Application Note Heat Transport in Agitated Vessels

Estimating the Heat Transfer Coefficient

Authors: S .Choudhury, L. Utiger, R. Riesen, U. Groth, METTLER TOLEDO

Batch or semi-batch reactors represent an important means of production in the chemical

and pharmaceutical industry. Scaling a process from lab to plant is a challenging process
and is associated with numerous issues, such as heat transfer, cooling capacity, reactant
accumulation, mixing, mass transfer and many more. While personal experience and
empirical data can be used to a certain extent, the investigation of chemical processes
requires the involvement of a number of disciplines, such as characterization of the equip-
ment, the exploration of the thermodynamics, and mixing and mass transfer studies, as
well as the research of the reaction kinetics and the hazardous potential.

Heat dissipation in a stirred tank reactor is decisive for the safety and efficiency of a process,
and production times are often determined by the heat transport. If thermal resistances
and reaction rates are only approximately known, then large safety margins must be applied.
This results in an increase in batch times, and lowers the productivity of the particular
process significantly. It is therefore of particular interest to use scale-up models to predict
or simulate heat transfer conditions in the plant reactor as accurately as possible. Empirical
correlations with characteristic values are used to simplify complicated differential equations
describing the system. The use of the METTLER TOLEDO Reaction Calorimeter allows
accurate measurement of the thermal resistances and the heat evolved from reactions in
the laboratory.

Contents
1 Heat Transfer Through the Reactor Wall
Wilson Method
Example for a Wilson Plot Experiment Using the RC1e
Reaction Calorimeter
2 Case Study
Doubling a Plant's Production Capacity
3 Case Study Conclusions
4 References
 1 Heat Transfer Through the Reactor Wall
Application Note

Heat transfer is impacted by the reaction mass and its physical properties as well mechanical properties such
as the stirring speed and the reactor material. The overall heat transfer coefficient (U) consists of three individual
resistances, the reactor-side film (h r), the reactor wall (dw/), and the oil-side film (h j ).

The heat transfer can be described

Tr dw Tj as follows:
1/U = 1/h r + dw/+ 1/h j (eq. 1)

U overall heat transfer coefficient

Tr
h r heat transfer coefficient
due to reactor-side film
(reaction mass side)
T (C) film (hr) film (hj) h j heat transfer coefficient
due to the oil-side film
Tj
(cooling media side)
dw l (mm) thermal conductivity of
the reactor wall
dw thickness of the reactor wall
Figure 1: Description of the temperature profile (thermal resistances) in the laboratory reactor

While the reactor wall (dw) and the oil-side film (h j ) depend on the reactor design and the heat exchange system,
the reactor-side film (h r) depends on the properties of the reaction mass (e.g. thermal conductivity, density,
viscosity, etc.), the stirring speed, and the temperature.

In many cases, the thermal resistances of the cooling medium and the reactor wall in the plant reactor are
known from earlier measurements or from the suppliers of the equipment. The heat transfer of the reactor-side film
can be calculated from the overall resistance U by the Wilson method[3], initially developed for heat exchangers.
With a slight modification it can also be applied to agitated vessels. The overall coefficient U of a lab reactor is
measured using a METTLER TOLEDO Reaction Calorimeter.

Wilson Method
For the purpose of simplification, the thermal resistance of the wall and the cooling medium in equation 1 can
be grouped in the term (resistance due to the apparatus), and the term hr, describing the reactor side
resistance. For the same heat transfer, fluid at a constant velocity the term only depends on temperature.
1/U = + 1/h r (eq. 2)

2 Application Note
METTLERTOLEDO
For a specific reaction mass, the heat transfer coefficient depends exclusively on the stirring speed, the
temperature, and the viscosity. Uhl et al.[4] used the following dependency based on the ratio of the speed N
to a reference speed N 0:
1/hr = (N/N 0)-2/3 (eq. 3)

The intercept and the slope are obtained from measurements of the overall thermal resistance U of a
defined reaction mass at constant temperature and varying agitation speeds. Combining equations 2 and 3,
and subsequently plotting 1/U against (N/N0)-2/3, leads to the Wilson plot.

1/U = + (N/N 0)-2/3 (eq. 4)

1/U
1/hr

(Tr)

N (N/NO)-2/3
Figure 2: Wilson Plot

What information can be gained from the slope of the Wilson plot?
Essentially, the slope can be interpreted as a function of the reactor film coefficient, depending on the reactor
geometry, the material data of the respective reaction mass, and the constant and can be expressed as:
= ( V Z)-1
(eq. 5)

In the above equation, V and Z are the characteristics of the reaction mass and the reactor respectively, while
is the reactor constant. In essence, the material characteristic V depends on the physical properties of the reaction
medium, and is defined according to the following equation:
V = (cp g 2 2 -1)1/3
(eq. 6)

The vessel number Z is a dimensionless number that depends solely on the reactor geometry.
Z = (d4 N 0 2 g-1 D-1)1/3
(eq. 7)

As the heat transfer due to reaction mass (hr) is included in the slope of the Wilson plot equation, it can be
calculated based on the following equation:
1/h r = (N/N 0)-2/3 (eq. 3) hr = V Z (N/N 0)-2/3
(eq. 8)

The reactor constant of the lab reactor can be derived from equation 5. However, detailed information about
the Wilson plot and its theory can be obtained from the literature referred to at the end of the paper.

Application Note
METTLERTOLEDO
3
 Example for a Wilson Plot Experiment Using the RC1e
Application Note
Reaction Calorimeter
While the Wilson plot can be determined with either the RC1e or the OptiMax HFCal Reaction Calorimeter, the
present example is carried out in an RC1e with an MP10 medium pressure reactor. To study the impact of the
stirring speed on the overall heat transfer coefficient, an experiment was carried out with a series of different stirrer
speeds each followed by a calibration. The calculated heat transfer coefficients were subsequently plotted as U-1
vs. N -2/3 to obtain the Wilson plot. The experimental setup consisted of a standard RC1e Reaction Calorimeter and
a glass reactor fitted with an anchor stirrer, calibration heater, and baffles.

dw
D

hs
Reactor Specifications
Reactor type MP10
Reactor data D = 82 mm dw = 9 mm
Stirrer data d = 75 mm hs = 81 mm
Figure 3: Reactor geometry Table 1: Reactor specifications

The sequences of the entire experiment were pre-programmed and executed, unattended, overnight. During the
experiment, the data was captured continuously and evaluated upon completion of the experiment automatically.
With agitation steps of 25 rpm each between the measurements, the stirring speed dependency of the heat
transfer coefficient was determined in the interval from 75 rpm to 250 rpm. As the calculation of the heat transfer,
coefficient U requires the heat exchange area to be known; the virtual volume was determined and recorded
multiple times during the experiment.

The heat transfer coefficient is calculated from calibrations, during which a well-defined amount of energy is
supplied to the reaction mass by a calibration heater under isothermal conditions. As there are no other heat flows
except the one from the electrical heater, the heat transfer coefficient can be calculated as follows:
q c = qflow = U A (Tr-Ta)
(eq. 10)
U = q c dt / A (Tr-Ta) dt
(eq. 11)

The heat exchange area used are Stirrer Speed UA Virtual Volume Area U
calculated from the virtual volume [min-1] [W/K] [L] [m2] [W/m2K]
and the reactor geometry. Finally, the 75 3.405 0.664 0.0357 95.5
results of the heat transfer measure- 100 3.564 0.667 0.0358 99.0
ments are summarized in Table 2. 125 3.675 0.675 0.0362 101.5
150 3.800 0.687 0.0368 103.3
175 3.899 0.699 0.0374 104.4
200 3.976 0.707 0.0378 105.3
225 4.079 0.723 0.0386 105.8
250 4.267 0.755 0.0401 106.4
Table 2: Heat transfer coefficients of toluene determined in an MP10 glass reactor with
anchor stirrer

4 Application Note
METTLERTOLEDO
With these results, the Wilson plot can be created, and the slope as well as the intercept can be
determined (Figure 4).

0.0106

0.0104

0.0102

0.01
1/U

0.0098

0.0096

0.0094
Results of Wilson Plot

0.0092 Slope 0.00222 m2 K/W

Intercept (30 C) 0.00851 m2 K/W
0.35 0.45 0.55 0.65 0.75 0.85 0.95
(N/NO)-2/3
Figure 4: Wilson plot of toluene determined in an MP10 glass reactor with anchor stirrer

From the known material and reactor data, the values for V and Z can be calculated as described in equations
7 and 8.

Material Properties
Substance Specific heat capacity Density Viscosity Thermal conductivity
[J/kg K] [kg/m3] [Pa s] [W/m K]
Toluene 1760 850 0.000526 0.139

These are used to compute the constant (eq. 5), which is constant for Vessel number Z 0.180
Material characteristics V 7641 W/m2 K
a specific reactor setup and only differs within the experimental error.
Reactor constant 0.326
For toluene and the described setup, the following values are received:

Finally, the reactor-side heat transfer coefficient is calculated from the constant , the vessel number Z of the
laboratory reactor, and the material characteristic V of the reaction mixture. Assuming a stirrer speed of 150 rpm,
it results in h r = 828.5 W/m2 K.

Understanding the reactor side coefficient of the lab reactor, there are several possibilities to estimate the heat
transfer coefficient of the plant reactor. One is basically using the material properties, while another one is based
on the geometrical similarity between the lab and plant reactor. Details are also found in the literature references
at the end of the article.

Webinar on Demand
Applications of Reaction Calorimetry in the Chemical Process Industry
Moderator: Reinaldo M. Machado (RM2 Technologies, LLC)
www.mt.com/Rxn-Calorimetry-Webinar

Application Note
METTLERTOLEDO
5
 2 Case Study
Application Note

Doubling a Plant's Production Capacity

A new plant with double the capacity is planned for a production process in the pharmaceutical intermediates
sector. Due to the sensitive nature of the process and for safety reasons, the simplest solution is adding an addi-
tional reactor in parallel, and using the current process. However, this would require high investment costs. A
reaction calorimetry study was undertaken using an RC1e to investigate the feasibility and acceptability of simply
increasing the batch size. The process in question was a discontinuous two-stage synthesis performed in an
agitated vessel. Both stages were set up as semi-batch processes. The first stage involved generation of the cata-
lyst needed for a dimerization reaction in the second stage. In what follows the critical second stage, which
exhibits complex kinetics, will be described.

In the dimerization, the reaction mass must be maintained at a temperature sufficiently above the solidification
point of approximately 0 C to ensure that no solid collects at the reactor wall and reduces the cooling effective-
ness. At only a slightly higher temperature, however, a strongly exothermic consecutive reaction is initiated. Above
20 C process runaway occurs in the plant reactor. Figure 5 shows the heat flow curve obtained with the RC1e
when running the existing process. The monomer is added in two lots. The product accumulates as a crystalline
suspension.

Heat Generation Rate

20
Seeding
Watt

10

0:00:00 0:20:00 0:40:00 1:00:00 1:20:00 1:40:00 2:00:00

Time (h:m:s)

Dosing 1 Dosing 2
Figure 5: Heat generation curve of the dimerization using the existing method (RC1e experiment at Tr = 8 C)

To increase the productivity in the same plant, either the reaction rate or the concentration had to be increased.
Therefore, the dependence of the heat output of the dimerization on the dosing rate, the concentration, and the
reaction temperature was measured.

6 Application Note
METTLERTOLEDO
 Heat Generation Rate Figure 6 shows the progress of the reaction with
100 increased concentration at different reaction tempera-
20 C tures. The increase in the area under the reaction
90
peak with increasing temperature signifies the growing
80 influence of the undesired side reaction. These results
15 C
were used to derive a process strategy, in which the
70
reaction mass is kept at a constant temperature of
60
8 C through controlled dosing of the monomer and
maximum cooling. The data acquired with the RC1e
50 8 C allowed a survey of the heat exchange of the entire
process.
40
Watt

30 A heat balancing was then performed, incorporating

the data measured using the plant reactor (heat
20
transfer, cooling capacity). This demonstrated that
10 with optimum combination of the process parameters,
the planned doubling of the batch could safely be
0
implemented with the available cooling power.
0:00:00 1:00:00 2:00:00 3:00:00
Time (h:m:s)
Dosing
Figure 6: Heat flow trends at various temperatures measured under
isothermal conditions

The thermal resistance of the reaction mass at the reactor wall was determined in the RC1e using the
Wilson method:
Material-dependent component of heat transfer: V = 2700 W/m2 K

Heat transfer coefficient of inner film in the RC1e: h rL = 315 W/m2 K

When known factors for the apparatus are incorporated, the following values for the production unit resulted:
Heat transfer coefficient of inner film in the plant reactor: h rB = 380 W/m2 K

Overall heat transfer coefficient (U value): UB = 185 W/m2 K

From the evolved heat and the available
be calculated:
Heat of reaction: H r = 570,280 kJ
Temperature gradient: Tr-Ta = 20 K
Cooling area: A = 8 m2
cooling power, the admissible dosing time for production could
Heat of dosing (higher temperature of dosed material):
Q dos = 35,000 kJ
Cooling power: q cool = 30 kW
Dosing time: t dos = 5 h 20 min

3 Case Study Conclusions

The required increase in capacity could be safely realized by doubling the production batch size in the original
plant unit. The planned high capital investment could be avoided while the safety of the process was improved
by more efficient design and experimental testing of the emergency measures required in case of malfunction.

Application Note
METTLERTOLEDO
7
 4 References List
Application Note

[1] Newton, I.; Phil. Trans. Roy. Soc. 22, 824 (1701)
[2] Chilton, T.H., Drew, T.B., Jebens, R.H.; Ind. Eng. Chem. 36 510 (1944)
[3] Wilson, E.E.; Trans. Am. Soc. Mech. Engrs. 37 47 (1915)
[4] Uhl, V.W., Gray, J.B.; Mixing, Theory and Practice, Vol. 1, Academic Press (1966), Chapter 3.5
[5] Perry, J.H.; Chemical Engineers Handbook, 5 Edition 1973
[6] VDI-Wrmeatlas 2. Auflage 1974
[7] Brli, M.; berprfung einer neuen Methode zur Voraussage des Wrmeberganges in Rhrkesseln,
PhD Thesis ETH Zrich No 6479, (1977)
[8] Metzner, A.B., Otto, R.E.; AIChE Journal 3 3 (1957)
[9] Handbook of Chemistry and Physics, 66 Edition, CRC-Press, Florida 1985
[10] Post, Th.; Geometrical Influences on Local and Total Mass and Heat Transfer in an Agitated Tank,
PhD Thesis ETH Zrich No 7249 (1983)
[11] Bourne, J.R.; Chem. Eng. Sci., 202 (1964)
[12] Metzner, A.B., Taylor, J.S.; AlChE Journal, 6 109 (1969)
[13] Pollard, J., Kantyka, T.A.; Trans. lnst. Chem. Engrs. 47 21 (1969)
[14] Calderbank, P.H., Moo-Young, M.B.; Trans. lnst. Chem. Engrs. 39 338 (1961 )
[15] Drichen, K.; Chem. lng. Tech. 46, Heft 7 (1974)
[16] Kwasniak, J.; Verfahrenstechnik, 7 287 (1973)
[17] Sieder, E.N., Tate, G.E.; Ind. and Eng. Chem. 28 1429 (1936)
[18] Gautschi, W.; Estimating Parameters from Heatflow Measurement, PhD Thesis ETH Zrich
No 5652 (1976) in German

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