Acetaldehyde

L.I.T.
Nagpur 1
1. INTRODUCTION
Acetaldehyde CH3CHO (ethanal) first used extensively during World War І as

a starting material for making Acetone from Acetic Acid. It is an important
intermediate in industrial organic synthesis. Acetic acid, acetic anhydride n-butanol
and 2-ethyl hexanol are the major products derived from acetaldehyde. Smaller
amounts of acetaldehyde are also consumed in the manufacture of pentaerythritol,
trimethylolpropane, pyridines, peracetic acid, crontoaldehyde, chloral, 1, 3-butylene
glycol and lactic acid.
HISTORY
Acetaldehyde was first prepared by Scheele in 1774 by the action of

manganese dioxide and sulfuric acid on ethanol. The structure of acetaldehyde was
established in 1835 by Liebig from a pure sample prepared by oxidizing ethyl alcohol
with chromic acid. Liebig named the compound aldehyde from the Latin word
translated as al (cohol) dehyd(rogenated). The formation of acetaldehyde by the
addition of water to acetylene was observed by Kutscherow in 1881.
The first commercial application was the production of acetone via acetic acid
between 1914 and 1918 in Germany (Wacker-Chemie and Hoechst) and in
Canada(Shawinigan).
Production of Acetaldehyde
L.I.T. Nagpur 2
OCCURRENCE
Acetaldehyde is a product of most hydrocarbon oxidations. It is an

intermediate product in the respiration of higher plants. It occurs in traces in all ripe
fruits that have a tart taste before ripening. Acetaldehyde is an intermediate product
of alcoholic fermentation but it is reduced almost immediately to ethanol. It may form
in wine and other alcoholic beverages after exposure to air, and imparts an
unpleasant taste; the aldehyde reacts to form diethyl acetal and ethyl acetate.
Acetaldehyde is an intermediate product in the decomposition of sugars in the body
and, hence, occurs in traces in blood. Acetaldehyde also has been detected in plant
juices and essential oils, roasted coffee and tobacco, smoke.
Commercial production processes include
∗ Dehydrogenation or Oxidation of Ethanol.
∗ Addition of Water to Acetylene.
∗ Partial Oxidation of Hydrocarbon (Propane etc).
∗ Direct oxidation of Ethylene.
The ethylene route has become the most important.
L.I.T. Nagpur 3
PHYSICAL PROPERTIES
Acetaldehyde is a colorless, mobile liquid having a pungent, suffocating odor

that is somewhat fruity and quite pleasant in dilute concentrations.
Acetaldehyde is completely miscible with water and most organic solvents. It
forms no azeotrope with water, methanol, ethanol, acetone, acetic acid or benzene.
Binary azeotropes are formed with butane (BP - 70 C, 84 wt% of butane) and diethyl
ether (BP – 18.90 C, 23.5 wt % of ether).
General physical properties of acetaldehyde are presented in Table 1 through
3.
Table 1: Density of Acetaldehyde
Temperature 0 C Density
g/cm3
0 0.805
3 0.800
Temperature 0 C Density
6 0.797 g/cm3
9 0.792 12 0.789
16 0.784
18 0.781
20 0.779
L.I.T. Nagpur 4
Sr. Properties Values

No.
1. Formula weight 44.052
2. Boiling point at 101.3 KPa (1 atm) 0 C 20.16

3. Melting point, 0 C -123.5
4. Coefficient of thermal expansion / 0 C (0-300 C) 0.00169
5. Vapor density (air =1) 1.52
6. Surface tension at 20 0 C (dyn/cm) 21.2

7. Heat capacity liquid (J/g 0 C, 00 C) 2.1856
8. Heat capacity vapor (J/g 0 C,250 C) 1.4068

9. γ = Cp/Cv at 30 0 C and 101.3 KPa 1.145
10. Latent heat of fusion KJ/mol (cal /g) 3.24 (17.6)
11. Latent heat of vaporization KJ/mol (cal/g) 25.71 (139.5)
12. Heat of solution in water KJ/mol

At 00 C -8.20
At 250 C -6.82
13. Heat of combustion of liquid at constant pressure KJ/mol 12867.9
At 250 C
1169.01
14. Heat of formation KJ/mol
At 00 C -165.48
At 250 C -192.18
15. Critical temperature 0 C 181.5
16. Critical pressure MPa 6.4
17. Ignition temperature in air 0 C 165
18. Free energy of formation KJ/mol

At 00 C -136.40
At 250 C 3064.298
19. Explosive limits of mixtures with air vol % CH3CHO 4.5 - 60.5
20. Relative density (t 0 C) dt4=0.8045-
0.001325t
21. Relative index (t 0 C) ntD=1.34240-
0.0005635t
22. Molar volume of gas at 101.3 KPa L/mol
At 20.16 0 C 23.40
L.I.T. Nagpur 5
At 25.00 0 C 23.84
23. Thermal conductivity of liquid at 20 0 C Jm-1s-1K-1 0.174
24. Thermal conductivity of vapor at 25 0 C Jm-1s-1K-1 1.09x10-2
25. Entropy for gaseous acetaldehyde at 25 0 C J/mol K 265.9

26. Entropy for liquid acetaldehyde at 20.16 0 C J/mol K 172.9
27. Entropy of vaporization at 20.16 0 C J/mol K 91.75
28. Dissociation constant at 0 0 C mol/lit 0.7x10-14
29. Ionization potential eV 10.5
Table 3: Vapor pressure of acetaldehyde
Temperature Vapor Pressure Temperature Vapor Pressure

0
C KPa 0
C KPa
-50 2.5
20 100.6
20.16 101.3 -20 16.4
20.18 101.33 0 44.0
30 145.2 5 54.8
44.5 202.65 6.7 59.07
50 279.4 9.3 65.87
58.3 303.98 10 67.7
68.0 405.3 11.6 70.8
70 492.6 13.3 76.93
75.7 506.63 15 82.9
100 1014 17.6 90.93
L.I.T. Nagpur 6
CHEMICAL PROPERTIES
Acetaldehyde is a highly reactive compound which is commonly consumed at

the site of manufacture. Oxidation, hydrogenation and the numerous condensation,
addition and polymerization reactions are example of its reactivity.
∗ Decomposition: - Acetaldehyde decomposes at temperature above 400 0

C
forming principally methane and carbon monoxide. The activation energy of
the pyrolysis reaction is 97.7 KJ/mol.
∗ Oxidation: - The liquid phase oxidation of acetaldehyde with air (oxygen) is of

great industrial importance. Most acetic acid is produced by this route.
Acetaldehyde is readily oxidized with oxygen or air to acetic acid, acetic
anhydride and peracetic acid. The principal product depends on the reaction
conditions.
Nitric acid oxidation of acetaldehyde yields glyoxal.
When oxidized with oxygen, mono peracetate is formed as an
intermediate and decomposes into peracetic acid and acetaldehyde at
elevated temperature. In the presence of Mn +2 salts acetic acid is obtained
from acetaldehyde monoperacetate and in presence of Co+2 and Cu+2 salts
acetic anhydride can be formed.
∗ Reduction: - Acetaldehyde is readily reduced to ethanol. A wide variety of

catalyst may be used. Raney nickel, palladium, supported nickel and copper
oxide etc.
Prior to 1939, i.e. before petro chemically produced ethylene became
available in Europe; the reaction to produce ethanol from acetaldehyde was
used industrially.
∗ Polymerization: - Paraldehyde 2, 4, 6-trimethyl-1, 3-5-trioxane a cyclic trimer

of acetaldehyde is formed from mineral acid such as H2SO4, HCl, and
Phosphoric. Distillation of paraldehyde in the presence of small amounts of
L.I.T. Nagpur 7
H2SO4 regenerates acetaldehyde. Being readily depolymerised paraldehyde is

used to replace acetaldehyde in reactions where acetaldehyde volatility is
problem.
Metaldehyde a cyclic tetramer of acetaldehyde is formed at
temperature below 0 0 C in presence of dry HCl.
Polyacetaldehyde a rubbery polymer is unstable and depolymerises in
few days to acetaldehyde.
∗ Reaction with Nitrogen Compounds: - With primary amines, Schiff bases

CH3CH=NR are formed.
∗ Reaction with Halogens and Halogen Compounds: - Halogen readily replaces

the hydrogen atoms of the acetaldehyde’s methyl group. Phosgene is
produced by the reaction of the carbon tetrachloride with acetaldehyde in the
presence of anhydrous aluminum chloride.
∗ Miscellaneous reactions: - Hydrocyanic acid adds to acetaldehyde in the

presence of an alkali catalyst to form cyanohydrins. Grignard reagents add
readily to acetaldehyde the final product being a secondary alcohol.
L.I.T. Nagpur 8
HANDLING
In handling acetaldehyde one has to remember that it is an extremely reactive

compound that can be easily oxidized, reduced or polymerized and is highly reactive
with oxygen. It has to be treated as a volatile, flammable and toxic material. The
following is a list of precautions recommended when handling acetaldehyde.
1. Nitrogen or other inert gases should be used as a blanketing material
whenever exposure to air is a possibility.
2. Safety goggles should be used.
3. Transfer should be made in open air structures or using suitable gas mask or
self contained breathing equipment if necessary.
4. Drums should be stored out of doors avoiding direct exposure to sunlight.
5. Acetaldehyde should be chilled before transferring and a nitrogen blanket
should be used.
L.I.T. Nagpur 9
SHIPPING AND STORAGE
Acetaldehyde is shipped in 5-10 or 55-gal drums insulated tank trucks and

insulated tank cars. Acetaldehyde in the liquid state is non corrosive to most metals,
but it can be easily oxidized to acetic acid, especially in vapor stage. Suitable
materials of constructioN are stainless steel and aluminum. Drums coatad with
phenolic res)ns Have9aLso `een u3eD. If a darker cmlor9and soe iron contamInation
are Jot objectionable, carbon steel may be used. Because acetaldehyde is classed
as flammable liquid, It requires a ‘red DOT’ (Department of Transportation) shipping
label.
Bulk storage held at low temperature and pressure is recommended over
storage in a pressure vessel.
According to regulation in Japan, outer storage tanks must not be made of
copper, magnesium, silver, mercury or alloys of these metals. They must be
0
equipped with cooling facilities in order to keep the temperature below 15 C and
also with an inert gas sealing system.
L.I.T. Nagpur 10
CAPACITY AND MARKET SURVEY
Today the most important production process worldwide is the direct oxidation
of ethylene. In Western Europe there is also some capacity for the production of
acetaldehyde by oxidation of ethanol (<15%) and hydration of acetylene (2%). In
Eastern Europe the hydration is even more important. It is estimated that in Eastern
about 235000 T (44% of the annual capacity) of acetaldehyde can be produced by
this route. The worldwide production of acetaldehyde has been nearly constant since
the early 1980s. Table 1 gives production data for acetaldehyde.
Table 4: - Production of Acetaldehyde (103 T)
Year USA W. Europe Mexico Japan Total

1923 259 554 212 256 1281
1987 270 564 193 285 1312
1990 274 596 190 284 1444
1993 147 606 249 349 1351
No accurate data are available for world production. Production data are
difficult to obtain because most of the acetaldehyde produced is consumed internally
by the manufacturer. Therefore estimated world production is only crude and should
be taken with caution.
Table 5 gives important producers and their production capacities (103 T) are
listed.
Table 6 gives the major producers and estimated capacities in the United
States in 1970.
Table 5:- Worldwide Production & their capacities (103 T)
L.I.T. Nagpur 11
Sr. No. Producers Capacity
1. Azot PO, Ukraine 100
2. BP Chemicals Ltd, Italy 140
3. Doljchim, Romania 4.5
4. Eastman Chemical Company, US 250
5. Erkimia SA, Spain 75
6. Hoechst AG, Germany 290
7. Huls AG, Germany 80
8. Japan Aldehyde Company Ltd, Japan 69
9. Kyowa Yuka Company Ltd, Japan 62
10. Mitsui Petrochemical Industries Ltd, Japan 53
11. Morelos, Mexico 150
12. Neftechim, Bulgaria 90
13. Omskiy Zavod Synnth. Caoutch, Russia 100
14. Pajaritos, Mexico 44
15. Petroleos Mexicanos (PEMEX), Mexico 100
16. Salavatnephteorgsyntez, Russia 100
17. Showa Denko KK, Japan 140
18. Societe Francaise Hoechst SA, France 96
19. Tokuyama Petrochemical Company Ltd, Japan 100
20. Wacker Cheme GmbH, Germany 65
21. Zacklady Chemiezne, Poland 90
L.I.T. Nagpur 12
Table 6:- Acetaldehyde United States Capacity 1970
Sr. Producer and Location Capacity

No. (million lb/year)
1. Celanese, Bay City, Texas 250
2. Celanese, Bishop, Texas 240
3. Celanese, Clear Lake City, Texas 500
4. Celanese, Pampa, Texas 10
5. Eastman, Longview Texas 500
6. Publicker, Philadelphia, Pennysylvania 70
7. Union Carbide Institute, West Virginia, Texas 650

City, Texas
8. Others 20
Total 2240
L.I.T. Nagpur 13
MARKET SURVEY IN INDIA
Acetaldehyde is a very common organic compound, large

amounts of which are being used in the manufacture of various useful products. The
consumer industries are showing rapid growth in our country. With the increasing
population and industrialization these industries are likely to grow more rapidly in the
coming years. This ensures a very good future demand for acetaldehyde in our
country.
1.9 MANUFACTURERS OF ACETALDEHYDE IN

INDIA
1. Somaiya Organo Chemicals, Mumbai.

2. Laxmi Organic Industries Ltd, Mumbai.
3. Shree Ganesh Chemicals, Mumbai.
4. Apra Enterprise, Mumbai.
5. Ashok Chem-Pharma International, Mumbai.
6. Indian Organics Limited, Pune.
L.I.T. Nagpur 14
1.10 ECONOMIC ASPECTS AND FUTURE

TRENDS
The economics of acetaldehyde processes are highly sensitive

to product yield and raw material prices. This is apparent from the raw material and
energy requirements and the relative simplicity of the processes. Therefore the
process with a significantly lower net raw material cost will have an advantage. This
is the reason ethylene oxidation processes have dominated the acetaldehyde for the
last few years and they will probably continue to do so at least until the mid 1980s.
The production pattern for acetaldehyde has undergone
significant changes since the principal industrial routes to acetaldehyde were
hydration of acetylene and oxidation of ethanol. First increasing acetylene costs
made this feedstock economically unattractive. Then the two aldehyde Wacker-
Hoechst GmbH processes for the liquid phase oxidation of ethylene to acetaldehyde
began commercial operation. Western Europe and China are the largest consumers
of acetaldehyde.
Import and export of acetaldehyde are negligible as it is mainly
consumed at the process site.
L.I.T. Nagpur 15
1.11 HEALTH AND SAFETY FACTORS
The main toxic effect of acetaldehyde is irritation of the eyes and

membranes. Anesthesia is the dominant effect of acetaldehyde. Acetaldehyde
appears to paralyze respiratory muscles, causing panic. It has a general narcotic
action which accelerates heart action. During industrial exposure acetaldehyde
vapors produce local irritation to the eyes and to a lesser extent to the throat and
nose. Coughing, burning sensation, headaches and stupefaction are symptoms of
gross exposure.
Prolonged exposure causes a decrease of both red and white
blood cells; there is also a sustained rise in blood pressure. In normal industrial
operations there is no health hazard in handling acetaldehyde provided normal
precaution are taken.
Mixtures of acetaldehyde vapor and air are flammable; they are
explosive if the concentrations of aldehyde and oxygen rise above 4% and 9%
respectively. The maximum allowable concentration in air has been set to 200 ppm.
In water concentration are generally less than 0.1 µg/L, therefore contribution from
drinking water are considered negligible.
Acetaldehyde and its vapors have a highly irritative effect on the
eyes, nose and respiratory passages and a slightly irritative effect on the skin.
Irreversible injury is possible. Those working with acetaldehyde should wear
protective clothing, protective gloves and tightly fitting goggles. Any splashes on the
skin or in the eyes should be rinsed away with plenty of water (a doctor should be
called if necessary). Contaminated clothing should be changed at once. If
acetaldehyde is swallowed, a doctor should be called immediately
In the case of fire, water, carbon dioxide, and dry extinguishing
agents should be used for fire fighting. Foam is less suitable because acetaldehyde
vapors break through the foam blanket owning to their high pressure at normal
temperature.
L.I.T. Nagpur 16
2. PRODUCTION
Raw materials that have been used for the production of

acetaldehyde are:
1. Ethanol from fermentation of carbohydrates or from hydration of ethylene.

2. Acetylene
3. Ethylene
4. Lower hydrocarbon e.g. butane
5. Carbon monoxide and hydrogen (Synthesis gas)
6. Methanol
1. i) From Ethanol and Air :
Acetaldehyde is produced commercially by the catalytic

oxidation of ethyl alcohol. Passing alcohol vapors and preheated air over a silver
catalyst at 4800 C carries out the oxidation.
CH3CH2OH + ½ O2 → CH3CHO + H2O, ∆H = 242 KJ/mol (57.84 kcal / mol)

Ethanol Oxygen
With a multitubular reactor, conversions of 74-82% per pass can
be obtained while generating steam to be used elsewhere in the process.
1. ii) From Dehydrogenation of Ethyl alcohol :

Acetaldehyde also, produced commercially by the
dehydrogenation of ethyl alcohol.
Reaction:
C2H5OH → CH3CHO + H2
Ethanol Acetaldehyde
L.I.T. Nagpur 17
2. Oxidation of Ethylene:
Wacker – Chemie and Farbwerke Hoechst developed the direct

liquid phase oxidation of ethylene in 1957 – 1959. The catalyst is an aqueous
solution of PdCl2 and CuCl2. In 1894, F.C. Phillips observed the reaction of ethylene
with an aqueous palladium chloride solution to form acetaldehyde.
C2H4+PdCl2 + H2O → CH3CHO +Pd +2HCl
The metallic palladium is reoxidized to PdCl2 with CuCl2 and

the cuprous chloride formed is reoxidized with oxygen or air.
Pd + 2CuCl2→ PdCl2 +2CuCl
2CuCl+1/2 O2 + 2HCl → 2CuCl2 + H2O
The net result is a process in which ethylene is oxidized

continuously through a series of oxidation – reduction reactions.
C2H4 + ½ O2→ CH3CHO ∆H = -244 kJ(102.1 kcal)
Studies of the reaction mechanism of the catalytic oxidation

have suggested that a cis – hydroxyethylene – palladium π complex is formed
initially, followed by an intramolecular exchange of hydrogen and palladium to give a
gem – hydroxyethyl palladium species which leads to acetaldehyde and metallic
palladium.
There are two variations for the production of acetaldehyde by
the oxidation of ethylene; the two – stage process developed by Wacker – Chemie
and the one – stage process developed by Farbwerke Hoechst. In the two – stage
process ethylene and oxygen (air) react in the liquid phase in two stages. In the first
stage ethylene is almost completely converted to acetaldehyde in one pass in a
tubular plug-flow reactor made of titanium. The reaction is conducted at 125-1300C
L.I.T. Nagpur 18
and 3 atm palladium and cupric chloride catalysts. Acetaldehyde produced in the
first reactor is removed from the reaction loop by adiabatic flashing in a tower. The
flash step also removes the heat of reaction. The catalyst solution is recycled from
the flash – tower base to the second stage (or oxidation) reactor where the cuprous
salt is oxidized to the cupric state with air. The high pressure off – gas from the
oxidation reactor, mostly nitrogen, is separated from the liquid – catalyst solution and
scrubbed to remove acetaldehyde before venting. A small portion of the catalyst
stream is heated in the catalyst regenerator to destroy undesirable copper oxalate.
The flasher overhead is fed to a distillation system where water is removed for
recycle to the reactor system and organic impurities, including chlorinated
aldehydes, are separated from the purified acetaldehyde product.
In the one-stage process ethylene, oxygen, and recycle gas are
directed to a vertical reactor for contact with the catalyst solution under 3 atm
pressure and 1300 C
 . The water evaporated during the reaction absorbs the heat
evolved, and make – up water is fed as necessary to maintain the catalytic solution
concentration. The gases are water – scrubbed and the resulting acetaldehyde
solution is fed to a distillation column. The tail – gas from the scrubber is recycled to
the reactor.
Inerts are eliminated from the recycle gas in a bled – stream
which flows to an auxiliary reactor for additional ethylene conversion. This oxidation
process for olefins has been exploited commercially principally for the production of
acetaldehyde, but the reaction can also be applied to the production of acetone from
propylene and methyl ethyl ketone from butanes. Careful control of the potential of
the catalyst with the oxygen stream induced commercially by a variation of this
reaction.
L.I.T. Nagpur 19
3. From Acetylene
Although acetaldehyde has been produced commercially by the

hydration of acetylene since 1916, this procedure has been replaced almost
completely by the direct oxidation of ethylene.
HC≡ CH + H2O → CH3CHO

Acetylene Water Acetaldehyde
4. From Synthesis Gas
A rhodium catalyzed process capable of converting synthesis

gas directly into acetaldehyde in a single step has been reported.
CO + H2 → CH3CHO + other products
L.I.T. Nagpur 20
3. SELECTION OF PROCESS
The economy of the commercial processes depends essentially

upon prices and the availability of raw materials. In highly industrializedCountries
maintaining high prices for ethanol by Fiscal measures or where petrochemical
ethanol was not available, as in Germany or Japan before 1939, Acetylene was the
favored starting material for acetaldehyde. The acetylene process is still operated in
some Eastern European Countries and also by companies where cheap acetylene is
available. Petro chemically produced ethanol, however, was the favored raw material
in the other countries whereas ethanol made by fermentation was and still is used on
a small scale in countries with less chemical industry.
In Western countries including Japan, all these processes have
now been almost completely replaced by the direct oxidation process developed in
the late 1950s by Wacker-Chemie and Hoechst. This is because ethylene is
available at lower price then acetylene.
Generally all processes based on acetylene, ethylene and
ethanol are more selective than the oxidation of saturated hydrocarbons. This is
because in the later case, other oxidation products are formed in addition to
acetaldehyde. Because of the great expense of separating the product mixture, such
processes are economically only in large units and when all main and secondary
products obtained in the process are utilized.
The ethylene route has become the most important. Since 1960,
the liquid phase oxidation of ethylene has been the process of choice for the
manufacture of acetaldehyde. In the 1970s the world capacity of this process
increases to over 2x106 T/annum.
L.I.T. Nagpur 21
4. MANUFACTURE OF ACETALDEHYDE FROM

ETHYLENE
Process Description:
A flow sheet for the single stage reactor process using oxygen is
shown in Figure. Fresh oxygen and ethylene are fed independently to a vertical
ceramic- lined reactor vessel which contains a water solution of catalyst. During the
process development serious problems have been caused by the extremely
corrosive aqueous CuCl2 – PdCl2 solution. In one stage process the reactor is lined
with acid proof ceramic material, the tubing is made of titanium, and certain others
parts are of titanium .The oxygen content of the recycle gas is limited to a maximum
of 9 mol % to stay safely below the flammable range. The reactor is operated to 120
0
– 130 C and about 3 atm. The heat of reaction is removed by evaporation of
acetaldehyde and water from the catalyst solution. The ethylene conversion per pass
0
is about 75 %. The vapor from the reactor is cooled by 20 C and scrubbed with
water to condense and remove the acetaldehyde. The scrubbing operation, which is
done at low pressure, requires a high scrub water volume and is responsible for the
low concentration of acetaldehyde (∼ 9 wt %) in the crude product. Most of the vent
gas is recycled to recover ethylene, but a gas purge is necessary to remove inerts
from the system. For this reason, high purity ethylene and oxygen are required to
minimize ethylene losses in the purge. The residue from the scrubber contains 8 to
10 wt % acetaldehyde and is fed to distillation column.
There are two way of manufacture:
L.I.T. Nagpur 22
1. One Stage Process

2. Two Stage Process
One Stage versus Two Stage Process
→ Advantages of the One Stage Over the Two Stage Process are :
∗ Less by product formation.

∗ No liquid recycle, the catalyst always stays in one vessel, minimizing
possibilities of catalyst loses and avoiding expensive liquid recirculation
equipment.
∗ Lower operating pressure which results in lower compression costs for
oxygen vs. air.
∗ Lower volume of vent gases.
∗ Effluent may be biologically treated because of the higher dilution of the
chlorinated acetaldehydes.
∗ Lower in unit capital costs due to use of ceramic equipment and less
titanium because the diluted streams are less corrosive.
→ Advantages of the Two Stage over the One Stage Process are :
∗ Safety (Ethylene and the air are reacted in different vessels).

∗ No ethylene or oxygen recycle (almost complete conversion).
∗ Less liquid effluent.
Process Reactor Temp 0 C P Catalyst Conversio Yield %

phase (atm) n%
One Liquid 100-130 3 Palladium 75 93-95
Stage
Two Liquid 125-130 10 Palladium 99.5 93-95
Stage
L.I.T. Nagpur 23
As it can be seen that in the above comparison both variations

of the process offer advantages and disadvantages. Also since the process are very
raw material sensitive and the ethylene yields are the same then the economics are
probably very close. All of this reflected in the fact that there are about the same
number of one and two stage units in operation.
L.I.T. Nagpur 24
5. Thermodynamics:-
The word ‘thermodynamics’ implies flow of heat. It deals with

energy changes accompanying all types of physical and chemical processes.
Thermodynamics also helps to lay down the criteria for predicting
feasibility or spontaneity of a process, including a chemical reaction, under a
given set of conditions. In other words, it helps to predict whether a given
process or a chemical reaction is feasible under the given conditions of
temperature, pressure and concentration. It also helps to determine the extent
to which a process, including a chemical reaction, can proceed before attainment
of equilibrium.
Therefore to determine the feasibility of a chemical reaction Gibb’s
free energy change of chemical reaction is determine and the conditions for the
feasibility of a chemical reaction are mentioned below:
ΔG < 0, reaction can take place spontaneously, i.e. it is feasible
0 < ΔG <40,000 KJ/kmol, the reaction may or may not be possible and needs
further study.
ΔG > 40,000 KJ/kmol, the reaction is very unfavorable.
Free energy of formation is considered as a function of

temperature, while doing calculations.
L.I.T. Nagpur 25
Thermodynamic properties of raw materials & product are as given

below:-
Property as a function of temperature can be written as
Property = A + BT + CT2 +DT3 + ET4
(i) Ethylene :-
Property A B C D E
Specific 32.003 -1.4831 x 10-2 2.4774 × 10-4 -2.3766× 6.8274 × 10-11
Heat(Cp), 10-7
KJ/kmol K
∆Hf 63.053 -4.1076 × 10-2 1.6598×10-5 - -
(KJ/mol)
∆G 51.752 4.9338 × 10-2 1.7284 × 10-5 - -
(KJ/mol)
(ii) Acetaldehyde :-
Property A B C D E
Specific 34.140 4.002 × 10-2 2.5034 × -1.6445 × 4.7248×10-11

Heat(Cp), 10-4 10-7
KJ/kmol K
∆Hf -154.122 -4.7166 ×10-2 2.0279 × - -
(KJ/mol) 10-5
∆G -167.052 1.0714 × 10-1 1.8665 × - -
(KJ/mol) 10-5
L.I.T. Nagpur 26
Reaction :-
C2H4 + 0.5O2 → CH3CHO

Ethylene Oxygen Acetaldehyde
2C2H4 + O2 → 2CH3CHO
a) Heat of Reaction :-
Ethylene :-
∆H0 = A + BT + CT2 (KJ/mol)
∆H0 = 63.053 – 4.1076×10-2T + 1.6598×10-5×T2
Therefore. at 298K
∆H0298 = 63.053 – 4.1076×10-2 x 298 + 1.6598×10-5×2982

= 52.286 KJ/mol
And, at 130 ºC that is at 403 K
∆H0403 = 63.053 – 4.1076×10-2 x 403 + 1.6598×10-5×4032

= 49.195 KJ/mol
Acetaldehyde:-
∆H0 = A + BT + CT2 (KJ/mol)
∆H0 = -154.122 – 4.7166×10-2×T + 2.0279×10-5×T2
L.I.T. Nagpur 27
Therefore. at 298K
∆H0298 = -154.122 – 4.7166×10-2×298 + 2.0279×10-5×2982

= -166.377 KJ/mol
And at 403K
∆H0403 = -154.122 – 4.7166×10-2×403 + 2.0279×10-5×4032

= -169.836 KJ/mol
Therefore, At 298K
∆H0reaction = ∑ H products – ∑ H reactants

= 2 [(∆H0acetaldehyde ) – (∆H0ethylene )]
]
= 2 [(-166.377) – (52.286)]
= - 437.336 KJ/mol
And at 403K
∆H0reaction = ∑ H products – ∑ H reactants
= 2[ (∆H0acetaldehyde) – (∆H0ethylene)]
= 2[(- 169.836) – (49.195)]
= - 438.062 KJ/mol
(b) Feasibility of Reaction :-
L.I.T. Nagpur 28
Ethylene :-
∆G0 = A + BT + CT2 (KJ/mol)
∆G0 = 51.752 + 4.9338×10-2×T + 1.7284 ×10-5×T2

Therefore, At 298K
∆G0298 = 51.752 + 4.9338×10-2×298 + 1.7284 ×10-5×2982

= 67.9896 KJ/mol
Acetaldehyde :-
∆G0 = A + BT + CT2 (KJ/mol)
∆G0 = -167.052 + 1.0714×10-1×T + 1.8665×10-5×T2

Therefore, At 298K
∆G0298 = -167.052 + 1.0714×10-1×298 + 1.8665×10-5×2982

= -135.1243 KJ/mol
Thus,
∆G0reaction = 2[∑ ∆G products – ∑ ∆G reactants]
= 2[(∆G0acetaldehyde ) – ( ∆G0ethylene)]
Therefore, at 298K
∆G0298 = 2(-135.1243) – (-67.9896)
= - 406.2278 KJ/mol
Now, ∆G0298 = -RT ln K
ln K1 = (406.2278×1000)/(8.314 × 298)
= 163.962
L.I.T. Nagpur 29
Therefore, K298 = 1.61×1071
Now,
dlnK ΔH o
=
dT RT
Therefore, ln(K2/K1) = (-∆H0298 /R) × [(1/T2)-(1/T1)]
ln(K2/K1) = (-437.336×1000/ 8.314) × [(1/403)-(1/298)]
= 45.99
Therefore, (K2/K1) = 9.412 × 1019

K2 = 1.711 x 1051
∆G0 403 = - RT (ln K2)
= -8.314 × 403 × ln (1.711 x 1051)
= -395.258 KJ/mol
Since, ∆G0 403 is negative, the reaction is feasible at 403K
L.I.T. Nagpur 30
6. Material Balance
Plant capacity = 4500 Ton/Annum = 4500/300 =15 T/day
= (15 x 1000)/3600
= 625 Kg/hr
= 14.21 Kmol/hr
Therefore Acetaldehyde to be produced = 625 Kg/hr
The main reaction taking place in the reactor is
C2H4 + 0.5O2 → CH3CHO
From available data,
For 1000 Kg of Acetaldehyde to be produced,
Ethylene required is 670 Kg and
Oxygen required is 410 Kg
The above reaction can again be written as
C2H4 + 0.5O2 → CH3CHO
Quantity 670 410 1000

(Kg)
Molecular 28 32 44
Weight
Moles 23.93 12.81 22.73
Stiochiometric 1 0.5 1
amount
For finding out the Limiting and excess reactant the above equation can be written
as
A + 0.5B → C
L.I.T. Nagpur 31
Where,
A = Ethylene
B = Oxygen
C= Acetaldehyde
The stiochiometric ratio of the reactant can be calculated as,
The feed ratio is calculated as,
As Stiochiometric ratio is more than the feed ratio,
‘A’ i.e. C2H4 is Limiting and ‘B’ i.e. O2 is in Excess.
Basis : For 1 hr of operation,
% conversion based on C2H4 fed = C2H4 reacted/C2H4 available
0.75 = x /y
∴ x = 0.75 y
% yield based on C2H4 reacted = CH3CHO produced/ C2H4 reacted
0.95 = CH3CHO produced/ x
As acetaldehyde formed is 99.5 % pure
∴ Acetaldehyde to be manufactured = 14.21/0.995 = 14.28 Kmol
Assume 6 % overall loss,
∴ Acetaldehyde produced in the first column i.e. reactor = 14.28 (1+0.06)
= 15.14 Kmol
L.I.T. Nagpur 32
∴ 0.95 = 15.14/ x
⇒ x = 15.94 Kmol
∴ y = x /0.75
⇒ y = 21.25 Kmol
∴ Ethylene fed = 21.25 Kmol
Ethylene reacted = 15.94 kmol
Unreacted Ethylene = 21.25 – 15.94
= 5.31Kmol
Calculation of O2 requirement:
From the main reaction,
1 Kmol of C2H4 ≡ 0.5 Kmol of O2
15.94 Kmol of C2H4 ≡ 7.97 Kmol of O2
O2 reacted = 7.97 Kmol = O2 consumed
Assume 42 % excess air to be supplied,
O2 in air supplied = 1.42 x 7.97 = 11.32 Kmol
N2 in air supplied = (1/99) x 11.32 = 0.114 Kmol
∴ O2 in air = 11.32 Kmol
N2 in air = 0.114 Kmol
This N2 will remain inert over the complete process,
∴ N2 in product from reactor = 0.114 Kmol
Oxygen fed = 11.32 Kmol
Oxygen reacted = 7.97 Kmol
L.I.T. Nagpur 33
Oxygen unreacted = 11.32 – 7.97
= 3.347 Kmol
Over the Reactor and Scrubber :
Mixed Components Fed are
Ethylene C2H4 = 21.25 Kmol
Oxygen O2 = 11.32 Kmol
Nitrogen = 0.114 Kmol
Quantity reacted are
Quantity unreacted are
Nitrogen = 0.114 Kmol
Components which are unreacted passes through the scrubber
∴ Gas leaving the scrubber from top = 5.31 + 3.347 +0.114
= 8.771 Kmol
mol % of N2 in gas leaving the scrubber from top = (0.114/8.771) = 0.01299
Concentration of N2 in gas leaving the scrubber from the top, in purge and in recycle
will be same.
L.I.T. Nagpur 34
Let, P be the Kmol of Purge and
R be the Kmol of Recycle feed
For steady state operation to avoid the built of N2 in the system we have,
N2 in fresh feed = N2 in purge = 0.01299 P
Let, m be the kmol of O2 in purge
n be the kmol of O2 in fresh feed
O2 balance after the scrubber will be,
O2 in gas leaving the scrubber from top = O2 in purge + O2 in recycle
∴ O2 in recycle =3.347 – m
O2 balance before reactor will be,
O2 in fresh feed + O2 in recycle = O2 in mixed feed
∴ n + 3.347 – m = 11.32
n = 7.973 + m
Air contains 99 mol % of O2 and 1 mol % N2
∴ N2 in fresh feed = (1/99) x (7.973 + m)
= 0.01 (7.793 + m)
Gas leaving the scrubber = 8.771 kmol
∴ mole fraction of O2 in gas leaving the scrubber from the top = 3.347/8.771
= 0.3816
mole fraction of O2 in purge = 0.3816
L.I.T. Nagpur 35
As concentration of O2 in gas leaving scrubber from the top, purge, and recycle is
same.
N2 in fresh feed = 0.01 (7.973 + m)
= 0.01299P
⇒ P = 0.769 (7.973 + m)
(O2 in purge/Total purge) = (m/P)
∴ (m/P) = (m)/ [0.769(7.973 + m)] = 0.3816
⇒ m = 3.31 kmol
O2 in purge = 3.31 kmol
N2 in fresh feed = 0.01 (7.973 + m)
= 0.1128 kmol
N2 in purge = N2 in fresh feed = 0.1128 kmol
P = 0.769 (7.973 + m)
⇒ P = 8.677 kmol
C2H4 in purge = P - O2 in purge - N2 in purge
= 8.6771 – 3.31 – 0.1128
C2H4 in purge = 5.2542 kmol
We have,
R + P = 8.771
R = 8.771 – 8.6771
L.I.T. Nagpur 36
R = 0.094 kmol
N2 balance after scrubber:
N2 in gas leaving the scrubber from top = N2 in recycle + N2 in purge
N2 in recycle = 0.114 – 0.1128
N2 in recycle = 0.0012 kmol
O2 balance after scrubber:
O2 in recycle = O2 in gas leaving the scrubber from top - O2 in purge
= 3.347 – 3.31
O2 in recycle= 0.037 kmol
C2H4 balance after scrubber:
C2H4 in recycle = C2H4 in gas leaving the scrubber from top - C2H4 in purge
= 5.31 – 5.2542
C2H4 in recycle = 0.0558 kmol
O2 balance before reactor:
O2 in fresh feed = O2 in mixed feed - O2 in recycle
= 11.32 – 0.037
O2 in fresh feed = 11.283 kmol
C2H4 balance before reactor:
C2H4 in fresh feed = C2H4 in mixed feed - C2H4 in recycle
= 21.25 – 0.0558
C2H4 in fresh feed = 21.1942
L.I.T. Nagpur 37
Fresh feed to the process = F F = 21.1942 + 11.283 + 0.1128
= 32.59 kmol
Recycle ratio = (R/F)
= (0.094/32.59)
= 0.288 x 10-2
Common feed ratio = (M F/F F)
= (21.25 + 11.32 + 0.114)/32.59
= 1.003
C2H4 into the process = C2H4 in fresh feed
C2H4 out = C2H4 in purge
Overall conversion = [C2H4 in - C2H4 out]/C2H4 in
= (21.1942 – 5.2542)/21.1942
= 75.21 %
After reactor:
C2H4 unreacted = 5.31 kmol = 148.68 kg
O2 unreacted = 3.347 kmol = 104.104 kg
N2 unreacted = 0.114 kmol = 3.192 kg
Total kmoles = 8.771
Total mass coming out = mass of unreacted C2H4, O2, N2 + mass of CH3CHO
Outlet of reactor consist 15.14 kmol of acetaldehyde
L.I.T. Nagpur 38
∴ kg of acetaldehyde will be = 15.14 x 44
= 666.16 kg
Total output coming from reactor in kg = 666.16 + 148.68 +107.104 +3.192
= 925.136 kg
Taking balance over Srubber :
Taking overall balance on scrubber:
Input mass = Output mass
K+L=M+N
Where,
K = total output in kg from reactor
L = total water supplied
M = Reused
N = Scrubbed
10 % of acetaldehyde is present in scrubbed
∴ 925.136 + L =M + N
Taking acetaldehyde balance on weight basis,
666.16 + L x 0 = M x 0 + N x 0.1
As water used is pure and no acetaldehyde is reused.
⇒ N = 6661.6 kg
∴ 925.136 + L = (148.68 + 107.104 + 3.192) + 6661.6
⇒ L = 5995.44 kg
Water to be fed = 5995.44 kg ≈ 6 m3

L.I.T. Nagpur 39
Taking balance over Distillation Column:
Total feed to the distillation column = 6661.6 kg
Feed contains 10 % acetaldehyde and remaining 90 % water
Xf1 (CH3CHO) = 0.1

Xf2 (H2O) = 0.9
Top Product (D):-
Mole fraction of components in the top product:-
Xd1 (CH3CHO) = 0.96
Xd2 (H2O) = 0.04
Bottom Product (W):
Mole fraction of components in the bottom product:-
Xw1 (CH3CHO) = 0.01

Xw2 (H2O) = 0.99
Taking overall material balance:-
F= D + W
Putting the values in above equation :-
6661.6 = D + W --------------------------------------------- (1)
Now, taking component balance:-
F Xf= D Xd +W Xw
L.I.T. Nagpur 40
For Acetaldehyde:-
6661.6 × 0.1 = D × 0.96 + W × 0.01
666.16 = 0.96 D + 0.01 W -------------------------------- (2)
Solving equations 1 & 2, we get:-
Top product (D) = 631.1 Kg
Bottom product (W) = 6030.5 Kg
Hence, acetaldehyde in the top product = 0.96 × 631.1 = 605.94 Kg
And, Water in the top product = 0.04 × 631.1 = 25.26 Kg
Acetaldehyde in the bottoms product = 0.01 × 6030.5 = 60.46 Kg
Water in the bottoms product = 0.99 × 6030.5 = 5969.94 Kg
Reflux Ratio = 0.69 (calculated below)
Hence, Ln = 0.69 × D = 0.69 × 631.1 = 435.46 Kg
Vn = Ln + D = 435.46 + 631.1 =1066.56 Kg
Lm = Ln+ F = 435.46 + 6661.6 = 7097.06 Kg
Vm = Lm – W = 7097.06-6030.5 = 1066.56 Kg
Degasser:
Feed contains 96 % of acetaldehyde and
Output from bottom contains 95.5 % acetaldehyde
Taking overall balance on Degasser,
I=G+O
L.I.T. Nagpur 41
Where,
I = input to degasser
G = Gas leaving from top
O = final output
631.1 = G + O
Taking acetaldehyde balance,
631.1 x 0.96 = 0 x G + 0.995 x O
Solving equations, we get
O = 608.9 kg
G = 22.2 kg
L.I.T. Nagpur 42
7. Energy Balance
Properties required for energy balance calculation
1. Specific Heat as a function of temperature
Component A B C D E
Ethylene 32.003 -1.4831× 10 -2
2.4774× 10-4 -2.3766× 10- 6.8274× 10-
7 11
Oxygen 29.526 -8.8999× 10-3 3.8083× 10-5 -3.2629× 10- 8.8607× 10-
8 12
Nitrogen 29.342 -3.5395× 10-3 1.0076× 10-5 -4.3116× 10- 2.5935× 10-
9 13
Acetaldehyd 34.140 4.0020× 10-2 2.5034× 10-4 -1.6445× 10- 4.7248× 10-
e 7 11
Water 92.053 -3.9953× 10-2 -2.1103× 10-4 5.3469× 10-7 -
2. Latent Heat of Vaporization KJ/kg
Component Temperature K λ
Acetaldehyde 294 1131.24
Water 294 2451.32
i. Reactor
Reaction temperature = 403 K

Reference temperature = 298 K
Outlet temperature = 383 K
Heat in Feed: Q1 + Q2 + Q3
L.I.T. Nagpur 43
Q1 = Heat energy associated with Ethylene

Q2 = Heat energy associated with Oxygen
Q3 = Heat energy associated with Nitrogen
a. Ethylene
Moles of Ethylene entering = 21.25 kmol
Tenter
Q1 = n× ∫ CpdT
Tref
403
(32.003 − 1.4831× 10−2 T + 2.4774× 10−4 T 2 −
= 21.25 × ∫ 2.3766× 10
298
−7
T 3 + 6.8274× 10−11T 4 )dT
= 21.25 (5048.5)
= 107.28 × 103 KJ
b. Oxygen
Moles of Oxygen entering = 11.32 kmol
Tenter
Q2 = n× ∫ CpdT
Tref
403
(29.526 − 8.8999× 10−3 T + 3.8083× 10−5 T 2 −
= 11.32 × ∫ 3.2629× 10
298
−8
T 3 + 8.8607× 10−12 T 4 )dT
= 11.32 (3130.74)
= 35.44 × 103 KJ
c. Nitrogen
L.I.T. Nagpur 44
Moles of Nitrogen entering = 0.114 kmol
Tenter
Q3 = n× ∫ CpdT
Tref
403
(29.342 − 3.5395× 10−3 T + 1.0076× 10−5 T 2 −
= 0.114× ∫ 4.3116× 10
298
−9
T 3 + 2.5935× 10−13 T 4 )dT
= 0.114 (3062.02)
= 0.3491 × 10 KJ
Heat in input = Q1 + Q2 + Q3
= (107.28 + 35.44 + 0.34907) × 103
= 143.07× 103 KJ
Heat associated with output = H1 +H2 + H3 + H4
H1 = Heat energy associated with Ethylene
H2 = Heat energy associated with Oxygen
H3 = Heat energy associated with Nitrogen
H4 = Heat energy associated with Acetaldehyde
L.I.T. Nagpur 45
a) Ethylene
Moles of Ethylene leaving = 5.31 kmol
Texit
H1 = n× ∫ CpdT
Tref
383
(32.003 − 1.4831× 10−2 T + 2.4774× 10−4 T 2 −
= 5.31× ∫ 2.3766× 10
298
−7
T 3 + 6.8274× 10−11T 4 )dT
3
= 25.419 × 10 KJ
b) Oxygen
Moles of Oxygen leaving = 3.35
Texit
H2 = n× ∫ CpdT
Tref
383
(29.526 − 8.8999× 10−3 T + 3.8083× 10−5 T 2 −
= 3.35 × ∫ 3.2629× 10
298
−8
T 3 + 8.8607× 10−12 T 4 )dT
3
= 9.985 × 10 KJ
c) Nitrogen
L.I.T. Nagpur 46
Moles of Nitrogen leaving = 0.114 kmol
Texit
H3 = n×
Tref
∫ CpdT
383
(29.342 − 3.5395× 10 −3 T + 1.0076× 10 −5 T 2 −
= 0.114 × ∫ 4.3116× 10
298
−9
T 3 + 2.5935× 10 −13 T 4 )dT
3
= 0.332× 10 KJ
d) Acetaldehyde
Moles of Acetaldehyde leaving =15.14 kmol
Texit
H4 = n×
Tref
∫ CpdT
383
(34.140 + 4.002 × 10 −2 T + 1.5634× 10−4 T 2 −
= 15.14 × ∫ 1.6445× 10
298
−7
T 3 + 4.7248× 10 −11 T 4 )dT
3
= 109.38 × 10 KJ
Heat associated with output = H1 +H2 + H3 + H4
= (25.419 + 9.985 + 0.332 + 109.38) × 103
= 145.116 × 103 KJ
Heat generated during the reaction = - 244 KJ/kmol
L.I.T. Nagpur 47
∴ For 15.14 kmol of acetaldehyde heat generated will be = - 244 × 15.14
∴ Heat released during the reaction = Input – Output + Generation
= (143.07 – 145.116 – 3.695) × 103
= - 5.741 × 103 KJ
Negative sign indicates that reaction is exothermic
ii. Around Cooler
Heat lost or removed = Heat gained by the cooling medium (water)
Inlet temperature of water = 25ºC
Outlet temperature of water = 40ºC
Cooling water flowrate =?
Heat gained = mwater × Cpwater × ∆T
m water = 5.741 × 103 / [4.184 × (313-298)]
= 91.44 kg
≈ 100 kg
iii. Balance around Scrubber

L.I.T. Nagpur 48
Taking Energy Balance around the scrubber, we get
I–O+G-C=0
As there is no generation of heat term G will be = 0
I–O-C=0
Where
I = Input
O = Output
C = Consumption or Removed
Input Heat Calculation: I1 + I2 + I3 + I4 + I5
Where
I1 = Heat associated with Ethylene
I2 = Heat associated with Oxygen
I3= Heat associated with Nitrogen
I4 = Heat associated with Acetaldehyde
I5 = Heat associated with water entering
Inlet temperature = 383 K

Water Inlet temperature = 298 K
A. Ethylene
Moles of ethylene entering = 5.31 kmol
Texit
I1 = n× ∫ CpdT
Tenter
L.I.T. Nagpur 49
313
(32.003 − 1.4831× 10 −2 T + 2.4774× 10 −4 T 2 −
= 5.31× ∫ 2.3766× 10
383
−7
T 3 + 6.8274× 10 −11 T 4 )dT
= - 13.455 × 103 KJ
B. Oxygen
Moles of oxygen entering = 3.35 kmol
Texit
I2 = n× ∫ CpdT
Tenter
313
(29.526 − 8.8999× 10 −3 T + 3.8083× 10−5 T 2 −
= 3.35 × ∫ 3.2629× 10
383
−8
T 3 + 8.8607× 10−12 T 4 )dT
= - 6.988 × 103 KJ
C. Nitrogen
Moles of nitrogen entering = 0.114 kmol
Texit
I3 = n× ∫ CpdT
Tenter
313
(29.342 − 3.5395× 10−3 T + 1.0076× 10−5 T 2 −
= 0.114 ×
383
∫ 4.3116× 10 −9
T 3 + 2.5935× 10−13 T 4 )dT
= - 0.2356 × 103 KJ
D. Acetaldehyde
Moles of acetaldehyde entering = 15.14 kmol
L.I.T. Nagpur 50
Texit
I4 = n× ∫ CpdT
Tenter
313
(34.140 + 4.002 × 10 −2 T + 1.5634× 10 −4 T 2 −
= 15.14 ×
383
∫ 1.6445× 10 −7
T 3 + 4.7248× 10−11T 4 )dT
= - 64.404 × 103 KJ
E. Water
5 water
I = (m Cp∆T)
= 5995.44 × 4.186 × (40 - 25)
= 376.45 × 103 KJ
Total heat in input = (-13.455 – 6.988 – 0.2356 – 64.404 + 376.45) × 103

3
= 291.37× 10 KJ
1 2 3 4 5
Outlet heat calculation: V + V + V + V + V
Where,
L.I.T. Nagpur 51
1
V = Heat associated with ethylene from top
2
V = Heat associated with oxygen from top
3
V = Heat associated with nitrogen from top
4
V = Heat associated with acetaldehyde from bottom
5
V = Heat associated with water from bottom
Temperature remains constant at output i.e. temperature in scrubber = outlet
temperature = 313 K
1)
Ethylene from top
-2 -4 2 -7 3 -11 4
1
V = 5.31 (32.003 – 1.4831× 10 T+2.4774× 10 T -2.3766× 10 T +6.8274× 10 T )
= 238.94 KJ
2) Oxygen from top
V2 = 3.35 (29.526 – 8.8999× 10-3 T+3.8083× 10-5 T2-3.2629× 10-8 T3+8.8607× 10-12T4)
= 99.012 KJ
L.I.T. Nagpur 52
3) Nitrogen from top
V3 = 0.114 (29.342 – 3.5395× 10-3 T+1.0076× 10-5 T2-4.3116× 10-9 T3+2.5935× 10-
13
T4)
= 3.316 KJ
4) Acetaldehyde from bottom
V4 =15.14 (34.14+4.002× 10-2 T+2.5034× 10-4 T2-1.6445× 10-7 T3+4.7248× 10-11T4)
= 1.0084 × 103 KJ
5) Water from bottom
V5 = 333.08 (92.053 –3.9953× 10-2 T-2.1103× 10-4 T2+5.3469× 10-7 T3)
= 25.071× 103 KJ
Total heat in output = 238.94 + 99.012 + 3.316 + (1.0084 + 25.071) × 103 KJ
= 26.42 × 103 KJ
Heat removed = Total Input heat – Total Output heat
= (291.37 – 26.42) × 103 KJ
= 264.95 × 103 KJ
iv. Distillation Column :-
Temperature of feed = 313K
L.I.T. Nagpur 53
Temperature of distillate = 294K
Temperature of the bottoms product = 374K
Reference Temperature = 298K
Heat in feed (F×HF) = Heat in acetaldehyde + Heat in water
Texit Texit
= nacetaldehyde × ∫ CpdT
Tenter
+ nwater × ∫ CpdT
Tenter
313
(34.140 + 4.002× 10−2 T + 1.5634× 10−4 T 2 −
= 15.14 × ∫ 1.6445× 10
298
−7
T 3 + 4.7248× 10−11T 4 )dT
+
313
(92.053 − 3.9953× × 10−2 T −
333.08 × ∫ 2.1103× 10
298
−4
T 2 + 5.3469× 10− 7 T 3 )dT
= 13.088 × 103 + 1.131× 103
= 14.219 × 103 KJ/hr
Heat in Distillate (D×Hd) = Heat in acetaldehyde + Heat in water
Texit Texit
Tenter
Tenter
L.I.T. Nagpur 54
294
(34.140 + 4.002× 10−2 T + 1.5634× 10−4 T 2 −
= 13.77 × ∫ 1.6445× 10
298
−7
T 3 + 4.7248× 10−11T 4 )dT
+
294
(92.053 − 3.9953× × 10−2 T −
1.403× ∫ 2.1103× 10
298
−4
T 2 + 5.3469× 10− 7 T 3 )dT
(D×Hd) = -3.073× 103 – 0.424 × 103
= -3.497 × 103 KJ/hr
Heat in bottoms (WHW) = Heat in acetaldehyde + Heat in water
Texit Texit
Tenter
Tenter
374
(34.140 + 4.002 × 10 −2 T + 1.5634× 10 −4 T 2 −
= 1.374 × ∫ 1.6445× 10
298
−7
T 3 + 4.7248× 10 −11T 4 )dT
+
374
(92.053 − 3.9953× × 10−2 T −
331.66 × ∫ 2.1103× 10
298
−4
T 2 + 5.3469× 10 − 7 T 3 )dT
= 6.2249 × 103 + 1896.63 × 103
= 1920.86 × 103 KJ/hr
Average Latent heat ( Lavg ) = Lacetaldehyde × Xacetaldehyde + Lwater × Xwater
= 0.96 × 1131.24 + 2451.32 × 0.04
L.I.T. Nagpur 55
= 1184.04 KJ/kg
Condenser duty ( Qc ) = Vn × Lavg
= 1066.56 × 1184.04 ×
= 1262.85 × 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)
= (-3.497 + 1920.86 + 1262.85 – 14.219) × 103
= 3165.994 × 103 KJ/hr
Therefore, quantity of steam required = (Qr) / Lsteam
= 3165.994 × 103 / 2200
= 1439.089 Kg/hr
= 0.39975 Kg/sec
L.I.T. Nagpur 56
v. Taking Energy Balance around degasser :
Inlet temperature of feed = 294 K

Taking energy balance over degasser we get
I–O=0
There is one input and two outputs, one for final product and other for gases
Heat associated with the input:
Input contains 14.34 kmol of Acetaldehyde
Texit
Heat in input = nacetaldehyde × ∫ CpdT

Tenter
291
(34.140 + 4.002× 10−2 T + 1.5634× 10−4 T 2 −
= 14.34 × ∫ 1.6445× 10
294
−7
T 3 + 4.7248× 10−11T 4 )dT
= -2.386 × 103 KJ/hr
Texit
Heat in output = nacetaldehyde × ∫ CpdT

Tenter
with acetaldehyde
As temperature remains constant at output i.e. 291 K
= 13..84(34.140 + 4.002 × 10− 2 T + 1.5634 × 10− 4 T 2 − 1.6445 × 10− 7 T 3 + 4.7248 × 10− 11T 4 )
L.I.T. Nagpur 57
∴ Heat associated with acetaldehyde output = 0.765 KJ/hr
Input – Output from top – Output from Bottom = 0

Output from top = Input – Output from Bottom
∴ Heat associated with gases at output from top will be = input – output from bottom
= (- 2.386 - 0.765) × 103
= -3.151 × 103 KJ/hr
L.I.T. Nagpur 58
8. Equipment Design:-
Distillation column :-
Input Feed (F):
1) Acetaldehyde = 666.16 Kg/hr
2) Water = 5995.44 Kg/hr
Total feed to the distillation column = 5995.44+666.16

= 6661.6 Kg/hr
Mole fraction of components in the feed:-
Xf1 (CH3CHO) = 666.16/6661.6 = 0.1
Xf2 (H2O) = 5995.44/6661.6 = 0.9
Top Product (D) :-
Mole fraction of components in the top product:-
Xd1 (CH3CHO) = 0.96
Xd2 (H2O) = 0.04
Bottom Product (W):
Mole fraction of components in the bottom product:-
Xw1 (CH3CHO) = 0.01
Xw2 (H2O) = 0.99
Taking overall material balance:-
F= D + W
Putting the values in above equation:-
6661.6 = D + W --------------------------------------------- (1)
Now, taking component balance:-
F Xf= D Xd +W Xw
L.I.T. Nagpur 59
For Acetaldehyde:-
6661.6 x 0.1 = D × 0.96 + W × 0.01
666.16 = 0.96 D + 0.01 W -------------------------------- (2)
Solving equations 1 & 2, we get :-
Top product (D) = 631.05 Kg/hr
Bottom product (W) = 6030.5 Kg/hr
Hence, acetaldehyde in the top product = 0.96 × 631.05 = 605.94 Kg/hr
Water in the top product =0.04 × 631.05 = 25.26 Kg/hr
Acetaldehyde in the bottoms product = 0.01 × 6030.5 = 60.46 Kg/hr
Water in the bottoms product = 0.99 × 6030.5 = 5969.94 Kg/hr
Boiling point of acetaldehyde = 20 ºC
Boiling point of water = 100 ºC
Hence, acetaldehyde is more volatile component (MVC)
Sr. Componen In Out

No t
F D W
Kmol/hr Kg/hr Kmol/hr Kg/hr Kmol/hr Kg/hr
1. CH3CHO 15.14 666.16 13.77 605.94 1.37 60.46

2. H2O 333.08 5995.44 1.41 25.26 331.66 5969.94
Mass in 6661.6 Mass out 6661.6
x – y data can be calculated with the help of avg. value of relative volatility.
0
α = PA
0
PB
Where A is MVC and B is LVC

Numerator and Denominator are the respective Vapor Pressure. Vapor pressure can
be calculated using Equation.
L.I.T. Nagpur 60
0
log10 PA (mm Hg) = A + B/T +C log10 T + D T + E T2
Sr. Component A B C D E
No.
1. CH3CHO 87.37 -3682.2 -31.548 0.020114 5.534E-13
2. H2O 29.8605 -3.1522E3 -7.3037 2.4274E-9 1.8090E-6
Using the above equation, the vapor pressure can be calculated at the top and
bottom.
0 0 0 0
Sr. Condition Temperature PA PB α=PA /PB
No. °K (CH3CHO) (H2O)
1. Top 294 801 20 40.05
2. Bottom 374 7727 812 9.52
αavg= (α1 x α2)0.5 = (40.05 x 9.52)0.5 = 19.53

Y = αavg X / (1+ (aavg-1) X
Using the above equations the X-Y data is generated as follows
X 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50
Y 0.51 0.69 0.78 0.83 0.87 0.89 0.91 0.93 0.94 0.95
X 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.0
Y 0.96 0.97 0.97 0.98 0.98 0.99 0.99 0.99 0.99 1.0
From Graph
[Xd/(R+1)] min = 0.66
[0.96/(R+1)] min = 0.66
Therefore, Rmin = 0.46
But, Ropt = 1.5 Rmin
L.I.T. Nagpur 61
Therefore, Ropt = 1.5 x 0.46 = 0.69

R = Ln/D
Hence, Ln = 0.69 x 631.1 = 435.46 Kg/hr
As D = 631.1 Kg/hr
Vn = Ln + D = 435.46 + 631.1 =1066.56 Kg/hr
Lm = Ln+ F = 435.46 + 6661.6 = 7097.06 Kg/ hr
Vm = Lm – W = 7097.06-6030.5 = 1066.56 Kg/hr
Therefore equation of upper of upper operating line :
R x
yn = x n +1 + d
R +1 R +1
0.69 0.96
yn = x n +1 +
1.69 1.69
Therefore, yn = 0.408xn+1 + 0.568
Hence y intercept = 0.568 and corresponding slope = 0.408
Equation of Lower operating line (LOL):
LM Wx w
y m +1 = xM −
VM VM
7097.06 6030.5 × 0.01
∴ y m +1 = xm −
1066.56 1066.56
∴ y m +1 = 6.654 x m − 0.0565
Therefore from graph

Number of theoretical plates = 5-1 = 4
One plate is accounted for rebolier
Efficiency of the column = 60 %
Therefore actual number of plates required = 4/0.6 = 7
Feed plate = 3
Let tray spacing = 500 mm
Height of distillation column = (N+1) x 0.5
= 8 x 0.5
L.I.T. Nagpur 62
=4m
Take 100 mm of water as the pressure drop per plate in the column.
Therefore, column pressure drop = 100 × 10−3 × 1000 × 9.81× 7
= 6867 Pa = 6.867 KPa.
Therefore, Top pressure = 101.325 KPa.
Bottom pressure = 101.325 + 6.867= 108.192KPa.
At the bottom of the distillation column vapor density can be calculated as follows;
P × M avg
( ρ v ) bottom =
RT
108.192 × (44 × 0.01 + 18 × 0.99) × 273

∴ ( ρ v ) bottom =
101.325 × 22.414 × 374
∴ ( ρ v ) bottom = 0.6349 Kg / m 3 .
The density of liquid at the bottom of the column can be calculated by multiplying
the density of each component with the mole fraction.
( ρ l ) bottom = 784 × 0.01 + 1000 × 0.99
∴ ( ρ l ) bottom = 997.84 Kg / m 3 .
At the top of the distillation column vapor density can be calculated as follows;
P × M avg
( ρ v ) top =
RT
101.325 × (44 × 0.96 + 18 × 0.04) × 273

∴ ( ρ v ) top =
101.325 × 22.414 × 294
∴ ( ρ v ) top = 1.7798 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.I.T. Nagpur 63
( ρ l ) top = 784 × 0.96 + 1000 × 0.04
∴ ( ρ l ) top = 792.64 Kg / m 3 .
Calculation of Parachor value (P):-
Ptop = 118 × 0.96 + 48.4 × 0.04 = 115.216

Pbottom = 118 × 0.01 + 48.4 × 0.99 = 49.096
Surface tension:-
4
 P × ( ρ L − ρV ) 
σ top =  × 10
−12
 M 
4
115.216 × (792.64 − 1.727 ) 
∴ σ top =  × 10
−12
 (44 × 0.96 + 18 × 0.04) 
∴ σ top = 20.25dyne / cm = 0.02025 N / m
Similarly:-
4
 P × ( ρ L − ρV ) 
σ bottom =  × 10
−12
 M 
∴ σ top = 0.05165 N / m
Liquid-vapor flowrate factor FLV is given by :-
Ln ρV
∴ FLV ( top ) =
Vn ρL
435.46 1.7798
= = 0.01934.
1066.56 792.64
L.I.T. Nagpur 64
ρV
L
FLV ( bottom ) = m ρL
Vm
= 0.1678
Tray spacing = 0.5 m.
From graph in RC-6 page-568 we get;
Bottom k1 = 0.08, Top k1 = 0.09
For liquid surface tension (0.02 N/m) take K1 as it is otherwise:-

0.2
 σ 
K 1 ( bottom ) = 0.08
 0.02 
= 0.096
K 1 (top ) = 0.09
Maximum velocity at top and bottom can be calculated as follows;
ρ L − ρV 997.84 − 0.6349
Bottom: u f = k1 = 0.096 = 3.81m / s.
ρV 0.6349
ρ L − ρV 792.64 − 1.7798
Top: u f = k1 = 0.09 = 1.897 m / s.
ρV 1.7798
Now we will design the column for 70% flooding, therefore the velocities will be given
by;
Bottom: uf = 3.81 × 0.7 = 2.667 m/s.
Top: uf = 1.897 × 0.7 = 1.3279 m/s.
Maximum volumetric flow rate of vapor can be calculated as follows:
L.I.T. Nagpur 65
Vm 1066.56
Bottom Q = = = 0.4667 m 3 / s.
ρV × 3600 0.6349 × 3600
1066.56
Top Q = = 0.1665m 3 / s.
1.7798 × 3600
Now area at the bottom and at the top of the tower can be calculated as follows:
Q 0.4667
Net area (An) bottom = = = 0.1749m 2 .
uv 2.667
Q 0.1665
Net area (An) top = = = 0.1254m 2 .
u v 1.3229
Now let us take 20% of the area as the downcomer area,

Ad = 0.2AT
But, AT = An + Ad
Therefore, An/0.8 = AT
0.1749
Therefore, Bottom area = = 0.21863m 2 .
0.8
0.1254
Top area = = 0.15675m 2 .
0 .8
π
× di .
2
Now, area =
4
Column diameter can be calculated as follows;

0.21863 × 4
Bottom = = 0.5276m
π
.
0.15675 × 4
Top = = 0.4467 m.
π
Take 0.5276 m as inside diameter of the column.
L.I.T. Nagpur 66
LIQUID FLOW PATTERN:
Now, maximum volumetric flow rate at the bottom

7097.06
= = 1.9756 × 10 −3 m 3 / sec .
997.84 × 3600
PROVISIONAL PLATE DESIGN:
Column diameter Dc = 0.5276 m.

π
Area of column, Ac = × 0.5276 2 = 0.2186m 2 .
4
Now area of downcomer is 20% of the area of the column.
Ad = 0.2 × Ac = 0.04372m 2 .
Also Net area is given by, An = Ac − Ad = 0.2186 − 0.04372 = 0.1749m .

2
Active area, Aa = Ac − 2 Ad = 0.2186 − 2 × 0.04372 = 0.13116m .

2
Take hole area as 10% of active area.

Therefore Ah = 0.1×0.13116 = 0.013116 m2.
Iw
For 20% downcomer area, from graph of (Ad/Ac) ×100 Vs
Dc
Iw
For, (Ad/Ac) = 0.2, = 0.86
Dc
Therefore Length of the weir, Iw = 0.86 × 0.5276 = 0.4537 m.
Take weir height as 50 mm.
Plate thickness = 5mm
Hole diameter = 5mm
CHECK WEEPING:
Maximum liquid rate,
7097.06
LW = = 1.9714kg / sec .
3600
At 70% turndown the liquid rate is,
= 0.7 × 1.9714 = 1.3799 kg/sec.
L.I.T. Nagpur 67
The height of the liquid crest over the weir can be estimated using the Francis weir
formula. For a segmental down comer this can be written as:
Lw 2 / 3
how = 750( )
ρ L lw
Where, lw = weir length, m,
how = weir crest, mm liquid,
Lw = liquid flow-rate, kg/s.
At the maximum flow rate of liquid the liquid crest over the weir can be calculated
using the maximum liquid flow rate calculated above, while for the conditions at
minimum flowrate are assumed to be the 70% turndown conditions.
1.9714
Maximum how = 750( ) 2 / 3 = 19.99 mm.
997.84 × 0.4537
1.3799
Minimum how = 750( ) 2 / 3 = 15.76 mm.
997.84 × 0.4537
At minimum rate, hw + how = 50 + 15.76 = 65.76 mm.

From graph of K2 Vs (hw + how), K2 = 30.4
Where, K2 is a constant dependent on the depth of the clear liquid on the plate.
The minimum design vapour velocity is given by

,
[ K 2 − 0.9(25.4 − d h )]
uh =
ρV
Where, uh = minimum vapour velocity through the holes(based on the hole
area), m/s,
dh = hole diameter, mm,
K2 = a constant, dependent on the depth of clear liquid on the plate
30.4 − 0.9(25.4 − 5)
uh = = 15.11m / sec .
0.6349
L.I.T. Nagpur 68
Actual minimum vapor velocity is given by,

Actual uh = Minimum vapor rate/Ah
0.7 × 0.4667
uh = = 24.91m / sec .
0.013116
This is well above the weeping velocity (minimum vapor velocity), therefore the
design is acceptable.
PLATE PRESSURE DROP:-

Maximum vapor velocity through the holes is given by,
Vmax 0.4667
u h (max) = = = 35.58m / sec .
hole area 0.013116
For (plate thickness)/(hole dia) = 1, from graph of (Ah/Aa)×100 Vs Co

For, (Ah/Aa)= 0.1;
Co = 0.84
The pressure drop through the dry plate can be estimated using expressions derived
for flow through orifices.
u h 2 ρV
hD = 51[ ]
Co ρ L
35.58 2 0.6349
= 51[ ] × = 58.22mm. ……..(bottom)
0.84 997.84
RESIDUAL HEAD:
12.5 ×10 3
hr =
ρL
= 12.53 mm.
L.I.T. Nagpur 69
TOTAL HEAD:
ht = hD + (hw + how ) + hr
= 58.22 + (50 + 15.76) + 12.53 = 136.51mm. of H 2 O
Comment:This is higher than the assumed per plate pressure drop of 100
mm, however it won’t cause a large change in the physical properties, even if
everything were recalculated, thus it is acceptable.
DOWNCOMER LIQUID BACK UP:
The height above the bottom edge of the apron is calculated as follows:
hap = hw − 10 = 50 − 10 = 40mm.
Thus the clearance area under the apron is given by,
Aap = haplw = 0.04×0.4531 = 0.0182 m2.
This is less than the area of the downcomer Ad.
Thus use Aap in the equation given below :-
Head loss in the downcomer can be estimated by the following equation:
Lwd 2
hdc = 166[ ]
ρ L Am
Where, Am = Ad or Aap whichever is smaller.

Lwd = liquid flowrate in the downcomer.
1.9714
∴ hdc = 166[ ]2 = 1.956mm
997.84 × 0.0182
L.I.T. Nagpur 70
In terms of clear liquid, the downcomer backup is given by;
hb = ( hw + how ) + ht + hdc
= 50 + 15.76 + 136.51+ 1.956 = 204.23 mm.
= 0.204 m.
Now tray spacing + weir height = 0.4537 + 0.05 = 0.504 m.
1
hb 〈 × 0.504
2
Therefore he tray spacing is within acceptable limits.
DOWNCOMER RESIDENCE TIME:
The residence time of the liquid over the downcomer is given by;
Ad hbc ρ L 0.04372 × 0.204 × 997.84

tr = = = 4.52 sec .
Lwd 1.9714
This is greater than 3 seconds therefore it is acceptable.
ENTRAINMENT:
The entrainment can be estimated by the following relationships which give
entrainment as a function of percentage flooding.
max imun bottom vapor. flowrate 0.4667

uv = = = 2.1m / sec .
An 0.1749
uv 2 .1
% flooding = = × 100 = 75.5%
u f ( bottom ) 2.78
Therefore from graph of FLV Vs % flooding.

(fractional entrainment), ψ = 0.013 , this is less than 0.1, therefore it is acceptable.
L.I.T. Nagpur 71
TRIAL LAYOUT:
0.4537m 0.5276m
NUMBER OF HOLES:
Area of one hole,

π
A1 = × d 2 = 1.964 × 10 −5 m 2 / hole
4
Number of holes,
Ah 0.013116
N= = = 668.33 ≈ 669 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 52.76)/(2 x 1420 x 0.85 – 1.1363)
= 0.248 mm
Taking allowance = 3 mm
Shell thickness = 3.248
Use thickness of 3.5 mm
L.I.T. Nagpur 72
Therefore, Outer diameter of the column (Do) = Di + 2t
= 0.5346m
Design of heads:-
Elliptical heads are used

th = (P DiV)/(2fJ)
Where,
Di = internal diameter of the column
P = design pressure = 1.1363 kg/cm2
th = thickness of head
J = welded joint efficiency = 0.85
V = stress intensity factor
And, V = (2 + k2)/6
k = ratio of major axis to minor axis = 2:1 =2
Therefore, V = 1
th = (1.1363 x 52.76 x 1) / (2x1420 x0.85)
=0.02484 cm
= 0.2484 mm
Taking allowance = 3 mm
Thickness of head = 3.2484 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
L.I.T. Nagpur 73
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
= 1.010
Gi = 52.76 + 2 x 0.0816
= 52.9232 cm
Go = 1.010 x 52.9232
= 53.45cm
Mean gasket diameter G = (Go + Gi)/2

= 53.185 cm
Basic gasket sitting width
bo = ( Go - Gi )/4
= 0.1325 cm
= 1.4 mm
Taking it as 1 mm.
Effective gasket sitting width as bo is less than 6.3 mm

b = bo
b = 1.4 mm
Force acting on bolt under atmospheric condition
Wm1 = 3.14 x b x G x Ya
= 3.14 x 0.14 x 53.185 x 112
= 2619.9 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
L.I.T. Nagpur 74
= 3.14 x 2 x0.12 x 53.185 x2 x1.1363 + 3.14 x 53.1852 x 1.1363 / 4

= 2630.74 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 = 2619.9/545
= 4.801 cm2
Am2 = 2630.74/545
= 4.827 cm2
Therefore, minimum bolting area is taken as 4.827 cm2
No. of bolts = mean diameter of gasket/2.5

= 53.185/2.5
= 21.274
Since the total no. of bolts must be a multiple of 4
No. of bolts = 24
If Am is the area of one bolt then,
Am x 24 = 4.827
Am = 0.201125 cm2
Therefore, 3.142 x db2 /4 = 0.201125
db = 0.5060 cm
Diameter of bolt = 0.506 cm
Pitch circle diameter = outside diameter of gasket + 2xdiameter of bolt + 1.2
L.I.T. Nagpur 75
= Go + 2 x db + 1.2
= 53.45+ 2 x 0.506 + 1.2
= 55.662 cm
Bolt spacing = (3.14 x pitch circle diameter)/no. of bolts
= 3.14 x 55.662 / 24
= 7.283 cm
Flange design:-
Outside diameter of the flange = Pitch circle diameter + 2 x diameter of bolt

= 55.662 + 2 x 0.5060
= 56.674 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
Wm = maximum bolt load = 53678.106 kg

Hg = radial distance from gasket load reaction to the bolt circle
= (pitch circle diameter – G)/2

= (55.662 – 53.185)/2
= 1.2385 cm
H = hydrostatic end force

= (3.14 x G2 x Pi)/4
= (3.14 x 53.1852x 1.1363)/4
= 2523.14 Kg
k = 1/[0.3 +(1.5 x 53678.106 x 1.2045)/(1956.6x 46.835)]
L.I.T. Nagpur 76
= 0.9587
tf = 53.185 x (1.1363/0.9587x1420)0.5
= 1.536 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:
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 = 0.5276 m = 20.78 inches
P = design pressure (Psig)

= 1.1363 kg / cm2 = (14.7 x 1.1363)/1.1 = 15.185 Psig
L.I.T. Nagpur 77
L = column height of cylindrical shell and heads (inches)

L = 4 m = 157.48 inches
Therefore, B = 3159.56 kg
W = 2443.83 kg
Weight of the contents = volume of contents x Avg density
= [(3.14 x 0.52762 x 4) x (0.1 x 784 + 0.9 x 1000)]/4
= 1025.465 kg
Assume, Weight of accessories = 200 kg
∑W = 5552.86 + 1025.465 + 200

= 3669.295 kg
Dsk = Gi = 52.93 cm
fd = ∑W/(3.14 x Dsk x tsk)
= 3669.295/(3.14 x 52.93 x tsk)
= 22.078 / 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 = 128 kg/m2 (assuming)
L.I.T. Nagpur 78
Do = 0.5346 m
H=4+2=6m
PLW = K1 x K2 x P x H x Do
= 0.7 x 1 x 128 x 0.5346 x 6

= 287.4 kg
The bending moment due to wind at the base of skirt is
Mw = PLW x H/2
= 287.4 x 6/2
= 862.2 kg-m
f w = Mw / Z
= 862.2/[(3.14 D2sk tsk)/4]
= 3920.45/tsk kg / m2
= 0.392 / tsk kg /cm2
1. 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=4+2=6m
W = 3669.295 kg; Do = 0.5346 m
L.I.T. Nagpur 79
fs = (2 x4 x 0.8 x 6 x 3669.295)/(3 x 3.14 x 0.5346 2 x tsk)
= 5.234/tsk kg/cm2
Maximum tensile stress at the bottom of the skirt
= fd - (fw or fs)
= (21.863-5.234)/tsk
= 16.629/tsk kg/ cm2
Permissible tensile stress = 1420 kg/ cm2
tsk = 16.629 / 1420

= 0.01171 cm
= 0.117 mm
fc (max) = (21.863/tsk) + (5.234/tsk)

= 27.097/tsk kg/ cm2
fc (permissible ) = yield point stress / 3

= 2000 / 3
= 666 kg/ cm2
tsk = 27.097/ 666

= 0.0407 cm
= 0.41 mm
Therefore, thickness of 1 mm is used.
L.I.T. Nagpur 80
Material of Construction:
Many factors have to be considered when selecting engineering

materials, but for chemical process plant the overriding consideration is usually the
ability to resist corrosion. The process designer will be responsible for
recommending materials that will be suitable for the process conditions. He must
also consider the requirements of the mechanical design engineer; the material
selected must have sufficient strength and be easily worked. The most economical
material that satisfies both process and mechanical requirements should be
selected; this will be the material that gives the lowest cost over the working life of
the plant, allowing for maintenance and replacement.
One of the major problems with direct ethylene oxidation processes is
the extremely corrosive properties of the catalyst solution. Titanium or brick lined
equipment must be used.For the distillation column mild steel can be used as there
is no problem of corrosion. Pressure maintained in the column is 1 atmosphere.
L.I.T. Nagpur 81
9. COST ESTIMATION
All prices are in Lakh
Chemical Engineering Plant Cost Index:

Cost index in 1999 = 365
Cost index in 2006 = 606.5
Estimation of Capital Investment Cost:

I. Direct Costs: material and labor involved in actual installation
of complete facility
a) Equipment + installation + instrumentation + piping + electrical
+ insulation + Painting
1. Purchased equipment cost (PEC):
i.e., PEC = Rs. 1450
Present cost of equipment will be = 1450 × 606.5/365
= 2409.383562
2. Installation, including insulation and painting:

(25-55% of purchased equipment cost.)
Consider the Installation cost = 40% of Purchased
equipment cost
= 40% of 2409.383562
= Rs. 963.7534247
3. Instrumentation and controls, installed: (6-30% of

Purchased equipment cost.)
Consider the installation cost = 15% of Purchased
equipment cost = 15% of 2409.383562
= Rs. 361.4075343
L.I.T. Nagpur 82
4. Piping installed: (10-80% of Purchased equipment cost)

Consider the piping cost = 40% Purchased equipment cost
= 40% of 2409.383562
= Rs. 963.7534247
5. Electrical, installed: (10-40% of Purchased equipment cost)

Consider Electrical cost = 25% of Purchased equipment cost
= 25% of 2409.383562 = Rs. 602.3458905
Hence total cost of (1+2+3+4+5) =Rs. 5300.643836
B. Buildings, process and Auxiliary: (10-70% of Purchased equipment

cost)
Consider Buildings, process and auxiliary cost = 40% of PEC
= 40% of 2409.383562 =Rs. 963.7534247
C. Service facilities and yard improvement: (40-100% of Purchased

equipment cost)
Consider the cost of service facilities and yard improvement = 62% of
PEC
= 62% of 2409.383562 = Rs. 1493.817808
D. Land: (1-2% of fixed capital investment or 4-8% of Purchased

equipment cost)
Consider the cost of land = 5% of PEC = 5% of 2409.383562
= Rs. 120.4691781
Thus, Direct cost = Rs. 7878.684247
II. Indirect costs: expenses which are not directly involved with
material and labour of actual installation of complete facility
L.I.T. Nagpur 83
A. Engineering and Supervision: (5-30% of direct costs)

Consider the cost of engineering and supervision = 15% of Direct
costs
i.e., cost of engineering and supervision = 15% 7878.684247
= Rs. 1181.802637
B. Construction Expense and Contractor’s fee: (6-30% of direct costs)

Consider the construction expense and contractor’s fee = 10% of
Direct costs
i.e., construction expense and contractor’s fee = 10% of 7878.684247
= Rs. 787.8684247
C. Contingency: (5-15% of PEC)

Consider the contingency cost = 10% of 2409.383562
i.e., Contingency cost = Rs. 240.9383562
Thus, Indirect Costs = Rs. 2210.609418
III. Fixed Capital Investment:

Fixed capital investment = Direct costs + Indirect costs
= 7878.684247 + 2210.609418
i.e., Fixed capital investment = Rs. 10089.29367
IV. Working Capital: (10-20% of Fixed-capital investment)

Consider the Working Capital = 15% of Fixed-capital investment
i.e., Working capital = 15% of 10089.29367

= Rs. 1513.39405
L.I.T. Nagpur 84
V. Total Capital Investment (TCI):

Total capital investment = Fixed capital investment + Working
capital
= 10089.29367 + 1513.39405
i.e., Total capital investment = Rs. 11602.68772
Estimation of Total Product cost:
I. Manufacturing Cost = Direct production cost + Fixed charges + Plant

overhead cost.
A. Fixed Charges: (10-20% total product cost)
i. Depreciation: (depends on life period, salvage value and method of

calculation-about 10% of FCI for machinery and equipment, and 2-3%
for Building Value for Buildings)
Consider depreciation = 10% of FCI for machinery and equipment, and 3%

for Building Value for Buildings)
i.e., Depreciation = (0.10× 10089.29367) + (0.03× 963.7534247)

= Rs. 1037.84197
ii. Local Taxes: (1-4% of fixed capital investment)

Consider the local taxes = 4% of fixed capital investment
i.e. Local Taxes = 0.04× 10089.29367= Rs. 403.5717468
iii. Insurances: (0.4-1% of fixed capital investment)

Consider the Insurance = 0.6% of fixed capital investment
i.e. Insurance = 0.006× 10089.29367= Rs. 60.53576202
L.I.T. Nagpur 85
iv. Rent: (8-12% fixed capital investment)

Consider rent = 10% of fixed capital investment
= 10% of 10089.29367
Rent = Rs. 1008.929367
Thus, Fixed Charges = Rs. 2510.878846
B. Direct Production Cost:

Now we have Fixed charges = 10-20% of total product charges – (given)
Consider the Fixed charges = 15% of total product cost
Total product cost = fixed charges/15%
Total product cost =2510.878846/0.15
Total product cost (TPC) = Rs.16739.19231
i. Raw Materials: (10-50% of total product cost)

Consider the cost of raw materials= 30% of TPC
Raw material cost = 30% of 16739.19231
Raw material cost = Rs. 5021.757692
ii. Operating Labor (OL): (10-20% of total product cost)

Consider the cost of operating labor = 15% 1673.19231
Operating labor cost = 15% of 16739.19231
Operating labor cost = Rs. 2510.878847
iii. Direct Supervisory and Clerical Labor (DS & CL):(10-25% of OL)
Consider the cost for Direct supervisory and clerical labor = 12% of OL
Direct supervisory and clerical labor cost = 12% of 2510.878847
Direct supervisory and clerical labor cost = Rs. 301.3054616
L.I.T. Nagpur 86
iv. Utilities: (10-20% of total product cost)

Consider the cost of Utilities = 15% of total product cost
Utilities cost= 15% of 16739.19231
Utilities cost = Rs. 2510.878847
v. Maintenance and repairs (M & R): (2-10% of fixed capital

investment)
Consider the maintenance and repair cost = 5% of fixed capital
investment
i.e. Maintenance and repair cost = 0.05× 10089.29367
= Rs. 504.4646835
vi. Operating Supplies: (10-20% of M & R or 0.5-1% of FCI)

Consider the cost of Operating supplies = 15% of M & R
Operating supplies cost = 15% of 504.4646835
Operating supplies cost = Rs. 75.66970253
vii. Laboratory Charges: (10-20% of OL)

Consider the Laboratory charges = 15% of OL
Laboratory charges = 15% of 2510.878847
Laboratory charges = Rs. 376.6318271
viii. Patent and Royalties: (2-6% of total product cost)

Consider the cost of Patent and royalties = 5% of total product cost
Patent and Royalties = 5% of 16739.19231
Patent and Royalties cost = Rs. 836.9596155
Thus, Direct Production Cost = 5021.757692+2510.878847+301.3054616

+2510.878847+504.4646835+75.66970253+376.6318271+836.9596155
Direct Production Cost = Rs. 12138.54668
L.I.T. Nagpur 87
C. Plant overhead Costs (50-70% of Operating labor, supervision, and

maintenance or 5-15% of total product cost); includes for the following:
general plant upkeep and overhead, payroll overhead, packaging,
medical services, safety and protection, restaurants, recreation, salvage,
laboratories, and storage facilities.
Consider the plant overhead cost = 60% of OL, DS & CL, and M & R
Plant overhead cost = 60% of (2510.878847+301.3054616+504.4646835)
Plant overhead cost = Rs. 1995.389395
Manufacture cost = Direct production cost + Fixed charges + Plant overhead

costs.
Manufacture cost = 12138.54668+2510.878846+1995.389395
Manufacture cost = Rs. 16644.81492
II. General Expenses = Administrative costs + distribution and selling costs +

research and development costs
A. Administrative costs:(40-60% of operating labor)

Consider the Administrative costs = 50% of operating labor
Administrative costs = 50% of 2510.878847
Administrative costs = Rs. 1255.439424
B. Distribution and Selling costs: (2-20% of total product cost);

Includes costs for sales offices, salesmen, shipping, and advertising.
Consider the Distribution and selling costs = 10% of total product cost
Distribution and selling costs = 10% of 16739.19231
Distribution and Selling costs = Rs. 1673.919231
L.I.T. Nagpur 88
C. Research and Development costs: (about 3% of total product

cost)
Consider the Research and development costs = 3% of total product cost
Research and Development costs = 3% of 16739.19231
Research and Development costs = Rs. 502.1757693
Thus, General Expenses = Rs.1255.439424+1673.919231+502.1757693

= Rs. 3431.534424
III. Total Production cost = Manufacture cost + General Expenses

= 16644.81492+ 3431.534424
Total production cost = Rs. 20076.34934
IV. Gross Earnings/Income:
Selling Price of acetaldehyde per kg = Rs. 570 × 10-5

Total Income = Selling price × Quantity of product
manufactured
= 570× (15× 103 /day) × (300 days/year) × 10-5
Total Income = Rs. 25650
Gross income = Total Income – Total Production Cost
= (25650) – (20076.34934)
Gross Income = Rs. 5573.65066
Let the Tax rate be 45% (common)

Taxes = 45% of Gross income
= 45% of 5573.65066
Taxes = Rs. 2508.142797
Net Profit = Gross income - Taxes
=5573.65066 - 2508.142797
Net profit = Rs. 3065.507863
L.I.T. Nagpur 89
Rate of Return:
Rate of return = Net profit× 100/Total Capital Investment
Rate of Return = 3065.507863/ (11602.68772)
Rate of Return = 0.26421
Rate of Return = 26.421%
Pay Back Period

Pay back period = 1/rate of return
= 3.785 years
Pay Back Period = 45.42 months
L.I.T. Nagpur 90
10. Process control, Instrumentation &

Automation
Process control and automation, together with their associated

instruments can be regarded as the mechanical brain and nerves of modern
chemical processing. Thus a properly instrumented and controlled plant ensures:
1. Increased productivity and low cost.
2. Better and more uniform quality of the product.
3. Greater safety for operating personnel.
Instrumentation usually will incure a proportionately large increment of
engineering design cost because of the extensive analysis and relatively large
amount of detailed associated with the intelligent specification of even the lowest
cost instrument item. This coupled with the high cost of installation emphasizes the
need for close scrutiny into the essentiality of every element in the instrumentation
system.
Direct Digital Feedforward-Feedback Control of Distillation

Column:-
The direct digital feedforward- feedback control of distillation

column is shown in Figure.
The two principal disturbances inlet feed flowrate and the inlet
feed composition are measured and the signals are sampled through the sampler
switches. The discrete time signals are converted into digital signals by the analog to
digital converters. The electronic comparators are used to generate the errors which
are the difference between the set points and the measured values. The generated
errors are minimized by the electronic feedforward controller monitored by the
computer. The output command signals from the computer which are in the digital
forms are converted into the analog forms by the digital to analog converters. The
discrete time signals are converted into continuous signals by the hold elements.
L.I.T. Nagpur 91
The electro-pneumatic transducers are used to convert electric signals into the
pneumatic signals. The pneumatic signals of the electronic pneumatic transducer in
the transmission line of feed composition act on the diaphragm actuator of the
control valve which in turns regulates the steam pressure in the reboiler.
The composition of the distillate is measured and the signals are
sampled through the sampler switches. The discrete time signal is converted into the
digital signals by the analog to digital converter. The electronic comparator is used to
generate the error which is the difference between the set point and the measured
value. The generated error is minimized by the electronic controller which is
monitored by the computer. The output command signal from the computer which is
in the digital form is converted into analog form by the digital to analog converter.
The hold element is used to convert the discrete time signal into the continuous
signal. The electro-pneumatic transducer is used to convert the electric signal into
the pneumatic signal.
The pneumatic signal of the electro-pneumatic transducer in the
transmission line of the inlet feed composition measurement in the feedforward
control and the pneumatic signal of the electro-pneumatic transducer in the
transmission line of the distillate composition measurement act on the diaphragm
actuator of the control valve which in turn regulates the reflux ratio.
SCADA CONTROL
The supervisory control and data acquisition SCADA refers to a

type of industrial control system which is used to collect data from the various
sensors of the plant that are either in close proximity or off site sometimes miles
away from the process plants and then sends this data to the SCADA master
computer control station from a remote location.
The SCADA system is used for controlling and monitoring
chemical or transport processes and for the distribution and transmission of power.
The SCADA is used to control the complete site spread out over a very long distance
from few kilometers to several miles for efficient control.
L.I.T. Nagpur 92
SCADA Configuration:-
The SCADA system configuration consists of following

control units.
1) Supervisory control station

2) Programmable Logic Controller & Remote Terminal Unit
3) Computer network segment.
The process information such as temperature,

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

1 Reactor Thermocouple
2 Cooler Thermocouple
3 Scrubber Thermocouple,
Mass spectrometer
4 Distillation Column Venturimeter,
Mass spectrometer
5 Degasser Mass spectrometer
L.I.T. Nagpur 93
11. 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 the plant should be
located where the minimum cost of production and distribution can be obtained, but
other factors, such as room for expansion and safe living conditions for plant
operation as well as the surrounding community, are also important.. 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. Flood and Fire Protection.
8. Environmental impact, and effluent disposal.
9. Local community considerations.
10. Climate.
11. Political and strategic considerations.
Marketing Area:-
Acetaldehyde is widely used as an intermediate. Hence, it is

necessary to locate the plant near to factories where it is major raw material. From
this prospective Mumbai is the ideal place for acetaldehyde plant since many
factories are located close to Mumbai. That’s why most of acetaldehyde
manufacturing unit are located in Mumbai.
L.I.T. Nagpur 94
Raw Materials:-
The raw material for the plant is ethylene. As Most of the

ethylene 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; 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.
L.I.T. Nagpur 95
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.
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 96
Flood and fire protection:-
Many industrial plants are located along rivers ornear large

bodies of water, and there are risks of flood or hurricane damage. Before selecting a
plant site, the regional history of natural events of this type should be examined and
the consequences of such occurrences considered. Protection from losses by fire is
another important factor in selecting a plant location. In case of a major fire,
assistance from outside fire departments should be available. Fire hazards in the
immediate area surrounding the plant site must not be overlooked.
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:-
A dverse climatic condition 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.
L.I.T. Nagpur 97
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.
PLANT LAYOUT
After the process flow diagrams are completed and before detailed
piping, structural, and electrical design can begin, the layout of process units in a
plant and the equipment within these process units must be planned. This layout can
play an important part in determining construction and manufacturing costs, and thus
must be planned carefully with attention being given to future problems that may
arise. Since each plant differs in many ways and no two plant sites are exactly alike,
there is no one ideal plant layout. However, proper layout in each case will include
arrangement of processing areas, storage areas, and handling areas in efficient
coordination and with regard to such factors as:
1) New site development or addition to previously developed site

2) Economic distribution of utilities and services
3) Health and safety considerations
4) Waste-disposal requirements
5) Auxiliary equipment
6) Space available and space required
7) Roads and railroads
8) Possible future expansion
L.I.T. Nagpur 98

Acetaldehyde

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L.I.T.

Acetaldehyde CH3CHO (ethanal) first used extensively during World War І as

Acetaldehyde was first prepared by Scheele in 1774 by the action of

Acetaldehyde is a product of most hydrocarbon oxidations. It is an

Acetaldehyde is a colorless, mobile liquid having a pungent, suffocating odor

Table 1: Density of Acetaldehyde

Sr. Properties Values

2. Boiling point at 101.3 KPa (1 atm) 0 C 20.16

5. Vapor density (air =1) 1.52

6. Surface tension at 20 0 C (dyn/cm) 21.2

8. Heat capacity vapor (J/g 0 C,250 C) 1.4068

10. Latent heat of fusion KJ/mol (cal /g) 3.24 (17.6)

11. Latent heat of vaporization KJ/mol (cal/g) 25.71 (139.5)

12. Heat of solution in water KJ/mol

18. Free energy of formation KJ/mol

24. Thermal conductivity of vapor at 25 0 C Jm-1s-1K-1 1.09x10-2

25. Entropy for gaseous acetaldehyde at 25 0 C J/mol K 265.9

Table 3: Vapor pressure of acetaldehyde

Temperature Vapor Pressure Temperature Vapor Pressure

Acetaldehyde is a highly reactive compound which is commonly consumed at

∗ Decomposition: - Acetaldehyde decomposes at temperature above 400 0

∗ Oxidation: - The liquid phase oxidation of acetaldehyde with air (oxygen) is of

∗ Reduction: - Acetaldehyde is readily reduced to ethanol. A wide variety of

∗ Polymerization: - Paraldehyde 2, 4, 6-trimethyl-1, 3-5-trioxane a cyclic trimer

H2SO4 regenerates acetaldehyde. Being readily depolymerised paraldehyde is

∗ Reaction with Nitrogen Compounds: - With primary amines, Schiff bases

∗ Reaction with Halogens and Halogen Compounds: - Halogen readily replaces

∗ Miscellaneous reactions: - Hydrocyanic acid adds to acetaldehyde in the

In handling acetaldehyde one has to remember that it is an extremely reactive

SHIPPING AND STORAGE

Acetaldehyde is shipped in 5-10 or 55-gal drums insulated tank trucks and

CAPACITY AND MARKET SURVEY

Year USA W. Europe Mexico Japan Total

Table 5:- Worldwide Production & their capacities (103 T)

Sr. No. Producers Capacity

1. Azot PO, Ukraine 100

2. BP Chemicals Ltd, Italy 140

3. Doljchim, Romania 4.5

4. Eastman Chemical Company, US 250

5. Erkimia SA, Spain 75

6. Hoechst AG, Germany 290

7. Huls AG, Germany 80

8. Japan Aldehyde Company Ltd, Japan 69

9. Kyowa Yuka Company Ltd, Japan 62

10. Mitsui Petrochemical Industries Ltd, Japan 53

11. Morelos, Mexico 150

12. Neftechim, Bulgaria 90

13. Omskiy Zavod Synnth. Caoutch, Russia 100

14. Pajaritos, Mexico 44

15. Petroleos Mexicanos (PEMEX), Mexico 100

16. Salavatnephteorgsyntez, Russia 100

17. Showa Denko KK, Japan 140

18. Societe Francaise Hoechst SA, France 96

19. Tokuyama Petrochemical Company Ltd, Japan 100

20. Wacker Cheme GmbH, Germany 65

21. Zacklady Chemiezne, Poland 90

Table 6:- Acetaldehyde United States Capacity 1970

Sr. Producer and Location Capacity

1. Celanese, Bay City, Texas 250

2. Celanese, Bishop, Texas 240

3. Celanese, Clear Lake City, Texas 500

4. Celanese, Pampa, Texas 10

5. Eastman, Longview Texas 500