See

discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/263352558

Final BCUD Research Project Report

Technical Report August 2009

CITATIONS READS

0 91

1 author:

Dr.Kiran D. Patil
Maharashtra Institute of Technology
58 PUBLICATIONS 56 CITATIONS

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Design of Three Phase separator View project

PREHEAT NETWORK RECONFIGURATION OF A KERO HYDRO DESULPHURIZATION UNIT View project

All content following this page was uploaded by Dr.Kiran D. Patil on 25 June 2014.

The user has requested enhancement of the downloaded file.

 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

1. PROJECT TITLE: STUDIES IN REACTIVE SEPARATIONS

1.1 Preamble:

The discipline of Chemical Engineering is undergoing a major transformation. A new

paradigm of "borderless chemical engineering science" is emerging. The demands from the
Society for `cleaner technologies rather `clean-up technologies, the emergence of
`performance chemicals and materials etc., is driving the profession towards achieving
symbiotic relationship with other disciplines. The need for more efficient and
environmentally cleaner processes has led to a growing interest in novel processes and
hybrid process systems, which combine conventional and non-conventional processes. A
drive towards `Process Intensification is leading to the search of novel reactor
configurations, which will enhance selectivity as well as productivity. Combination of
reaction and separation in a `combo system is likely to bring large dividends. Enhancement
in conversion, selectivity, energy utilization, reduction in equipment cost and separation of
otherwise difficult to separate mixtures are some of the motives behind its several
applications. It has become an attractive technology not only for reaction engineers but also
for separation technologists.

1.2 Introduction:

Reactive distillation (RD) is a combination of reaction and separation in a single vessel owing
to which it enjoys a number of specific advantages over conventional sequential approach of
reaction followed by distillation or other separation techniques. RD processes have wide
prospects to apply it to chemical engineering and other industry fields. Improved selectivity,
increased conversion, better heat control, effective utilization of reaction heat, scope for
difficult separations and the avoidance of azeotropes are a few of the advantages that RD
offers. Completely, advantages of the combined reactive mass exchanges processes (RD)
play special role at creation of low waste technologies for producing various organic
substances. Special meaning, as was shown, has increase of selectivity and reagents
conversion by one pass.

1.3 Motivation:

The increased interest in industrial and academic field in reactive distillation has led to
increasing number of publications and patents on this subject in the last decade, many of
which are dealt with the modelling aspects of reactive distillation processes. To improve the
economics, flexibility, operability, and safety of column-based separation processes, design
that considers steady state as well as dynamic behaviour is desired.

The chemical and petroleum industries are experiencing fundamental changes. Rapid
globalisation of the industries, economic and political changes in the world order,
environmentally driven governmental regulations and social pressures (e.g. decrease of
consumption, increase of reuse and recycling), declining reserves of some raw materials, and
increasing competition and overcapacity are the circumstances in which companies are
fighting for their future existence.

Several technical issues also motivated this study. Reactive distillation is now an established
unit operation in process technology and can be seen as the front-runner in the field of

1
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

process intensification, there are still significant gaps in the current body of knowledge
particurily concerning the rigorous experimental work for the purpose of validation of the
model. With expertise available in the associated areas, the current work was an opportunity
to direct effort towards this aspect of reactive distillation using a combining of simulation and
experimentations.

1.4 Plan of Research:

a) Literature search to assess the potential of reactive distillation technology to provide

tools for design, synthesis and operational issues of these processes.
b) Literature review for various methodologies of process modeling, simulation, reaction
kinetics and thermodynamics, phase equilibrium studies, hardware structure and
design, conceptual design to evaluate feasibility, experimental work on laboratory
cum pilot scale and understand their strengths and drawbacks.
c) The development of EQ and NEQ models for reactive distillation and generation of
computer programs and source codes in MATLAB from the available algorithms for
the novel methodologies of process modeling. Development of simulation strategy
using Aspen plus.
d) The design, construction and commissioning of the experimental facility for reactive
distillation processes.
e) The generation of VLE data in the laboratory and to calculate BIP'S using NRTL
model. Performance of conceptual design studies to generate RCM and to understand
the azeotrope behavior of the system.
f) The generation of rigorous experimental data in batch reactor to study the effects of
various parameters (such as temperature, stirrer speed, mole ratio, catalyst loading
etc.) and fit the kinetic model(s) for solid catalyst esterification reaction.
g) The experimental plans on continuous reactive distillation to study the influence of
various operating parameters such as a feed flow rate, feed compositions, feed
locations, boil-up rate etc. on the conversion and separation.
h) Analysis and comparison of results and judging the performance of the proposed
methodologies.

Scope of reactive separations is very wide and vast, therefore after initial literature
review, we have decided to focus and restrict further work on Reactive Distillation
(RD). Therefore in this thesis only the technique of RD has been studied. Reactive
distillation, also called catalytic distillation (CD), can be considered as reaction and
distillation combined into one new unit operation.

2. METHODOLOGY:

The aspect considered in the proposal is to develop a methodology for design, simulation and
analysis of RD processes. There is a need for more rigorous experimental work with the
express purpose of model validation. Hence our main aim to develop experimental facilities
to study two-esterification test systems discussed above via RD. Control studies for kinetic
controlled processes are missing to a large extent in open literature for the test system chosen
and hence research is also focused to close this gap.

For the development reactive distillation technology needs enormous support from research
on various aspects. The main focus will be on study of:
a) Reaction Kinetics and Thermodynamics

2
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

b) Phase equilibrium studies

c) Hardware structure and design
d) Conceptual design to evaluate feasibility
e) Modeling and simulation
f) Experimental work on laboratory and pilot scale

The reaction kinetics was developed and VLE data available in literature is used to predict
the RD column performance. Both equilibrium and non-equilibrium stage models is used.
Experimental results are compared with simulation results obtained by commercial simulators
such as Aspen Plus.

2.1 MATHEMATICAL MODELLING:

The esterification of acetic acid (with isoamyl alcohol) is considered inside a RD column.
The column has a total condenser and a reboiler. The theoretical stages are numbered from
top to bottom. The condenser is represented by stage 1 and reboiler is represented by stage
27.
2.1.1 Model Assumptions:
The various assumptions made during the development of model were as follows:
1. The vapor and liquid on each plate and leaving on each plate are perfectly mixed.
Moreover, the liquid on the plate has the same compositions as the liquid leaving the
plate.
2. Constant molar liquid holdup is assumed for each stage.
3. Molar vapor holdup is negligible in comparison with the molar liquid holdup.
4. Simple or complex reaction(s) proceed only in the liquid phase and their rate can be
described by an appropriate kinetic expression(s). (Preferably second order reaction
kinetics)
5. The liquid phase is in equilibrium with the vapor phase leaving the plate.
6. Phase splitting is considered only in the decanter; liquid-liquid splitting inside the
column is neglected.

The assumptions above lead to a model that consists of a set of ordinary differential and
algebraic equations (DAEs). From the mass and energy dynamic balances on the jth plate
according to figure 1, the model is derived as follows:

Figure 1 RD column for esterification reaction Figure 2 Single stage (j) in the column
showing the corresponding streams
The Mass balance of component i around plate j is given by:

3
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

d(x i, jM j )
= Vj + 1yi, j + 1 L jx i, j + L j 1x i, j 1 Vjyi, j + R i, j (1)
dt

dx i, j dM j
+Mj+ x = Vj + 1yi, j + 1 L jx i, j + L j 1x i, j 1 Vjyi, j + R i, j (2)
dt dt i, j
This is combined with overall mass balance around plate J:
dM j
= Vj+1 L j + L j1 Vj + R j (3)
dt
The subscripts i range in value from 1 to the number of components in the mixture. The
subscripts j ranges in value from 1 to the number of plates, N.

The Equilibrium equation:

yi, j = K i, jx i, j (4)
Where K= equilibrium constant
giving,
d(x i, j )
M j = Vj + 1K i, j + 1x i, j + 1 L jx i, j + L j 1x i, j 1 VjK i, jx i, j + R i, j
dt (5)
(Vj + 1 L j + L j 1 Vj + R j )x i, j

The Energy balance equation around the plate j is given by:

d(Hi, jM j )
= Vj + 1h i, j + 1 L jHi, j + L j 1Hi, j 1 V jh i, j (6)
dt
dHi, j dM j
Mj + Hi, j = Vj + 1h i, j + 1 L jHi, j + L j 1Hi, j 1 Vjh i, j (7)
dt dt
This is combined with overall energy balance around plate J:
dHi, j
M j = Vj + 1h i, j + 1 L jHi, j + L j 1Hi, j 1 Vjh i, j
dt (8)
(Vj + 1 L j + L j 1 Vj + R j ) + Hi, j
These equations are coupled with algebraic equations for reaction kinetics and vapor-liquid
equilibrium.

2.1.2 Solutions of Model Equations:

The model equations form a mixed set of set of ordinary differential equations (ODEs) and
algebraic equations. The equations for 27 stages for the system and four-component system
can be solved in MATLAB by ODE 15 S solver (which is an ordinary differential and
algebraic equation (DAE) solver for stiff equations, variable order method) and using Aspen
plus simulation.

4
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

3 EXPERIMENTAL WORK:
This work is focused to investigate the potential of RD for feasibility studies:
(a) Design of Experimental set up for RD
(b) Catalyst selection
(c) Temperature range in reaction kinetics experiments
(d) Operation procedure for RD column
(e) Sensitivity studies using simulation as well as experiment

3.1 REACTION KINETICS STUDIES

Esterification of Acetic acid with Iso amyl Alcohol catalyzed by an Acidic Ion Exchange
Resin
3.1.1 Introduction:

Esterification reactions are ubiquitous reactions especially in pharmaceutical, perfumery and

polymer industries, wherein; both heterogeneous and homogeneous catalysts have been
widely used. The conventional esterification process employing sulfuric acid,
methanesulfonic acid or p-toluenesulfonic, results in sulfur contamination of the final
product, which is unacceptable. Other organic and inorganic acid catalysts also pose the same
problem. (Yadav et al, 2008). Further, the use of homogeneous catalyst requires
neutralization with an alkali, which leads to serious effluent problems on industrial scale. The
concept of Green chemistry has been pursued vigorously since early 1990s as a new
approach for chemical industry to adopt rather than to continue with old traditional and
polluting pathways.

Esterification (e.g. synthesis of iso- amyl acetate) has been the model reaction for the
research studies in reactive distillation. Reaction of acetic acid with higher alcohols falls in a
category of typical class of reacting systems. The alcohol is sparingly soluble in water and
esters and water are almost immiscible.

In the present study, an attempt is made to explore the kinetics of the model reaction
catalyzed by TULSIONTM MP-T-63, T-62 and T-66, cation ion - exchange resin.

Table 1 Properties Catalyst used (Thermax Ltd., India)

Cataly Particle Exchang Bulk Moistu Porosit Temp Specific Pore Dia Cross
st size e density re y stabilit Sur.area (A) linking
( m) capacity (kg/m3) content (%) y (m2/gm) (%)
(meqiv/d (%) (K)
ry g)
T-62 300-1200 4.8 NA <1 NA 403 35 NA 15

T-63 300-1200 4.9 NA <1 40 403 35 400 15

T-66 300-1200 5.0 NA <1 NA 403 NA NA NA

Test System I: Synthesis of Isoamyl Acetate from acetic acid and amyl alcohol
k
CH3 - COOH + C5 H11 - OH C5H11 - COO - CH 3 + H 2O (9)
(Acetic acid) (iso amyl alcohol) (iso amyl acetate) (Water)

5
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

3.1.2 Materials
Acetic acid (99.8%) and iso-amyl alcohol (99%) were purchased from Merck India Ltd.,
Mumbai. Iso amyl acetate (> 99% purity) was purchased from S.D. Fine Chemicals Ltd.,
Mumbai and distilled water was used for experimental work. TULSIONR T- 63 MP, cation
ion exchange resin (Thermax India Ltd., Pune) equivalent with Amberlyst-15 (ROHM
HAAS, USA) was used as a solid catalyst for batch reaction kinetic studies.

3.1.3 Parameters studied

1. Temperature: 90 0 C, 100 0 C, 105 0 C, 110 0 C, 120 0 C and 130 0 C

2. Catalyst Loading: 3 gm, 5 gm, 7 gm, and 10 gm
3. Mole ratio of reactants (ISAMOH/HOAC): 1:1, 2:1, 3:1 and 1:2
4. Stirrer Speed: 400 rpm, 600 rpm, 800 rpm, and 1000 rpm
5. Different catalyst: T-63, T-62 AND T-66 (Thermax Ltd., India)
6. Catalyst Reusability
3.1.4 Experimental Set-up:
The experimental set-up consists of heating chamber whose temperature can be set
independently as shown in figure 3. The reaction is performed in a 750 ml glass reactors
equipped with stirrer and condenser and placed in heating chambers for the attainment of the
required temperature. A motor drives the stirrer with a control over the speed of agitation.
The speed can be measured using a non-contact type tachometer. Digital temperature
indicator is provided to measure the temperature of the reaction mixture in the reactor.

Figure 3 Schematic Diagram of Batch Kinetics for Esterification

Setup

6
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

(1) Effect of Temperature Variations

3.1.5 Observations and Results

Table 2 Effect of Temperature Variations

T= 90 0 C T= 100 0 C T= 105 0 C T= 110 0 C

Time HOAC AMAC Conv of HOAC AMAC Conv of HOAC AMAC Conv. of HOAC AMAC Conv of
(min.) Conc. Conc. HOAC Conc. Conc. HOAC Conc. Conc. HOAC Conc. Conc. HOAC
(gm/ml) (gm/ml) (%) (gm/ml) (gm/ml) (%) (gm/ml) (gm/ml) (%) (gm/ml) (gm/ml) (%)
0 0 0 0 0 0 0 0 0 0 0 0 0
5 0.4764 0.5476 53.47 0.438 0.586 57.22 0.4056 0.6184 60.39 0.33 0.694 67.77
10 0.4392 0.5848 57.10 0.426 0.598 58.39 0.354 0.67 65.42 0.2988 0.7252 70.82
20 0.3828 0.6412 62.61 0.378 0.646 63.08 0.3276 0.6964 68.00 0.2676 0.7564 73.86
30 0.3588 0.6652 64.96 0.3732 0.6508 63.55 0.3036 0.7204 70.35 0.252 0.772 75.39
45 0.327 0.697 68.06 0.3384 0.6856 66.95 0.288 0.736 71.87 0.2448 0.7792 76.09
60 0.312 0.712 69.53 0.3192 0.7048 68.82 0.2784 0.7456 72.81 0.2388 0.7852 76.67
75 0.3084 0.7156 69.88 0.305 0.719 70.21 0.2676 0.7564 73.86 0.2292 0.7948 77.61
90 0.2988 0.7252 70.82 0.2976 0.7264 70.93 0.2628 0.7612 74.33 0.2244 0.7996 78.08
120 0.2964 0.7276 71.05 0.2844 0.7396 72.22 0.2508 0.7732 75.50 0.2208 0.8032 78.43
150 0.2892 0.7348 71.75 0.2832 0.7408 72.34 0.2484 0.7756 75.74 0.2105 0.806 78.71
180 0.2905 0.7335 71.63 0.2856 0.7384 72.10 - - - - - -

(Contd,)

7
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

T= 120 0 C T= 130 0 C
Time HOAC AMAC Conv of HOAC AMAC Conv of
(min.) Conc. Conc. HOAC Conc. Conc. HOAC
(gm/ml) (gm/ml) (%) (gm/ml) (gm/ml) (%)
0 0 0 0 0 0 0
5 0.3384 0.6856 66.95 0.2664 0.7576 73.9
10 0.2988 0.7252 70.82 0.1848 0.8392 81.9
20 0.252 0.772 75.39 0.138 0.886 86.5
30 0.2376 0.7864 76.79 0.1272 0.8968 87.5
45 0.2124 0.8116 79.25 0.114 0.9099 88.86
60 0.2076 0.8164 79.72 0.102 0.922 90.03
75 0.1956 0.8284 80.89 0.09 0.934 91.21
90 0.1956 0.8284 80.89 0.0864 0.9376 91.56
120 0.1932 0.8308 81.13 0.0792 0.9448 92.26
150 0.1896 0.8344 81.48 0.0756 0.9484 92.61

1) Temperature: 90 0 C, 100 0 C, 105 0 C, 110 0 C, 120 0 C and 130 0 C

2) Catalyst Loading: 5 gm
3) Mole ratio of reactants (ISAMOH/HOAC): 1:1
4) Stirrer Speed: 400 rpm
5) Catalyst: TULSION MP T-63 (Cation Ion exchange resin), Thermax India, Pune

100

90
Conversion of acetic acid (%)

80

70

T=363K
60
T=373K
T=378K
50 T=383K
T=393K
T=403K
40
0 30 60 90 120 150 180 210
Time(minutes)

Figure 4 Effect of temperature on acetic acid conversion

Catalyst loading: 5 gm, Mole ratio= 1:1, Stirrer Speed: 400 rpm,
Catalyst: TULSION MP T-63, Particle size= 0.3-1.2 mm

8
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

0.6

T=363
0.5
T=373

Concentration of acetic acid (gm/ml)

T=378
T=383
0.4 T=393
T=403

0.3

0.2

0.1

0.0
0 30 60 90 120 150 180 210

Time(minutes)

Figure 5 Effect of temperature on acetic acid concentration

Catalyst loading: 5 gm, Mole ratio= 1:1, Stirrer Speed: 400 rpm,
Catalyst: TULSION MP T-63, Particle size= 0.3-1.2 mm

Result Discussions:

The study on the effect of temperature is very important for a heterogeneously catalyzed
reaction, as this information is useful in calculating the activation energy for this reaction.

Moreover, the intrinsic rate constants are strong functions of temperatures. Figure 4 presents
the variation of conversion of acetic acid at different reaction temperatures in the range 363 K
to 403 K at a feed mole ratio (alcohol to acid) of 1:1, at a stirrer speed of 400 rpm, and at 5
gm of catalyst loading. It shows that the higher temperature yields the greater conversion of
acetic acid at a fixed contact time under otherwise identical conditions. Increasing the
temperature is apparently favorable for the acceleration of the forward reaction. However, the
equilibrium conversions were nearly equal (about 90%) the equilibrium conversion of acetic
acid was independent of catalyst loading (after 3 h of reaction).

9
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

(2) Effect of Mole ratio Variations

Observations and Results:

Table 3 Effect of Mole ratio Variations

Mole ratio: 1:2 Mole ratio: 1:1 Mole ratio: 2:1 Mole ratio: 3:1
Time HOAC AMAC Conv of HOAC AMAC Conv of HOAC AMAC Conv of HOAC AMAC Conv. of
(min.) Conc. Conc. HOAC Conc. Conc. HOAC Conc. Conc. HOAC Conc. Conc. HOAC
(%) (gm/ml) (%) (gm/ml) (gm/ml) (%) (gm/ml) (gm/ml) (%) (gm/ml) (gm/ml) (%)
0 0 0 0 0 0 0 0 0 0 0 0 0
10 0.54 0.484 47.26 0.33 0.694 67.77 0.2148 0.8092 79.0 0.1368 0.8872 86.64
20 0.504 0.52 50.78 0.2988 0.7252 70.82 0.18 0.844 82.40 0.102 0.922 90.03
30 0.4776 0.5464 53.35 0.2676 0.7564 73.86 0.162 0.862 84.10 0.084 0.94 91.79
45 0.4668 0.5572 54.41 0.252 0.772 75.39 0.1476 0.876 85.50 0.072 0.952 92.96
60 0.4548 0.5692 55.58 0.2448 0.7792 76.09 0.1380 0.8859 86.52 0.0684 0.9556 93.32
90 0.4476 0.5764 56.28 0.2388 0.7852 76.67 0.1356 0.8884 86.75 0.0624 0.9616 93.90
120 0.4464 0.5776 56.40 0.2292 0.7948 77.61 0.1332 0.8908 86.92 0.048 0.976 95.31
150 0.4416 0.5824 56.87 0.2244 0.7996 78.08 0.1320 0.8944 87.34 0.048 0.976 95.31
180 - - - 0.2208 0.8032 78.43 - - - - - -
200 - - - 0.2105 0.806 78.71 - - - - - -

1) Mole ratio of reactants (ISAMOH/HOAC): 1:2 ,1:1, 2:1 and 3:1

2) Catalyst Loading: 5 gm
3) Temperature: 110 0 C
4) Stirrer Speed: 400 rpm
5) Catalyst: TULSION MP T-63 (Cation Ion exchange resin), Thermax India, Pune

10
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

100

90

Conversion of acetic acid (%)

80

70

60

50
mole ratio= 1:2
mole ratio= 1:1
40 mole ratio= 2:1
mole ratio= 3:1
30
0 30 60 90 120 150 180 210 240

Time (Minutes)

Figure 6 Effect of mole ratio on acetic acid conversion

Temperature =383K, Stirrer Speed: 400 rpm, Catalyst loading =5 gm,
Catalyst: TULSION MP T-63, Particle size= 0.2 mm-1.3mm

0.60

0.55 Mole ratio=1:2

Mole ratio=1:1
Concentration of acetic acid (gm/ml)

0.50
Mole ratio=2:1
0.45 Mole ratio=3:1
0.40

0.35

0.30

0.25

0.20

0.15

0.10

0.05

0.00
0 30 60 90 120 150 180 210 240

Time(minutes)

Figure 7 Effect of mole ratio on acetic acid concentration

Temperature =383K, Stirrer Speed: 400 rpm, Catalyst loading =5 gm,
Catalyst: TULSION MP T-63, Particle size= 0.2 mm-1.3mm

Result Discussions:

Esterification of acetic acid with isoamyl alcohol is an equilibrium-limited chemical reaction

and because the position of equilibrium controls the amount of ester formed, the use of an
excess of isoamyl alcohol increases the conversion of acetic acid. The initial molar ratio of
isoamyl alcohol to acetic acid was varied from 1: 1 to 3:1 at a temperature of 383 K, 5 gm of
catalyst loading, and stirrer speed 400 rpm. The results are shown in Figure 6 As observed,
the equilibrium conversion increases with the initial isoamyl alcohol-to-acetic acid mole ratio
under otherwise identical conditions. The equilibrium conversion of acetic acid increased
from about 52% at a feed mole ratio (alcohol to acid) of 1:1 to 87.34 % at a feed mole ratio
(alcohol to acid) of 3:1.

11
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

(3) Effect of Stirrer speed:

100

95

Conversion of acetic acid (%)

90

85

80

Stirrer speed= 400 rpm

75 Stirrer speed=600 rpm
Stirrer speed=800 rpm
Stirrer speed=1000 rpm
70
0 30 60 90 120 150 180

Time (minutes)

Figure 8 Effect of Stirrer speed on Acetic acid conversion

Temperature =383K, mole ratio=2:1, Catalyst loading =5 gm,
Catalyst: TULSION MP T-63, Particle size= 0.2 mm-1.3mm
0.25
Stirrer speed =400 rpm
Stirrer speed =600 rpm
0.20 Stirrer speed =800 rpm
Concentration of acetic acid (gm/ml)

Stirrer speed =1000 rpm

0.15

0.10

0.05

0.00
0 30 60 90 120 150 180
Time (minutes)

Figure 9 Effect of Stirrer speed on Acetic acid concentration

Temperature =383K, mole ratio=2:1, Catalyst loading =5 gm,
Catalyst: TULSION MP T-63, Particle size= 0.2 mm-1.3mm

Result Discussions:

In order to check the influence of external diffusion resistance, the experiments were
conducted at different stirrer speeds, namely 400-100- rpm at constant values of reaction
temperature and catalyst loading. The results are shown in Figure 8. In this range of stirrer
speed, the experiments showed that there was very little effect of the speed of agitation, that
is, no influence on external diffusion resistance from the bulk liquid to the surface of the
catalyst was observed. Hence, all the further experiments were conducted at a stirrer speed of
1000 rpm.

12
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

(4) Effect of catalyst loading:

100
Catalyst loading=3 gm
Catalyst loading=5 gm
95 Catalyst loading=7 gm
Catalyst loading=10 gm

Conversion of acetic acid (%)

90

85

80

75

70
0 30 60 90 120 150 180 210 240

Time(minutes)

Figure 10 Effect of catalyst loading on Acetic acid conversion

Temperature =383K, Mole ratio= 2:1, Stirrer Speed: 400 rpm,
Catalyst: TULSION MP T-63, Particle size=0.2- 1.3 mm
0.35
Catalyst loading =3 gm
0.30 Catalyst loading =5 gm
Concentration of acetic acid (gm/ml)

Catalyst loading =7 gm
Catalyst loading =10 gm
0.25

0.20

0.15

0.10

0.05

0.00
0 30 60 90 120 150 180 210 240

Time (minutes)

Figure 11 Effect of catalyst loading on Acetic acid concentration

Temperature =383K, Mole ratio= 2:1, Stirrer Speed: 400 rpm,
Catalyst: TULSION MP T-63, Particle size=0.2- 1.3 mm

Result Discussions:

The catalyst loading was varied from 3 to 10 g dry-resin at a temperature of 383 K, feed mole
ratio of 2:1, and stirrer speed of 1000 rpm. Figure 10 shows the plot of conversion vs. time at
different catalyst loadings. It can be observed that the rate of reaction increases as the catalyst
loading is increased.

13
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

(5) Effect of catalyst reusability:

100

90

Conversion of acetic acid (%)

80

70

60 Fresh catalyst
First resuse
Second reuse
50
0 30 60 90 120 150 180 210
Time (minutes)

Figure 12 Effect of catalyst reusability on conversion of acetic acid

Stirrer Speed: 600 rpm, Mole ratio= 2:1, Catalyst Loading: 3 gm,
Temperature: 383K

0.40
Fresh catalyst
0.35 First reuse
Concentration of acetic acid (gm/ml)

Second reuse
0.30

0.25

0.20

0.15

0.10

0.05

0.00
0 30 60 90 120 150 180 210

Time (minutes)

Figure 13 Effect of catalyst reusability on conversion of acetic acid

Stirrer Speed: 600 rpm, Mole ratio= 2:1, Catalyst Loading: 5 gm, Temperature: 383K

0.35
Fresh catalyst
0.30 First reuse
Concentration of acetic acid (gm/ml)

Second reuse

0.25

0.20

0.15

0.10

0.05

0.00
0 30 60 90 120 150

Time (minutes)

Figure 14 Effect of catalyst reusability on concentration of acetic acid

Stirrer Speed: 600 rpm, Mole ratio= 2:1, Catalyst Loading: 5 gm, Temperature: 383K
Result Discussions:
Reusability of TULSION MP-T-63 was tested by conducting two runs Figure 13 shows effect
of catalyst reusability on conversion of acetic acid. After completion of the experiment, the
catalyst was filtered, washed with of acetic acid and dried at 110 0 C for 3h. It was observed
that the there was only a marginal decrease in conversion. Thus the catalyst was reusable.
Hence, we can say that catalyst the can be used repeatedly for this reaction without
sacrificing catalytic activity.

14
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

(6) Effect of different catalyst

100
T-63
T-62
95
T-66

Cinversion of acetic acid (%)

90

85

80

75

70
0 30 60 90 120 150 180 210
Time (minutes)

Figure 15 Effect of different catalyst on acetic acid conversion

Temperature =383K, Mole ratio= 2: 1, Stirrer Speed: 600 rpm,
Catalyst loading= 5 gm

100
T-63
T-62
95 T-66
Conversion of acetic acid (%)

90

85

80

75
0 30 60 90 120 150 180 210

Time(minutes)

Figure 16 Effect of different catalyst on acetic acid conversion

Temperature =383K, Mole ratio= 2: 1, Stirrer Speed: 600 rpm,
Catalyst loading= 10 gm

3.1.6 Kinetic Models

Langmuir-Hinshelwood-Hougen-Watson (LHHW) model

Eley-Rideal (E-R) model
Quasi-Homogeneous (QH) model

LHHW and E-R model requires seven parameters: reaction equilibrium constant, pre-
exponential factor, activation energy and four-adsorption constants.
The QH model only requires three parameters:
The activation energy, reaction equilibrium constants, and the pre-exponential factor.
The Arrhenius equation was used as it expresses the relationship between the rate
constant and the activation energy of a reaction.

15
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

3.1.7 Reaction Kinetics Results:

Table 4 Reaction Kinetics Results

Model Pre-exponential factor Activation energy K1a K2b K3c K4d SRS
(mols/g*min) (KJ/mol)

LHHW 2.4 x 105 47 0.23 2.12 0.34 2.12 2.37 x 10-9

E-R 3.65 x 105 46.7 0.99 6.10 2.41 8.97 4.35 x 10-9

QH 3.39 x 103 40.3 - - - - 8.30 x 10-9

16
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

3.2 PHASE EQUILIBRIUM STUDIES

3.2.1 Experimental setup

The apparatus shown in Figure 18 is known as a vapor-liquid equilibrium still and has two
essential parts: (1) Vaporizer, (2) Flash chamber or Equilibrium chamber. An electrical
heating coil in the vaporizer at a slow rate vaporizes the binary liquid mixture. The vapor
from this rises to the equilibrium chamber. Vapor and liquid equilibrium at the temperature
and pressure of the chamber is established. The thermometer records the temperature or the
chamber, which extends well inside the equilibrium chamber. Connecting the vapor line to
vacuum or pressure header may regulate the pressure of the chamber. The vapor and liquid
phases separate from each other in the flash chamber. The liquid flows down the liquid line
through a water-cooled joint to the feeder line, through which the mixture again goes back to
the vaporizer. The still may be drained through the feeder line and may be charged through
either the vapor or the liquid line.

PT 100 Bulb

Glass Packings

Drain Holes

Vacuum Jacket
Magnetic Stirrer S2

Mixing Spiral
S1

Insulated Cottrell Pump

Vacuum Jacket

Heating Element

Capillary

Figure 18 Schematic Diagram of VLE Setup

3.2.2 Material:

Acetic acid (99.8%) and iso-amyl alcohol (99%) were purchased from Merck India Ltd.,
Mumbai. Isoamyl acetate (> 99% purity) was purchased from S.D. Fine Chemicals Ltd.,
Mumbai and distilled water was used for experimental work.

17
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

3.3.3 Observations and Results

Table 5 VLE Results
1) Iso Amyl Alcohol+ Water
Steady State Temperature, 0C Density of Liquid, gm/cc Density of Vapor, gm/cc
89 0.956 0.882
90 0.962 0.878
95 0.985 0.842
113 0.852 0.798
134 0.795 0.78
138 0.789 0.763
(2) Acetic Acid +Water
Steady State Temperature, 0C Density of Liquid, gm/cc Density of Vapor, gm/cc
94 1.002 0.9946
95 1.0061 1.009
96 1.0156 1.0145
98 1.0315 1.0366
103 1.0095 1.0386
118 1.027 1.048
(3) Acetic Acid+ iso Amyl Alcohol
Steady State Temperature, 0C Density of Liquid, gm/cc Density of Vapor, gm/cc
106 0.977 0.994
111 0.954 0.945
116 0.8904 0.879
132 0.854 0.827
138 0.796 0.786
(4) Water +Amyl Acetate
Steady State Temperature, 0C Density of Liquid, gm/cc Density of Vapor, gm/cc
86 0.921 0.894
88 0.967 0.893
92 0.978 0.884
127 0.852 0.8408
149 0.832 0.838
(5) Acetic Acid +I so Amyl Acetate
Steady State Temperature, 0C Density of Liquid, gm/cc Density of Vapor, gm/cc
107 0.995 0.99
110 0.974 0.959
115 0.951 0.923
131 0.894 0.894
149 0.868 0.857
(6) Iso Amyl Alcohol+iso Amyl Acetate
Steady State Temperature, 0C Density of Liquid, gm/cc Density of Vapor, gm/cc
117 0.801 0.797
119 0.8025 0.805
122 0.786 0.799
130 0.811 0.806
149 0.832 0.814

18
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

3.4 CONTINUOUS REACTIVE DISTILLATION EXPERIMENTS

3.4.1 Industrial Importance:

Amyl acetate has been used in the industry as a solvent, and extractants, and polishing agent.
It is used as artificial flavoring in banana-flavored bubble gums, as preservative in sodas and
soft drinks as well as artificial scent for covering unpleasant odors (Teo and Saha, 2004). It is
also used in large quantities in artificially pear- flavored food articles as additive in cigarettes,
and as a solvent for tannins, nitrocellulose, lacquers, celluloid, and camphor. It is also used to
manufacture celluloid cements, water proof varnishes, artificial silk, leather or pearls,
photographic films, bronzing liquids and metallic paints, perfuming shoe polishes and dyeing
and finishing textiles. (Teo et. al, 2004).

3.4.2 Why RD?

It can be synthesized from acetic acid and amyl alcohol via esterification reaction as follows
k
CH 3 - COOH + C5 H11 - OH C5H11 - COO - CH 3 + H 2O [10]
(Acetic acid) (iso amyl alcohol) ( iso amyl acetate) (Water)

H 2O CH3COOH C5 H11 - OH C5 H11 COO - CH 3

o o o
(100 C) (118 C) (137.8 C) ( 148.8oC)

Since the self-catalyzed reaction is rather slow, reaction (5.1) is commonly catalyzed using
strong inorganic acid, like sulfuric acid, or strongly acidic ion exchange resins. Most of
previous researcher used acidic cation exchange resin, for example Amberlyst 15 (Chiang et
al, 2002), Purolite CT- 175 (Saha et.al, 2005)

The two reactants, acetic acid and amyl alcohol, are intermediate boilers, whereas the
products, water and amyl acetate, are low and high boilers respectively. As iso-amyl acetate
and water are the heaviest and lightest boiling substances respectively in the quaternary
system, they can be continuously removed from the reaction zone in a RD column so that
high conversions can be achieved, thus RD an attractive process for producing iso-amyl
acetate. Thats why reactions (1) are well suited for reactive distillation. However, the large
boiling temperature difference between the reactants can be unfavorable from the reactions
point of view.

3.4.3 Material and catalysts:

Acetic acid (99.8%) and iso-amyl alcohol (99%) were purchased from Merck India Ltd.,
Mumbai. Isoamyl acetate (> 99% purity) was purchased from S.D. Fine Chemicals Ltd.,
Mumbai. In the reactive zone TULSIONR T- 63 MP, cation ion exchange resin (Thermax
India Ltd., Pune) equivalent with Amberlyst-15 (ROHM HAAS, USA) is used as a catalyst.
In reactive section, FENIX DM structured Packing for RD is used. In stripping and rectifying
sections (non-catalytic sections), HYFLUX structured packings were used. (High efficiency,
low-pressure drop distillation packing) is used.

19
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

3.4.4 Apparatus and procedure:

The simulation studies on the present test system also conducted and indicate that this option
can be better than conducting the entire reaction in a reactive distillation column. The present
work is aimed at performing an experimental investigation on a reactive distillation column
operated in such a mode.

The experimental setup of a laboratory scale reactive distillation consists of 2.5 m tall
distillation column of inside diameter 50 mm that operates at atmospheric pressure is used is
as shown in figure 20.The reboiler (2 lit) is heated with the help of a heating coil provided in
the reboiler. The non-reactive rectifying and stripping sections were packed with wire mesh
packing supplied by Evergreen Technologies India Pvt.Ltd., Mumbai.

The middle reactive zone is packed with structured packing supplied by Fenix process
Technology, Pune (FENIX DM Structured Packing for RD) embedded with Thermax
TULSIONR T- 63 MP (ion exchange resin) as a catalyst. The stripping section is 0.75 m tall,
reactive section 1 m, and rectification section 0.75 m tall in height respectively. A proper
insulation (with asbestos) with external wall heating arrangement was provided to minimize
the heat losses to the surrounding. The reaction mixture consisting of acetic acid, iso amyl
alcohol is fed continuously to the column through a feed module. Two separate Peristaltic
pumps were used to transfer the liquid from the two feed tanks to the two locations on the RD
column.

In the condenser, two immiscible phases are formed, an aqueous phase i.e. almost pure water
and an organic phase containing water, amyl alcohol and amyl acetate .The feed is preheated
before introducing it to the column. Phase separator with the condenser is used to provide
reflux to the column and to continuously withdraw water formed during the reaction.
Thermometer wells are provided at different locations in the column to measure these
temperatures (Position 1- Position 7)

Figure 19 gives photograph of the setup, which is functional in the Petrochemical Processes
Lab, Department of Petrochemical Engineering at M.I.T., Pune. The design, construction and
commissioning of this setup is the part of two ongoing research projects funded by BCUD,
University of Pune and AICTE-RPS Scheme, New Delhi.

20
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

Figure 19 Photograph of Experimental setup for Continuous Reactive Distillation

Column, which is functional at Petrochemical Processes Lab. at MIT, Pune

21
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

LEGENDS
1 Reboiler
2 250 mm from Reboiler
3 750 mm from Reboiler
4 1250 mm from Reboiler
5 1750 mm from Reboiler
6 2000 mm from Reboiler
7 2250 mm from Reboiler
8 Organic phase sampling point
9 Aqueous phase sampling point
10 Aqueous phase (Pure Water)

Organic phase

T8 T7

T6 T5

T4 T3

T2 T1

Figure 20 Experimental setup for Continuous RD Column

22
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

3.4.5 Laboratory Scale RD Column Specifications:

Diameter of column =ID: 50 mm, OD: 58 mm (MOC: Borosilicate glass)
Rectification Section:
Height = 0.75 m, Type of packing = HYFLUX Packings (Evergreen Technologies Pvt. Ltd.,
Mumbai) (MOC: SS 316, Size: 2 in. 4 in., Pad density = 432 kg/m3)
Reactive Section:
Height, h = 1 m, Packings: FX PAK DM structured packing (Fenix Process Technologies
Pvt. Ltd., Pune), (MOC: SS 316L, Size: 2 in. 4 in.)
Stripping Section:
Height = 0.75 m, Type of packing = HYFLUX Packings
(Evergreen Technologies Pvt. Ltd., Mumbai)
Catalyst Type: TULSIONR T- 63 MP (Cation Ion exchange resin, Thermax India Ltd.)
Operating Pressure= Atmospheric
Temperature = 373-423 K
Insulation: Asbestos rope
Digital Temperature Indicator: Total 8 points, Pt 100, Range: 0-300oC, Accuracy: 0.1o C
Peristaltic Pumps: 2 in Numbers (Range: 0.1 to 4 liters/hour)
Aspirator bottles (Feed Tanks): 2 in Nos, 10 liters (MOC: Borosilicate glass)
Glass Rotameters: For Acid and Alkali (0.1 4 liters/hours)
Reboiler: 2 Liter capacity with heating arrangement (2 KW)
Heating Mantle: 2 KW capacity
Wattmeter: Digital, Range 0-3 KW capacity
Condenser (Double surface) with Dean stark arrangement: (MOC: Borosilicate glass)
Teflon Disc: Total 6 in Nos.
Sampling valves: Total 6 in Nos.

3.4.6 Analysis Procedure:

The samples were analyzed using glass capillary column gas chromatograph attached with
mass spectrometer (GC, 5890-II, make HP). The results obtained by GC were confirmed by
independent titration using standard sodium hydroxide solution using phenolphthalein as
indicator.

3.4.7 Details of Experiments:

EXPERIMENTAL RUNS ON CONTINUOUS REACTIVE DISTILLATION COLUMN (RDC)

This section gives the experimental data generated during the course of experimental runs on
Continuous Reactive Distillation (CRD). The results given here are essentially in tabular
form since it is convenient to correlate the experimental results with modelling and
simulation studies results for RD column performance.

23
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

RUN # 5
Table 6 Details of the RD Experiment

Parameter Value
Feed Composition Acetic Acid = 400 ml
(Initial charged in the reboiler) Iso amyl alcohol = 600 ml
Column Pressure 1 atm
Reboiler Duty 1.2 kW
Feed Flow Rate 0.0525 kmol/hr
Feed Locations Acetic Acid on section 3 on RD column
(Below reactive zone)

Iso amyl alcohol on section 5 on RD column

(Above reactive zone)
Conversion Iso amyl acetate = 99.28%
Water = 99.95%
Purity of Product 98.1%

Table 7 Mole fractions of Water at steady state (Top Product)

Position/Section of RD Mole fractions of Water [-]

Column
1 0.00026
2 0.0017
3 0.013
4 0.099
5 0.12
6 0.055
7 Two Phase
8 0.3408
9 0.895

Table 8 Mole fractions of Iso amyl acetate at steady state

(Bottom Product)

Position/Section of RD Mole fractions of Iso amyl

Column acetate [-]
1 0.9835
2 0.9044
3 0.7509
4 0.675
5 0.645
6 05580
7 Two Phase
8 0.3716
9 0.0746

24
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

Table 9 Mole fractions of Iso amyl alcohol at steady state

(Reactant 1)

Position/Section of RD Mole fractions of Iso amyl

Column alcohol [-]
1 0
2 0
3 0.010
4 0.10
5 0.15
6 0.29
7 Two Phase
8 0.38
9 0.09

Table 10 Mole fractions of Acetic acid at steady state

(Reactant 2)

Position/Section of RD Mole fractions of Acetic acid [-]

Column
1 0.0021
2 0.15
3 0.24
4 0.28
5 0.32
6 0.042
7 Two Phase
8 0.08
9 0.096

Table 11 Steady State Temperature Profile in RD column

Position/Section of RD Column Temperature (oC)

Column
1(Bottom) 145
2 140
3 133
4 132
5 130
6 102
7(Top) 92

25
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

4. RESULTS AND DISCUSSIONS

4.1 Matlab Results

1.0

0.8

Mole Fraction
0.6 HOAC
ISAMOH
H2O
0.4
ISAMAC

0.2

0.0
2 4 6 8 10 12 14 16 18 20 22 24 26

Stage Number

Figure 23 Steady state composition profile (MATLAB)

4.2 Aspen plus Results

WATER

ISAMOH

RDCOLUMN

HOAC

ISAMAC

Figure 24 Process flow sheet for iso-amyl acetate synthesis

1.0

0.8
Mole Fraction (X)

HOAC
0.6
ISAMOH
H2O
0.4 ISAMAC

0.2

0.0
2 4 6 8 10 12 14 16 18 20 22 24 26 28

Stage No.

Figure 25 Steady state composition profile (Aspen plus)

26
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

160

150 0
Temperature C
140

Temperature, C
130

0
120

110

100

90

80
2 4 6 8 10 12 14 16 18 20 22 24 26 28

Stage No.

Figure 26 Steady state temperature profile

4.3 Model Validations: Comparison of Experimental results with Aspen Plus

(# RUN NO.5)

1.0

0.9

0.8

0.7
HOAC-Experiment
Mole fraction (x)

HOAC-Aspen Plus
0.6
ISAMOH-Experiment
ISAMOH-Aspen Plus
0.5 H2O-Experiment
H2O-Aspen plus
0.4 H ISAMC-Experiment
IISAMC-Aspen plus
0.3

0.2

0.1

0.0
2 4 6 8 10 12 14 16 18 20 22 24 26 28
Stage Number

Figure 27 Comparisons of Simulation and Experimental Results

(# Run 5) for Composition Profiles

160

140
Steady state temperature ( C )
0

120

100

80

Aspen Plus
60 Experiment

40
2 4 6 8 10 12 14 16 18 20 22 24 26 28
Stage number

Figure 28 Comparisons of Simulation and Experimental Results

(# Run 5) for Temperature Profiles

27
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

4.4 SENSITIVITY STUDIES RESULTS:

4.4.1 Effect of Boil up Ratio:

0.9998

0.9996

Purity of Product (Mole Fractions)

0.9994

0.9992

0.9990

0.9988

0.9986

0.9984

0.9982

0.9980

0.9978

0.9976
4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0
Boil up Ratio

Figure 29 Effect of Boil up Ratio on Purity

4.4.2 Effect of Reflux Ratio:
1.00

0.95
Purity of Product (Mole Fractions)

0.90

0.85

0.80

0.75

0.70

0.65

0.60

0.55

0.50
0.5 1.0 1.5 2.0 2.5
Reflux Ratio

Figure 30 Effect of Reflux Ratio on Purity

4.4.3 Effect of Feed stage location :( Iso amyl alcohol)

Reactive section: from stage 13 to 18

Best Location for Iso Amyl Alcohol: From Stage 18

1.00
0.95
0.90
0.85
0.80
Purity of Product

0.75
0.70
0.65
0.60
0.55
0.50
0.45
0.40
10 11 12 13 14 15 16 17 18 19 20 21 22 23 24
Feed Stage Location ( Iso Amyl Alcohol)

Figure 31 Effect of Feed Stage Location (Iso Amyl Alcohol) on Purity

28
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

4.4 Effect of Feed stage location :( Acetic Acid)

Reactive section: from stage 13 to 18
Best Location for Iso Amyl Alcohol: From Stage 13

1.0

Purity of Product ( Mole Fractions)

0.8

0.6

0.4

0.2

10 11 12 13 14 15 16 17 18 19 20 21 22 23 24
Feed Stage Location ( Acetic Acid)

Figure 32 Effect of Feed Stage Location (Acetic Acid) on Purity

4.4.5 Discussions and comments on Research Findings:

The typical temperature profiles for typical run are shown in figure 4.19. As can be seen from
the experimental results, conversion o 99.5% of isoamyl acetate, with iso amyl acetate
purities of 88.4 %was achieved. The extremely low concentration of water in the reactive
zone helps reaction to proceed near completion. The composition at position 7 is
compromises of two phases viz. organic and aqueous phase. In all the runs the temperature in
reactive zone is in the range 120-130 oC. Sufficiently high temperature ensure reaction to be
at the chemical equilibrium and driven by distillation. The temperature is below the limit set
by the thermal stability of the catalyst (135 0 C) (TULSION MP T-63, T-62 and T-66
catalyst, Thermax Ltd., India)

[1] Feed flow rate:

The residence time for the reactants inside the reactive zone is strongly influenced by the feed
flow rate. The experiments were performed for different feed flow rates over the range of 1 -3
lph. It was observed that better results were obtained at lower flow rates due to large
residence time offered under this condition.
[2] Reboiler duty:
In the present system, the relative proportions of organic phase and aqueous phase in the top
product decide reflux ratio and it is not a variable. The only operating variable that can make
significant impact on the separation and reaction is the boil-up rate. Hence, it was decided to
study the effect of boil-up rate on conversion over a wide range 0.8 1.7 KW for excess
alcohol in feed. It was observed that as a boil-up increase, the amount of alcohol, which is
excess in the feed, increases the conversion of top product. As anticipated, the time required
to attain the steady state was more for lower boil-up rate.

[3] Feed Location:

In the present work heavy reactant (isoamyl alcohol) is fed from the top of the reactive zone
and light reactant (acetic acid) is fed from bottom of the reactive zone. Thus provides
countercurrent flow of liquid and vapor in RD column.

29
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

[4] Mole ratio:

The experiments were carried out using different mole ratio of isoamyl alcohol and acetic
acid. It is observed that at higher mole ratio of isoamyl alcohol and acetic acid, conversion
and purity of product increases.

5. SCOPE FOR FUTURE WORK

The experimental results obtained in these studies were compared with equilibrium model
developed by us and simulation performed using Aspen Plus and MATLAB. However,
equilibrium model assumes phase equilibrium with incoming and outgoing streams.

In practical multicomponent multistage distillation operation, stages rarely operate at

equilibrium. Mass transfer in multicomponent mixtures is more complicated than that in
binary system because of the possible coupling between the individual concentration
gradients. Thus it will lead to the use of non-equilibrium model to replace the equilibrium
efficiency model for the modeling of the RD process. Non-equilibrium stage model is
rigorous but more realistic and involves additional effects due to mass transfer and heat
transfer.

The results obtained in these studies may be explained with the help of more realistic non-
equilibrium model. Once the model is validated, one can perform dynamic studies (through
both experiments and simulation) and propose a proper control strategy for RD operation.

6 CONCLUSION AND RECOMMENDATIONS

The experiments were carried out for the synthesis of iso amyl acetate using laboratory cum
pilot scale reactive distillation column to study the influence of various operating parameters
such as a feed flow rate, feed compositions, boil-up rate etc. on the conversion and
separation.

It was observed that as boil-up increases, the amount of iso amyl alcohol, which is excess in
the feed, increases in top product thereby improving the purity of the bottom product. As
anticipated, the time required to attain the steady state was more for lower boil-up rate. It can
be seen that though the conversion and purity levels were substantially high, better results
were obtained at lower flow rates due to large residence time offered under this condition.

It is observed that time required to attain steady state is reduced due to utilization of phase
separator arrangement, increase in condenser capacity, increase in heating mantle capacity in
the present experimental facility.

The equilibrium model for synthesis of iso amyl acetate was developed. The simulation
studies were performed in aspen plus and MATLAB. The Published experimental data on
phase equilibrium and reaction studies was used to verify the model predictions. The
experimental results were compared with model predictions and were found to be close to
those available in the literature.

30
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

Literature Cited

1) Santi Kulprathipanja, Reactive Separation Processes, Taylor & Francis Group, 2002
2) Taylor, R., R. Krishna, Modeling reactive distillation, Chem. Eng. Sci, 55, 2000, pp 5183-5229.
3) Harmsen, G. Jan, Reactive distillation: The front-runner of industrial process intensification. A full
review of commercial applications, research, scale-up, design and operation , Chemical Engineering
and Processing, 46 ,2007, pp 774780
4) Sundmacher, K., Kienle, A., Eds, Reactive Distillation-Status and Future Trends, Wiley-VCH: New
York, 2003.
5) Doherty, M.F.; Malone, M.F., Conceptual Design of Distillation Systems, McGraw Hill, New York,
2001.
6) Chiang S. F., Chien Lin Kuo, Cheng Ching Yu, D. S. H. Wong, Design alternative for the amyl acetate
process: coupled reactor/ column and reactive distillation, Ind. Eng. Chem. Res., 41, 2002, pp 3233-
3246.
7) Ajay Singh, Anand Tiwari, Sanjay M. Mahajani and Ravindra D. Gudi, Recovery of Acetic Acid from
Aqueous Solutions by Reactive Distillation, Ind. Eng. Chem. Res. 2006, 45,pp 2017-2025.
8) Teo, H. T. R., B. Saha and A. Alqahtani, iso-Amyl acetate synthesis by catalytic distillation,
International Journal of Chemical Reactor Engineering, 3, 2005,Article A11, pp 1-14.
9) Lee, M. J., Wu, H.T. and Lin, H-M, Kinetics of catalytic esterification of acetic acid and amyl alcohol
over Dowex, Industrial and Engineering Chemistry Research, 39,2000, pp 4094-4099.
10) Teo, H. T. R., and B. Saha, Heterogeneously catalyzed esterification of acetic acid with iso-amyl
alcohol: kinetic studies, Journal of Catalysis, 228, 2004,pp 174-182.
11) Malone, M.F., Doherty, M.F., Reactive Distillation, Ind. Eng. Chem. Res. 2000, 39, 3953-3957
12) Malone, M.F., Doherty, M.F., Huss, R.S., Green Chemical Engineering aspects of Reactive
Distillation, Environ. Sci. & Technol, 2000,
13) Almeida-Rivera, C.P., Swinkels, P.L.J., Grevink., Designing reactive distillation processes: present and
future, Computers and Chemical Engineering 2004),28,1997-2020
14) Sharma, M. M.; Mahajani, S. M. Industrial application of reactive distillation (A review). In Reactive
Distillation-status and future trends; Sundmacher, K., Kienle, A., Eds.; Wiley-VCH: New York, 2003;
pp 1-29 (ISBN 3-527-30579-3.
15) R. Krishnamurthy, R. Taylor, "A nonequilibrium stage model of multicomponent separation processes.
Part III: the influence of unequal component efficiencies in process design problems", AIChE J., 1985,
31, 1973-1985.
16) Hiwale, R. S.; Bhate, N. V.; Mahajani, Y, S.; Mahajani, S. M. Industrial Applications of Reactive
Distillation: Recent Trends. Ind. J. Chem. Reactor Eng. 2004, 2, R1.
17) Wan-Jen Hung, I-Kuan Lai Yi-Wei Chen, Shih-Bo Hung, Hsiao-Ping Huang, Ming-Jer Lee, and
Cheng-Ching Yu, Process Chemistry and Design Alternatives for Converting Dilute Acetic Acid to
Esters in Reactive Distillation, Ind. Eng. Chem. Res. 2006, 45, 1722-1733
18) Kloker et al., Influence of operating conditions and column configurations on the development of RD
columns with liquid- liquid separators, The Canadian Journal of Chemical Engineering, 2003, 81,725-
732
19) Wan-Jen Hung, I-Kuan Lai, Shih-Bo Hung, Hsiao-Ping Huang, Ming-Jer Lee, and Cheng-Ching Yu,
Control Of Reactive Distillation Columns For Amyl Acetate Production Using Dilute Acetic Acid,
Journal of the Chinese Institute of Engineers, 2006, Vol. 29, No. 2, pp. 319-335
20) Young-Tarang Tang, Yi-Wei Cheng, Huang, Yu, Design of Reactive Distillation for acetic acid
esterification, AIChE Journal, 2005, 51,6, 1683-1699
21) Chang et al., Design alternative for the amyl acetate process: coupled reactor/ column and reactive
distillation, Ind. Eng. Chem. Res., 2002, 41, 3233-3246
22) Saha et al., Production of Isoamyl acetate: Heterogeneous kinetics and techno feasibility evaluation for
catalytic distillation, International Journal of Chemical Reactor Engineering, 3, 2005, 30
23) Saha et al., Heterogeneous catalyzed esterification of acetic acid with iso-amyl alcohol: kinetic studies,
Journal of Catalysis, 2004, 228, 174-182
24) Li et al., Kinetics of esterification of acetic acid with amyl alcohol over Amberlyst 15, Journal of
Chemical Engineering Japan, 2001, 34,, 960-963
25) Bianchi, C. L., Ragaini, V., Pirola, C. and Carvoli, G., A new method to clean industrial water from
acetic acid via esterification, Applied Catalysis B: Environmental, 2003, 40, 93-99
26) Dhale, A.D., Myrant, L. K., Chopade, S. P., Jackson, J. E. and Miller, D. J., Propylene glycol and
ethylene glycol recovery from aqueous solution via reactive distillation, Chemical Engineering
Science 2004,59, 2881-2890

31
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

27) Gangadwaga, J., Mankar, S. and Mahajani, S., Esterification of acetic acid with butanol in the
presence of ion exchange resins as catalysts, Industrial and Engineering Chemistry Research 2003,42,
2146-2155
28) Ajay Singh, Anand Tiwari, Sanjay M. Mahajani and Ravindra D. Gudi, Recovery of Acetic Acid from
Aqueous Solutions by Reactive Distillation, Ind. Eng. Chem. Res. 2006, 45, 2017-2025
29) Lee, M. J., Wu, H-T. and Lin, H-M, Kinetics of catalytic esterification of acetic acid and amyl alcohol
over Dowex, Industrial and Engineering Chemistry Research, 2000,39, 4094-4099
30) Saha, B., Chopade, S. P. and Mahajani, S. M., Recovery of dilute acetic acid through esterification in
a reactive distillation column, Catalysis Today, 2000,60, 147-157
31) Ajay Singh, Anand Tiwari, S. M. Mahajani and R. D. Gudi, "Recovery of Acetic acid from Aqueous
Solutions by Reactive Distillation". Ind. Eng. Chem. Res. 45(6), 2006, 2017-2025
32) Talwalkar S., Chauhan M., Aghalayam P., Mahajani S., Qi Z. and Sundmacher K. Kinetics of
dimerisation of isobutylene in the presence of ion exchange resin catalyst, Chemical Engineering
Transactions, Vol.7, 213-216, 2005
33) Kamath, R., Qi Z., Sundmacher K., Aghalayam P., Mahajani S., Process Analysis of dimerisation of
isobutene in a reactive distillation column. Ind. Eng. Chem. Res., 2006, 45, 1575-1582
34) Ravindra S. Kamath, Zhiwen Qi, Kai Sundmacher, Preeti Aghalayam, and Sanjay M. Mahajani,
"Comparison of Reactive Distillation with Process Alternatives for the Isobutene Dimerization
Reaction" Ind. Engg. Chem. Res. 2006, 2707 2714
35) Katariya A., Moudgalya K. and Mahajani S., "Non-linear dynamic effects in reactive distillation for
synthesis of TAME", Ind. Eng. Chem. Res., 2006 in press
36) Teo, H. T. R. and Saha, B., Heterogeneously catalyzed esterification of acetic acid with iso-amyl
alcohol: kinetic studies, Journal of Catalysis, 228, 2004,174-182
37) Xu, Z. P. and Chuang, K. T., Kinetics of acetic acid esterification over ion exchange catalysts, The
Canadian Journal of Chemical Engineering, 1996,74, 493-500
38) A.Higler, Modeling Reactive Distillation, PhD. Thesis, Clarkson University, NY 1999
39) Sundmacher, K., Rihko, L. K., & Hoffmann, U., Classification of reactive distillation processes by
dimensionless numbers. Chemical Engineering Communication, 1994, 127, 151- 167.
40) Ung, S., & Doherty, M. F., Calculation of residue curve maps for mixtures with multiple equilibrium
chemical reactions. Industrial and Engineering Chemistry Research, 1995a, 34, 3195-3202.

32
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

Annexure 1
6 c Report of the work done

SUMMARY OF BCUD RESEARCH PROJECT

This project work mainly deals with synthesis of iso-amyl acetate via reactive distillation
(RD). In this project the experimental studies involved study of reaction kinetics, phase
equilibrium and continuous RD experiments on laboratory cum pilot scale.
Here is the brief summary of work done in connection with BCUD research Project:

[1] Modeling: Both EQ and NEQ (rate based model) were developed.
[2] Modeling and Simulation: both EQ and NEQ models were developed. EQ modeling
equations were solved using ODE 15 S solver in MATLAB and aspen plus were used to for
simulation work. Detailed results are available, which is used to compare our own
experimental results on Lab. RD column. The Published experimental data on phase
equilibrium and reaction studies was used to verify the model predictions. The experimental
results were compared with model predictions and were found to be close to those available
in the literature.
[3] VLE and Kinetics Studies: Approximately 32 experimental runs were performed in
batch reactor to study the effects of various parameters (such as type of catalyst, catalyst
loading, temperature, stirrer speed, mole ratio of reactants etc.) Comprehensive database is
available. Now I am developing kinetic models (such as PH, QH, LHHW, and ER). VLE data
generated in the lab is used to calculate BIP'S using NRTL model. This data is also used for
conceptual design studies (RCM, understanding the azeotrope behavior etc.)
[4] Batch RD Experiments: 7 runs were performed to obtain conversion expected in batch
operation mode. Conversion expected was typically in the range of 62-74%. The evidence of
low conversion was due to leakages and heat losses, which was corrected for continuous RD
experiments.

[5] Continuous RD Experiments: 10 experimental runs were performed, achieving

conversion of about 95% and product purity of 92.66 %. Still these results are not
encouraging and scope for further improvements.

[6] Modifications in continuous reactive Distillation experimental set up

Energy meter was purchased to vary the reboiler duty (reboiler duty= 2 KW for present set
up). In the present system, the relative proportions of organic phase and aqueous phase in the
top product decide reflux ratio and it is not a variable. The only operating variable that can
make significant impact on the separation and reaction is the boil-up rate. Hence, it was
decided to study the effect of boil-up rate on conversion over a wide range 0.8 1.7 KW for
excess alcohol in feed. It was observed that as boil-up increases, the amount of alcohol,
which is excess in the feed, increases the conversion of top product. As anticipated, the time
required to attain the steady state was more for lower boil-up rate.

The existing temperature sensors (Pt 100) were changed to new one with good resolution and
accuracy. The calibration of the electronic driven pumps and rotameters was done to ensure
constant flow to RD column. The typical parameters to vary in RDC are reboiler duty, feed
flow rate, feed locations, catalyst loading etc.

33
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

6 c (i) Brief Objectives of the Project:

The aspect considered in the proposal is to develop a methodology for design, simulation and
analysis of RD processes. There is a need for more rigorous experimental work with the
express purpose of model validation. Hence our main aim to develop experimental facilities
to study two-esterification test systems discussed above via RD. Control studies for kinetic
controlled processes are missing to a large extent in open literature for these test systems and
hence research is also focused to close this gap.

RD being a relatively new field, the research on various aspects such as modeling and
simulation, process synthesis, column hardware, non-linear dynamics and control etc. is in
progress. The suitability of RD for a particular reaction depends on various factors such as
volatilities of reactants and products, reaction and distillation temperatures etc. and hence, the
use of RD for every reaction may not be feasible.

A relatively wide focus was assumed for this research to permit significant contributions to
be made in several areas. In particular, an improved understanding of the behavior of hybrid
reactive distillation columns and associated design issues will help to reduce the technical
risk in developing this technology (especially locally) and experimental work will provide the
basis for further work which should clearly demonstrate that this technology is feasible and
profitable.

This research project was undertaken with the objective of making technical contributions to
the body of knowledge associated with synthesis of isoamyl acetate in hybrid reactive
distillation column in the following areas:
a) Development of effective modeling techniques for both steady state and dynamic
simulation of RD columns.
b) The understanding of obscure operating characteristics for RD.
c) Design strategy for hybrid RD
d) Development of simulation strategy using Aspen plus.
e) Generation of phase equilibrium and reaction kinetic data in the laboratory
f) Construction and testing of a lab-scale cum pilot scale RD column for Batch /
continuous RD operations
g) Examination of process parameters, including the operating temperatures, feeding
positions, feed flow rate, reboiler duty, catalyst loading.

6 c (ii) Publications:
a) Kiran Patil, Furquan Momin, Iso amyl acetate Synthesis via Reactive Distillation:
Simulation Studies, Presented in National Conference, NUCONE 2008, NIT,
Ahemadabad
b) Kiran Patil, Furquan Momin, Siddesh Phatare, Saloni Salvi, Process for the
Continuous Production of Iso Amyl Acetate via Reactive Distillation National
Conference, Presented in CHEMCON 2008, Indian Institute of Chemical Engineers,
Chandigad, 2008

c) Kiran Patil, Puneet Karan, Furquan Momin, Kinetics of synthesis of isoamyl acetate
synthesis using Ion Exchange Resign, Accepted in International Journal of
Chemical Reaction Engineering, 2008

34
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

d) Pradnya Baviskar, Kiran Patil, Puneet Karan, Production of fatty Acid Esters by
Reactive Distillation: Experimental studies, Communicated to Chemical and Process
Engineering, 2008

6 c (v) A summary of the work done for the period (Annual Basis):
Please refer to enclosed sheet for details.

6 c (vi) Summary of the findings of the study:

Please refer to enclosed sheet for details

6 c (vii) Any other information which would help in evaluation of work done on the
Project:
Preamble:
The Honble Vice-Chancellor has allocated budget to fund research projects to be undertaken
by the faculty pursuing research in various areas. The aim of the scheme is to strengthen the
research activity especially among the young faculty members, which will act as a catalyst
for them to apply to the various funding agencies for major grants.

The Principal Investigator (PI) received grant of Rs. 3.00 lakhs from BCUD, University of
Pune [Ref: BCUD/578, date 10/02/2007]. In addition, PI also received grant of Rs. 4.30 lakhs
[Ref. F.No.8023/BOR/RPS/-11/2006-07, Date: 26/02/2007] for his ongoing research work
leading to Ph. D degree in Chemical Engineering from University of Pune.

(a) Manpower Trained:

In this research project, nine undergraduate students worked, participated in AVISHKAR
2008 and in conferences. The details are as under:
Students working under this project:

Current Students (AY 2008-09)

1. Pradnya Baviskar, B.E. (Petrochemical)
2. Suyog Mahtre, B.E. (Petrochemical) Ongoing B.E. Project

1. Puneet Karan, TE. (Petrochemical)

2. Priyanka Kadam, TE. (Petrochemical
3. Sneha Daga, T.E. (Petrochemical)
4. Preshit Kulkarni, T.E. (Petrochemical)
Participated in AVISHKAR 2008
5. Atul Meshram, T.E. (Petrochemical)
6. Pearl Thomas, T.E. (Petrochemical)

Past Students: :( AY 2007-08)

1. Saloni Salvi (currently pursuing MS)

2. Furquan Momin (Now with PRAJ) Completed B.E. Project work in June 2008
3. Siddesh Pathare (currently pursuing MS)

35
 Prof. Kiran Patil, MAEERs, M.I.T., Pune-411 038

(b) Ph. D degree awarded:

The PI of this research project pursuing Doctorial research work under the guidance of Dr.
B.D. Kulkarni, Head and Dy. Director, Chemical and Process Engineering Division, National
Chemical Laboratory, Pune-411 008. He will be submit his Ph. D thesis within three months
to University of Pune [March 2009]

(c) Publication of results: Please see 6 c (ii) for publication arises from this project

a) Results from this project will be reported and published in various forms of
deliverables, e.g., journal papers, Conference/Professional presentations, technical
posters, and possibly patents.
b) Information will also be prepared for industry, and other sub-technical audience to
promote application of the resulted technology in commercial applications.
c) After studying in depth the technological flow sheet on laboratory cum pilot scale,
calculation of static operating parameters of technological flow sheet and operating
parameters for separates devices, dynamic simulation for separate devices and
technological flow sheet, preliminary economical estimation based in material and energy
balances and selection of monitoring system and automatic control for the target product
manufacturing, the technology developed by this research project may be introduced to
industry.
(d) Other Impact, If any:

1. The work to be performed under this research project and experienced gained is used for
exploring other complex reactive distillation processes, which are commercially
important.

2. This research work and facilities developed may be extended to UG and PG level
project work as part of the curriculum.
3. This research project is definitely enhancing the R & D activities in the department.
4. Student exposure to Laboratory cum Pilot scale experimental facilities for continuous
reactive distillation processes and latest software in Chemical Engineering field is
possible.
5. There is a possibility to generate funds for future Research/Consultancy Work.

36

View publication stats