooling
towers
Control
Room
Tank Yard
Power
Wash and
Changing
Utilities
Station
Room
Generation
Parking
Space
Security
Training
Administration
Centre
Building
Canteen
Garden
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