INTRODUCTION

Acrylic acid and its derivatives are primarily used in the preparation of solution and
emulsion polymers. The objective of this project is to design an acrylic acid plant that will produce
glacial acrylic acid, which is at 99.0% purity. Because acetic acid, a byproduct, is also a
marketable commodity, purification of acetic acid to 95% purity is also desirable. Acrylic acid is
produced via the catalytic partial oxidation of propylene. The desired products must be separated
from the rest of the reactor product stream. This stream consists of acrylic acid, acetic acid, water,
oxygen, nitrogen, and carbon dioxide.
Goal is to produce 200 TPD of 99.0% acrylic acid utilizing 8000 hours a year. The one
month of shut-down time is most likely for catalyst regeneration and equipment maintenance.

PRODUCT IDENTITY

Common name: Acrylic acid

CAS name: 2-Propenoic acid
CAS registry number: 79-10-7
EEC No: 607-061-00-8
DOT UN: 22-18-29
RTECS Number: AS 4375000
Synonyms: acroleic acid
2-propenoic acid
vinylformic acid
propene acid
ethylenecarboxylic acid
propenoic acid
ethene carboxylic acid
Chemical formula: C3H4O2

GENERAL PROPERTIES:

State: Clear Liquid, colourless

Water Solubility: Soluble
Melting Point: 12ºc
Boiling Point: 141-142ºc
Specific Gravity: 1.047-1.051
Auto- ignition: 435ºc
Molar Mass: 72.06 gm/mol
 PROPERTIES OF ACRYLIC ACID

Acrylic acid is a colorless liquid with an irritating acrid odor at room temperature and
pressure. Its odor threshold is low (0.20-3.14 mg/m3). It is miscible in water and most organic
solvents.
Acrylic acid is commercially available in two grades: technical grade (94%) for
esterification, and glacial grade (98-99.5% by weight and a maximum of 0.3% water by weight)
for production of water-soluble resins. Acrylic acid polymerizes easily when exposed to heat,
light or metals, and so a polymerization inhibitor is added to commercial acrylic acid to prevent
the strong exothermic polymerization. The inhibitors that are usually used in acrylic acid
preparations are the:

 Monomethyl ether of hydroquinone (methoxyphenol) at 200 ± 20 ppm

 Phenothiazine at 0.1%
 Hydroquinone at 0.1%
 Methylene blue at 0.5 to 1.0%
 N,N'-diphenyl- p-phenylenediamine at 0.05% can also be used.

Acrylic acid reacts readily with free radicals and electrophilic or nucleophilic agents. It
may polymerize in the presence of acids (sulfuric acid, chlorosulfonic acid), alkalis (ammonium
hydroxide), amines (ethylenediamine, ethyleneimine, 2-aminoethanol), iron salts, elevated
temperature, light, peroxides, and other compounds that form peroxides or free radicals. The
presence of oxygen is required for the stabilizer to function effectively. Acrylic acid must never
be handled under an inert atmosphere.
Freezing of acrylic acid occurs at 13°C. Rethawing under inappropriate temperature
conditions is another frequent reason for acrylic acid polymerization. Acrylic acid is a strong
corrosive agent to many metals, such as unalloyed steel, copper and brass.

CHEMICAL PROPERTIES:
Acrylic acid undergo reactions characteristics of both unsaturated acids and aliphatic
carbolic acids or esters. The high reactivity of these compounds stems from the two unsaturated
centers situated in the conjugated position. The β carbon atom, polarized by carbonyl group,
behaves as an electrophile; this fovours the addition of large variety of nucleophiles and active
hydrogen compounds to the vinyl group. Moreover, the carbon-carbon double bond undergoes
radical-initiated addition reactions, Diels-Alder reactions with dienes, and polymerization
reactions.
The carboxyl function is subject to the displacement reactions typical of aliphatic acids
and esters, such as esterification and transesterification. Joint reactions of the vinyl and carboxyl
functions, especially with bifunctional reagents, often constitute convenient route to polycyclic
and heterocyclic substances.
Acrylic acids polymerise very easily. The polymerization is catalysed by heat, light, and
peroxides and inhibited by stabilizers, such as monomethyle ether of hydroquinone or
hydroquinone itself. These phenolic inhibiters are effective only in the presence of oxygen.
Thehighly exothermic, spontaneous polymerization of acrylic acid is extremely violent.
 USES OF ACRYLIC ACIDS

Acrylic acid undergoes the typical reactions of a carboxylic acid and forms acrylic esters
- basic alkyl esters are methyl, butyl, ethyl acrylate, and 2-ethylhexyl acrylate. Acrylic acid and
its esters undergo the reactions of the double bond which readily combine with themselves or
other monomers (e.g amides, methacrylates, acrylonitrile, vinyl, styrene and butadiene) to form
homopolymers or co-polymers which are used in the production of coatings, adhesives,
elastomers, super absorbent polymers, flocculants, as well as fibres and plastics. Acrylate
polymers show a wide range of properties dependent on the type of the monomers and reaction
conditions.

Alkyl acrylates are clear, volatile liquid; slightly soluble in water and complete soluble in
alcohols, ethers and almost organic solvents; Acrylate esters containing a double bond and
functional carboxyl group are used chiefly as a monomer or co-monomer in making acrylic and
modacrylic fibers. It is used in formulating paints and dispersions for paints, inks, and adhesives.
It is used in making cleaning products, antioxidant agents, amphoteric surfactants. It is used in
making aqueous resins and dispersions for textiles and papers. Methyl acrylate also used in
making vitamin B1

The worldwide production of acrylic acid in 1994 was estimated to be approximately 2

million tonnes. Acrylic acid is used primarily as a starting material in the production of acrylic
esters; as a monomer for polyacrylic acid and salts, as a comonomer with acrylamide for polymers
used as flocculants, with ethylene for ion exchange resin polymers, with methyl ester for
polymers.

Acrylic acid is used in the field of application of:

 plastics
 paper manufacture and coating
 exterior house paints for wood and masonry
 coatings for compressed board and related building materials
 flocculation of mineral ore fines and waste water , and treatment of sewage
 printing inks
 interior wall paints
 floor polishes
 floor and wall coverings
 industrial primers
 textile sizing, treatment and finishing
 leather impregnation and finishing
 masonry sealers
 lubricating and fuel oil additives
 lacquers for automotive, appliance and furniture finishes
 pharmaceutical binders
 hot metal coatings.
 VARIOUS COMMERCIAL PROCESSES

Ethylene Cyanohydrin Method: This process involves the acidic hydrolysis and
dehydration of ethylene cyanohydrin (from ethylene oxide and hydrogen cyanide) and the
removal of the product from the reaction mixture by distillation. Like all other preparation of
polymerizable monomers, care must be exercised to remove the product from the reaction mixture
and either inhibit or appropriately cool it before uncontrolled polymerization can ensue .
H2SO4
HOCH2CH2CN + H2O HOCH2CH2COOH CH2=CHCOOH +H2O
-NH3

Propiolactone Method: This commercial method is based on the polymerization of β-

propiolactone and the destructive distillation of this polymer to form acrylic acid.

CH2CH2CO -CH2CH2COOCH2CH2COOCH2CH2COO- CH2=CHCOOH

Carbonyl Reaction: Basic raw materials in the preparation of acrylic acid by the carbonyl
reaction are acetylene carbon monoxide (supplied as such or in the form of nickel carbonyl ) , and
water . Three distinct methods are known.

Stoichiometric Carbonyl Reaction: The reaction is very rapid at atmospheric pressure and at mild
temperature . The hydrogen shown in the accompanying equation does not appear in gaseous form
but is consumed by side reactions

Ni(CO)4 + 4 HC≡CH + 4H2O + 2H+ 4 CH2 =CHCOOH + Ni++ + 2H

Catalytic Carbonyl reaction: The catalytic reaction requires elevated temperature and
superatmospheric pressures. Nickle salts or complexes thereof are used as catalysts.

CO + HC≡CH + H2O CH2=CHCOOH

Semicatalytic Carbonyl Reaction: The catalytic reaction ( catalytic as regards nickel carbonyl) of
acetylene, carbon monoxide and water is superimposed upon the stoichiometric reaction of nickel
carbonyl , acetylene , water and acid. In this way the very mild conditions characteristic of the
stoichiometric reaction can be used , with a large proportion of the total CO being supplied as
carbon monoxide gas, the remainder being supplied in the form of nickel carbonyl.

Acrylonitrile Method: Care must be exercised in this acid hydrolysis since both the starting
Acrylonitrile and the product acrylic acid are polymerizable. The Acrylonitrile should remain in
the reaction zone and , hence, must be well inhibited . A major advantage of this method is the
increase in molecular weight on hydrolysis from 53 to 72, which provides a definite yield
improvement.
2 CH2= CH CN + H2SO4 + 4 H20 CH2=CHCOOH + (NH4)2SO4
Propylene Method: This recently developed process involves the oxidation of propylene to
hydroxypropionic acid : oxides of nitrogen or nitric acid act as catalyst for the reaction.
Subsequent dehydration yields acrylic acid. The stepwise representation can be shown as follows:

CH3CH=CH2 + 3/2 O2 CH 3CHOHCOOH CH2=CHCOOH + H2O

An alternative route is the catalytic oxidation to acrolein , CH2CHCHO , and then to acrylic acid
with oxygen and certain metallic catalyst such as Mo, Co, or Ce.

Acrylic Ester Method: This method is hamperaed by the ready polymerisability of the
starting material , and the low boiling points of the most available esters and the formed alchohols
as compared with that of the product , acrylic acid.
H2SO4
CH2=CHCOOCH3 + H2O CH2=CHCOOH + CH3OH

It is generally preferable to saponify the ester to form the corresponding salt.

CH2=CHCOOCH3 + NaOH CH2=CHCOONa + CH3OH

The salt can then be converted to the acid by :

 Neutralizing the calcium salt with sulphuric acid, removing precipitated calcium sulfate
by a difficult filtration procedure, and obtaining the formed acrylic acid in aqueous
concentrate.
 Treating an aqueous solution of sodium salt with ion- exchange resin to remove sodium
ions, removing the resin by filtration, and obtaining an aqueous concentrate of acrylic acid.

Maleic Acid Method: This patented method involves the decarboxylation of maleic acid to
form the desired acrylic acid.

HOOCCH=CHCOOH CH2=CHCOOH + CO2

Potassium Vinyl Method: The low temperature conversion of vinly chloride with potassium
metal and a subsequent treatment of the cold vinyl potassium with dry ice is reported to give
potassium acrylate in 70% conversion . Customery methods produce acrylic acid.

K CO2
CH2=CHCl CH2=CHK CH2=CHCOOK

Vinyl Grignard Method: This interesting synthesis involves the use of the well known
carboxylation of a Grignard reagent to form the acid.
HX
CH2=CHMgX + CO2 CH2=CHCOOMgX CH2=CHCOOH + MgX2
 CHOICE OF PROCESS

Various methods for the manufacture of acrylic acid are mentioned above. For a route to
be commercially attractive the raw material costs and utilization must be low, plant investment
and operating cost not excessive, and waste disposal charges minimal.

Acrylic acid commercially is, and here also is being produced from propylene which is a
by-product of ethylene and gasoline production.

CH2=CHCH3 + 3/2 O2 CH2=CHCOOH + H2O

A lead time of several years for development and plant construction is important in a
period where and availability of hydrocarbon raw materials are changing rapidly and significantly.
Natural gas costs are expected to increase steadily while the supply is decreasing. Acetylene
should be in short supply with rising costs in the next decade unless new technology based on
coal is developed . Hence, acrylic acid manufacture by acetylene routes will be increasingly
uneconomical. Ethylene cost, dependent on crude oil are expected to increase ,but not sharply.
Propylene may be considered a byproduct from the large volume manufacture of ethylene from
heavy petroleum feed stocks. New ethylene facilities , based on naphtha and other heavy feed
stocks will ensure a large supply of coproducts including propylene. Propylene requirements for
acrylic acid will be small,compared to other chemical uses ( polypropylene , Acrylonitrile,
propylene oxide , isopropanol and cumene for acetone and phenol). Hence , although the cost of
propylene is expected to rise, this should be at a slower rate than the increases for any of the other
raw materials . The favourable supply and cost projection for propylene suggest that all new
acrylic acid plants will employ propylene oxidation technology for atleast the next two decades.

The most economical process for the manufacture of acrylic acid is based on the two stage
vapour phase oxidation of propylene to acrylic acid. Process based on acetylene - the high pressure
Reppe process (BASF), the modified Reppe process (Rohm Haas) - or on Acrylonitrile are still
being used for the production of acrylic acid. A ketone and an ethylene cyanohydrin process were
once commercially important, but are no longer used.

The propylene oxidation process is attractive because of the availability of highly active
and selective catalysts and the relatively low cost of propylene.
 PROCESS DESCRIPTION

The reactors are of the fixed-bed shell-and-tube type (about 3-5m long and 2.5cm in
diameter) with a molten salt coolant on the shell side. The tubes are packed with catalyst, a small
amount of inert material at the top serving as a preheater section for the feed gases. Vaporized
propylene is mixed with steam and air and fed to the firststage reactor.

The preheated gases react exothermically over the first-stage catalyst with the peak
temperature in the range of 330 - 4300c, depending on conditions and catalyst selectivity. At the
end of the catalyst bed, the temperature of the mixture drops toward that of the molten salt coolant.

The acrolein rich gaseous mixture containing some acrylic acid is then passed to the
second stage reactor, which is similar to the first stage reactor but packed with catalyst designed
for selective conversion of acrolein to acrylic acid. Here the temperature peaks in the range of 280
– 3600c depending on condition. The temperature of the effluent from the second stage reactor
again approximates that of the salt coolant. The heat of reaction is recovered as steam in external
waste heat boiler.

The process is operated at the lowest temperature consistent with high conversion.
Conversion increases with temperature: the selectivity generally decreases only with large
increase in temperature. Catalysts are designed to give high performance over a range of operating
condition permitting gradual increase of salt temperature over the operating life of the catalysts
to maintain productivity and selectivity near the initial levels, thus compensating for gradual loss
of catalyst activity.

The first unit the product stream enters is the absorption tower, which quickly lowers the
temperature of the entering stream from about 220oc to less than 800c. The purpose is to put the
acrylic acid into a cool, liquid state that will not readily dimerize. Also, this separates out the
gaseous material in the product stream such as nitrogen, carbon dioxide, oxygen, and propylene.
These components exit out the top along with some fugitive acrylic and acetic acid that is still in
the vapor phase. The gases entering the gas absorber are absorbed using deionized water. The
water absorbs the acrylic and acetic acids and allows the other gases to continue on to an
incinerator to be burned.The aqueous effluent from the bottom of the absorber is 20 - 30 % acrylic
acid which is sent to the recovery .The overall yield of acrylic acid in the oxidation reaction steps
is in the range of 73 - 83 % depending on the catalysts and condition employed.

The acrylic acid is extracted from the absorber effluent with a solvent. The acid extractor
is a liquid-liquid extraction column. The acid containing water enters through the bottom feed
stream. The top feed stream contains an organic solvent . The two liquid phases flow counter-
currently through a liquid-liquid extractor. The acids enter solution with the solvent and exit out
the top stream with a fraction of the water, and the water exits out the bottom stream with a very
small amount of solvent.
 The top stream continues on to the solvent tower, which is a packed distillation column.
Because of acrylic acid's ability to dimerize easily at high temperatures, all of the distillation
processes are performed in part with vacuum distillation. The solvent and remaining water leave
in the distillate stream at 0.12 bar and 13oC. Refrigerated water is used to condense the distillate.
Some is refluxed back into the column, but the distillate is then heated up to 40oC and used as a
recycle and is re-fed into the acid extractor.

Meanwhile, the acids leave the solvent tower in the bottoms and are fed into the acid tower.
The acid tower is a distillation column that again operates in vacuum conditions. The acetic acid
leaves the top at 0.07 bar, while the acrylic acid leaves in the bottoms. Both the acrylic and acetic
acids are warmed and compressed to normal pressure levels. Both now meet the given
requirements. Namely, that acrylic acid must be 99% pure and that acetic acid must be 95% pure.

Only one detail remains. The bottom stream from the acid extractor is nearly completely
water save for a small amount of solvent. This stream is fed to another distillation column. Here,
the solvent is separated out the top stream and then joins the solvent recycle stream re-entering
the acid extractor tower. The bottom stream is sent to wastewater treatment

The oxidation process flow sheet shows equipment and typical operating conditions.
 DETAILED MATERIAL BALANCE

Basis: 100 TPD of Acrylic Acid .

CH2=CHCH3 + O2 CH2 = CHCHO + H2O

(acrolein)

CH2=CHCHO + ½ O2 CH2=CHCOOH
(acrylic acid)
Molecular weights: Propylene = 42; Acrylic acid(AA) = 72; Acetic acid = 60;
Acrolein = 56; Oxygen = 16; Carbon dioxide = 44

ACID TOWER ( Designed as a major equipment )

Assumption : Top product is 95 wt. % acetic acid

Bottom product is 99.5 wt.% acrylic acid.

Apply Overall Balance=

Y*64.81=0.05*6.944 +0.995*57.87
Y=0.8938

Input Feed : Acrylic acid = 0.8938*64.81=57.92 kmol/hr

Acetic acid = 64.81-57.92=6.88 kmol/hr

SOLVENT RECOVERY COLUMN :

Assumption: 1. Complete recovery of solvent and water occurs.

2. Bottom product contains only acetic acid and acrylic acid.
3. 98% of solvent entering in extraction column present in extract phase(Feed to
Solvent tower).
4. 0.5% of acetic acid and acrylic acid present in feed stream is present in recycle
Stream.

OUTPUT=
Acrylic acid=57.92 kmol/hr
Acetic acid=6.88 kmol/hr.

By applying balance we get:

Feed : Extract phase from the liquid-liquid extractor:
Acrylic acid = 58.21 kmol/hr.
Acetic acid = 6.9145kmol/hr
Water = 10.83 kmol/hr
Solvent = 245 kmol/hr

Upstream contains (recycled to extraction column) :

Solvent = 245kmol/hr
Acrylic acid = 0.29 kmol/hr
Acetic acid = 0.0345 kmol/hr
Water = 10.83 kmol/hr

SOLVENT EXTRACTION COLUMN :

Solvent with high solubility for acrylic acid and acetic acid , and low solubility with water is
used to extract AA acid from absorber stream.
X=Acetic acid
Y=Acrylic acid

Assumptions: 1. Solvent required for 99 .5% extraction of AA is 250 kmol/hr.

2. All acrylic and acetic acid in recycle stream went to raffinate phase.
3. 0.5 of acrylic and acetic acid feed is in raffinate phase.
4. 98% of solvent entering is in extract phase.

Recycled stream from solvent recovery column and waste tower.

Acrylic acid = 0.29 kmol/hr
Acetic acid = 0.3450 kmol/hr
Water = 10.83 kmol/hr

Extract phase contains (to solvent recovery plant):

Acrylic acid = 58.21 kmol/hr.
Acetic acid = 6.9145 kmol/hr
Water = 10.83 kmol/hr
Solvent = 245 kmol/hr

Raffinate phase contains ( to waste tower)X

Acrylic acid = 0.005*Y +0.29 kmol/hr
Acetic acid = 0.005*X +0.0345kmol/hr
Water = 595.6 kmol/hr
Solvent = 5 kmol/ hr

By applying balance we get:

Feed from the bottom the absorber: Acrylic acid = 58.79 kmol/hr
Acetic acid = 6.984 kmol/hr
water = 541.42 kmol/hr
ABSORBER:

From literature: Acrylic acid and acetic acid is absorbed using water as solvent.
Gases CO2 , O2 , N2 and small amount of steam leave the absorber at the top.

Assumptions: 1% of acrylic and acetic acid feed went to off gases.

Solvent: Water entering at the top = 244.3 kmol/hr

Off gases leaving at the top: CO2 = 6.399 kmol/hr

N2 = 458.75 kmol/hr
O2 = 20.784 kmol/hr
AA = 0.5632 kmol/hr
Acetic acid = 0.07695 kmol/hr
Steam=33.0135 kmol/hr
Product liquid leaving at the bottom of the absorber to recovery section:
Acrylic acid = 58.79 kmol/hr
Acetic acid = 6.984 kmol/hr
water = 541.42 kmol/hr

By material balance we get:-

Feed entering at the bottom of the absorber: Acrylic acid =59.38 kmol/hr
Acetic acid = 7.055 kmol/hr
CO2 = 6.399 kmol/hr
O2 =20.784 kmol/hr
N2 = 458.75 kmol/hr
Steam =330.135 kmol/hr

REACTOR II: Oxidation of Acrolein to Acrylic acid

CH2=CHCHO + ½ O2 CH2=CHCOOH
(acrylic acid)
Catalyst composition= Mo12 V1.9 Al 1.0 Cu2.2 ( support - Al sponge)
Contact time = 1 - 3 sec
Average temperature = 300oc
Acrolein conversion = 100%
Yield of AA = 97.5%

ASSUMPTIONS=1. 97.5% conversion of acrolein to acrylic acid.

2. 2.5% converted to acetic acid and CO2.
Output:-

Total AA formed in 2 reactors = 59.38 kmol/hr

Total Acetic acid produced = 7.055 kmol/hr
Total CO2 produced = 7.055 kmol/hr
N2 in = N2 out = 458.75 kmol/hr

By applying balance we get:=

Feed: O2 = 47.01 kmol/hr

N2 = 458.75 kmol/hr
Steam = 333.135 kmol/hr
Acrolein = 52.4515 kmol/hr
Acrylic acid = 8.2424 kmol/hr
Acetic acid = 6.399kmol/hr
CO2 = 6.399 kmol/hr

O2 reacted = 26.225 kmol/hr

O2 unreacted = 20.784 kmol/hr

REACTOR I: Oxidation of Propylene to Acrolein .

CH2=CHCH3 + O2 CH2 =CHCHO + H2O

(acrolein)
Catalyst composition= Ni. Fe. Zn. Bi. or Zn + Co (Fe promotion )
Contact time = 3.6 sec
Average temperature = 355oc
ASSUMPTIONS=1. Feed Composition= C3H6 : Air : Steam :: 1 : 7.75 : 3.75
2. Overall conversion of C3H6 = 100%
3. Conversion to acrolein = 70%
4. Conversion to AA = 11%
OUTPUT GIVEN=
Acrolein produced = 52.4515 kmol/hr
AA produced = 8.2424 kmol/hr
Steam produced = 51.93 kmol/hr
Side products produced (CO2 + Acetic acid)=12.80 kmol/hr
Total steam leaving the reactor = 333.135 kmol/hr

By applying balance we get=

C3H6 fed = 74.188 kmol/hr

Steam fed = 280.987 kmol/hr
Air fed = 580.7075 kmol/hr
O2 entering = 121.74 kmol/hr
N2 in = N2 out = 458.75 kmol/ hr
O2 used in the reactor = 74.188 kmol/hr
O2 left unreacted = 47.01 kmol/hr
 DETAILED ENERGY BALANCE

Data:
Heat capacity:
C3H6 : 2.85 + .23 x 10-2 T - 1.2 x 10-4 T 2 + 2.3 x 10-8 T 3 ( kJ/kmol K )
C3H4O : 3.7957 + 4.4 x 10-2 T - 0.1304 x 10-4 T 2 - 0.2848 x 10-8 T 3 (cal / mol K)
C3H4O2: 1.6828 + 6.9212 x 10-2 T - 0.4475 x 10-4 T2 + 1.10186 x 10-8 T3 ( cal / mol K)
C2H4O2: 2.0142 + 5.6065 x 10-2 T - 0.3401 x 10-4 T 2 + 0.802 x 10-8 T 3(cal / mol K)

REACTOR I
Heat in:
Feed is preheated to 200oc (Molten Salt Coolant Temperature)
473

Heat in with C3H6 = m ∆Hf at 25oc + m ∫298 Cp dT

473

= 74.188 ( 20.27 x 10 3 + ∫298 Cp dT) = 2499675.27 kJ / hr

Heat in with air(Compressed to 5 bar) = m Cp∆T

= 574.957 x 1.015x 29x (200-25) = 2961742.34 kJ / hr
Heat in with steam = mλ+mCp∆T = 278.205 x ( 2676 x 18 + 2.291 x 18 ) x (200-25)
= 15408286.55 kJ / hr
Total heat in = 20869704.03 kJ / hr

Heat Generated :
Heat generated by reaction 1 = 340.8 kJ / mol
Heat generated by reaction 2 = 254.1 kJ / mol
Heat generated by other side reactions are neglected.
Total heat generated = 340.8 x 103 x 51.93 + 254.1 x 103 x 8.16 = 19771200 kJ / hr

Heat removed by Coolant :

The temperature in the reactor reaches an average peak temperature of 355oc due to the
exothermic reaction.
At the end of the catalyst bed, the temperature drops toward that of molten salt coolant (2100c)
483 483

Heat with acrolein = m ∫628 Cp dT= 51.93 x ∫628 Cp dT

= 746491.31 kJ / hr
483 483

Heat with Acrylic acid = m∫628 Cp dT = 8.16x ∫628 Cp dT

= 139424.3 kJ / hr
483 483

Heat with Acetic acid = m∫628 Cp dT = 7.045 x∫628 Cp dT

= 102482.9 kJ / hr
Heat with air = m Cp ∆T
= 500.762 x 30.35 x ( 628-483) = 2203728.37 kJ / hr
Heat with CO2 = m Cp ∆T
=7.045 x 47.896 x ( 628-483) = 48926.96 kJ / hr
Heat with steam = m Cp ∆T
= 330.135 x 36.173 x ( 628-483) = 1731586.13 kJ / hr
Total heat removed by the Coolant = 49726399.74 kJ/hr

Heat out:
298 298

Heat out with Acrolein = m∫483 Cp dT = 51.93 ∫628 Cp dT

= 754594.56 kJ/hr
298 298

Heat with Acrylic acid = m∫483 Cp dT = 8.16 x∫483 Cp dT

= 141806.91 kJ/hr
298 298

Heat with Acetic acid = m∫483 Cp dT = 7.045 x∫483 Cp dT

= 104244.7 kJ / hr

Heat with air = m Cp ∆T

= 500.762 x 30.35 x ( 483-298) = 2811653.44 kJ / hr

Heat with CO2 = m Cp ∆T

= 7.045 x 42.37 x ( 483-298) = 55221.88 kJ / hr

Heat with steam = m Cp ∆T

= 330.135 x 33.913 x ( 483-298) = 2071235.62 kJ / hr
Total heat out = 5938757.11 kJ/hr

Heat to Waste heat boiler

=Heat in + Heat generated - Heat removed by coolant - Heat out
=29729506.95 kJ/hr

Water required in boiler = m = 59459205.41/λ

= 11109.68 kg/hr

REACTOR II

Heat in from reactor I = 5938757.11 kJ/hr

Heat generated = 254.1 x 10 3 kJ/kmol of Acrylic acid
= 254.1 x 10 3 x 50.63 = 12865083 kJ/hr

Heat removed by coolant:

The feed to the second reactor enters at temperature of 210oc
The temperature in the reactor reaches an average peak temperature of 300oc due to the
exothermic reaction. At the end of the catalyst bed, the temperature drops toward that of molten
salt coolant (210oc)
483 483

Heat with Acrylic acid = m∫573 Cp dT = 58.79 x∫573 Cp dT

= 605576.04 kJ / hr
483 483
Heat with Acetic acid = m∫573 Cp dT = 7.695 x∫573 Cp dT
= 67473.46 kJ / hr

Heat with air = m Cp ∆T = 474.488 x 30.35 x ( 573-483)

= 1294207.915 kJ / hr

Heat with CO2 = m Cp ∆T = 7.695 x 46.0548 x ( 573-483)

= 31903.955 kJ / hr

Heat with steam = m Cp ∆T = 330.135 x 35.42 x ( 573-483)

= 1052439.6 kJ / hr
Total heat removed by the Coolant = 3051600.975 kJ/hr

Heat out:
298 298

Heat with Acrylic acid = m∫483 Cp dT = 58.79 x∫483 Cp dT

= 1021671.95 kJ / hr
298 298

Heat with Acetic acid = m∫483 Cp dT = 7.695 x∫483 Cp dT

= 27221.275 kJ / hr

Heat with air = m Cp ∆T = 474.488 x 30.35 x ( 483-298)

= 2664131.498 kJ / hr

Heat with CO2 = m Cp ∆T = 7.695 x 40.528 x ( 483-298)

= 57710.71 kJ / hr

Heat with steam = m Cp ∆T = 330.135 x 36.913 x ( 483-298)

= 2254460.552 kJ / hr
Total heat out = 5930875.925 kJ/hr.

Heat to Waste heat boiler

=Heat in + Heat generated - Heat removed by coolant - Heat out
=9821363.21 kJ/hr

Water required in boiler = 9821363.21/λ

= 3670.16 kg/hr

ABSORBER:
Heat in:
Heat in from the second reactor =5930875.925 kJ/hr
Absorbing solvent water enters at 30oc

Heat in with water = m Cp ∆T = 244.3 x 4.186 x 18 x (30-25)

=92037.55.1 kJ/hr
Total heat in = 6022912.925 kJ/hr
Heat out along with the offgas:
The off gas leave the column at 70oc
298 298

Heat with Acrylic acid = m∫343 Cp dT = 0.5632 x∫343 Cp dT = 2080.07 kJ / hr

298 298

Heat with Acetic acid = m∫343 Cp dT = 0.07695 x∫343 Cp dT

= 242.52 kJ/hr

Heat with air = m Cp ∆T = 474.488 x 30.35 x ( 343-298)

= 648031.986 kJ / hr

Heat with CO2 = m Cp ∆T = 7.695 x 40.52 x ( 343-298)

= 14031.06 kJ / hr

Heat with water = m Cp ∆T = 33.0143 x 33.913 x ( 343-298)

= 5034.7 kJ / hr

Total heat out with the off gas= 714732.63 kJ/hr.

Heat out along with the bottom product:

The bottom products leave the column at 80oc
298 298

Heat with Acrylic acid = m∫353 Cp dT = 58.22 x∫353 Cp dT

= 265746.83 kJ / hr
298 298

Heat with Acetic acid = m∫353 Cp dT = 7.695 x∫353 Cp dT

= 30510.825 kJ / hr

Heat with water = m Cp ∆T = 541.42 x 4.186 x 18x ( 343-298)

= 2243740.995 kJ / hr
Total heat out with the bottom product = 2539998.65 kJ/hr.

Heat to inter stage cooler (Minor equipment)

=Heat in - Heat out with off gas - Heat out at the bottom
= 2768181.645 kJ/hr
 PROCESS DESIGN
(Vacuum distillation Tower)

Feed to the distillation tower = 57.655 kmol/ hr of acrylic acid

+ 7.54 kmol / hr of acetic acid.
= 65.195 kmol/ hr.

Top product from the distillation tower is 95 wt% acetic acid.

Bottom product from the distillation tower is 99.5 wt% acrylic acid .

Feed:
Flow rate of feed = 65.195 kmol/ hr.
Mol fraction of acetic acid in feed = 7.54 / 65.195 = 0.1156
Average molecular weight of feed = 70.37 kg/kmol

Distillate:
Flow rate of distillate = 0.1156/0.958 x 65.195 = 7.867 kmol/hr
Mol fraction of acetic acid =( 95/60 )/ [ (95/60 )+ (5/72)] = 0.958
Average molecular weight of distillate = 60.5 kg/kmol .

Residue:
Flow rate of residue = 65.195-7.867 = 57.328 kmol/hr.
Mol fraction of acetic acid = (0.5/ 60 ) / [( 99.5/72 )+ (0.5/ 60)] = 0.006
Average molecular weight = 71.92 kg/kmol.
 VLE data :
Liquid
Mole 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
frac of
acetic
acid (x)
Vapor
Mole 0.0 0.21 0.37 0.51 0.63 0.715 0.795 0.86 0.92 0.96 1.0
frac of
acetic
acid (y)

Feed is a liquid at its boiling point

q=1; i.e. q line is vertical line passing through x=y=xF .
From x-y plot ,
xD / (Rm + 1) = 0.13
 Rm = 6.369
Therefore, Optimum reflux ratio R= 15
Number of ideal stages in enriching section = 6
Number of ideal stages in stripping section = 4+1(reboiler)
Number of stages = 11
Slope of bottom operating line = 1.313
Slope of top product = 0.959

Flow Rates:

Molecular weight of feed = 70.37 kg/kmol

Flow rate of feed = 65.195 kmol/hr = F
Flow rate of distillate = 7.867 kmol/hr = D
Flow rate of residue = 57.328 kmol/hr = F-D

Physical Properties:

Estimate base pressure, assume column efficiency of 60%

Take reboiler as equivalent to 1 stage,
No. of real stages = (11-1)/0.6 = 17
Assume 100mm water pressure drop per plate.
Column pressure drop = 100 x 10-3 x 1000 x 9.81 x 17 = 16677 Pa
Top pressure, 1 atm(14.7 lb/in2) = 101.4 x 103 Pa
Estimate bottom pressure = 101.4 x 103 + 16677
= 118077 Pa = 1.18077 bar

Column Diameter:

Flv = (L/G)x(ρL/ρG)1/2
At bottom, L= 11294.9kg/hr
G= 8961.94kg/hr
ρL= 1078.32 kg/m3
ρG= 0.1767 kg/m3
(Ref: digitallibrary.srmuniv.ac.in/4001.pdf)
Therefore, Flv(bottom) = 0.814

At top, L= 6819.25kg/hr
G= 7273.9kg/hr
ρL= 1083.94 kg/m3
ρG= 0.1569 kg/m3
(Ref: digitallibrary.srmuniv.ac.in/4001.pdf)
Therefore, Flv(top) = 0.0113

From Richardson vol. 6 Fig 11.27, taking tray spacing 0.5m,

Base k1= 8x10-2
Top k1= 9.1x10-2

Correction for surface tension,

Base k2= (57/20)0.2x 8x10-2 = 0.0986
Top k2= (23/20)0.2x 9.1x10-2 = 0.0935

Base uf = 0.0986 x((1078.32-0.1767)/0.1767)1/2 = 7.7 m/s (R&C vol.6 eq 11.81)

Top uf = 0.0935 x((1083.94-0.1569)/0.1569)1/2 = 7.77 m/s (R&C vol.6 eq 11.81)

Design for 85% flooding at maximum flow rate

Base Uv = 7.7x0.85=6.545 m/s
Top Uv = 7.77x0.85=6.6045 m/s

Maximum flow rate

Slope of bottom operating line = 1.313
Lm`/Vm` = 1.313
Vm`= Lm`-57.328 = 1.313 Vm` - 57.328
 Vm`= 183.156 kmol/hr
 Lm`= 240.48 kmol/hr

Therefore, for base, maximum flow rate= (183.156x71.92)/(0.1767x3600)= 20.71 m3/hr

for top, maximum flow rate= (240.464x60.5)/(0.1569x3600) = 25.76 m3/hr

Net area required,

Bottom= 20.71/6.545 = 3.165 m2
Top= 25.76/6.6045 = 3.9 m2

At first trial take downcomer area as 12% of total.

Column cross-sectional area, base= 3.165/0.88= 3.597m2
Top= 3.9/0.88= 4.43m2

Column diameter, base= (3.597x4/3.14)1/2 = 2.14m

Top= (4.43x4/3.14)1/2 = 2.38m
Use same diameter above and below feed, reducing the perforated area for plates above the feed.

Liquid flow pattern

Maximum volumetric liquid rate= (240.48x71.92)/(3600x1078.32)=0.0045 m3/hr

Provisional plate design

Column diameter Dc = 2.38m

Area Ac = 4.43m2
Downcomer area Ad = 0.12x4.43 = 0.5316m2 (at 12%)

Net area An = Ac- Ad = 4.43-0.5316 m2 = 3.8984m2

Active area Aa = Ac- 2Ad = 3.3668m2

Hole area Ah(take 10% Aa at first trial) = 0.33668m2

From R&C vol.6 fig 11.31, Lw/Dc = 0.77

 Weir length = Lw = 2.336m
 PROCESS DESIGN
(INTER STAGE COOLER)
(Shell and tube heat exchanger)

Exchanger Duty:
Q = 2768181.645 kJ/hr = 768.93 kJ/sec
Coolant used is Water at 27oc

Cooling water balance:

Q = m Cp ∆T
 768.93 = m x 4.187 x (32 - 27)
 Mw = 36.72 kg/ sec.

Flow rate of liq mix to be cooled, mmix = 3.998 kg/sec

Liquid mixture Balance,
Q = mmix x Cpmix x (Ti - 80 )
 768.93 = 3.998 x 3.212 x (Ti - 80)
 Ti = 140oc
Hence the liquid mixture must be cooled from a temperature of 140oc to 40oc

Properties (at mean temperature),

Water: ρ= 993.68 kg/m3
Cp= 4.187 kJ/kgoK
μ= 1 cp
k= 0.578 W/mok

Liq. Mix: ρ= 992.99 kg/m3

Cp= 3.212 kJ/kgoK
μ= 0.1612 cp
k= 0.513 W/mok

Log Mean Temperature Difference (∆Tlm):

∆Tlm = [(T1 - t2 ) - (T2 - t1 ) ] / ln [(T1 - t2 )/ (T2 - t1 )].

(T1 - t2) = 140 - 32 = 108
(T2 - t1) = 80 - 27 =53
∆Tlm = 77.2oc
R = (T1 - T2 ) / ( t2 - t1) = 12
S = ( t2 - t1) / (T1 - t1) = 0.044
{From PERRY Fig 10-14, P.No.: 10-27}
FT = 0.985

Routing of Fluids:

Water - Tube side

Liquid Mixture - Shell Side
Heat Transfer Area:

{From PERRY Table 10-10 P.No.: 10-44}

Assumed Value of Overall heat transfer Coefficient, Ud = 550 W/m2 K.
Dirt factor = 5.1 x 10-4 m2 K/ W.
Q = U A( ∆Tlm ) FT.
 A= (768.93 x 103 ) / (570 x 73.21 x 0.97) = 18.38 m2

Number of Tubes:
Choosing D0 (Tube outside dia) = ¾ in = 0.01905 m
Di (Tube inside dia) = 0.62 in = 0.01575 m
Length = L = 14 ft = 2.13 m
Heat transfer Area: a = 3.14xDo = 3.14 x 0.01905 = 0.05987 m2 / m length
Heat transfer Area for one tube = 0.05987 x 2.13 = 0.1277 m2 / tube
Number of Tubes = 18.38 / 0.1277 = 144

From Tube Count Table (PERRY : table 11-3 ; P.No. 11-13)

TEMA P or S ; for 1-2 pass,
Number of tubes Nt = 228
Shell ID = 438 mm
Corrected Heat Transfer Area = 228 x 0.1277= 29.11 m2
Corrected Ud = 427.977 W/m2 K.

Tube Side (Cooling water) Velocity and Heat transfer Coefficient (hi)

Flow Area = at = 3.14 / 4 x Di2 x(Nt / Np )

= 0.0222 m2
Velocity = vt = ( mt /ρ at) = 36.72 / 993.68 x 0.0222 = 2.12 m / sec
Reynolds Number NRe = vt Di ρ/μ
= 2.12 x 0.01575 x 993.68 / 1.00 x 10-3
=33178.9
Prandtl Number NPr = μ Cp/k = 1x10-3 x 4.187 x 103 )/ 0.578
= 7.2439
Nusselt Number NNu = 0.023 ( NRe)0.8 (NPr)1/3
= 184.1
Heat transfer coefficient hi = NNu K / Di
= 6756.17 W/m2 K.

Shell Side ( Liquid Mixture ) Velocity and Heat Transfer Coefficient ho:

Assumption: Shell Dia is equal to tube bundle dia.

Pitch: Equilateral Triangular Pitch is used.
P' = standard pitch = 1 in = 25.4 mm.
Sm = Cross flow area at center of shell
= [(P' - Do ) Ls ] Ds / P'
Ls = baffle spacing .
= Ds / 2 = 0.219 m
Nb = number of baffles
Nb + 1 = L / Ls = 20
 Nb = 19
2
 Sm = 0.02398 m
Shell side velocity = vs = ms / Sm ρ
= 3.998 / 0.02398 x 992.99
= 0.1678 m/sec
Reynolds Number NRe = vs Do ρ/μ
= 0.1678 x 0.01905 x 992.99 / 0.16128 x 10-3
= 19681.18
Prandtl Number NPr = μCp/k = 0.16128x10-3 x 3.205 x 103)/ 0.513
= 1.0076
Nusselt Number NNu = jH (NRe) (NPr)1/3
(From PERRY : Fig 10- 19 ; P.No 10-29 )
jH = 5 x 10-3
NNu = 98.65
Heat transfer coefficient ho = NNu K / Do
= 2656.67 W/m2 K.

Overall Heat Transfer Coefficient Uo:

(1/ Uo) clean = 1/ ho + 1/ hi (Do / Di ) + Do ln (Do / Di ) / 2 Kw

Kw = 50 W/m2 K.
(1/ Uo)clean = [1/2656.67]+[(1/6756.17)(0.01905/ 0.01575)]
+[(0.01905 ln (0.01905/ 0.01575))/(2x100)]
= 5.9165 x 10-4
(1/ Uo) dirt = 5.9165 x 10-4 + 5.1 x 10-4
Uo = 907 W/m2 K

This is greater than the assumed Uo, Hence design is acceptable.

 COST ESTIMATION AND ECONOMICS

C2 = C1 ( Q2 / Q1)n
C1 = Fixed capital cost of a plant of Capacity Q1
C2 = Fixed capital cost of a plant of Capacity Q2
n= 0.6(Pg.186, Table 19, P. Timmerhaus)

For the year 1999(as reference)

Utilizing 8000 operating hours/year (Ref: digitallibrary.srmuniv.ac.in)
Q1 = 50000 tons/year
Q2 = 33333.335 tons / year.
C1 = $ 24000000.
C2 = 24000000 x (33333.335 / 50000)0.6 = $ 18.8 x 106

Cost of the plant in 2016:

(Cost of plant in 2016 / Cost of plant in 1999) = (Cost index in 2016 / Cost index in 1999)
Cost of plant in 2016 = 18.8 x 106 x(852 / 389.9) = $ 41.08 x 106

Fixed Capital Investment (FCI) required = $ 41.08 x 106 = Rs 2246.66 x 106

Direct cost: (70 - 85 % of FCI )

A. 1. Purchased Equipment (PEC) ( 15 - 40% of FCI)

25% of FCI = Rs 561.66 x 106
2. Installation including insulation and painting ( 25 - 55% of PEC)
30% of PEC = Rs 168.49 x 106
3. Instrumentation and Controls, Installed (6 - 30 % of PEC)
25% of PEC = Rs 140.41 x 106
4. Piping, Installed (10 - 80 % of PEC)
30% of PEC = Rs. 168.49 x 106
5. Electrical ,Installed (10 - 40% of PEC)
25% of PEC = Rs. 140.41 x 106
B. Building, process and auxiliary (10 - 70% of PEC)
40% of PEC = Rs.224.66 x 106
C. Service Facilities and Yard Improvements (40 - 100% of PEC)
60% of PEC = Rs.336.696 x 106
D. Land ( 1- 2% of FCI or 4- 8% of PEC)
5% of PEC = Rs. 28.083 x 106
Total Direct Cost = Rs 1468.39 x 106

Indirect Costs: (15 - 30 % of FCI)

A. Engineering and Supervision (5 - 30 % of Direct Cost)

10% of Direct cost = Rs. 146.889 x 106
B. Construction Expense and Contractors Fee (6 - 30% of Direct cost)
10% of Direct costs = Rs. 146.889 x 106
C. Contingency (5- 15% of FCI)
 5.5% of FCI = Rs. 30.89 x 106
Total Indirect Cost = Rs 324.66 x 106

Working Capital: (10 - 20% of TCI)

15% of TCI = Rs. 336.99 x 106

Total Capital Investment (TCI):

TCI = FCI + Working Capital
 TCI = Rs. 2583.65 x 106

ESTIMATION OF TOTAL PRODUCT COST (TPC):

Manufacturing Cost:

A. Fixed Charges (10 - 20% of TPC)

1. Depreciation (10% of FCI + 2 - 3% of building value for building )
10% of FCI + 2.5% of Building value = Rs. 230.28 x 106
2. Local Taxes (1-4% of FCI )
4% of FCI = Rs 89.86 x 106
3. Insurance (0.4 - 1% of FCI)
0.7% of FCI = Rs. 15.72 x 106
Total Fixed Charges = Rs. 335.86 x 106

Total Product Cost

TPC = Fixed Charges / 0.15 = Rs. 2239.06 x 106

B. Direct Production Costs (about 60 % of TPC)

1. Raw Materials (10 - 50 % of TPC)
10% of TPC = Rs. 223.906 x 106
2. Operating Labor (10 - 20 % of TPC)
15% of TPC = Rs.335.859 x 109
3. Direct Supervisory and Clerical Labor (10 - 25 % of Operating labor)
15% of Operating Labor = Rs. 50.37 x 106
4. Utilities (10 - 20% of TPC)
10 % of TPC = Rs 223.906 x 106
5. Maintenance and Repairs (2- 10% of FCI)
5% of FCI = Rs. 112.33 x 106
6. Operating supplies (10 - 20% of cost for maintenance and repairs)
15% of cost for maintenance and repairs = Rs. 16.34 x 106
7. Laboratory Charges (10 - 20% of Operating Labor)
15% of Operating Charges = Rs 50.37 x 106
8. Patents and Royalties (0 - 6% of TPC )
2% of TPC = Rs 44.78 x 106
Total Direct Production Cost = Rs 1053.36 x 106
C. Plant Overhead Cost (5 - 10% of TPC)
7% of TPC = Rs 156.73 x 106
Total Manufacturing Cost = Rs. 1547.95 x 106
General Expenses:
A. Administrative Costs (2- 6% of TPC)
5% of TPC = Rs. 111.953 x 106
B. Distribution and Selling Costs (2 - 20% of TPC)
18% of TPC = Rs. 403.03 x 106
C. Research and development cost (5% of TPC)
5% of TPC = Rs. 111.953 x 106
D. Financing (0- 10 % of TCI)
= Rs. 77.509 x 106
Total General Expenses = Rs. 704.44 x 106

SELLING PRICE:

Acrylic acid produced = 100 TPD

Selling price of Acrylic acid = $2.9 /kg (Ref: Chemical Marketing Reporter)
Acetic acid produced = 10.33 TPD
Selling price of Acetic acid = $ 0.8 /kg (Ref: Chemical Marketing Reporter)
Total income = selling price x qty of product produced
= Rs. 5455.81 x 106
Gross Earning = Total income - Total product cost
= 5455.81 x 106 – 2239.06 x 106
= Rs 3216.75 x 106
Tax on gross earning = 40% of gross earning.
Net Profit = Gross earning [1 - tax rate]
= Rs. 1930.05 x 106
Rate of return = Net profit / Total capital investment
= 1930.05 x 106 / 2583.65 x 106
= 0.74

Payback Period = 2246.66/(1930.05+230.28)

= 1.03 years
 SITE CONSIDERATION AND PLANT LAYOUT

The location of the plant can have a crucial effect on the profitability of a project, and the scope
for future expansion. Factors considered while selecting a plant site are:

 Transportation
 Sources and costs of raw materials
 Prospective market for products
 Corporation long range planning
 Water source - quality and quantity
 Special incentive
 Climatic conditions
 Pollution requirements(Waste disposal)
 Utilities - cost, quantity and reliability; fuel - costs, reliability and availability
 Amount of site preparation necessary(site conditions)
 Construction costs
 Operating labor
 Taxes
 Living conditions
 Corrosion
 Expansion possibilities
 Other factors.

Three factors are usually considered the most important. These are the location of the markets and
raw materials and the type of transportation to be used.

Transportation: 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. The
least expensive method of shipping is usually by water; the most expensive is by truck.

Raw materials: The availability and price of suitable raw materials will often determine the site
location. Propylene is the major raw material for the manufacture of Acrylic acid, hence the plant
can be located near any plant producing propylene. It will reduce transportation and storage costs.

Location of markets: Consumer products often are delivered in small shipment to a large number
of customers. In an international market, there may be an advantage to be gained by locating the
plant within an area with preferential tariff agreements. Since acrylic acid acts as a raw material
for the production of consumer goods like paints, plastics, pharmaceutical binders etc., it is always
advantages for the plant to be situated in a industrial area.

Long Range Corporate Planning: The object of long range planning is to optimize a whole
network of operations instead of each one individually. This means that each plant site is not
considered only for itself and that its chosen location might not be the one that would be selected
if only the economics of the one plant had been considered. Placing the plants throughout the
country allows each plant to be located optimally.
Water: Water is needed by every processing plant for a number of different purposes. Potable
water is needed for drinking and food preparation. The plant site must have an adequate amount
of each type of water at all times of the year. Not only the amount and quality but the temperature
of the water is important. The size of the heat exchanger is inversely proportional to the
temperature difference between the cooling water and the material being cooled.

Climatic Conditions: Adverse climatic conditions at a site will increase costs. Abnormally low
temperatures will require the provision of additional insulation and special heating for equipment
and pipe runs. Stronger structures will be needed at locations subject to high winds or earthquake.

Pollution and Ecological Factors: 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 must be met.

Site Conditions: An ideal chemical plant site is above the flood plain, flat, has good drainage , a
high soil- bearing capability , and consists of sufficient land for the proposed plant and for future
expansion.

Availability of labor: Labor 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 labor available locally; and labor suitable for training to operate the
plant.

Political and Strategic considerations: Capital grants, tax concession and other inducements are
often given by governments to direct new investment to preferred locations; such as areas of high
unemployment.

Local Community Considerations: The proposed plant must fit in with and be acceptable to the
local 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.

Corrosion: Once the general area for the plant has been determined, the effect of neighboring
industries should be considered when picking the specific site. Their presence may indicate an
increased corrosion rate.
 PLANT LAYOUT

The economic construction and efficient operation of a process depend on how well the
plant and equipment specified on the process flow sheet is laid out. The principal factors to be
considered are:
 Economic consideration: construction and operating costs.
 The process requirement.
 Convenience of operation.
 Convenience of maintenance
 Safety.
 Future expansion
 Modular construction

Costs: The cost of construction can be minimized by adopting a layout that gives the shortest run
of connecting pipe between equipment, and the least amount of structural steel works.

Operation: Equipment that needs to have frequent operator attention should be located
convenient to the control room. Valves, sample points and instruments should be located at
convenient positions and heights. Sufficient working space and headroom must be provided to
allow easy access to equipments.

Safety: Blast walls may be neede to isolate potentially hazardous equipment, and confine the
effects of an explosion. At least two escape routes for operators must be provided from each level
in process buildings.

Plant expansion: Equipments should be located so that it can be conveniently tied in with future
expansion of the process.

Modular construction: In recent years there has been a move to assemble sections of plant at the
plant manufacturer’s site. These modules will include the equipment, structural steel , piping and
instrumentation. The modules are then transported to the plant site, by road or sea. The advantages
of modular construction are:
 Improved quality control.
 Reduced construction cost.
 Less need for skilled labor on site.
Some of the disadvantages are,
 Higher design costs & more structural steel work.
 More flanged constructions & possible problems with assembly, on site.

General consideration: Open, structural steelwork, buildings are normally used for process
equipment; closed buildings are only used for process operations that require protection from the
weather.
A TYPICAL PLANT LAYOUT:-
 INSTRUMENT AND PROCESS CONTROL

Instrumentation is the most important factor in ensuring safety and smooth working of the
plant. A separate control room is provided in modern plants where on panels indicators and
recorders are present. Instruments are used in the industry to measure process variables such as
temperature, pressure, density, level specific heat, conductivity, humidity, flow rate, chemical
composition etc.
The primary objectives of the designer when specifying instrumentation and control schemes are:

1. Safe plant operation:

(a) To keep the process variables within known safe operating limits.
(b) To detect dangerous situations as they develop and to provide alarms and automatic shut-down
systems.
(c) To provide interlocks and alarms to prevent dangerous operating procedures.
2. Production rate:To achieve the design product output.
3. Product quality:
To maintain the product composition within the specified quality standards.
4. Cost:
To operate at the lowest production cost, commensurate with the other objectives.
These are not separate objectives and must be considered together.

TEMPERATURE CONTROL / MEASUREMENTS:

Various instruments are used for eg.
1. Thermocouple
2. Resistance Thermometers
3. Thermistors
4. Mercury in Glass Thermometers.

Controllers are used to maintain temperature within specified limits. Every temperature
control problems is essential one. The temperature lay involved in the measurement of this
variable is an important factor. Thermal element is usually placed in a well to protect it and allow
servicing of element without interrupting the process. The location of the temperature element
often has as much to do with the efficiency element often as other parts of the control loops.
Temperature bulb should always be located at point where the coefficient of heat transfer will be
as large as possible e.g. if vapors and liquid are at same temperature, then bulb should be kept in
liquid because of high heat transfer coefficients.

PRESSURE CONTROL / MEASUREMENTS:

It is quite necessary for most system handling vapours of gas. It can be measured by using
pressure gauges. Self operated pressure regulation is often used in pressure control. It is installed
directly in the line the control sensing apparatus is paced about 10 diameter from the unit. This
location eliminates erroneous pressure caused by turbulence. Sudden change in velocity, shock
and vibrations difficulties often occur when self operated regulation are used with liquids.

LEVEL CONTROL / MEASUREMENT:

 The measurement of level can be defined as the determination of location of interface with
respect to a fixed plane. The main objective of a level control system is to maintain the level of
the liquid in a tank at the Act point value. The different is pressure transmitter senses the pressure
difference / a function of liquid level in the tank) and gives out an electrical signal, which after
signal conditioning is given to the P.I.D. controller. The controller compares the measured
variables with the set point and depending upon the error, gives an output to the control valve.
The control value, in turn controls the flow. Due to the control of flow, the level is controlled to
its set point.

FLOW CONTROL / MEASUREMENTS:

It is defined as volume per unit time at specific temperature and pressure conditions. It is
generally measured by positive displacement of rate meters.

CONDENSER CONTROL:

Temperature control is unlikely to be effective for condensers, unless the liquid stream is
sub-cooled. Pressure control is often used, or control can be based on the outlet coolant
temperature.

DISTILLATION COLUMN CONTROL:

The primary objective of distillation column control is to maintain the specified

composition of the top and bottom products, and any side streams; correcting for the effects of
disturbances in:

1. Feed flow-rate, composition and temperature.

2. Steam supply pressure.
3. Cooling water pressure and header temperature.
4. Ambient conditions, which cause changes in internal reflux.

The compositions are controlled by regulating reflux flow and boil-up. The column overall
material balance must also be controlled; distillation columns have little surge capacity (hold-up)
and the flow of distillate and bottom product (and side-streams) must match the feed flows. The
feed flow-rate is often set by the level controller on a preceding column. It can be independently
controlled if the column is fed from a storage or surge tank. Feed temperature is not normally
controlled, unless a feed pre heater is used. Temperature is often used as an indication of
composition. The temperature sensor should be located at the position in the column where the
rate of change of temperature with change in composition of the key component is a maximum.
Near the top and bottom of the column the change is usually small. With multi component
systems, temperature is not a unique function of composition. Top temperatures are usually
controlled by varying the reflux ratio, and bottom temperatures by varying the boil-up rate. If
reliable on-line analyzers are available they can be incorporated in the control loop, but more
complex control equipment will be needed.

PID LEGENDS
 Instrument locally mounted Process connecting lines

Instrument at control center Orifice for flow meas.

Instrument transmitting Electric lines

Control valve pneumatic Pneumetic lines

Controller self contained Capillary lines

FIRST LETTER SECOND LETTER THIRD LETTER

D- Density A-Alarm A-Alarm
F-Flow C-Control C-Control
H-Hand activated E-Element V-Valve
L-Level G-Glass
M-Moisture I-Indicating
P-pressure R-Recorder
T-Temperature S-Safety weir
 PID OF DISTILLATION COLUMN

Temperature Control Composition Control (R controlled and bottom

product as fixed ratio of feed flow)

Composition Control (Top product controlled by feed)

 PID OF REACTOR

INSTRUCTIONS FOR OPERATION

Before starting, always make sure that the followings:
 No visible damage is evident in the system.
 All electrical switches are turned off.
 All water valves are closed.
 All valves are tightly closed.

Start up procedure.
 Check the level in the tank.
 Switch on the main supply.
 Turn on the main pump.
 Open valve for pump.
 Start mechanical pump.
 Open the steam valve.
 Check the flow, temperature& pressure during the operation.

System shut down.

 Reduce the flow of the feed & steam.
 Reduce all flow rates & wait for pasture to drop.
 Turn off the pump.
 When the flow slow down close the valve tightly to avoid cavitations.
 Disconnect the packing line.
 POLLUTION CONTROL AND SAFETY

Acrylic acid is a colorless liquid with an irritating acrid odor at room temperature and
pressure. Its odor threshold is low (0.20-3.14 mg/m3). It is miscible in water and most organic
solvents. Acrylic acid polymerizes easily when exposed to heat, light or metals, and so a
polymerization inhibitor is added to commercial acrylic acid to prevent the strong exothermic
polymerization. The inhibitors that are usually used in acrylic acid preparations are:

 monomethyl ether of hydroquinone (methoxyphenol) at 200 ± 20 ppm

 phenothiazine at 0.1%
 hydroquinone at 0.1%.
 Methylene blue at 0.5 to 1.0%
 N,N'-diphenyl- p-phenylenediamine at 0.05%

The presence of oxygen is required for the stabilizer to function effectively. A head space
containing sufficient air should always be maintained above the monomer to ensure inhibitor
effectiveness. Dissolved oxygen takes part in the inhibition reaction and therefore is gradually
consumed. The level of dissolved oxygen should periodically be replenished. This can be
accomplished by thoroughly aerating the liquid phase, i.e. recirculation of the inventory in tanks
or agitating drums (rotating).
Acrylic acid must never be handled under an inert atmosphere. Freezing of acrylic acid occurs
at 13°C. Rethawing under inappropriate temperature conditions is another frequent reason for
acrylic acid polymerization. During the crystallization process the inhibitor and oxygen
concentrate in the mother liquor. Therefore no mother liquor should be withdrawn from a partially
frozen container. This may result in a severe deficiency of the inhibitor system in the crystalline
matrix. If direct heat is applied, polymerization will start immediately, often with great violence.
Under no circumstances must steam be used to thaw frozen acrylic acid, nor must thawing be
carried out at temperatures above 35°C.
Acrylic acid is a strong corrosive agent to many metals, such as unalloyed steel, copper and
brass. Frequently the hydrolysis of such metalic materials generates a deep discoloration in acrylic
acid. Polyvalent metal salts formed during hydrolytic reactions could also induce polymerization.
Therefore, under no circumstances should acrylic acid be stored or transported with equipment
which contains the above-mentioned metals. Acrylic acid does not affect stainless steel.

Analytical Methods
Acrylic acid residues in air and other media can be quantified by means of gas chromatographic,
high performance liquid chromatographiC was found to be 14 mg/m3 (14 ppm) in air and down to
1 mg/kg or 1 mg/litre (1 ppm) in other media.

Human Exposure
No data on general population exposure are available. However, consumers may be exposed to
unreacted acrylic acid in household goods such as polishes, paints and coatings, adhesives, rug
backing, plastics, textiles and paper finishes. A potential source of internal exposure to acrylic
acid may result from metabolism of absorbed acrylic acid esters. Acrylic acid also occurs in
wastewater effluent from its production. It is estimated that thousands of workers could be
exposed to acrylic acid, but exact figures are not available.
Kinetics and Metabolism
Inhalation and contact with skin are important routes of occupational exposure. Regardless of the
route of exposure, acrylic acid is rapidly absorbed and metabolized. It is extensively metabolized,
mainly to 3-hydroxypropionic acid, CO2 and mercapturic acid, which are eliminated in the expired
air and urine. Owing to its rapid metabolism and elimination, the half-life of acrylic acid is short
(minutes) and therefore it has no potential for bioaccumulation.

Effects on Animals
Most data indicate that acrylic acid is of low to moderate acute toxicity by the oral route, and of
moderate acute toxicity by the inhalation and dermal routes. Acrylic acid is corrosive or irritant
to skin and eyes. It is unclear what concentration is non-irritant. It is also a strong irritant to the
respiratory tract. A chronic drinking-water study on rats showed no effect at the highest dose
tested (78 mg/kg body weight per day). For inhalation studies a lowest-observed- adverse effect
level (LOAEL) of 15 mg/m3 (5 ppm) was observed in mice exposed to acrylic acid for 90 days.
Available data do not provide evidence for an indication of carcinogenicity of acrylic acid, but
the data are inadequate to conclude that no carcinogenic hazard exist.

Effects on Humans
There have been no reports of poisoning incidents in the general population. No occupational
epidemiological studies have been reported. Because acrylic acid toxicity occurs at the site of
contact, separate guidance values are recommended for oral and inhalation exposure. Guidance
values of 9.9 mg/litre for drinking-water and 54 μg/m3 for ambient air for the general population
are proposed.

Effects of the Environment

No quantitative data on environmental levels of acrylic acid in ambient air, drinking-water or soil
have been reported. Acrylic acid is miscible with water and, therefore, would not be expected to
adsorb significantly to soil or sediment. Under soil conditions, chemicals with low Henry's Law
constants are essentially non-volatile. However, the vapour pressure of acrylic acid would suggest
that it may volatilize from surfaces and dry soil. Acrylic acid may be formed by
Hydrolysis of acrylamide monomer from industrial waste in soil, especially under aerobic
conditions. The toxicity of acrylic acid to bacteria and soil microorganisms is low. Acrylic acid
emitted into the atmosphere will react with photochemically produced hydroxyl radicals and
ozone, resulting in rapid degradation. There is no potential for long-range atmospheric transport
of acrylic acid because it has an atmospheric lifetime of less than one month. When released into
water, acrylic acid readily biodegrades. The fate of acrylic acid in water depends on chemical and
microbial degradation. When added to water acrylic acid is rapidly oxidized, and so it can
potentially deplete oxygen if discharged in large quantities into a body of water. Acrylic acid has
been shown to be degraded under both aerobic and anaerobic conditions.
On the basis of the low octanol-water partition coefficient of acrylic acid, bioconcentration
in aquatic organisms is unlikely. There have been no reports of biomagnification of acrylic acid
in food chains.

Symptoms of poisoning
The principal hazard of acrylic acid is its corrosive effect on tissues. Both vapour and liquid can
be irritating or corrosive to the mucous membranes, skin and eyes. The severity of these effects
is dependent on the duration of contact, which, if prolonged, may result in blisters and burns.
Blister formation can appear as late as 24 h after exposure. Severe corneal burns could occur to
the eyes. Permanent tissue damage may result if prompt and appropriate emergency response is
not provided. Inhalation of concentrated vapours and mist could produce moderate to severe
irritation of the respiratory tract. High concentrations could result in pulmonary oedema
while lower concentrations could produce nasal and throat irritation. Lacrymation may also result
from inhalation exposure. Although ingestion is not an expected route of human exposure,
swallowing of acrylic acid may cause severe irritation or burning of the mouth, throat, oesophagus
or stomach. No serious health effects have been reported to result from single exposure or repeated
exposure at low concentrations of acrylic acid.

Safety in Use
Acrylic acid should only be handled in well-aerated and well-ventilated places. If exposure to
concentrated vapour can not be excluded (as in the case of an accident), selfcontained breathing
apparatus or air supply masks must be worn. Care must be taken when using filter-type masks to
ensure that the filter capacity is not exceeded for the intended time of use and expected
concentration. In areas where a release of acrylic acid is possible, eye protection devices, face
shields, neoprene gloves and rubber boots should be worn. A chemical suit with a selfcontained
breathing apparatus is strongly recommended if larger spills or emissions have to be cleared.
Appropriate protective clothing should be worn for work involving
breaking or entering into a closed acrylic acid system. Owing to its vapour pressure, the
concentration of acrylic acid in closed rooms can reach high values.
If clothing or shoes have accidentally been contaminated with acrylic acid, they must be
removed immediately. Contaminated leather shoes or other leather goods must be discarded. For
timely and appropriate emergency response, it is advisable to provide complete sets of safety
protection equipment near places where accidents with acrylic acid are possible.

Explosion and Fire Hazards

Acrylic acid has a flash point of 54-68°C and does not form explosible vapour mixtures at ordinary
ambient temperatures. However, ignition may occur if excessive amounts of mist or aerosols have
formed in air. Ignition sources can include spark discharges from static electricity, and this can
occur when acrylic acid is flowing through or being discharged from a line. During transfer from
one container into another, the containers should be electrically interconnected and properly
grounded. Splashing into a tank should be avoided by using a dip tube. Since acrylic acid and
water are miscible in any proportion, water can be used to extinguish fires. Small fires can be
fought with carbon dioxide or dry chemical extinguishers, whereas for larger fires foam (alcohol
or universal type) can be used. If a fire occurs in or close to a tank farm containing acrylic acid,
tanks and pipes should be cooled by spraying with water in order to prevent the acid from
polymerizing.

Storage
Acrylic acid should be stored in a detached, cool, well-ventilated, non-combustible place and its
containers should be protected against physical damage. Acrylic acid can be stored only in vessels
lined with glass, stainless steel, aluminum or polyethylene. In order to inhibit polymerization
during transport and storage, 200 ppm MeHQ (the monomethyl ether of hydroquinone) is
commonly added to acrylic acid by the manufacturer. The presence of oxygen is required for the
inhibitor to be effective. A major concern during the storage of acrylic acid is the avoidance of
elevated temperatures as well as freezing, since both can lead to a failure of the inhibitor system.
Ideally acrylic acid should be stored within a temperature range of 15 to 25°C.
Acrylic acid and its solutions should be kept out of reach of children and unauthorized persons as
well as away from food, drink and animal feed. If any container in the store is leaking, appropriate
precautions should be taken and personal protective equipment used.
Transport
Acrylic acid is shipped in containers in compliance with regulations according to
ADR/RID/GGVS/GGVE, Class 8 Packing Group B specifications. Acrylic acid is commonly
shipped in steel drums with polyethylene inserts or in self-supporting highdensity polyethylene
drums impermeable to ultraviolet light. White polyethylene container are translucent to ultraviolet
light and therefore may promote polymerization. Stainless steel ISO containers are recommended
for the transport of quantities of acrylic acid up to 1 tonne.

Spillage
Before dealing with any spillage, appropriate personal protective equipment should be used. Small
spills of up to 5 litres can be absorbed in commercially available clean-up kits (using sand or
clay). If a wastewater sewer is close by, the spill can also be washed down with water provided
that it is not a storm-sewer or ditch that is routed to surface water. Large spills should be contained,
if possible, within a dike area. A temporary dike can be arranged by stacking sand bags or similar
devices. Avoid run-off into storm sewers routed to public surface water. If possible, the material
should be recovered in appropriate containers for reuse or disposal. During all handling operations
of large spills a chemical suit with a self-contained or air-supplied breathing device must be worn.
In the event of accidental spillage of acrylic acid to surface water or to a municipal sewer system,
the pollution control agencies must be notified promptly. However, acrylic acid may be toxic to
the system if the bacteria have not been conditioned properly to this material. Accordingly, the
initial feed rate should be low with a stepwise increase if a significant amount is to be fed into the
biological treatment plant. The maximum concentration should not exceed 1000 mg per litre. It
should be kept in mind, however, that large quantities may affect the optimal acidity of the milieu
and may therefore need to be neutralized by the simultaneous addition of sodium hydroxide.

Disposal
Acrylic acid is a highly corrosive material. Accordingly it should always be handled with
appropriate safety equipment. Solid materials containing acrylic acid, such as absorbents or
polymeric material, can be disposed of by incineration. Disposal in landfills must be thoroughly
checked with the authorities and should be practiced only as a last resort. For the disposal of waste
materials originating from laboratory samples, great care must be taken to keep the monomer
separated from incompatible material, such as peroxides, which may initiate polymerization.
 REFERENCES

Books:

 Sinnot, R.K, “Coulson and Richardson’s Chemical Engineering”, vol-6, Fourth edition,
2005
 Trrybal, Robert E., “Mass transfer Operations”, Third edition, 1981
 Perry, Robert H, Green, Don W., “Chemical Engineers’ Handbook”, 1999, 7th edition.
 Chattopadhyay, P “Unit Opeartions of Chemical Engineering”, vol-1, 2003
 McCabe, Warren L, Smith, Julian C, Harriott Peter “Unit Operations Of Chemical
Engineering”, Sixth edition, 2001
 Eckman, Donald P., “Industrial Instrumentation”, 1991
 Hesse, Herman C., Rushton, J.Henry, “Process Equipment Design”,
 Peters, Max S.,Timmerhaus,Klaus D. “Process Design and Economics for Chemical
Engineers”, Fourth edition , 1958
 Loh, H.P, Lyons, Jennifer, “Process Equipment Cost Estimation”, Jan 2002
 Raju, K.S. “Fluid Mechanics, Heat Transfer and Mass Transfer: Chemical Engineering
Practice.”

Internet References:

 www.google.co.in
 www.wikipedia.org/wiki/acrylic acid
 digitallibrary.srmuniv.ac.in/4001.pdf
 sbioinformatics.com
 www.chemicalland21.com