# Chemical

Engineering Science

PERGAMON Chemical Engineering Science 54 (1999) 1499-1504

Mass transfer and kinetics in ethoxylation

spray tower loop reactors

E. Santacesaria, M. Di Serio, P. Iengo

Dipartimento di Chimica, Universita di Napoli "Federico II", via Mezzocannone, 4 (80134) Napoli, Italy

Abstract - A mathematical model has been developed for describing the behaviour of the spray tower loop reactors.

Th reactors are characterised by the fact that mass transfer and reaction occurs independently in two distinct zone of

the reactor. The model has been used for simulating the performance of a pilot plant both by assuming liquid drops

internally stagnant and turbulent. The last assumption gives the better results. © 1999 Elsevier Science Ltd. All

rights reserved.

Keywords: Spray reactors, Ethoxylation, Mass transfer, Kinetics

INTRODUCTION

Ethoxylation is performed in industry for producing

surfactants and polyglycols. The reaction is normally

promoted by alkaline catalyst (NaOH, KOH) and is

performed in gas-liquid well-mixed reactors, Venturi

loop reactors and spray tower loop reactors.

. In the fIrst two types of reactors the gas phase is

dispersed into the liquid phase; on the contrary, in the

last case, the liquid phase is dispersed in the gaseous

one.

Kinetics and mass transfer models for simulating the

performances of well stirred gas-liquid reactors are

reported in the literature (Di Serio et a!., 1995). A model

to describe the behaviour of well stirred spray reactor has

also been published (Hall and Agrawal ,1990). On the

contrary very few paper have been published on the use

of Venturi loop reactor and spray tower loop reactor

(Santacesaria et al. 1995).

In the present paper the ethoxylation performed in spray

tower loop reactors is studied and a model able to

simulate the behaviour of these reactors is reported.

A MATHEMATICAL MODEL TO DESCRIBE

SPRAY TOWER LOOP REACTOR

PERFORMANCES

A scheme of a spray tower loop reactor is reported in

Fig. 1. As it can be seen, reacting liquid, containing the

catalyst, is sprayed in an atmosphere of gaseous ethylene

oxide (EO). Small drops of liquid are formed and are

promptly saturated of the gaseous reagent.

For small drops the flight times are normally enough for

achieving saturation of ethylene oxide, but are negligible

for the occurrence of the reaction (Di Serio et a!., 1995;

Santacesaria et a!., 1995). The reaction occurs in the

liquid phase and ethylene oxide is consumed, more or

less, from the top to the bottom of the liquid column,

according to the recirculating feed rate. Therefore, we

can recognize that in this type of reactors, mass transfer

and chemical reaction occur independently in two

different zones of the reactor.

.I

-I ~ : ~ - 1 .

----

EO

~ ,

- - I

ex

_'_ _ _ J_

I r

I

roo ......

I xm

h*

Qj

Cl

c:

I

co

rm h ~

cu

(;j

v---- --

cu

.c:

'--r--

hi

... I'

Fig. 1 Spray tower loop reactor scheme

The reaction is exothermic and the temperature of the

liquid column increases from the top to the bottom. An

heat exchanger cools the liquid stream before the

injection in the spray nozzle, placed at the top of the

mass transfer zone, as it can be seen in Fig. 1

Description of the Mass Transfer zone

The mean concentration of EO in the falling drops at

the end of the flight (C\o), can be calculated by

integrating the following equation:

(1)

0009-2509/99/$-see front matter © 1999 Elsevier Science Ltd. All rights reserved.

1500 E. Santacesaria et al.lChemical Engineering Science 54 (1999) 1499-1504

from 0 to the average flight time (ttin).

To solve this equation the following data must be

known: (i) the equilibrium solubility of EO (C*EO); (ii)

the average specific surface of the drops (aim); (iii) the

average flight time (iv) the average mass transfer

coefficient (v) the concentration of EO in the

sprayed liquid (c

B

EO)'

Let us consider now each point:

(i)The value of the equilibrium EO solubility (C*Eo)

depends on the temperature, pressure and liquid

composition[1 ].

The solubility of EO in respectively nonylphenol,

dodeacanol, dodecanoic acid and their ethoxylated

oligomers with different number of EO adducts shows a

high non - ideal behaviour (Di Serio et aI., 1995;

Santacesaria et al., 1995).

By comparing different methods for calculating activity

coefficients such as: UNIF AC (Fredeslund et al., 1977) ,

NRTL (Renon and Prausnitz, 1968) and Wilson (Wilson,

1964), Di Serio et al. (1995) observed that Wilson

method was the best one for the description of EO

solubility in binary and multicomponent mixtures.

The Wilson parameters resulted dependent in a simple

way on the mean number of EO adduct in the EO-

oligomers mixtures and independent of the temperature.

In same case also UIFAC gives satisfactory results (Di

Serio et aI, 1996) and is commonly used when

experimental data of solubility are not available.

A correct determination of EO solubility is very

important for a correct evaluation of both mass transfer

and kinetics of the ethoxylation reaction, as it has been

stressed in a recently published paper (Di Serio et al.,

1995; Santacesaria et al., 1995).

(ii) The average interfacial surface area drops is

calculated as:

Surface area of drops

a, =

m Volume of drops

"I 3 - n.d.

6 . I I

I

Where d32 is the Sauter diameter defmed as

d

32

= Ln;d; ILn;d;2

I

(2)

The overall surface area of the flying drops can be

calculated as:

(3)

Sauter diameter can nonnally be estimated

experimentally by a Laser scattering technique. Water is

nonnally used in the experiments. The Sauter diameter

obtained for water can be converted in the Sauter

diameter of other sprayed liquids by using the following

relation (Perry and Green, 1984):

d)2 =

(d)2 )wa .. ,

(4)

The Sauter diameter have been assumed as average

drops diameter in the calculus of the average flight time

and the average kim, too.

In Fig. 2 an example of drop size distribution measured

with the laser scattering technique for a spray nozzle

with a cone angle of 90° is reported. The Sauter mean

diameter for the reported distribution is 21 0

1400

100 200 300 400 500

dlame18r !11m)

Fig.2 Typical distribution of the drop size ofa spray

nozzle with a cone angle of 90°

The given distribution has been determined just in a

small volume of the spray cone, but this distribution

does not change very much by changing the position of

the volume sample. This means that coalescence has a

small effect on the drop distribution size.

(iii) The average flight time is a function of the initial

drops velocity and of the average path of the drops

(x

m

),

The average path of the sprayed drops, for a cylindrical

reactor depends on: the distance of the liquid level from

the spray (h*); the angle of cone of drops (n); the

radius of the reactor (r). By assuming that all the

possible path have the same probability, the following,

the following general relation can be obtained:

(5)

Where

(6)

(7)

E. Santacesaria et al.lChemical Engineering Science 54 ( 1999) 1499-1504

(8)

All the mentioned geometrical quantities are reported in

the scheme of Fig. 1.

The average flight time can be calculated by integrating

the following equation corresponding to the uniformly

accelerated motion applied to the flying drops:

where Co is the friction coefficient (Foust et aI., 1967)

and Vo is the initial drops velocity corresponding to:

(10)

where, M is the pressure drop across the nozzle(Perry

and Green, 1984).

(iv) In order to predict the average mass-transfer

coefficient we have to know if the drops are internally

stagnant or well mixed.

For internally stagnant drops the problem has been faced

by Crank (1958) that given an analitical solution for the

relation:

oC;o =D [02C;0 + ~ OC;o] (11)

at EO or} rd or

d

Describing the evolution with concentration profile of

the gas adsorbing molecules in a liquid drop of spherical

shape. The profile for each time t can be calculated with

the relation

the mean concentration of EO in the drops at the end of

the flight time tm. can be calculated with the relation:

(13)

The average mass-transfer coefficient for stagnant

drops falling in a continuos phase can be calculated

using the Johnson et al. (1958) correlation:

The prediction of mass transfer coefficient in a

turbulent or well-mixed phase will depend on the

quantitative description of the fluid dynamic of the

phase that is a problem not completely solved.

Srinivasan and Aiken (1988) have shown that to

describe the mass transfer for internally well mixed

drops the Levich theory developed for describing the

mass transfer into a turbulent liquid can be applied.

From this theory they have derived a correlation useful

to predict the mass transfer coefficient for well mixed

drops falling in a continuos phase:

(v) The value of C

B

EO

corresponds to the EO

concentration at the bottom of the liquid column and

must be calculated by an appropriate kinetic model

applied to the reaction zone. This aspect will be

examined in detail in the next section.

Description of the reaction zone

The drops saturated with EO fall on the liquid surface

forming a layer that begins to react and moves toward

the bottom of reactor.

The EO concentration profile along the liquid column

can be calculated together with the temperature profile,

by assuming as a first approximation a plug-flow

behaviour and by integrating the equations of mass and

heat balance from the top of liquid column (z=O) to the

bottom (z=h\). The assumption of a plug flow

behaviour is justified by the observation that the

difference of temperature between the top and the

bottom of the liquid column is relatively small, that is

about lOOC. Therefore, free convection circulation

should be moderate. On the other hand, as the

conversion of ethylene oxide in the liquid column is

relatively low (about 30%) the assumption of more

complicated model does not bring to very different

conclusion.

Besides, by assuming a pseudo steady-state condition

for the mentioned profiles, the mass and the heat

balance can be expressed with the following ordinary

differential equations:

1501

1502 E. Santacesaria et al.lChemical Engineering Science 54 (1999) 1499-1504

dCEO 41Z1"2

--=---r

dz Q/ EO

(16)

dT Ml dCEO

-=----- (17)

As the reaction is exothermic, the temperature increases

and CEO decreases from the top to the bottom of the

liquid column.

Liquid volume and composition are considered constant

during the integration and can be updated at the end of

each integration, solving the related mass balance

equations.

The change of CEO in the external loop has been

neglected because the volume of this loop is small with

respect to the liquid column inside the reactor.

rEO can be determined when a kinetic model and related

parameters are available.

In the case of ethoxylation performed by using as starters

alkylphenols or fatty alcohols in the presence of alkaline

catalysts the following reaction scheme has been

suggested by Di Serio et al. (1995):

RXH+M+OH- RX-M+ + H2o!

RX-M+ + EO RXEO-M+

Catalyst

formation

nitiation

RX(EOrM+ + EO RX(EO);+l-M+ Propagation

i=1,2, ....

Ke

RX-(EO)jM+ + RX(EO) RX(EO)jH + RX(EO) i-M+

Proton transfer

On the basis of this mechanism, the following rates of

EO consumption in each step can be written:

Initiation rate

(18)

Propagation rates

So the overall EO consumption is:

(20)

The concentration of charged species can be calculated

by combining equations of proton transfer equilibria

with those of material and charge balances.

From proton transfer equilibria reaction, we can write:

Ke

[RXH][RX(EO); M+]

[RX- M+][RX(EO)jH]

(21)

By assuming with a reasonable approximation that:

[RXH] + [RXM+] == [RXH] (22)

it results:

Defming:

n

B

O

= j - M+] (25)

j=O

it is possible to write:

then:

[RX- M+] = __ __

j=1

Consequently:

[RX(EO); M+]

[RXH] + Ke t [RX(EO) j H]

j=1

(27)

(28)

Therefore, it is possible to evaluate the concentration of

each ionic couple by introducing the corresponding

equilibrium constant Ke.

By using the equations (27) and (28) the relation (20)

can be rewrite :

ko[RXH] + kpKe t[RX(EO) jH]

j=1 BOC

rEO = ----------":....::....----- EO

[RXH] + Ke t [RX(EO) j H]

j=1

(29)

E. Santacesaria et al.lChemicai Engineering Science 54 (1999) /499-/504

So the rate of EO consumption depends on the

concentration of respectively: catalyst, EO, starter and

ethoxylated oligomers.

SIMULATION OF THE PERFORMANCES OF A

PILOT PLANT REACTOR

By integrating relation (I) the EO concentration at the

top of the liquid column can be determined. The EO

consumption during the absorption into the drops is

negligible because the flight time is of the order of 10-

2

s,

that is, very small if compared with the residence time of

the liquid in the column. The ethylene oxide conversion

from the top to the bottom resulted about 30% in the

simulated runs.

The integration of relations (16) and (18) gives profiles

of ethylene oxide and of temperature along the liquid

column. In particular the EO concentration, at the bottom

of the reactor, is about the same of the liquid sprayed

after recirculation, while the temperature of the liquid, at

the bottom, is adjusted to the desired value by cooling

the liquid stream with the heat exchanger, before

recirculation.

The integration of equations (12-13) has been made by

considering the liquid column divided in N fmite

elements of equal volume. This procedure of

discretization is necessary for increasing the accuracy of

the calculations, considering that for a discretization step

with N=I the gas-phase behaviour can be updated only

after a time equal to the residence time of the liquid,

otherwise, this time becomes lIN the residence time.

By using the described model the behaviour of a pilot

plant reactor has been simulated for the ethoxylation of

nonylphenol. The values of initiation (kj) and

propagation (k

p

) and of the equilibrium proton transfer

(Ke), used in the simulation are reported in a previously

published paper by Di Serio et al. (1995).

The simulation has been made both by assuming the

drops internally stagnant and turbulent. An example of

simulation is reported in Fig. 3 for the amount of EO fed

as a function of time and in Fig. 4 for the temperature

measured at the bottom of the reactor.

lurbul

""

/.

;"" \

•

,,"" stagnanldrop

/'

4"

time

(arbitrary unlls)

Fig. 3 Simulation of EO alimentation for a nonilphenol

ethoxylation in pilot spray loop reactor by using

turbulent drop model and stagnant drop model.

atagnanldrop

lime

(arbitrary un"s)

FigA Simulation of Bottom liquid temperature for a

nonilphenol ethoxylation in pilot spray loop reactor by

using turbulent drop model and stagnant drop model.

As it can be seen the assumption of internally turbulent

drops gives place to a better simulation.

As matter of fact by assuming the drops internally

stagnant an EO consumption lower than the one

experimentally observed can be predicted because the

calculated mass transfer rate is much less active than

the one considering the drops internally turbulent.

We have so demonstrate in agreement with other

authors (Srinivasan and Aiken, 1988) that by using

efficient spray nozzle drops formed are internally well

mixed. The consequence is a very high mass transfer

rate giving drops saturation in a short time and space.

ACKNOWLEDGEMENTS

Thanks are due to Pressindustria SpA and Scientific

Design for the fmancial support.

NOTATION

aim = average specific interfacial surface area of

drops (cm

2

cm-

3

)

at = total interfacial surface area of flying drops

(cm

2

)

BO = catalyst concentration (mol cm·

3

)

Co = friction coefficient

C

p

= liquid specific heat U g.1 K·

1

)

dj = diameter of i fraction drops (cm)

D

EO

= EO diffusion coefficient (cm

2

S-I)

d32 = Sauter diameter (cm)

(d

32

)water = Sauter diameter of water drops (cm)

CEO = bulk EO concentration (mol cm·

3

)

c

r

EO = concentration of EO in the point rd

g

(mol cm·

3

)

= interface gas-liquid equilibrium EO

concentration (mol cm-

3

)

= bulk EO concentration at Bottom of liquid

phase (mol cm·

3

)

= bulk EO concentration at Top ofliquid

phase (mol cm-

3

)

= gravity acceleration (cm

2

S-2)

1503

1504

E. Santacesaria et al.lChemical Engineering Science 54 (1999) 1499-1504

kbn = average mass transfer gas-liquid coefficient

(cm S·I)

leo = constant rate of initiation (cm

3

mor

l

S·I)

kp = constant rate of propagation (cm

3

mor

l

S·I)

Ke = equilibrium constants of the proton

exchange reaction

nj = number of drops with diameter dj

QI = liquid circulation rate (cm

3

S·I)

r = reactor radius (cm)

rd = distance from the center of drop (cm)

rEO = rate of EO reaction (mol cm·

3

S·I)

T = temperature (K)

tm = average flight time (s)

Xm = average path of sprayed drops (cm)

Vo = initial drops velocity (cm s· )

v = drops velocity (em S·I )

[RXHO] = initial starter concentration (mol cm·

3

)

[RXH] = starter concentration ( mol cm·

3

)

[RX(EO)jH] = oligomer concentration with i

- adducts in the chain ( mol cm·

3

)

Greek Letter

J.1 = viscosity of substrate (cP)

P = density of substrate (g cm·

3

)

PG = density of gas phase (g cm·

3

)

(J = interfacial tension of substrate (dyn cm·

l

)

cp = spray nozzle efficiency

m = reaction heat (j mor

l

)

REFERENCES

Crank, 1., The Mathematics of diffusion, Clarendon

Press, Oxford, 1958

Di Serio, M., Tesser, R., Felippone, F. and Santacesaria,

E., (1995), Ind. Eng. Chern. Res., 34, 4092

Di Serio, M., Yairo, G., Iengo, P., Felippone, F.,

Santacesaria, E., (1996), Ind. Eng. Chern. Res., 35, 3848

Foust, A. S., Wenzel, L. A., Clump, C. W., Maus, L. and

Anderson, L. B. I principi delle operazioni unitarie,

Ambrosiana, Milano 1967. •

Fredeslund, A., Gmenhling, J. and Rasmussen, P.,

Vapour-Liquid Equilibria using UNIFAC: a group-

contribution method method, Elsevier Publishing,

Amsterdam, 1977

Hall, C.A. and Agrawal, P.K., (1990) The Can. J. oj

Chern. Eng., 68, 104

Johnson, A. I., Hamielic, A. E., Ward D. and Golding,

A., (1958), The Can. J. Chern. Eng., 36, 221

Perry, R.H. and Green, D. W., Chemical Engineer's

Handbook, 6

th

edition McGraw-Hill Book Company,

New York, 1984

Renon, H., and Prausnitz, 1., (1968), AIChE J., 14, 135

Santacesaria, E., Di Serio and M., Tesser, R., (1995),

Catalysis Today, 24, 23

Srinivasan, Y. and Aiken, R. C., (1988)Chem. Eng. Sci.,

43,3141

Wilson, G. M., (1964),J. Am. Chern. Soc., 86,127