INVESTIGATION OF ETHYL LACTATE

REACTIVE DISTILLATION PROCESS

J. Gao1,2
, X. M. Zhao2, L. Y. Zhou1 and Z. H. Huang1

1
School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin, People’s
Republic of China.
2
School of Chemical Engineering and Technology, Tianjin University, Tianjin, People’s Republic of
China.

Abstract: In this paper, extensive investigation is carried out for the synthesis of ethyl lactate by
super-fine magnetic solid super-acid SO22 4 /ZrO2 –Fe3O4 catalysed reactive distillation for the
first time. The feasibility of ethyl lactate synthesis is examined using the reactive distillation
lines diagram. The factors investigated include: the effects of the reflux ratio, the ratio of ethanol
to lactic acid, lactic acid feeding flux and the position of the feed points. The optimum operating
conditions are given. The kinetics of the reversible reaction of ethanol and lactic acid in the
presence of super-fine magnetic solid super-acid SO22 4 /ZrO2 –Fe3O4 are experimentally
determined. Numerical simulation of the process using ASPEN Plus simulator has also been
performed, which agreed with experiments very well.

Keywords: reactive distillation; ethyl lactate; solid super-acid; numerical simulation.

INTRODUCTION Halpern gave a modified process comprising

Correspondence to:
Professor J. Gao, School of
Chemical Engineering and
Technology, Hebei University
of Technology, Tianjin
300130, People’s Republic of
China.
E-mail: jgao@hebut.edu.cn
DOI: 10.1205/cherd06026
0263–8762/07/
$30.00 þ 0.00
Chemical Engineering
Research and Design
Trans IChemE,
Part A, April 2007
# 2007 Institution
of Chemical Engineers
Ethyl lactate is nontoxic, biodegradable, and
has excellent solvent properties. It can
replace toxic and halogenated solvents for a
wide range of industrial applications. It could
eventually find its way into the composition
or production of a multitude of common
household products, such as packaging, bio-
degradable plastics, paints, paint strippers,
grease removers and cleansers, as well as
semiconductor chips in computers and consu-
mer electronics. Thus, the environmental
benefits would be pervasive, from lower
toxic exposures directly in the consumer’s
household, to indirect but large-scale benefits
from ‘greener’ chemical production and indus-
trial cleaning (Argonne National Laboratory,
2005; Gao et al., 2004; Zhao et al., 2006).
Ethyl lactate is produced by esterification of
lactic acid with ethanol. At present, the method
of production is usually batch in industry. The
catalyst used is sulphuric acid, which leads to
a series of problems such as the equipments
corrosion and more by products. Some attempts
have been made to resolve these problems,
e.g., water-permeable membrane reactors
have been reported using of vapour permeation
with a zeolite T membrane (Kazuhiro et al.,
2002) and with zeolite A membrane (Jalal
et al., 2002) to aid the esterification of lactic
acid with ethanol. Datta proposed a method for
esterifying ammonium lactate with ethanol
using pervaporation (Datta and Tsai, 1998).
reacting ammonium lactate with ethanol using
inert fluid. The role of the inert fluid is to drive
off ammonia and thus eliminate amides as
competing products (Halpern, 2003).
Reactive distillation (RD) is widely used in
many processes where a reversible reaction
takes place (Malone and Doberty, 2000;
Taylor and Krishna, 2000). RD process has
shown great economical and environmental
benefits in many existing applications (Jakobs-
son and Pyhalahti, 2002; Andreas and Franz,
2002; Wang and Shen, 2000; Kening et al.,
2001), e.g., production of MTBE, methyl acet-
ate, and so on. A comprehensive review article
on RD has been published recently (Halpern,
2003). By using a solid super-acid catalysts
fixed inside a catalytic zone of a distillation
column, RD brings new possibilities of simplifi-
cation to the ethyl lactate technology, making
the process more environmental friendly com-
pared with common homogeneous processes.
In general, reactive distillation seems to be a
simple, energy-saving process with lower
investment and operation costs (Doherty and
Buzad, 1992; Sundmacher and Homann,
1994). In this paper, RD is applied for synthesis
of ethyl lactate.
KINETIC MODELLING
Lactic acid reacts with ethanol to give ethyl
lactate, which is an equilibrium limited chemi-
cal reaction. The reaction takes place in

525 Vol 85 (A4) 525–529

526 GAO et al.

the presence of super-fine magnetic solid super-acid

SO22
4 /ZrO2 – Fe3O4 catalyst.
The reaction is

A 250 ml, three-necked round bottom flask is equipped

with a reflux condenser and a large egg-shaped magnetic
stir bar. The flask is charged with lactic acid, ethanol and
catalyst. The reaction mixture is heated to reflux for 3 h, the
reaction temperature is 908C. The products are analysed
by gas chromatography. The results show that the reaction
is not affected by diffusion resistance when the rotating
speed exceeds 85 rpm. In the absence of diffusion
resistance, the kinetics of heterogeneous catalysis can be
accurately described as a pseudo-homogeneous catalytic
process (Helfferich, 1962; Popten et al., 2000).
The kinetic model is obtained by experiment and simulation
(Gao et al., 2006). The effect of diffusion resistance on reac-
tion is eliminated firstly, then the curves of ethyl lactate
concentration to time in different temperature are measured,
the Arrhenius(k)factor and active energy (Ea) are obtained by
linear simulation lastly. The following equation represents the
kinetics of the reaction
dCester
¼ Kþ Clactate Cethanol  k
dt
where
Kþ ¼ 228:2e26500=RT
K ¼ 720:1e43200=RT
Ci denotes mole concentration of components, kþ and k2
denote the rate constants of the esterification and hydrolysis
reaction, respectively.
The catalyst affect the reaction rate constant in the kinetic
equation through change reactive active energy. Because
the catalyst is excess in the kinetic modeling experiments,
the amount of the catalyst does not affect reaction rate.
So the amount of catalyst does not appear in the kinetic
equation.
Figure 1. Flow sheet of reactive distillation experiments for ethyl lac-
tate. 1. ethanol tank; 2. lactic acid tank; 3. condenser; 4. thermometer;
5. flask of sampling; 6. controller of reflux ratio; 7. manometer;
8. samples of tower bottom; A –H. entrance of feeds or measuring
temperature.
rings respectively. Lactic acid is fed above ethanol. The
reason is that the boiling point of lactic acid is higher than
that of ethanol. Lactic acid and ethanol may thoroughly mix
and react in this way. Between the ethanol and lactic acid
feed point is reactive zone. The height of the reaction zone
is determined by the feed point, the distance of each feed
point from A to H is 100 mm respectively. The section between
the ethanol and lactic acid feed point is reactive zone.
The column is supplied with protective heating to ensure
adiabatic operation. Temperature is measured at the
bottom, the reactive zone and at the top. Samples are
taken from the bottom and the distillate and concentration
are measured. The main product, ethyl lactate, and etha-
nol –water azeotrope are withdrawn from the re-boiler and
the top respectively. The experimental apparatus is shown
in Figure 1.
The varied parameters are: the reflux ratio; the feed flow
rate; the feed ratio of ethanol to lactic acid; and the feed
locations.

REACTION DISTILLATION EXPERIMENT AND

RESULTS
RD Experiment
RD experiments are performed for the heterogeneously cat-
alysed esterification of lactic acid and ethanol to produce ethyl
lactate and water at atmospheric pressure. The super-fine
solid super-acid is chosen as a heterogeneous catalyst. The
dimensions of the glass column are total height: 1100 mm
and internal diameter: 40 mm. The column consists of three
distinct parts: (1) non-reactive stripping section; (2) reactive
catalytic packed section and (3) non-reactive enriching sec-
tion. The column is equipped with a total condenser and a
forced circulation re-boiler. The height of the reaction catalytic
zone is 700 mm and is filled with super-fine solid super-acid
confined in stainless steel wire mesh bags. The stripping sec-
tion below point H and enriching section above point A was
packed to a height of 200 mm with 3.5 mm  3.5 mm Dixon
Results and Discussion
Effect of the reflux ratio
The effect of reflux ratio to yield is studied under the
following conditions: the feed flow rate of lactic acid:
0.9260 mol h21, the ratio of ethanol to lactic acid: 4:1 and
the feed location: AH. The results of the experiment (see
Figure 2) show that the yield of ethyl lactate is maximal,
when the reflux ratio is 1:1.
Effect of feed mole ratio of ethanol to lactic acid
The effect of the ratio of ethanol to lactic acid is studied
under the following conditions: the feed flow rate of lactic
acid: 0.9260 mol h21, the reflux ratio: 1:1 and the feed
locations: AH. The results of the experiment (see Figure 3)
show that the yield of ethyl lactate is maximal, when the
feed ratio of ethanol to lactic acid is 4:1.

Trans IChemE, Part A, Chemical Engineering Research and Design, 2007, 85(A4): 525– 529
 INVESTIGATION OF ETHYL LACTATE REACTIVE DISTILLATION PROCESS 527

Table 1. Effect of the feed points on yield of ethyl lactate.

Feed location AH BG CF DE AG

Yield of ethyl lactate, % 51.64 42.02 40.55 42.07 50.56

section performance as well as on the reaction component

Figure 2. Effect of the reflux ratio on yield of ethyl lactate.
Effect of the feed flow rate
The effect of the feed flow rate is studied under the follow-
ing conditions: the reflux ratio: 1:1, the feed locations: AH and
mole ratio of ethanol to lactic acid: 4:1. The results of the
experiment (see Figure 4) show that the yield of ethyl
lactate is maximal, when the feed-flow rate of lactic acid is
0.6384 mol h21.
Effect of the feed points
The effect of the feed point is studied under the following
conditions: the reflux ratio: 1:1, the feed ratio of ethanol to
lactic acid: 4:1, the feed-flow rate of lactic acid:
0.6384 mol h21. The product quality depends on the reaction
feed configuration, because feed location affects reaction
section performance. The results of the experiment (see
Table 1) show that the yield of ethyl lactate is maximal,
when the feet points are AH.
Based on the above discussion and analysis, it is found
that the optimum conditions for this system are: the reflux
ratio is 1:1, the feed locations are lactic acid fed to the
upper part of the reaction zone and ethanol fed to the lower
part of the reaction zone, lactic acid feed-flow rate is
0.6284 mol h21, and the feed mole ratio of ethanol to lactic
acid is 4:1.
NUMERICAL SIMULATION
The mathematical model is developed based on mass and
heat balances, vapour –liquid equilibrium and the chemical
kinetics on every stage of the reactive distillation column
obtained recently (Smejkal et al., 2001; Nitin, 2000). In
addition, several assumptions are made: (1) the operation
reaches steady state; (2) the reactions take place entirely
in the liquid bulk; (3) the fugacity coefficients of the vapor
phase are unity because of the low pressure (Luo, 2001);
and (4) to simplify the calculation, pressure drop along the
column was neglected so the whole equipment was sup-
posed to operate under atmospheric pressure.
The stages were numbered from the top of the column
(condenser) to the column bottom (re-boiler). The MESH
equations (mass balance, phase equilibrium, summation
equations and energy balance, respectively) are described
as follows:
The mass balance:

dxj,i
Lj1 xj1,i þ Vjþ1 yjþ1,i þ Fj zj,i  Vj yj,i  Lj xj,i  rj,i ¼ Uj
di
( j ¼ 1, 2, . . . , N  1; i ¼ 1, 2, . . . , M)
LN1 xN1,i  (VN yN,i þ LN xN,i ) ¼ 0
Figure 3. Effect of the feed ratio on yield of ethyl lactate. (N stage re-boiler; i ¼ 1, 2, . . . , M)
V1 y1,i  (L0 þ D)x0,i ¼ 0
(0 stage condenser; i ¼ 1, 2, . . . , M)

The phase equilibrium:

yj,i P ¼ xj,i gi PiS ( j ¼ 1, 2, . . . , N; i ¼ 1, 2, . . . , M)

The summation equations:

P
M
xj,i  1:0 ¼ 0 ( j ¼ 1, 2, . . . , N)
i¼1

and

P
M
yj,i  1:0 ¼ 0 ( j ¼ 1, 2, . . . , N)
Figure 4. Effect of the feed flow rate on yield of ethyl lactate. i¼1

Trans IChemE, Part A, Chemical Engineering Research and Design, 2007, 85(A4): 525–529
528 GAO et al.

The energy balance: CONCLUSIONS

In this work, extensive investigation is carried out for the
L V
Lj1 Hj1 þ Vjþ1 Hjþ1 þ Fj HjF  Lj HjL  Vj HjV þ Qr ¼ 0 synthesis of ethyl lactate by heterogeneously catalysed RD.
( j ¼ 1,2, . . . , N  1) The feasibility of the process is examined and a configuration
I
LN1 HN1  (VN HNV þ LN HNL ) þ Qb ¼ 0 of the RD column is proposed. It turns out that the product
(N stage re-boiler) quality strongly depends on the reaction section performance
V1 H1V  (L0 þ D)H0L þ QC ¼ 0 as well as feed location. The combination of an esterification
(0 stage condenser) reactor and a reactive distillation column makes the single
pass yield of ethyl lactate increases 82% compared to the
simple esterification reactors in the same reaction conditions.
The kinetic equation: The reaction conditions investigated in this study provide a
good solution for industrial practice.
dCester It has been confirmed both by simulation and experimental
¼ 228:2e26500=RT Clactate Cethanol  720:1e43200=RT results that it is viable to produce ethyl lactate via reactive
di
distillation, ethyl lactate being withdrawn from the bottom of
the column, and reaction water being distilled overhead in
COMPARISON OF SIMULATION AND EXPERIMENT the form of heterogeneous ethanol –water azeotropic mix-
Using simulation software ASPEN Plus (2000) three ture. The simulation results fit the experimental results well.
variants (the tower top stream compositions, the tower This study provides a ‘green’ technology with realistic
bottom stream compositions and the tower temperature) of conversion, high purity product and little pollution on the
the technology setup are tested. The applied computer environment. The process investigated will have prospective
model is the implemented equilibrium stage model RAD- applications in the future.
FRAC. The interaction parameters (ki,j) refer to the Aspen
database and to Rehfinger and Hoffmann (1990). Reaction
kinetics is implemented as a Fortran model. The value of
NOMENCLATURE
HETP is 50 mm heights of section in simulations. Ci liquid concentration of component i, mol L21
The simulated top and bottom stream compositions are D liquid flow from the condenser, mol h21
Fi feed flow rate, mol h21
compared with the experimental data, which is shown in H Fj feed enthalpy, J mol21
Table 2. The comparison of the simulation results and the H Lj liquid enthalpy, J mol21
experimental axial temperature profile along the column is HVj vapour enthalpy, J mol21
also presented in Figure 5. It is evident that experimental k reaction rate constant, mol21 l h21
data fit well to the calculation results. Lj liquid flow rate, mol h21
M number of components
N number of stages
P pressure, Pa
Table 2. Comparison of numerical simulation (sim.) and experiment Psi saturated vapor pressure under the system temperature,
(exp.). Pa
Qb heat duty of reboiler, J h21
Stream Bottom Top
Qc heat duty of condenser, J h21
Qr the heat of reaction, J h21
Composition (wt%) Exp. Sim. Exp. Sim. gj,i reaction rate of i component on stage j, mol h21
R gas constant, 8.3144 J/(mol K21)
Ethyl lactate 52.85 51.50 0 0 t time, h
Lactic acid 26.10 24.93 0 0 T temperature, K
Ethanol 17.42 20.52 92.78 94.60 Uj liquid hold-up on stage j, mol
Water 3.63 3.05 7.22 5.40 Vj vapour flow rate, mol h21
xi,j molar fraction of component i at liquid phase of stage j
yi,j molar fraction of component i at vapour phase of stage j
zi,j molar composition of component i at the feed stage j
gi activity coefficients

Superscripts
F feeds
L liquid
V gas

Subscripts
þ forward reaction
2 reverse reaction
i component number i 2 1, 2, . . . , M
j stage number j 2 1, 2, . . . , N

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ACKNOWLEDGEMENTS
This work has been supported by the Chinese National Fund For
Natural Science (20036010), the Hebei Province Fund For Natural
Science (200014) and Hebei Province Education Fund For Natural
Science (2002150), P. R. China.
The manuscript was received 27 February 2006 and accepted for
publication after revision 1 January 2007.