Process Design and Modeling of Batch Reactors

Abstract

Chemical Industry is facing new challenges due to Increased Fuel / Feed Stock Cost, Reduced
Engineering Staff, Global Competitions, Short Product Life Cycle and Strict Environmental
Regulations. In face of these challenges, Innovation is critical for the on-going success of any
enterprise. Institutions that don’t innovate disappear. In order to continuously innovate new
process and technology, it is necessary to adapt modern tools that allow the engineers /
technologist to design, test, and implement the concept with rapid pace. Use of simulation and
computer added design software tools have proved to be very helpful in development of new
processes and technology.

In this article, case study has been presented for designing of batch reactor. This Case study
shows that simulation provides a convenient tool for scale up from laboratory data. The
significance of this can easily be visualized. Normal experiments may take 3-4 months, while a
process simulation can provide virtual plant results in a matter of 3-4 days. The product
development cycle time is greatly reduced which helps in bringing new products to the market in
lesser time

Introduction

Optimum Design of Process equipment not only contribute to capital cost saving, it also
contributes to reduced operating cost and trouble free plant operation. Process Simulation and
use of design tools avoids the uncertainty in the design and presents very clear picture of plant
performance even before the installation of the plant. It also helps in reducing the design and
process scale up time and helps in avoiding unnecessary experimentations and guessing. In the
present article, the design procedure of batch reactor using a commercial simulation program
has been illustrated through case study.

Design of Batch Reactor for Manufacturing N-Butyl Acetate

Problem Statement: N-Butyl acetate is to be manufactured by esterification of N-Butanol with

Acetic Acid in a batch process. In order to manufacture 2500 Kg per day, a suitable batch
reactor is to be designed. What size of the reactor will be optimum? What is the Batch time?
What is the optimum operating (Temperature, Pressure, RPM) condition?

Solution:

In order to be able to use the simulation, we must know the reaction chemistry with balanced
stochiometric equation. The reaction in this case is:

CH3CH2CH2CH2OH + HOOCH3C <==> CH3CH2CH2CH2OOCH3C + H2O

The esterification reaction is a reversible reaction.

The Design equation for Batch Reactor is:

dCA/dt = k1* CAa * CB b – k2 *CCc * Cdd ----------------------------------------------------(1)

Where

CA = Concentration of N – butanol
CB = Concentration of Acetic Acid
CC = Concentration of N-Butyl Acetate
CD = Concentration of Water
a, b, c, d are the Order of reaction w.r.t. to corresponding reactant or products
k1, k2 are the rate constants for the forward and reverse reactions.

Temperature Dependency of the reaction is given by Arrhenius Equation:

K = A* e –E/RT----------------------------------------------------------------------------------(2)

Where, A = Activation Energy, E = Frequency Factor, R = Gas Constant

The next step is to carry out lab experiment to generate the reaction kinetics data. For the
present case studies, following experimental data has been used which has been taken from
the published literature. The experiment was carried out in isothermal condition at two
temperatures and the molar concentration was recorded at various time intervals. The data has
been tabulated below which was used for regression to generate the kinetics.

Time Temp. Deg C N-Butanol Acetic Acid N-Butyl Acetate Water

0.00 90 11.00 0.00 0.00 0.00

0.16 90 10.20 1.00 0.80 0.80

0.33 90 8.70 1.50 2.20 2.20

0.50 90 7.50 2.00 3.49 3.49

0.66 90 6.40 2.65 4.65 4.65

1.00 90 4.50 4.50 6.50 6.50

Table 1 : Time vs Concentration Data for the Esterification Reaction at 90 Deg C

Time Temp. Deg C N-Butanol Acetic Acid N-Butyl Acetate Water

0.00 120 11.00 0.00 0.00 0.00

0.17 120 9.70 0.55 1.30 1.30

0.33 120 8.20 0.58 2.85 2.85

0.50 120 7.30 1.30 4.20 4.20

0.67 120 5.60 5.60 5.44 5.44

1.00 120 3.85 3.75 7.3 7.3

Table 2 : Time vs Concentration Data for the Esterification Reaction at 120 Deg C
 Fig 1 : Schematic for rate regression using Experimental Data

Following Table 1 and 2 shows the Regression Result generated using Chemstations software
suite CC Reacs

Temperature 90 Deg C
N-Butanol Acetic Acid N-Butyl Acetate
Time(hr) Experiment Calculated Error Experiment Calculated Error Experiment Calculated Error
0 1.10E+01 1.10E+01 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00
0.167 1.02E+01 1.02E+01 3.52E-03 1.00E+00 1.01E+00 -2.52E-03 8.00E-01 8.19E-01 -3.54E-03
0.333 8.70E+00 8.87E+00 -3.01E-02 1.50E+00 1.53E+00 -5.81E-03 2.20E+00 2.13E+00 1.19E-02
0.5 7.50E+00 7.55E+00 -8.24E-03 2.00E+00 2.05E+00 -8.22E-03 3.49E+00 3.45E+00 6.40E-03
0.667 6.40E+00 6.34E+00 1.16E-02 2.65E+00 2.67E+00 -3.52E-03 4.65E+00 4.66E+00 -2.54E-03
1 4.50E+00 4.37E+00 2.45E-02 4.50E+00 4.37E+00 2.45E-02 6.50E+00 6.63E+00 -2.45E-02

Table 3 : Regression Result of the Rate Parameters at 90 deg C

Temperature 120 Deg C

N-Butanol Acetic Acid N-Butyl Acetate
Time(hr) Experiment Calculated Error Experiment Calculated Error Experiment Calculated Error
0 1.10E+01 1.10E+01 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00
0.167 9.70E+00 9.73E+00 -4.99E-03 5.50E-01 5.60E-01 -1.85E-03 1.30E+00 1.27E+00 4.88E-03
0.333 8.20E+00 8.19E+00 2.35E-03 5.85E-01 8.53E-01 -4.87E-02 2.85E+00 2.81E+00 6.63E-03
0.5 7.30E+00 6.79E+00 9.21E-02 1.30E+00 1.29E+00 1.31E-03 4.20E+00 4.21E+00 -1.31E-03
0.667 5.60E+00 5.58E+00 2.91E-03 5.60E+00 1.92E+00 6.70E-01 5.44E+00 5.42E+00 4.25E-03
1 3.85E+00 3.75E+00 1.80E-02 3.75E+00 3.75E+00 -9.39E-05 7.30E+00 7.25E+00 9.18E-03

Table 4 : Regression Result of the Rate Parameters at 90 deg C

Average (Error)**2 = 0.00228837

Regression Result , SI units

Reaction Activation Energy Frequency Factor

Forward 3.64E+04 1.36E+05
Reverse 3.82E+04 4.64E+04

Table 5 : Kinetic Parameters for the Esterification Reaction

Now using above kinetic data of Activation Energy and Frequency Factor, Simulation was
carried out for various operating condition. The calculation involves following steps at each time
interval to determine concentration changes in the reactor

1. Calculate the Reactor temperature: This requires determining unsteady state heat transfer
coefficient.

Q = U * A * ∆ T--------------------------------------------------------------------------(3)

U = 1 / (1/hi + fi + xw/kw + fo + 1/ho)---------------------------------------------(4)

Where

hi = Film coefficient inside the reactor wall

ho = Film coefficient out side the reactor wall ( jacket side )
fi = Reactor side fouling factor
fo = Jacket side fouling factor
xw = Reactor wall thickness
kw = Reactor Material Thermal Conductivity
∆T = the temperature difference between the reactor inside temperature
and the bulk of the jacket fluid temperature.
hi is calculated using the Sider Tate equation given below:

Nu = f * Re * Pr
a b
µ
*( b/ µ c
w ) --------------------------------------------------------(5)

Nu (Nusselt Number) = hi * D / k

hi = heat transfer coefficient

Re (Reynolds Number) of agitation is calculated using the impeller speed (Re = n D

2
ρ
/µ )
Pr is the prandtl Number given by Cp µ /k

µ b and µ w are the Viscosities of the reaction mixture at the bulk temperature and
Reactor inside wall temp.

f, a, b, c are geometrical constants for the given type of impeller. Typical values for
various type of impeller are given in the table 6:

Agitator Type f a b c Range

Impeller 0.33 0.667 1/3 0.14 2X104 <Re<2X106

Anchor 0.55 0.667 ¼ 0.14 5X103 <Re<4X104
ONE
Turbine ( 6 Blades) 0.44 0.667 1/3 0.24 200<Re<1000
PIECE
Loop 0.36 0.667 1/3 0.14 300 <Re<4X104

CBT Turbine 0.48 0.667 1/3 0.14 2X104 <Re<2X106

FBT Turbine 0.69 0.667 1/3 0.14 4X102 <Re<3X105
YRO LOCK PBT Turbine 0.62 0.667 1/3 0.14 3X102 <Re<3X105
Turbofoil 0.55 0.667 1/3 0.14 1X103 <Re<1X106

Table 6 : Typical Agitator Constants in the Seider Tate Equation

Jacket side film coefficient ho depends on type of heating / cooling fluid, Type of Heat
Transfer Surface (jacket with or without mixing nozzles, external half coil, internal coil ).
Typical values in MKS units are given below in table 7:

Heating / Cooling Fluid Typical ho in Kcal/hr-m2-oC

Steam 7200 – 7300
Water 2400 – 2500
Thermic Fluid 1200 – 1250
Glycol / water Mix 120 - 150

Table 7 : Typical Jacket Side Film Coefficient

2. Calculate the Rate Constant k for the forward and reverse reaction using the
Arrhenius equation k = A* e –E/RT . Frequency Factor A and Activation Energy E is
known from the regression of experimental data for these reactions.
3. Solve the differential equation 1 using numerical method and a material balance to
determine the composition in side the reactor.

4. Finally do a Flash calculation of the calculated composition and temperature /

pressure conditions.

Above step 1 to 4 must be repeated for incremental scale for entire batch time. It
becomes very tedious if manual calculation is done. Simulation is necessary to achieve
stable and reproducible operating conditions for desired product purity, yield and batch
cycle time. The simulation result and design summary generated using Chemcad
Software is summarized below for two different process scheme. Since the reaction is
reversible, it is necessary to remove the water generated during the reaction in order to
shift the equilibrium in forward direction.

Fig 2 : Scheme 1 for the Butyl Acetate Process

Fig 3 : Scheme 2 for the Butyl Acetate Process

The Result of simulation is summarized in the table below:

Reactor volume m3 2.50 Reactor diameter m 1.56

Base volume m3 0.41 Wall thickness m 0.02
Base area m2 2.53 Wall cp kcal/kg-C 0.096
Impeller speed Hz 1.50 Impeller speed Hz 1.50
Wall therm. cond. 7.68 Coefficient b 0.33
(kcal/h-m-C)
Impeller diameter m 0.55 Coefficient f 0.33
Coefficient a 0.67 Wall thickness m 0.020
Coefficient c 0.1400 Jacket total vol. m3 0.3780
Amin, Min area m2 2.5344 Jacket height m 1.1469
Vmin, Min volume m3 0.4096 Amax, Max area m2 8.3000
Jacket annulus m 0.0380 Vmax, Max volume m3 2.5000
Jacket height m 1.1469 Inlet diameter m 0.0380
Jacket total vol. m3 0.3780 No. of nozzles 2
 Time vs Compostion in the Reactor
905

805

705

605
Mass in Kg

N Butanol
505
Acetic Acid
N-Butyl Acetate
405 Water

305

205

105

5
0 50 100 150 200 250 300 350
Time in Minute

Fig 1 : Composition of Reactor Content For Scheme 1

 Reactor Temp.

120

100

80
Temp. Deg C

60 Reactor Temp.

40

20

0
0 50 100 150 200 250 300 350
Time , Minute

Fig 5 : Time vs. Reactor Temperature for Scheme 1.

1000

900

800

700

600 N-Butanol
Acetic Acid
500
N-Butyl Acetate
400 Series4

300

200

100

0
0 100 200 300 400 500

Fig 6 : Composition of Reactor Content for Scheme 2

 140
Reactor Temp

120

100
Temp. Deg C

80

60 Reactor Temp

40

20

0
0 100 200 300 400 500 600
Time Minutes

Fig 7 : Time vs Reactor Temp. For Scheme 2

It is obvious from the plots that using a distillation column helps in improving the purity because
of better water removal from the system compared to using only a decanter. As more water is
removed from the reactor, equilibrium shifts to forward direction, resulting in more conversion.
A distillation column with 4 ideal stage would be sufficient for this batch size.

Conclusion: Process design of batch reactor using Simulation helps in accurately predicting
the conversion, temperature, heat duties and over all performance of the reactor. Scale up from
Lab data to commercial production can be quickly done. Kinetics information generated using
regression can be used for leveraging corporate knowledge and technology transfer. Simulation
also helps in control scheme design and Reaction Condition Optimization.

References:

1. J.E. Edward, Dynamic Modeling of Batch Reactor and Batch Distillation, UK Chemcad
Seminar 2000 (available as down load from website: www.pidesign.co.uk )
2. R.H. Perry and D Green, Chemical Engineers Hand Book , 6th Edition, McGraw Hill, 1984

3. CCR Training Manual, Chemstations Inc. USA ( www.chemstaions.net )