Kinetic Study of Esterification Reaction Using Ion Exchange Resin

Kinetic Study Of Esterification Reaction Using Ion Exchange Resin Catalyst
Abstract
The reaction kinetics of the n-butanol esterification and acetic acid on acidic solid
catalyst named SERALITE SRC-120 under atmospheric pressure was investigated in
this work. Reaction experiments were carried out in a stirred batch reactor at
temperature range of 353 to 356 K, under various catalyst loads and various starting
reactants feed ratios. The experimental data were fitted to estimate the kinetic
parameters for reaction mechanisms. The chemical equilibrium composition was
measured and kinetic information was obtained at the same temperature range. The
results show that the activation energy of n-butanol esterification reaction was found
to be 622.28 KJ/mol.
Finally the results of produced reaction mechanisms were compared with
Experimental results to validate the reaction mechanism. Then it was conclude that
the model results with the regressed kinetic parameters are in excellent agreement
with the experimental results.
Keywords: Esterification, Heterogenous catalyst, n-butyl acetate, Reaction
Kinetics.
Department of Chemical Engineering P.V.P.I.T. (Budhgaon). Page 1

Objective of Project
1) To learn collection of literature.

2) To learn manufacturing process for butyl ester
3) To check the results for various process conditions.
4) To learn formation of experimental set up.
5) To learn execution of material balance, energy balance, reaction kinetics,
design of equipment.
6) To see the overall economics of the process
Outcomes of Project
1) Learnt the search methods for the collection of literature survey.
2) Learnt method of manufacturing of butyl acetate.
3) Learnt the implementation and control of various process conditions.
4) Learnt about collection and attachments of all instruments and equipments
5) Learnt about all applications of all process needs during design of process.
6) Understood collection and use of various information required in plant

scale up.

Literature Survey
Amrit Pal Toor , Mamta Sharma, Sakshi Thakur, and R.K.Wanchoo

(2011)explained about the kinetic behavior of esterification of lactic acid with
isopropanol over an acidic cation exchange resin, Amberlyst 15, was studied under
isothermal condition. Isopropyl lactate synthesized in this reaction is an important
pharmaceutical intermediate. The experiments were carried out in a stirred batch
reactor in the temperature range of 323.15 to 353.15 K. The effect of various
parameters such as temperature, molar ratio and catalyst loading was studied.
Variation in parameters on rate of reaction demonstrated that the reaction was
intrinsically controlled. Kinetic modeling was performed using Eley-Rideal model
which acceptably fits the experimental data. The activation energy was found to be
22.007 KJ/mole and frequency factor was 0.036809 g-1 mol-1 min-1for forward
reaction. The value of entropy for the forward reaction was found to be 182.317 J K-1
mol-1.
Kiran D. Patil1, Bhaskar D. Kulkarni.(2014)Studied that, the esterification of
acetic acid with iso-amyl alcohol catalyzed by acidic ion-exchange resins
(TULSIONR T-62, T-63 and T-66 MP) in a batch reactor to determine the intrinsic
reaction kinetics. Iso-amyl acetate is synthesized in this reaction, has the fragrance of
strong odor (similar to both banana and pear). The effects of various parameters on
the rate of reaction (such as temperature, mole ratio, catalyst loading, and stirrer
speed) are studied. The solid liquid external mass transfer resistance as observed
using various stirring speeds is absent and the rate of reaction depends on
temperature. Further pseudo-homogenous model is developed for an intrinsically
kinetically controlled reaction, which is free from either intra-particle diffusion or
external mass transfer resistance. The rate expression developed in this work would
be useful in the simulation and design of reactive distillation column for the
production of iso-amyl acetate. The resultant kinetic model fitted the experimental
data well. The activation energy is found to be 41.88 kJ /kmole for the formation of
iso-amyl acetate.
Dr. Zaidoon M. Shakoor , Dr.Khalid A. Sukkar &Mohammed S. Baqer (2011)
studied the reaction kinetics of the n-butanol esterification and acetic acid on acidic

solid catalyst named Dowex50 under atmospheric pressure .Reaction experiments

were carried out in a stirred batch reactor at temperature range of 343 to 363 K, under
various catalyst loads and various starting reactants feed ratios. The experimental data
were fitted to estimate the kinetic parameters for reaction mechanisms by using
MATLAB 7 software. The chemical equilibrium composition was measured and
kinetic information was obtained at the same temperature range. The results show that
the activation energy of n-butanol esterification reaction was found to be39.975
kJ/mol. Finally the results of produced reaction mechanisms were compared with
experimental results to validate the reaction mechanism. Then it was conclude that the
model results with the regressed kinetic parameters are in excellent agreement with
the experimental results.
M.Bengi Taysun, EmineSert, Ferhan Atalay. Investigate the esterification
reaction between maleic acid and n-butanol using different environmentally friendly
catalysts. Catalytic performance of Amberlyst 15-dry ,Amberlyst 15-wet, Amberlyst
131H+ and two deep eutectic solvents were studied at 1:10 molar ratio of acid to
alcohol at temperature of 358 and 363 K and with catalyst loading of 0.0375 g/ml.
Among the ion exchange resins studied, Amberlyst 131H+ was found to have the best
performance and the effect of the water content in the reaction mixture was studied
for this catalyst. The catalytic performances of DES’s are found to be comparable and
some cases significantly higher than the ion exchange resins.
Firas Khalil Ismail (2003) explained that in reactive distillation simultaneous
reaction and separation occur. These processes lead to complex interaction between
mass transfer, heat transfer, and chemical reaction kinetics. In the present
investigation, two reactive distillation units were constructed to produce ethyl acetate
using heterogeneous solid catalysts. The maximum production rate of ethyl acetate
was achieved with acetic acid flow rate of (0.163 mole/ min) and heat duty of (450
W).The highest conversion of ethanol was (98%) after four hours, which indicated the
superiority of reactive distillation technology to carry out such type of reaction with
heterogeneous catalysts. The results indicated that the temperature distribution along
the reactive distillation column is distributed uniformly with slight increase in the
reaction zone due to exothermic effects of esterification reaction. Also, it was
concluded that the increase in acetic acid flow rate increases the reaction zone
temperature. This fact is regarded to increase reaction rate of the forward reaction in
the reactive distillation. The derived kinetic model can be used to calculate the
required weight of the solid catalyst successfully for esterification reaction to produce
ethyl acetate. On the other hand, the first order kinetic assumption for the forward
reaction is regarded a good assumption due to high reaction rate of the forward
reaction in comparison with backward reaction in reactive distillation.
Jiri Hanika, Jiri Kolena, Magdalena Kucharova, Karla Havlickova (2003) said
that Alkylacetate synthesis is commonly based on esterification reaction of acetic acid
with pertinent alcohol. This reaction is controlled by chemical equilibrium and is
catalyzed by strong acids or acidic heterogeneous catalysts. The resulting reaction
mixture typically contains both the products, i.e. ester and water, and non-reacted
reaction components, i.e. alcohol and acetic acid. Reaction conversion can be shifted
beyond its equilibrium value combiningesterification and separation together in
reaction system. Reactive distillation process is anadvantageous variant in this sense.
The other possibility is an application of trickle bed reactor packed by a strongly
acidic ion exchange resin operated at temperature above the boiling point of
azeotropic mixture formed from the reaction products and/or reaction components.
The evaporation process during reaction shifts the reaction system to the higher
reaction conversion value compared to the equilibrium one without application of a
great molar excess of one reaction component in the feed. The combination of
specified trickle bed esterification reactor and reactive distillation column represents
another possible technological tool to overcome the chemical equilibrium limitation.
The esterification reaction of acetic acid and butanolwas investigated in this study.
The reaction was occurred in a trickle bed reactor, filled by a strong acid ion-
exchange resin. The reactor operated at temperature above boiling point of azeotropic
mixture containing except unconverted alcohol both reaction products, i.e. ester and
water. The reaction conditions corresponded to the situation when only part of liquid
reaction mixture was evaporated and product components removal during reaction is
possible. The influence of temperature and concentration of reaction components on
the reaction rate was investigated. The partial evaporation of reaction mixture and
consequently separation of reaction products in vapor and liquid phases shifted the
chemical equilibrium of the reaction and led to the production of concentrated ester.
The additional improvement of reaction & separation in trickle bed system was
focused on the feed optimum throughput to the system with respect to the reaction
conversion and chemical equilibrium shift.The trickle bed esterification reaction
operation can be additionally improved by modulation of feed rate under periodic
operation of the reactor. If the rate determining step is the evaporation of ternary
azeotropic mixture from the internal space of a catalyst pellet amount the periodic
feed can improve reactor throughput by enhancement of external mass transfer rate by
reduction of mean liquid film thickness flowing down along the catalyst bed. The
dynamic experiments & simulation were carried out with the aim to optimize the
relation between the feed period length and its split into “feed-on” and “feed-off”
parts and trickle bed reactor performance (throughput of product, the concentration of
key component in outgoing stream).

Introduction
Esterification reaction is one of the most important industrial reactions. Esters

are widely used in chemical industry such as a solvent for plastics, liquors, resins,
gums, and coatings. Butyl acetate is commonly synthesized through esterification of
acetic acid with n -butanol in the presence of a suitable acid catalyst by reversible and
kinetically controlled reaction. Several works have reported the kinetics of the
esterification reaction in the presence of ion exchange resin. The kinetics of
esterification in the presence of a strong cation exchange resin is studied. The
influence of various parameters on reaction rate and proposed the rate equation is
analyzed. There is recovery of butyl acetate could be in very high purity.
Conventional methods of recovery of 30% acetic acid by reaction with n butanol and
isoamyl alcohol in a reactive distillation column using macroporous ion-exchange
resin as a catalyst bed. They studied the esterification of acetic acid with n-butanol in
the presence of Amberlyst-15. They investigated the influence of various parameters
such as temperature, mole ratio, catalyst loading, and particle size and they proposed
the rate equation model. [1]
It was noted that, most of the previous studies performed in the literature have
focused on the modification of catalysts and only a rather limited number of papers
have focused on studying the influence of reaction conditions and the type of catalysts
on the activity and selectivity. On the other hand, few studies were focused on
production of butyl acetate [1]
The reaction progress is very slow in the absence of acid catalysis. Therefore,
both homogeneous and heterogeneous catalysis can be used. Although homogeneous
catalysts such as sulfuric acid, p-toluene sulfuric acid, and hydrochloric acid have a
strong catalytic effect, they can cause some issues such as the development of side
reactions resulting in a corrosive environment by the discharge of acid-containing
waste. . It also results in sulfur contamination of the final product, which is
unacceptable. Further, the use of homogeneous catalyst requires neutralization with an
alkali, which leads to severe effluent problems on industrial scale. In all kinetic
studies done with ion-exchange resins as catalysts, acidic ion-exchange gel-type

styrene-divinyl benzene (DVB) resins have been used .Research in catalysis by ion
exchange resins is undeniably interesting, not only from a purely physicochemical
point of view but also in terms of the advantages of these types of catalyst over the
conventional ones. Ion exchange resins increase the product yield, keep their activity
a long time, and do not pollute. Ion exchange resins separate from reaction media
easily and they regenerate easily for reuse. Heterogeneous catalysts such as zeolites,
ion-exchange resins, and acidic clay catalysts are gaining importance of high purity of
products, because they are easily removed from the reaction mixture and have lower
corrosive effects. The solid acid catalysts are non-corrosive, easy to separate from the
reaction mixture and a variety of reactor types and configurations can be adopted on
industrial scale. They can also be used repeatedly over prolonged period of time
without any difficulty in handling and storing.
Most reactions catalyzed by ion exchange resins can be classified as either
quasi-homogeneous or quasi-heterogeneous. The kinetics of this model reaction
catalyzed by Amberlyst-15 was described in previous investigations with both a
quasi- homogeneous and a quasi-heterogeneous model. A common method of
operating equilibrium-limited reactions is to use an excess of one reactant in order to
increase the conversion of the limiting reactant. In reactive distillation (RD), the
continual separation of products from reactants forces the reaction to surpass the
equilibrium conditions. RD is a process where separation of the components of a
reaction system is accompanied by a chemical reaction in a column. [6]

Esterification of Acetic Acid with Butanol using SERALITE

SRC-120 catalyst.
Esterification of carboxylic acids is an important class of reactions, the

kinetics and equilibrium of which have been investigated throughout the history of
physical chemistry, the dating back to pioneering efforts of Berthelot and Gilles
(1863). In 1914 at the beginning of the World War I, amyl acetate in the form of
fuel oil acetate was the best known ester solvent. The demand for airplane dope
and the corresponding need for cellulose nitrate and cellulose acetate solvents
increased rapidly during the war period. The only ester that was developed on a
large scale during the war to replace amyl acetate was methyl acetate, thus
Esterification of acetic acid with methanol got a boost as an important process.
Esters can be produced by different approaches on both laboratory and commercial
scales. There are several routes given by Ogliaruso and Wolfe (1991) for the
synthesis of esters as described in Fig. 1.1. Among all these, the simplest route to
produce esters with high yield is the direct Esterification of acids with alcohol in
presence of mineral acid or a heterogeneous catalyst.
CH3COOH + C4H9OH CH3COOC4H9 + H2O

(Acetic Acid) + (Butanol) (Butyl Acetate) + (Water)
Esterification reactions are equilibrium processes and must be displaced

toward the desired ester by the use of excess of one of the free reactants or by
continuous removal of water by azeotropic distillation. Removal of water by
chemical or adsorptive binding is also possible in preparative chemistry, while
calcium carbide, calcium hydride and calcium and magnesium sulfate have proved
successful in industrial application.

The rate of ester formation depends on the carboxylic acid and the alcohol
used. The lowest members, i.e. methanol and formic acid, react most readily.
Primary alcohols react faster than secondary alcohols and the latter react faster
than tertiary ones. Within each series, the reaction rate generally decreases with
increasing molecular mass. Straight-chain acids react more readily than branched
ones; particularly branching in the β-position lowers the rate of esterification.
Esterification of aromatic acids, e.g. benzoic acid, is generally slow. Experiments
with primary and secondary alcohols have shown that the oxygen in the water
formed during acid-catalyzed esterification originates from the acid, not from
alcohol. The reactions of tertiary alcohols are more complex and do not proceed
clearly via a tertiary carbonium ion. The mechanism of esterification reactions has
been discussed in detailed by Zimmermann and Rudolf (1965).
Generally, in industrial processes refluxing the reaction mixture until all the
water has been split off facilitates out esterification. The water or the esters formed
are removed from equilibrium mixture by distillation. The choice of a method to
achieve complete esterification depends on the boiling points of alcohols, acids,
and esters. With high boiling esters (esters of polyhydric alcohols), the water of
reaction may either be removed by evaporation or by means of inert gases. Steam
distillation can also be used to remove excess alcohol after the esterification is
complete. Esterification is usually carried out in a batch or continues mode
depending on the scale of operation. It can also be carried out in the vapor phase
by heating a mixture of acid, alcohol, ester, and catalyst to the desired temperature.
[3]

Esterification Catalysts and Processes
Esterification reactions proceed with or without a catalyst. In the absence

of a catalyst, the reaction is, however, extremely slow, since its rate depends on the
autoprotolysis of the carboxylic acid. Therefore, esterification is carried out in the
presence of an acid catalyst, which acts as a proton donor to the carboxylic acid.
[3]
Homogeneous acid catalysts
Catalysis by mineral acids has emerged as a field of growing interest and

importance in the last three decades with respect to new applications and detailed
investigations on catalysis and reaction engineering. Generally homogeneous acid
catalysts consist of inorganic mineral acids and heteropoly acids. Typical examples
include sulfuric acid, hydrochloric acid, arylsulfonic acids such as p-
toluenesulfonic acid and chlorosulfuric acid. Phosphoric acid, polyphosphoric
acids and mixtures of acids are also recommended but the disadvantage of mineral
acids is their miscibility with the reaction medium leading to corrosion hazards and
separation problems.
Heterogeneous acid catalysis
a) Metal ion complexes as catalysts
Metallic oxides and hydroxides of magnesium, zinc, titanium, zirconium

and metal oxide complexes have been used as catalysts for esterification reactions.
Insoluble poly (4-vinylpyridine-co-styrene) beads using divinyl benzene as the
cross linking agent to convert into poly (4-vinylpuridine-N-oxide) (PVPNO) under
per acetic acid conditions. The resulting polymer was functionalized with titanium
tetrachloride (TiCl4) to form the corresponding PVPNO-TiCl4 complex, which
showed good catalytic activity for esterification reactions.

b) Ion exchange resins as catalysts
Ion exchange resin catalysts have been used for several years in
esterification reactions. Ion exchange material may be broadly defined as an
insoluble matrix containing labile ions capable of exchanging with ions in the
surrounding medium without major physical change in its structure. Typical resin
catalysts are sulphonic acids fixed to a polymer carrier, such as polystyrene cross
linked with divinyl benzene (DVB). Several types of catalysts are commercially
available like Amberlyst resins (e.g. Amberlyst –15, Amberlite IR-120 etc.)[3]
c) Zeolites as catalysts
Zeolites are also used as esterification catalysts. The rare earth exchanged
RE H-Y zeolite is the best of the various zeolites catalysts. The Nb2O5.nH2O
catalyst is claimed to be more active than cation-exchange resin, SiO2, A2lO3 and
solid super acids.
d) Enzymes as catalysts
Enzymes have been widely used in esterification technology. In particular,

lipase enzymes are used for the resolution of racemic alcohols and carboxylic acids
through asymmetric hydrolysis of the corresponding esters. Yeast lipase (Candida
cylindraces), completely converts a carboxylic acid and an alcohol into the
corresponding ester in organic solvents, in a highly stereo selective manner.
Enzymes are highly stable in organic solvents compared to water. [3]

Table No 1:- Comparison between Homogenous & Heterogeneous Catalyst
Factors Homogeneous catalysis Heterogeneous catalysis

1.Reaction Rate Fast and high conversion Moderate conversion
2.After treatment Catalyst cannot be Can be recovered

recovered, must be
neutralized leading to
waste
3.Processing methodology Continuous fix bed

chemical production operation possible
4. Presence of water/free Not sensitive

fatty acids Limited use of continuous
Methodology Sensitive
5.Catalyst reuse Possible
Not possible
6.Emulsion Not possible
Possible
7.Neutralization Not Required
Required
8.Soap formation Does not take place

Takes place
9. Cost Potentially cheaper
Comparatively costly

Table No 2:- Overview on heterogeneous catalysts
Catalyst type Examples

Alkali metal carbonates and hydrogen Na2CO3, NaHCO3
carbonates K2CO3, KHCO
Alkali metal oxides K2O

(produced by burning oil crop waste)
Alkali metal salts of carboxylic acids Cs-laurate
Alkaline earth metal alcoholates Mixtures of alkali/alkaline earth metal

oxides and
Alcoholates
Alkaline earth metal carbonates CaCO3
Alkaline earth metal oxides CaO, SrO, BaO
Alkaline earth metal hydroxides Ba(OH)2
Alkaline earth metal salts of carboxylic Ca- and Ba- acetate

acids
Strong anion exchange resins Amberlyst A 26, A 27

Transition metal oxides, hydroxides and Fe2O3 (+ Al2O3), Fe2O3, Fe3O4, FeOOH,
carbonates NiO, Ni2O3,
NiCO3, Ni(OH)2 Al2O3
Transition metal salts of amino acids Zn- and Cd-arginate

Transition metal salts of fatty acids Zn- and Mn-palmitates and stearates

Kinetic Studies
Kinetics of ion exchange catalysis
The kinetics of ion exchange resin catalyzed reactions pointed that most of the
resin-catalyzed reactions can be classified either as quasi-homogeneous or as quasi-
heterogeneous. The idealized homogeneous state requires complete swelling of the
resin and total dissociation of the polymer-bound –SO3H group. They described that
in all cases which have so far been studied, and in which limitations due to slow
diffusion process could be ruled out, the kinetic order of the chemical reaction in the
particles was found to be the same as that observed in the homogeneous catalysis by a
dissolved electrolyte. However, there were differences in the reaction rates, even
when the amount of catalyst (in counter-ion equivalents) was the same in both cases.
A significant difference in the reaction rates of homogeneous catalysis and
heterogenenized homogeneous catalysis was due to the presence of diffusional
limitations in the later case. Three phenomena have been found to affect the rate of
overall reaction
(i) Diffusion of reactants and products across the film (Nernst diffusion layer)
surrounding the catalyst particle
(ii) Diffusion of the reactants and products in the interior of the catalyst particle and
(iii) Chemical reaction at the active sites.
If the film diffusion is sufficiently fast, the process is controlled by chemical

reaction at the surface. Intraparticle diffusion can affect the overall rate of reaction,
but it can never be the sole rate-determining step, as diffusion and chemical reaction
are parallel steps, occurring simultaneously within the resin bead. These
considerations suggest that, in the limiting cases, the overall rate of any ion exchange
resin catalyzed reaction is controlled by i) film diffusion ii) intraparticle diffusion
with reaction throughout the particle, and iii) chemical reaction at the active sites.[3]

Kinetics and Reaction Engineering of Esterification
Kinetics of esterification between organic acids and alcohols has been

extensively studied. There are two different opinions about the ways in which H+
performs its catalytic effect. One of the opinions is that the organic acid is
activated initially i.e. the organic acid molecule gets a hydrogen ion from the
catalyst before it is esterified with a molecule of primary or secondary alcohol. In
the case of tertiary alcohol, such as t-butyl alcohol, the hydroxyl group of the
alcohol, rather than that of the acid are eliminated. The other opinion was
introduced by Goldschmidt (1908) and further explored by Smith (1939). During
the period of 1895-1928 Goldschmidt demonstrated the fact that in acid catalyzed
esterification reactions, the H+ ions from the catalyst forms complexes with the
alcohol molecules, and that the esterification proceeds through interaction of
molecules of the complex with the molecules of organic acid. The rate of
formation of ester in this case is thus proportional to the momentary concentration
of the organic acid. Smith (1939) studied the kinetics of hydrogen ion catalyzed
esterification of seven n-organic acids in methyl alcohol. He has discussed the
influence of acids and the length of the carbon chain of the acid on the rate of its
esterification.
Kinetics of esterification of monobasic acid
A detailed literature survey on esterification of different monobasic

carboxylic acids with alcohols is studied. The kinetics of esterification of
monobasic carboxylic acids with alcohols in the presence of homogeneous
catalysts has been investigated to some extent in the past. Leyes and Othmer
(1945) investigated the sulfuric acid catalyzed esterification of acetic acid with
butanol. They found the reaction to be second order with respect to acetic acid
concentration up to 75 to 85 %, in a temperature range of 373 K-393 K. The rate
was a linear function of the catalyst concentration and the molar ratio of butanol to
acetic acid. They also found that the logarithm of the rate constant was

proportional to the reciprocal of absolute temperature as per Arrhenius law of

temperature dependence. Ronnback et al. (1997) developed a kinetic model for the
esterification of acetic acid with methanol in the presence of hydrogen iodide as
homogeneous acid catalyst at 353 K- 356 K. Plausible reaction mechanisms for
methyl acetate and methyl iodide formation were proposed. Rate equations,
concentration-based as well as activity-based, with UNIFAC activity coefficient
estimations were derived and the kinetic and equilibrium parameters included in
the rate equations were estimated from experimental data with regression analysis.
Shimizu and Hirai (1987) studied the solvent effect on the kinetics of resin
catalyzed esterification of octanoic acid with 1-butanol catalyzed by macro reticular
sulfonic acid resin (Amberlyst 15) in the presence of various organic solvents and
water. They concluded that the extent of the selectivity of the resin catalyst depend
on the alkyl chain length of n-fatty acids. When solvents with a strong electron
donor property were employed as diluents in the esterification with the macro
reticular sulfonic acid resin, they donor property of solvents, diminished the
number of unionized sulfonic acid groups, which act as catalytic species for the
heterogeneous reaction, and, consequently, a decrease in the total catalytic activity
was observed. Elewady et al. (1987) studied the esterification of formic, propionic,
butyric and valeric acids with ethanol in the presence of Amberlite IR-120 as a
catalyst. The activation energy of esterification reaction was found to increase with
increase in the size of the alkyl group in the acid moiety. [3]

Agitated Slurry Reactors
The agitated slurry reactors are most commonly used on industrial scales in liquid
phase esterification processes. In agitated reactors, the catalyst particles are used in a
smaller form and kept in suspension by means of mechanical agitation. Due to smaller
catalyst particle size, intraparticle diffusional effects are negligible in these reactors. Also
the overall mass and heat transfer efficiency is better than fixed bed reactors and these
reactors are preferred for reactions with mass transfer limitation and those with high level
of exothermicity. Many variations of these agitated slurry reactors are used in industry,
e.g. stirred reactors with multiple impellers, and with multiple temperature control
systems etc. The agitated slurry reactors can also be operated in a semi-batch or
continuous mode depending on the process requirement. Several studies on reaction
engineering aspects of esterification reactions are published previously. [3]
Fixed bed reactor
In this type of reactors, the gas and the liquid phase flow over a fixed bed of catalysts.
The fixed bed reactors can be mainly classified into three types, (i) co-current down-flow
of both gas and liquid phases (ii) downward flow of liquid with gas in the countercurrent
upward direction and (iii) co-current up-flow of both gas and liquid. Reactors with co-
current down-flow of gas and liquid is called as trickle bed reactors (TBR) and the co-
current up-flow reactors are also referred to as packed bubble column reactors. Trickle
bed reactors, wherein, the liquid reactant trickles down concurrently along with the
gaseous reactant, over a fixed bed of catalyst pellets finds its application in wide variety
of chemical, petrochemical and biochemical processes along with its application in waste
water treatment. These types of reactors are also applicable for esterification reactions.
[6]

Reactive Distillation
Reactive distillation is a combination of reaction and distillation in a single vessel

owing to which it enjoys a number of specific advantages over the conventional
sequential approach of reaction followed by distillation or other separation techniques.
Improved selectivity, increased conversion, better heat control, effective utilization of
reaction heat, scope of difficult separations and the avoidance of azeotropes are a few of
the advantages that reactive distillation offers.
Reactive distillation has received increasing attention over the past several years
as a promising alternative to conventional processes. Especially for equilibrium-limited
and consecutive reactions, reactive distillation offers distinct advantages through the
direct removal of the reaction products by distillation. Therefore, conversions far beyond
equilibrium conversions and higher selectivities can be obtained leading to significantly
lower investment and operating costs. The shortcomings of reactive distillation include
greater complexity in design and process control, often involving multiple steady states,
and high nonlinearity due to the strong interaction between process variables. Moreover,
the operating window of reactive distillation processes must be compatible with the
thermal stability of the catalyst in order to ensure long catalyst life. Reactive distillation
also requires a significant research and development effort in order to develop and
successfully scale up a promising process. Organic solvents such as acetate esters are
important chemicals for many industries. n-Butyl acetate having low toxicity and low
environmental impact is used in large quantities in paint; lacquer industry and coating
manufacture. It is usually synthesized with esterification reaction in the presence of a
strongly acidic catalyst such as ion exchange resin, sulphated zirconia5 or alumina
supported tungstophosphoric acid in a liquid phase system. Since the reaction is
Equilibrium-limited, the use of reactive distillation, which combines the reaction and
separation functions in one column, is an attractive option. Synthesis of butyl acetate is
commonly carried out by esterification of butanol with acetic acid in the presence of a
suitable acid catalyst. In our previous study, we investigated the esterification reaction
between acetic acid and butanol catalyzed by Saralite 120 SRC in a batch reactor. [4]
Thermodynamic aspect for Esterification system [4]
Equilibrium constant
Equilibrium constant can be calculated using thermodynamic data. Firstly,

equilibrium constant at a reference temperature is found from standard Gibbs energy of
reaction and equilibrium constant at different temperature are determined using the
integrated from of Van’t Hoff equation:
𝐻𝑜 1 1
lnK (T) = ln K (To) - (𝑇 − 𝑇𝑜)
𝑅
For the esterification of butanol with acetic acid, using the thermodynamic data, the
equilibrium data were calculated. Constant enthalpy is assumed because of the small
temperature interval investigated.
In our previous study, experimental equilibrium constant was found at temperature 356
K. Experimental & theoretical equilibrium constant values as a function of inverse of
temperature. The decrease in K values with increase in temperature shown that this
esterification is exothermic &increase in K values with decrease in temperature that
esterification is endothermic.
Pseudo-homogeneous Model [7]
Among the entire model, the simplest model is the Pseudo-homogeneous model.
Consider the reaction given by equation. The rate expression for this reaction is given by:
-rCH3COOH = k1 CCH3COOH . CCH3 (CH2)2CH2OH - k2 CC5H11OOH. CH2O
The reaction equilibrium constant is given by
K=k1/k2

The reaction equibrium constant is calculated from
Esterification reactions are known to be second order reversible reaction. Therefore,

for the bimolecular type second order reaction,
A + B C + D
With reaction that,
CAO = CBO and CCO = CDO = 0
The rate expression can be written as,
-rB = -dCA / dt = CAO. dXA / dt = k1 CA .CB - k2 CC. CD
= k1 C2AO (1- XA) 2 – k2 (CAO XA) 2
Where,
A = Acetic acid
B = Butyl alcohol
D = Water
At the equilibrium, -rA = 0
Hence the above equation, we determine the fractional conversion of A at equilibrium

condition by following equation:

K = CCe. CDe / CAe. CBe = X2Ae / (1 – XAe)2
The equilibrium constant is given by as,
K = k1 / k 2
Combining equation [3], [7] and [9] in term the equilibrium conversion, we obtain,
-dXA / dt = k1 CAO [ (1 –XA)2 - ( 1 – 1/ XAe ) . X2A]
With conversion measured in term of XAe , this may be indicated as a Pseudo second order
reversible reaction, which on integration gives, [4]
ln[ Xae - (2 Xae – 1) Xe ]/Xae - Xa = 2k1[ 1/Xae - 1] Cao t

Physical Properties of Acetic Acid
1) Physical state: Liquid.

2) Odor: Pungent, vinegar-like, sour (Strong.)
3) Taste: Vinegar, sour (Strong.)
4) Molecular Weight: 60.05 g/mole
5) Color: Colorless. Clear (Light.)
6) pH (1% soln/water): 2 [Acidic.]
7) Boiling Point: 118.1°C (244.6°F)
8) Melting Point: 16.6°C (61.9°F)
9) Critical Temperature: 321.67°C (611°F)
10) Specific Gravity: 1.049 (Water = 1)
11) Vapor Pressure: 1.5 kPa (@ 20°C)
12) Vapor Density: 2.07 (Air = 1)
13) Odor Threshold: 0.48 ppm
.
Physical Properties of Butanol
1) Appearance: Clear colorless liquid

2) Odor: Alcohol like
3) Boiling point: 117 0C
4) Flash point: 340C (c.c.)
5) Flammability: Flammable
6) Explosive properties: Explosive under open flame
7) Explosive limits in air: 1,4-11,25 % volume
8) Oxidizing properties: No oxidizing properties
9) Vapor pressure at 200C: 0.6 kPa
10) Specific gravity: 0.8089

Physical Properties of Butyl Acetate
1) Physical State: Liquid

2) Appearance: clear, colorless
3) Odor: ester-like - sweet, fruity odor
4) Vapor Pressure: 11.5 mm Hg @ 25 0C
5) Vapor Density: 4.0 (air=1)
6) Evaporation Rate: 5.8 (CCl4=1)
7) Viscosity: 0.73 cps @ 20 0 C
8) Boiling Point: 125 - 126 0C
9) Freezing/Melting Point:- 77 0C

Experimental Procedure
Materials
The reactants butanol and acetic acid used were of A.R. grade (99.8%) and were
obtained from Fume Chemicals, Kolhapur. The chemicals were used without further
purification.
Catalyst
The cation exchange resin Saralite 120 SC used as the catalyst before using for
experiments, the resin was pretreated using standard procedures. First, the resin was
washed with water the catalyst was soaked in distilled water for 15 minutes and then
charged into the column. Then, one liter of 0.1 M hydrochloric acid solution and 0.1 M
sodium hydroxide solution was passed through the catalyst bed to remove acid soluble
and alkali soluble impurities. After acid and alkali treatment each time, the resin was
washed with water to ensure complete removal of chloride and sodium ions from the
catalyst bed.
Table No 3:- Specifications of Saralite 120 SRC
___________________________________________________________________
Structure Macro porous Cross-linked Styrene-

DVB
Particle size range, mm 0.4 – 1.0
Moisture content, % (w/w) 20
Form -SO3H
Bulk density, gm/ml 0.5-0.6
H+ conc., meq/gm, dry 4.3.
Particle density, kg/m3 1.37 X 103
___________________________________________________________________

Reactor Setup
A schematic diagram of the experimental setup is shown in Fig.1
Fig. 1: Experimental setup of a batch slurry reactor for Esterification reaction
The esterification of acetic acid with butanol was carried out in a glass reactor
of 500 ml volume. The heating mental is used for heating purpose. The temperature in
the reactor was maintained within 80-90oC using a thermometer.

Experimental Procedure
In all the experiments, a known amount of butanol was charged to the reactor
and heated to the desired temperature. When the temperature remained constant, the
required amount of acetic acid was added under constant stirring. It was observed that
the temperature fall as a result of this addition was not significant and the temperature
equilibrium was reached in a short time. A sample was removed for analysis. This
was taken as the starting point of homogeneous (uncatalyzed) reaction. For the
catalytic reaction, after attaining the desired temperature, a known quantity of ion
exchange resin along with acetic acid was added to the reactor. The moment of resin
addition was taken as the starting time of reaction. Samples were withdrawn at regular
time intervals for analysis. The volume of sample withdrawn from the reactor during a
run was negligible compared with the total volume of the system.[6]
Analysis
The analysis of reactants and products was carried out using simple titration
with 1N NaOH solution and phenolphthalein as indicator. The end point of reaction is
colourless to faint pink.

Kinetics of Esterification
Preliminary Experiments
Some preliminary experiments were carried out to select a range of reaction

conditions suitable for studying the reaction kinetics and establish the product
distribution, material balance etc. The range of reaction conditions under which the
present study was carried out is given bellow
Table No 4:- Range of operating conditions
___________________________________________________________________
Reaction temperature, K 353 K
Catalyst loading, (percentage) 3% , 4% , 5%
Butanol : acetic acid ratio 4:1, 3:1 and 2:1

Particle size, mm. 0.458

Calculation
Run no.1
Molar ratio = 4:1 (Butanol/acetic acid)
Catalyst loading =17.8 gm
Temperature = 356 K
Table no: 5
Sr. no Time Burette reading Concentration Conversion

(hour) (ml) (mol/lit) XA
1 1 23.5 2.35 0.1628
2 1.5 21.4 2.14 0.2376
3 2 19.6 1.96 0.3017
4 2.5 16.1 1.61 0.4264
5 3 12.1 1.21 0.5689
6 3.5 11.1 1.11 0.6046

Run no.2
Temperature = 356 K
Table no: 6

1 1 23.7 2.37 0.1557
2 1.5 21.5 2.15 0.2341
3 2 20.1 2.01 0.2839
4 2.5 17.3 1.73 0.3837
5 3 13.4 1.34 0.5226
6 3.5 12.1 1.21 0.5689

Run no.3
Temperature = 356 K
Table no: 7

(hour) (ml) mol/lit XA
1 1 23.9 2.39 0.1486
2 1.5 22.0 2.20 0.2162
3 2 20.9 2.09 0.2554
4 2.5 18.0 1.80 0.3587
5 3 14.2 1.42 0.4941
6 3.5 13.4 1.34 0.5226

Run no.4
Temperature = 356 K
Table no: 8

1 1 25.8 2.58 0.1429
2 1.5 24.3 2.43 0.1927
3 2 23.7 2.37 0.2126
4 2.5 20.1 2.01 0.3322
5 3 18.9 1.89 0.3721
6 3.5 16.6 1.66 0.4485

Run no.5
Temperature = 356 K
Table no: 9

(hour) (ml) ( mol/lit) XA
1 1 26.7 2.67 0.1130
2 1.5 25.1 2.51 0.1661
3 2 24.8 2.48 0.1761
4 2.5 22.0 2.20 0.2691
5 3 19.7 1.97 0.3455
6 3.5 18.1 1.81 0.3987

Run no.6
Temperature = 356 K
Table no: 10

1 1 27.2 2.72 0.0963
2 1.5 25.9 2.59 0.1395
3 2 24.1 2.41 0.1993
4 2.5 23.9 2.39 0.2060
5 3 20.1 2.01 0.3322
6 3.5 18.9 1.89 0.3721

Run no.7
Temperature = 356 K
Table no: 11

1 1 34.3 3.43 0.1192
2 1.5 29.6 2.96 0.2399
3 2 25.5 2.55 0.3452
4 2.5 20.3 2.03 0.4787
5 3 18.7 1.87 0.5198
6 3.5 17.8 1.78 0.5429

Run no.8
Temperature = 356 K
Table no: 12

1 1 34.9 3.49 0.1038
2 1.5 30.7 3.07 0.2116
3 2 28.9 2.89 0.2579
4 2.5 22.1 2.21 0.4325
5 3 19.9 1.99 0.4890
6 3.5 18.2 1.82 0.5326

Run no.9
Temperature = 356 K
Table no: 13

1 1 36.3 3.63 0.0678
2 1.5 31.0 3.10 0.2039
3 2 27.0 2.70 0.3067
4 2.5 24.0 2.40 0.3837
5 3 22.4 2.24 0.4248
6 3.5 21.0 2.10 0.4607

Sample Calculation for Conversion of Acetic Acid
n-Butanol = 4 moles = 4*74 =296 gm
Acetic acid = 1 mole = 1*60 = 60 gm
Total wt. = 356 gm
Catalyst = 5% w/w
= 0.05* 356
=17.8 gm
Observations
1) Solution in burette: 1N NaOH

2) Volume of pipette out = 10 ml of reaction mixture.
3) Indicator = Phenolphthalein
4) End point of titration = colourless to pink.
5) Blank reading (CA0) = 25 ml

Titration reading
Table no: 14
Sr. Time Burette Concentration Conversion

No (hour) Reading (mole/lit) XA
(ml) CA
1 1 23.5 2.35 0.1628

2 1.5 21.4 2.14 0.2376
3 2 19.6 1.96 0.3017
4 2.5 16.1 1.61 0.4264
5 3 12.3 1.21 0.5610
6 3.5 11.1 1.11 0.6045
Assume:
A = Acetic acid.
B = Butanol.
Then,
Volume of Acetic acid = VA = (wt.of Acetic acid) / (density of Acetic acid)
VA = 60/0.81
VA = 74.074 cm3
Volume of Butanol = VB = (wt.of Butanol) / (density of Butanol)

VB= 296/1.049
VB= 282.173 cm3
Total Volume of mixture = VA + VB
= 74.074 + 282.173
= 356. 24 cm3
Initial concentration of Acetic acid= CAO= (Moles of Acetic acid / Total volume) *1000
CAO = (1/356.24) * 1000
CAO= 2.8070 mole/lit.
Initial concentration of Butanol= CBO= (Moles of Butanol/ Total volume)*1000
CBO= (4/356.24)*1000
CBO= 11.2283 mole/lit.

Now for titration (Run 1) Time = 1 hour
Normality of NaOH = 1N
Burette reading = V1= 23.5 ml
Normality of Acetic acid = N2=?
Sample pipette out = V2= 10 ml
We have,
N1V1 = N2V2
(NaOH) vs.(Acetic acid)
N2= N1V1/ V2
N2 = (1*23.5)/10
N2= 2.35 mole/lit
N2 =CA1= 2.35 mole/lit
Now conversion is given by
XA= (CAO - CA1)/ CAO
XA= (2.8070 – 2.35)/ 2.8070
XA= 0.1628
Conversion = 0.1628 *100 = 16.28 %
As there is no side reaction present, hence
Yield = Conversion= 16.28 %

Material Balance
Reaction
CH3 –CH2-CH2-CH2OH + CH3COOH CH3CH2CH2CH2COOH + H2O
BUTANOL + ACETIC ACID BUTYL ACETATE + WATER
74 (gm) + 60 (gm) ≡ 116 (gm) + 18 (gm)
1 moles + 1 mole ≡ 1 mole + 1 mole
134gm ≡ 134gm
Now, for reaction parameter M=4, XA=0.6045
4 mole butanol + 1 mole acetic acid 1 mole butyl acetate + 1 mole

water
74/0.81 + 60/1.049 ≡ 116/0.88 + 18/1
91.558cm3 + 57.197cm3 ≡ 131.44cm3 + 18cm3
60.45% conversion
148.75cm3 ≡ 90.33cm3
0.1488(lit) ≡ 0.0933(lit)
(Reactant) (Product)
Multiply by 12.56 to above equation
1.8689 (lit) ≡ 1 (lit) butyl acetate + 0.13(lit) water

Unreacted reactant = 1.8689(lit) - 1.1369(lit)
= 0.732 ((lit)
Feed of acetic acid = 0.0571 (lit)
Conversion =XA= 0.6045
Unreacted acetic acid = (1 - XA) = (1 – 0.6045)
= 0.0225(lit)
Assume
Basis = 100 lit/day production
186.89 (lit) ≡ 100 (lit) + 13.69(lit)
(Reactant) (Butyl acetate) (Water)
For batch reactor,
Excess volume = 40%
Reactor volume = 261.64(lit)
= 0.2616 cm3

Energy Balance
Energy in = Energy out

Heat added to the system = Sensible heat given to the reaction mixture
Q1 = Q2 ----------------------------------------------- (1)
1. Amount energy supplied to the reaction mixture is,
= Q2 = m*Cp*(T1-T2)
Calculation for specific heat of mixture and mass of reaction mixture,
Number of moles of butanol in feed = 4 mol
Number of moles of acetic acid in feed = 1 mole

4
Mole fraction of butanol = Xbutanol= 4+1= 0.8
1
Mole fraction of acetic acid = Xacetic acid = 4+1 = 0.2
Specific heat of butanol = Cp of butanol = 13.69 KJ/Kg-k

Specific heat of acetic acid = Cp of acetic = 7.8 KJ/Kg-k
Specific heat of mixture = Xbutanol*Cp of butanol+ Xacitic acid*Cp of acetic acid
= 0.8*13.69+ 0.2*7.8
= 12.5120 KJ/Kg-k
= 12.51*103 J/Kg-k
Mass of reaction mixture = 154.9131kg
Energy required for reaction mixture = m*Cp*(T2-T1)
Q2 = 154.91*12.51*103*(83-30)
= 102.71*106J
102.71∗10666
= J/s
3600
Q2 = 28527.77 watt.

Let, consider 10 % heat loss takes place when is transfer from water to reaction
mixture,
So, Heat transfer from water to reaction mixture = 28527.77+0.1*28527.77
= 31380.5470 watt.
Q1 = 98.24= m*Cp*(T3-T4)
= m*4.184*103*(80-75)
So, Mass rate of water required = m = 0.00469 Kg.

From equation (1),
Q1 = Q2 + Q3
98.24 = 93.57 + m* Latent heat of vaporization of butanol
98.24− 93.57
Rate of vaporization of ethanol = m = = 5.52*10-6 Kg/s
846∗103
2. Heat removed in condenser = Q3= m*Cp of water*(T4-T3)

= 0.0231*4.184*(35-28)
= 0.6765 watt.

Effect of molar ratio and catalyst loading
Molar ratio = 4:1
Catalyst = 5%
3
2.5 y = -0.5337x + 2.9309
R² = 0.9777
conc. CA
2
(gmole/lit)
1.5
1
0.5
0
0 1 2 3 4
time , (hour)
Fig no 2: Concentration Vs Time

Molar ratio = 4:1
Catalyst = 4%
2.5
y = -0.4863x + 2.8958
R² = 0.9796
2
conc. CA
(gmole/lit) 1.5
0.5
0
0 0.5 1time , (hour)
1.5 2 2.5 3 3.5 4

Molar ratio = 4:1
Catalyst = 3%
y = -0.4503x + 2.8865
R² = 0.9685
2.5
conc CA 2
(gmole/lit)
1.5
0.5
0
0 0.5 1 1.5 2 2.5 3 3.5 4
time (hour)

Molar ratio = 3:1
Catalyst = 5%
3
y = -0.376x + 3.0027
R² = 0.9684
2.5
conc CA
(gmole/lit) 1.5
0.5
0
0 0.5 1 1.5 2 2.5 3 3.5 4
time (hour)

Molar ratio = 3:1
Catalyst = 4%
3
y = -0.3543x + 3.0705
R² = 0.9666
2.5
2
conc CA
(gmole/lit) 1.5
0.5
0
0 1 2 3 4
time (hour)

Molar ratio = 3:1
Catalyst = 3%
3
y = -0.3223x + 3.0751
R² = 0.9591
2.5
2
conc CA
(gmole/lit)
1.5
0.5
0
0 0.5 1 1.5 2 2.5 3 3.5 4
time (hour)

Molar ratio = 2:1
Catalyst = 5%
3.5
y = -0.688x + 3.9847
3 R² = 0.9451
conc. CA
(gmole/lit) 2.5
2
1.5
0.5
0
0 0.5 1 1.5 2 2.5 3 3.5 4
time , (hour)

Molar ratio = 2:1
Catalyst = 4%
3.5
y = -0.7011x + 4.1559
R² = 0.9658
3
2.5
conc.CA
(gmole/lit)
2
1.5
0.5
0
0 0.5 1 1.5 2 2.5 3 3.5 4
time (hour)

Molar ratio = 2:1
Catalyst = 3%
4
y = -0.6017x + 4.0489
3.5 R² = 0.9393
conc. CA 2.5
(gmole/lit)
2
1.5
0.5
0
0 0.5 1 1.5 2 2.5 3 3.5 4
time( hour)

ESTIMATION OF THERMODYNAMIC PARAMETERS
The estimation of thermodynamic parameters is of importance while studying

the kinetics of esterification reaction. In general, thermodynamic describes heat liberated
or absorbed during the reaction and it also gives extent of this reaction. To calculate the
equilibrium of this reaction, it is necessary to have the values of standard formation
enthalpy of individual substances involved in the reaction.
Heat of reaction
The esterification reaction is
CH3COOH + C4H9OH CH3COOC4H9 + H2O
(Acetic Acid) + (Butanol) (Butyl Acetate) + (Water)
The heat of reaction ΔHoR is determined by using heat of formation data at 25oC.
The following table 11.1 summarizes the standard heat of formation (KJ/mol) at 25OC all
compounds involved in the reaction.
Table no 15:- Heat of formation data ΔHof [12]
Sr. No Compound Molecular formula ΔHof , KJ/mol(At 25oC)

1. Acetic acid CH3COOH -483.52
2. Butanol CH3-CH2-CH2- -327.01
CH2OH
3 Butyl acetate CH3COOCH3-CH2- -609.6
CH2-CH2
4 Water H2O -285.8

Heat of reaction for the above reaction based on heat of formation is determined by
following equation
ΔHoR = [ (ΔHof) BA +(ΔHof)WATER ] - [ (ΔHof)AA + (ΔHof)BuOH ]
= [(1 x -609.6) + (1 x-285.8)] – [(1 x -483.2) + (4x-327.01)]
= [-895.40] - [-1791.24]
= 895.84 KJ/mol
Since ΔHoR is positive, the esterification reaction is endothermic.
Heat of Reaction at Optimum Temperature (ΔHoT at 830C)
The heat of reaction at optimum temperature is calculated with help of heat

capacity data using following equation.
𝑇2
ΔHT = ΔHoR + ∮ 𝐶𝑝0 𝑑𝑇 -------------------------------------- 1
𝑇1
Where 𝐶𝑝˳ = 𝑎 + 𝑏𝑇 + 𝐶𝑇 2
The final integrated equation for calculation of heat of reaction at optimum temperature is
given by ,
ΔHT = ΔHo + Δa*T +Δb*T2/2 +Δc*T3/3 --------------------------- 2
Where
Δa = Σ a product - Σ a reactant
Δb = Σ b product - Σ b reactant ------------------------------------ 3
Δc = Σ c product - Σ c reactant3……………

The heat capacity data is summarized in following table 16
Table no 16:- Heat capacity data [12]
Compound a B C
Acetic acid -32.068 0.17 0.008894
Butanol -20.4676 0.43 0.02088
Butyl acetate -36.1324 0.58 0.02189
Water 67.41 0.28 0.0184
From Equation 3,
Δa = 83.8132 Δb = 0.26 Δc = 0.010216
From Equation 2,
ΔHT = ΔHo + ( 83.8132 *T) + (0.26 *T2/2) + (0.010216 *T3/3) -------------

-4
From Equation 4
When T = 298oK, ΔHT =895.84 KJ/mol, ΔHo= -128848 KJ/mol
To evaluate ΔHT at T = 830C or 3560K Put T=3560K and ΔHo= 3678.25 J/mol in
equation 4
ΔHT=830C = 71107.06 KJ/mol
Equilibrium Constant K from Thermodynamic data:
The equilibrium constant of the reaction can be determined by using standard free
energy ΔG0.

ΔG0 = -RT lnK -------------------①
Where,
ΔG0 = standard free energy
R = Ideal gas constant
T = Temperature in K
K = reaction thermodynamic equilibrium constant
The following table summarizes the standard Gibbs free energy (KJ/mol) at 25OC all
compounds involved in the reaction.
Table no 17:- Standard Gibbs free energy of the compounds [12]
Sr.no Compound ΔG0, KJ/mol(At 25OC)

1 Acetic acid -389.95
2 Butanol -162.51
3 Butyl acetate -312.3
4 Water -237.178
The net change in standard free energy can be estimated by following equation
ΔG0 = Σ ΔG0product - Σ ΔG0 reactant ------------------------------ 2
ΔG0 = [ ΔG0BA+ ΔG0WATER ] – [ΔG0AA + ΔG0BUoH ]
ΔG0 = [(1 x -312.3) + (-237.178)] – [(-389.95) + (4 x -162.51)]
ΔG = [-549.47] – [-1039.99]
ΔG0 = 490.51 KJ/mol.
Using equation ①, equilibrium constant can be determined

ΔG0 = -RT ln (K)
Putting all the values in above equation and simplifying it
-ΔG0/RT = ln (K)
K = e {- ΔG0/RT}
K= e {-490.51/8314x298}
K= 0.9998
The fractional conversion at equilibrium is given by
𝐾
𝑋𝐴𝑒 = 1+𝐾 ------------------------------③
0.999
𝑋𝐴𝑒 = 1+0.999
𝑋𝐴𝑒 = 0.5
The equilibrium conversion of acetic acid is 0.5. This indicates that the use
of catalyst is essential to enhance the conversion for commercial use of this reaction.
The equilibrium constant at optimum temperature of 830C can be calculated by using

Vant Hoff equation
𝐾2 ΔHT 1 1
ln(𝐾1) = - 𝑅
( − 𝑇1
𝑇2
) --------------------------- 4
Where,
K2= Equilibrium constant at optimum temperature T2=3560K
K1= Equilibrium constant at temperature T1=2980K =0.99
ΔHT = Heat of reaction at optimum temperature T2=3560K=71107.06 KJ/mol

Putting all the values in above equation and simplifying it
𝐾2 71107.06 1 1
ln(0.999)= - 8314
(356 − 298 )
K2 = 1.0036

REACTOR DESIGN
Volume of reactor = 0.2616 m3
Generally for stirred tank (H/D) = 1.5 (Assume)
𝜋 ∗ 𝐷2 ∗ 𝐻
Total volume =
4
𝜋
0.2616= 4 * 𝐷 2 * 1.5 D
D = 0.6056 m
H = 1.5 * 0.6056 = 0.9083 m
For shell
Operating pressure = H*ρ*g
=0.9083*828.9*9.81
= 7385.84 N/𝑚2 =0.007385 N/𝑚𝑚2
Design Pressure = 10% excess of operating pressure
Design pressure = 1.1* 0.007385
= 0.0081235 N/𝑚𝑚2
Design of shell
The thickness of shell is found by formula
𝑃∗𝐷𝑖
Ts =
2𝑓𝐽−𝑃

Where
P= Design pressure
Di = shell internal diameter
F = Permissible stress
J = joint efficiency
0.008123∗0.6056
Ts=
2∗98∗0.85−0.008123
Ts = 0.0295 mm
Take corrosion allowance = 2mm
Ts = 2+ 0.0295
=2.0295 mm
=3 mm
For rigidity purpose take thickness of shell as 5mm
Outside diameter of shell (Do) = Inside diameter of shell + 2* thickness
=605.6 +2*5
=615.6 mm
=0.6156 m
Design of head
At ther top -
A torispherical head is used and it is connected to shell by flanged joint.
Crown radius (Rc) = Di = 605.6 mm

Knuckle radius =(Rk) = 6 % of D = 363 mm
Thickness of torispherical head
𝑃∗𝑅𝑐∗𝑊
Th =
2𝑓𝐽
Where,
J= joint effiency = 0.85
W = stress intensification factor =
1 𝑅𝑐
W = 4*(3 + √ )
𝑅𝑘
= 1.0729
0.008123∗605.6∗1.0729
Th=
2∗98∗0.85
= 0.0317 m
= 3.17 mm
For rigidity of head select thickness of head same as shel =5 mm
Design of Straight Flange
Head and shell are connected by using small cylindrical ring connected by using small
cylindrical ring shape element which is known as straight flange.
Length of straight flange = 3* th
= 3* 3.17 =9.51 mm
Use min specified length as =20 mm
At the bottom

A similar torispherical head is welded at the bottom end of same thickness the top equals
to 5 mm.
Design of flange for head and shell ∶ −
Design of gasket and bolt
M. O. C of flange is Cs
I. D of flange is =605.6
Design of Gasket
M.O.C of gasket is corrugated asbestos and select thickness of gasket as 4 mm.
I.D of gasket + Gi= 605.6mm
Gasket Factor = m = 2.0
Gasket seating stress = Ya= 11.2 N/𝑚𝑚2
𝐺𝑜 𝑌𝑎 − 𝑀 ∗ 𝑃
= √
𝐺𝑖 𝑌𝑎 − 𝑀 ∗ 𝑃 − 𝑃
𝐺𝑜 11.2 − 2 ∗ 0.008123
= √
605.6 11.2 − 2 ∗ 0.00785 − 0.008123
Go =605.6 mm
Select Go = 611.7 mm
𝐺𝑖+𝐺𝑜
Mean gasket diameter (G) =( )s
2
605.6+611.7
=( )
2

= 608.65 mm
𝐺𝑜−𝐺𝑖
Gasket seating width = Bo= ( )
4
611.7−605.6
=( )
4
= 1.52 mm
Effective gasket seating width =b = 2.5 √1.52
= 3.08 mm
Under atmospheric condition bolt load due to gasket reaction is given by;
Wm1 = MIN bolt load under Atm condition
= Ag * Ya
=π * bG* Ya
= π* 3.08*608.65*11.2
= 65960.849 kg
Load under operating condition is given by;
π
Wm2 =π*2*b*GmP + 4 𝐺 2 ∗ 𝑝
π
=π* (2*3.08)*608.65*2.0*0.007385+4 608.652 ∗ 0.008123
= 2537.39 kg
Total boalt area is calculated on the basis of greater load;
Permissiable stress at Atm condition =fa =58.7 N/𝑚𝑚2
Permissiable stress at operating condition = fb= 54.54 N/𝑚𝑚2
𝑊𝑚1 65960.849
Am1 = =
𝑓𝑎 58.7

Am1 = 1123.69𝑚𝑚2
𝑊𝑚2 2537.39
Am2 = =
𝑓𝑏 54.54
Am2 = 46.523𝑚𝑚2
Am1 >Am2
Use Am2
No. Of bolts required for flanged joint (n)
𝑚𝑒𝑎𝑛 𝑔𝑎𝑠𝑘𝑒𝑡 𝑑𝑖𝑎𝑚𝑒𝑡𝑒𝑟 𝑖𝑛 𝑐𝑚

n=
2.5
608.65
n= = 243.46
2.5
But no. Of bolts are in multiple of 4
Select no. of bolts = 244
𝐴𝑚1 1123.69
Bolt area = Am = =
𝑛 64
=17.557𝑚𝑚2
𝜋
Am= 4 * 𝑑 2 v
4∗𝐴𝑚
d=√ = 4.73 mm
𝜋
Select size of m18 bolts having minor diameter = 18.500 mm and pitch diameter =
19.350 mm
𝜋 (𝑝𝑖𝑡𝑐ℎ 𝑑𝑖𝑎𝑚𝑒𝑡𝑒𝑟)2 +( 𝑚𝑖𝑛𝑜𝑟 𝑑𝑖𝑎𝑚𝑒𝑡𝑒𝑟)2

The actual bolt area available = 4 * n *( )
2
𝜋 (18.500)2 +( 19.350)2
=4 * n *( )
2

= 68434.13> Am2
Actual bolt area provided
2∗ 𝜋∗𝐺∗𝑁∗𝑌𝑎
Ab =
𝑓𝑎
𝐺𝑜−𝐺𝑖
N= 2
611.7−605.6
N=
2
N = 3.05
2∗𝜋∗608.65∗3.05∗11.2
Ab =
58.7
Ab = 2225.49𝑚𝑚2
Bolt area suggested is satisfactory
Now pitch of bolt = (3.2 to 5) diameter of bolt
= 4.75*18
=85.544 mm
𝐵𝑜𝑙𝑡 𝑃𝑖𝑡𝑐ℎ∗𝑛𝑜.𝑜𝑓 𝑏𝑜𝑙𝑡𝑠

Pitch circle dia. = B =
𝜋
85.544∗244
=
𝜋
= 6616.76 mm
Or
B = Go + 2*diameter of bolt + 12
= 611.7+ 2* 18 +12
=659.7 mm

Maximum B is selected
B= 659.7mm
O.D of flange = B+ 2*d
= 659.7+2* 18 =695.7mm
Flange Thickness
𝑃
Tf = G* √
𝐾∗𝑓
1
K= 1.5∗𝑊𝑚∗ℎ𝐺
0.3+
𝐻∗𝐺
Wm= max among Wm1 or Wm2
Wm= Wm1 =65690.84 kg
𝐵−𝐺 659.7−608.65
hG= = = 25.525 mm
2 2
𝝅
H= 𝟒 ∗ G2 ∗ P = 2363.42 kg
1
K= 1.5∗65690.84∗25.525 = 2.048
0.3+
2363.42∗608.65
0.008123
Tf = 608.65* √
2.048∗95
Tf = 3.932mm
Use corrosion allowance of 2 mm
Select thickness of flange = 12 mm

Design of Nozzle
Nozzle internal dia. = (di) =125mm
Min. nozzle thickness;
𝑝∗𝑑𝑖
tn=
2𝑓𝑗−𝑝
0.008123∗125
= =0.006094mm
2∗0.85∗98−0.008123
For rigidity purpose the thickness of nozzle is selected to be 3 mm.
Design of Support:
Data;
Dia.of vessel=605.6mm
Height of vessel=908.3mm
No. of lugs=4
Weight of vessel=π*D*th*H
=π*0.6056*3.17*10-3*0.908
=106.84kg
𝜋
Weight of 2 heads=2* 4 *𝑑2 *th*ρ
𝜋
=2* *0.6052 *0.019*10-3*7700
4
=14.03kg
Weight of content=0.2*1409 + 0.8*810
=1092.6kg

Total weight=1213.47kg
=1213.47*9.81
=11904.14N
The max.compressible load on one leg will be;
4∗𝑃𝑤(𝐻−𝐻𝑐) 𝑊𝑚𝑎𝑥
P= +
𝑛∗𝑐 𝑛
As reactor is indoor, no winds load;
𝑊𝑚𝑎𝑥
P=
𝑛
11904.14
= =2976.03 N
4

Base plate
Β=125mm
A=115mm
Avg. pressure on plate;
𝑃
Pavg=
𝑎∗𝛽
2976.03
=
115∗125
=0.1240N/𝑚𝑚2
But the load is only distributed in rectangular plate and supporting beam actual stress
may be 40% more
𝛽2 𝑎4
P=0.4*Pavg*( 2 )* 2 4
𝑇 𝑎 +𝛽
1252 1154
297.6=0.4*0.1240*( )*
𝑇2 1152 +1254
T=0.8175mm
Use 1 mm thickness of plate.

Cost Estimation [14]
An acceptable plant design must present a process that is capable of operating

under conditions which will yield a profit. Since,
Net profit = Total income – All expenses
It is essential that chemical engineer be aware of the many different types of cost
involved in manufacturing processes. Capital must be allocated for direct plant expenses,
such as those for raw materials, labor, and equipment. Besides direct expenses, many
other indirect expenses are incurred, and these must be included if a complete analysis of
the total cost is to be obtained. Some examples of these indirect expenses are
administrative salaries, product distribution costs and cost for interplant communication.
A capital investment is required for any industrial process and determination of
the necessary investment is an important part of a plant design project. The total
investment for any process consists of fixed capital investments for physical equipment
and facilities in the plant plus working capital which must be available to pay salaries,
keep raw materials and products on hand, and handle specialties requiring a direct cost
outlay. Thus in an analysis of cost in industrial processes, capital investment cost,
manufacturing cost, and general expenses including income taxes must be taken into
consideration.
CAPITAL INVESTMENT:
Before an industrial plant can be put into operation, a large sum of money must be
supplied to purchase and install the necessary machinery and equipment. Land and
service facilities must be obtained and the plant must be erected complete with all piping,
controls and service. In addition it is necessary to have money available for the payment
of expenses involved in the plant operation. The total capital required for installation and
working of a plant is called total capital investment.
Total Capital Investment = Fixed Capital + Working Capital

Fixed Capital Investment: the capital needed to supply necessary manufacturing and
plant facilities is called fixed capital investment. The fixed capital is further subdivided
into manufacturing fixed capital investment and non-manufacturing fixed capital
investment.
Working Capital: Te capital required for the operation of the plant is known as working
capital.
FIXED CAPITAL INVESTMENT INCLUDE

A. DIRECT COST
1. Purchased Equipment Cost
2. Purchased Equipment Installation
3. Installation Cost
4. Instrumentation and Controls
5. Piping
6. Electrical Installation
7. Building including services
8. Yard improvement
9. Service facilities
10. Land
B. INDIRECT COST
1. Engineering and supervision
2. Construction expenses
3. Contractors fee
4. Contingencies
5. Startup expenses
WORKING CAPITAL INCLUDES:

1. Raw materials and supplies carried in stock
2. Finished product in stock and semi finished products in the process of being
manufactured.

3. Accounts receivable.
4. Cash kept on hand for monthly payment of operating expenses, such as salaries, wages,
and raw material purchased.
5. Accounts payable.
6. Taxes payable.
TYPES OF CAPITAL COST ESTIMATES

An estimate of the capital investment for a process may vary from a predesigned
estimate based in the little information except the size of the proposed project to a
detailed estimate prepared from complete drawings and specifications. Between these
two extremes of capital investment estimates there can be numerous other estimates
which vary in accuracy depending upon the stage of development of the project. These
estimates are called by a variety of names, but the following five categories represent the
accuracy range and designation normally used for design purposes.
1. Order of magnitude estimate (ratio estimated based on similar previous cost date,
probable accuracy of estimate over 30%)
2. Study estimate (factor estimate) based on the knowledge of major items of equipment;
probable accuracy of estimate up to 30%)
3. Preliminary estimate (budget authorization estimate, scope estimate) based on
sufficient data to permit the estimate to be measured; probable accuracy of estimate
within 20%.Definitive estimate (project control estimate). It based on almost complete
date but before completion of drawings and specification, probable accuracy of estimate
within 10%.
5. Detailed estimate (contractors estimate). It based on complete engineering drawings,
specifications, site surveys, probable accuracy of estimate within 5%.

COST INDEXES
A cost index is merely an index value for a given point in time showing the cost that time
relative to certain base time. So, present cost is estimate from cost index as follows
Present Cost = Original Cost x (Index Value at Present Time/Index value at Time
Original Cost was Obtained)
Cost index can be used to give a general estimate.
Many different types of cost indexes are published regularly. Some of these can
be used for estimating equipment cost; other applies specifically tolabour, construction,
materials or others special fields. The most common of these indexes are the
i. Marshall and Swift all-industry and process industry equipment index
ii. Engineering news-record contraction cost index.
iii. The Nelson Farrar refinery construction index
iv. The chemical engineering plant cost index
v. Other index includes monthly labor view.
Batch reactor
Inside diameter = 0.6056 m

Height = 0.9083 m
Total capacity = 0.2616 m3
=69.10 gal.
Cost of reactor = $ 1500 (Peters P-628) (MOC= C.S)

10 % cost for cooling system = $ 150
Total cost = $ 1650
Cost index of 1990 = 924
Cost index of 2009 = 1511.9
1650∗1511.9
Cost in 2009 =
924
= $ 2699.82
Total Purchased Equipment Cost = $ 2699.82

Cost Estimates for Fluid Processing Plants
Purchased equipment (Delivered), E $ 2699.82
Purchased equipment installation, 47% E $ 1268.9154
Instrumentation and control (Installed), 18% E $ 485.9676
Piping (Installed), 66% E $ 1781.8812
Electrical Installed, 11% E $ 296.9802
Buildings (Including services), 18% E $ 485.9676
Yard Improvement, 10% E $ 269.9820
Services facilities installed, 70% E $ 1889.8740
Land, 6% E $ 161.9892
Total Direct Plant cost, D $ 9341.34
Engineering and Supervision, 33% E $ 890.9406
Construction Expenses, 41% E $ 1106.9262
Total Direct and Indirect Plant cost, (D + I) $ 11339.2
Contractor’s Fees, 21% E $ 566.9622
Contingency, 42% E $ 1133.9244
Fixed Capital Investment $13040.0866
Working Capital, 86% E $ 2321.8452
Total Capital Investment $15361.9318
= 15361.9318*60
= 952439.77 Rs

TOTAL PRODUCT COST (TPC)
Variable Cost
1. Raw material
Acetic acid = Rs 50.00/ lit (Adinath prtochem ltd)
For 100 lit production of butyl acetate
Acetic acid used =71.49 lit

=Rs 3574.81
Butanol = 95 Rs /lit (Adinath petrochem ltd)

For 100 lit. Of butyl acetate
Butanol required =114.99 lit
=Rs 10919.30
Total variable cost TVC = Rs 14494.11
Fixed Cost
1. Depreciation (10% FCI)
= 0.1 x 808485.36
= Rs 80848.53
2. Local Tax (1 -4% FCI)
= 0.025 x 808485.36
= Rs 20212.13
3. Insurance (0.5 -1 % FCI)
= 0.0075 x 808485.36
= Rs 6063.64
TPC = Variable cost + Fixed Cost
= Rs 121618.41
121618.41
Production cost = 330×100
= Rs 3.58 / ton

Selling Price = Rs 2, 00,000 /ton (International Market)
PAYBACK PERIOD
Profit/ton = Selling price – TPC
= 78381.59
𝑉−𝑉𝑠
Depreciation/yr = 𝑛
= Rs 80848.5
fixed capital investment
Payout Period =𝑝𝑟𝑜𝑓𝑖𝑡
+𝑑𝑒𝑝𝑟𝑒𝑐𝑖𝑎𝑡𝑖𝑜𝑛/𝑦𝑟
𝑦𝑟
= 9.97 years
Plant Safety

Plant Layout
Layout for manufacturing facilities
facility layout means planning for the location of all machines, utilities, employee
workstations, customer service areas, material storage areas, rest rooms, lunchrooms, drinking
fountains, internal walls, offices, and computer rooms, and for the flow patterns of materials
and people around, into, and within buildings. Through facility layouts, the physical
arrangement of these processes within and around buildings, the space necessary for the
operation of these processes and provided the space required for support functions. As process
planning and facility layout planning information continuous interchange between these two
planning activities, because each affects the other
Some Objectives of Facility Layouts
There are many objectives of facility layouts these are:-
1) Provide enough production capacity.

2)
Reduce materials-handling costs.
3) Conform to site and building constraints.
4) Allow space for production machines.
5) Allow high labor, machine, and space utilization and productivity.
6) Provide for volume and product flexibility.
7) Provide space for rest rooms, cafeterias, and other personal-care needs of employees .
8) Provide for employee safety and health.
9) Allow ease of supervision.
10) Allow ease of maintenance.
11) Achieve objectives with least capital investment.

Additional objectives for Warehouse operation layouts
1) Promote efficient loading and unloading of shipping vehicles.

2) Provide for effective stock picking, order filling, and unit loading.
3) Allow ease of inventory counts.
4) Promote accurate inventory record keeping.
Additional objectives for service operation layouts
1) Provide for customer comfort and convenience .

2) Provide appealing setting for customers.
3) Allow attractive display of merchandise.
4) Reduce travel of personnel or customers.
5) Provide for privacy in work areas.
6) Promote communication between work areas.
7) Provide for stock rotation for shelf life.
Additional objectives for office operation layouts
1) Reinforce organization structure.

2) Reduce travel of personnel or customers.
3) Provide for privacy in work areas.
4) Promote communication between work areas.

The objective of the facility layout study is to minimize total cost, this cost
(1) Construction cost.
(2) Installation cost.
(3) Material handling cost.
(4) Ease of future expansion.
(5) Production cost.
(6) Machine downtime cost.

(7) In-process storage cost.
(8) Safety cost.
(9) Ease of supervision.
Layout for manufacturing facilities
There are five basic types of layouts for manufacturing facilities ;process, product,
cellular manufacturing(CM) , fixed position and Hybrid Layouts :
Process layouts (functional layouts,)
They are designed to accommodate variety in product designs and small batches
.Process layout use general –purpose machines that can be changed over rapidly to new
operations for different product designs. These machines are usually arranged according to
type of process being performed.

Product layout (production lines)
They are designed to accommodate only a few product designs. the machinery or
equipments is arranged to ensure continuous flow of material in an orderly mode throughout
the plant. Examples of product layout, Paper mills, dairies, cement factories, and automotive
assembly plants, Auto manufacturing. Product layout use specialized machines that are set up
once to perform a specific operation for a long period of time on one product, this machine
requires great expense and long down times to change over to a new product design.
Companies that produce only a few product types often set up a different production
line for each product type. The facility layout would allow for the different product lines to
separate from each other. Workers repeatedly perform a narrow range of activities on only a
few product designs& required a small rate of skill, training and supervision.
The planning and scheduling activities are complex, they are not ongoing
(continuous), rather planning & scheduling tend to be done intermittently as product
changeovers occur. The primary objective is to minimize material handling cost by properly
arranging the equipment in the processing sequence. Many types of flow are possible. below
only a few.

Product Layout
Advantages
1) Since the layout corresponds to the sequence of operations, smooth and logical flow lines
result.
2) Since the work from one process is fed directly into the next, small in-process inventories
result.
3) Total production time per unit is short.
4) Since the machines are located in order to minimize distances between consecutive
operations, material handling is reduced.
5) Little skill is usually required by operators at the production line; hence, training is simple,
short, and inexpensive.
6) Simple production planning and control systems are possible.
7) Less space is occupied by work in transit and for temporary storage.
Limitations
1) A breakdown of one machine may lead to a complete stoppage of the line that follows a
machine.
2) Since the layout is determined by the product, a change in product design may require
major alterations in the layout.
3) The pace of production is determined by the slowest machine.
4) Supervision is general instead of specialized.
5) Comparatively high investment is required because identical machines (a few not fully
utilized) are sometimes distributed along the line.

Process Layout
Advantages
1) Better utilization of machines can result; consequently, fewer machines are required.
2) A high degree of flexibility exists relative to equipment or manpower allocation for specific
tasks.
3) Comparatively low investment in machines is required.
4) The diversity of tasks offers a more interesting and satisfying occupation for the operator.
5) Specialized supervision is possible.
Limitations
1) Since longer flow lines usually result, material handling is more expensive.
2) Production, planning, and control systems are more involved.
3) Total production time is usually longer.
4) Comparatively large amounts of in-process inventory result.
5) Space and capital are tied up by work in process.
6) Because of the diversity of the jobs in specialized departments, high grades of skill are
required.

Fig. no 11 – Simple Plant Layout

Applications of Butyl Acetate [15, 16]
1) Butyl acetate is used in the production of homopolymers and co-polymers such as

acrylic acid and its salts.
2) n-Butyl acetate is an important solvent in the paints industry on account of its
versatility. It is an excellent solvent for cellulose nitrate, resins and polymers
and for oils and fats.
3) n-Butyl acetate is often employed in combination with n-butanol in paints,
because n-butanol enhances the resistance to blushing and increases the solvency
in many cases.
4) n-butyl acetate can also be employed as an extractant in the manufacture of
pharmaceutical preparations.
5) n-butyl acetate can also be employed as an ingredient of cleaners, essences and
fragrances.

Conclusion
1. The esterification reaction between butanol and acetic acid performed over an
acidic ion exchange resin Saralite SRC 120 .
2. The interaction between the solid catalyst and the reactants will consider in the
model.
3. The rate constant and conversion increases with increasing the temperature of the
reaction at a certain mole ratio of reactants.
4. The use of excess reactants on the conversion is studied.

Reference
1) Dr.Zaidoon M. Shakoor , Dr.Khalid A. Sukkar & Mohammed S. Baqer Reaction

Kinetics of Acetic Acid and n-Butanol Esterification Catalyzed by Dowex 50
Catalyst Eng. & Tech. Journal ,Vol.29 , No.10 , 2011
2) M. Bengi TAYSUN, Emine SERT, Ferhan S. ATALAY Esterification of Maleic
Acid with Butanol Catalyzed by Environmentally Friendly Catalysts Ege
University, Department of Chemical Engineering, İzmir, TURKEY
3) Charubala Ananda Phalak Reaction Engineering Studies In Ion Exchange Resin
Catalyze Esterification Reactions Homogenous Catalysis Division National
Chemical Laboratory Pune FEBRUARY 2004
4) E. Sert and F. S. Atalay Ege University, Chemical Engineering Department,
35100, Bornova, Izmir, Turkey Esterification of Acetic Acid with Butanol:
Operation in a Packed Bed Reactive Distillation Column Chem. Biochem. Eng.
Q. 25 (2) 221–227 (2011) Original scientific paper Received: January 3, 2011
5) Jiri Hanika, Jiri Kolena, Magdalena Kucharova, Karla Havlickova Alkyl acetates
synthesis in multi-functional trickle bed reactor Institute of Chemical Technology,
Tatranske Matliare, Slovak 26 Republic, May 26 – 30, 2003
6) Amrit Pal Toor , Mamta Sharma, Sakshi Thakur, and R.K.Wanchoo Ion-exchange
Resin Catalyzed Esterification of Lactic Acid with Isopropanol: a Kinetic Study
Bulletin of Chemical Reaction Engineering & Catalysis, 6 (1), 2011, 39 – 45
7) Kiran D. Patil, Bhaskar D. Kulkarni Kinetics Studies on Esterification Reaction
of Acetic acid with Iso-amyl Alcohol over Ion Exchange Resin as Catalysts
International Journal of Engineering Research ISSN:2319-6890)(online),2347-
5013(print) Volume No.3, Issue No.8, pp : 488-493
8) T. E. Jordan, Publicker Industries, Inc.; "Esters, Organic" in Encyclopedia of
Chemical Technology 1st ed., Vol. 5, pp. 824−950,

9) Pierluigi Barbaro, and Francesca Liguori Ion Exchange Resins: Catalyst Recovery
and Recycle Chem. Rev., 2009, 109 (2), 515-529• Publication Date (Web): 23
December 2008
10) Nada S. Ahmed Zeki Maha H. Al-Hassani Haider A. Al-Jendeel Kinetic Study of
Esterification Reaction Al-Khwarizmi Engineering Journal, Vol. 6, No. 2, PP 33-
42 (2010)
11) Octave levenspiel Chemical Reaction Engineering Third Edition page no (58-
59,207-209)
12) Carl Yaws Handbook of Physical properties and Thermodynamic properties.
13) Material Data Sheet for compounds (www.msds.com)
14) Max S. Peters and Ronald E.West Plant Design and Economics For Chemical
Engineer Fifth edition page no. (626-628)
15) Technical Data Sheet Dow Chemical Company Form No. 745-00109-1004-AA
page no 2
16) Technical Leaflet BASF Chemical Company. Supersedes edition dated March
2008

Kinetic Study of Esterification Reaction Using Ion Exchange Resin

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Kinetic Study Of Esterification Reaction Using Ion Exchange Resin Catalyst

Department of Chemical Engineering P.V.P.I.T. (Budhgaon). Page 1

1) To learn collection of literature.

1) Learnt the search methods for the collection of literature survey.

2) Learnt method of manufacturing of butyl acetate.

3) Learnt the implementation and control of various process conditions.

4) Learnt about collection and attachments of all instruments and equipments

6) Understood collection and use of various information required in plant

Department of Chemical Engineering P.V.P.I.T. (Budhgaon). Page 2

Amrit Pal Toor , Mamta Sharma, Sakshi Thakur, and R.K.Wanchoo

Department of Chemical Engineering P.V.P.I.T. (Budhgaon). Page 3

solid catalyst named Dowex50 under atmospheric pressure .Reaction experiments

Department of Chemical Engineering P.V.P.I.T. (Budhgaon). Page 6

Esterification reaction is one of the most important industrial reactions. Esters

Department of Chemical Engineering P.V.P.I.T. (Budhgaon). Page 7

Department of Chemical Engineering P.V.P.I.T. (Budhgaon). Page 8

Esterification of Acetic Acid with Butanol using SERALITE

Esterification of carboxylic acids is an important class of reactions, the

CH3COOH + C4H9OH CH3COOC4H9 + H2O

Esterification reactions are equilibrium processes and must be displaced

Department of Chemical Engineering P.V.P.I.T. (Budhgaon). Page 9

Department of Chemical Engineering P.V.P.I.T. (Budhgaon). Page 10

Esterification Catalysts and Processes

Esterification reactions proceed with or without a catalyst. In the absence

Homogeneous acid catalysts

Catalysis by mineral acids has emerged as a field of growing interest and

Heterogeneous acid catalysis

a) Metal ion complexes as catalysts

Metallic oxides and hydroxides of magnesium, zinc, titanium, zirconium

Department of Chemical Engineering P.V.P.I.T. (Budhgaon). Page 11

b) Ion exchange resins as catalysts

Enzymes have been widely used in esterification technology. In particular,

Department of Chemical Engineering P.V.P.I.T. (Budhgaon). Page 12

Table No 1:- Comparison between Homogenous & Heterogeneous Catalyst

Factors Homogeneous catalysis Heterogeneous catalysis

2.After treatment Catalyst cannot be Can be recovered

3.Processing methodology Continuous fix bed

4. Presence of water/free Not sensitive

8.Soap formation Does not take place

Department of Chemical Engineering P.V.P.I.T. (Budhgaon). Page 13

Table No 2:- Overview on heterogeneous catalysts

Catalyst type Examples

Alkali metal oxides K2O

Alkaline earth metal alcoholates Mixtures of alkali/alkaline earth metal

Alkaline earth metal oxides CaO, SrO, BaO

Alkaline earth metal hydroxides Ba(OH)2

Alkaline earth metal salts of carboxylic Ca- and Ba- acetate

Strong anion exchange resins Amberlyst A 26, A 27

Transition metal salts of amino acids Zn- and Cd-arginate

Department of Chemical Engineering P.V.P.I.T. (Budhgaon). Page 14

Kinetics of ion exchange catalysis

(iii) Chemical reaction at the active sites.

If the film diffusion is sufficiently fast, the process is controlled by chemical

Department of Chemical Engineering P.V.P.I.T. (Budhgaon). Page 15

Kinetics and Reaction Engineering of Esterification

Kinetics of esterification between organic acids and alcohols has been

Kinetics of esterification of monobasic acid

A detailed literature survey on esterification of different monobasic

Department of Chemical Engineering P.V.P.I.T. (Budhgaon). Page 16

proportional to the reciprocal of absolute temperature as per Arrhenius law of

Department of Chemical Engineering P.V.P.I.T. (Budhgaon). Page 17

Agitated Slurry Reactors