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Separation and Purification Technology 49 (2006) 4348

Extraction and purification of lactic acid from fermentation


broth by esterification and hydrolysis method
Xiaohong Sun a , Qunhui Wang a,b, , Wenchao Zhao a , Hongzhi Ma a , Kazunori Sakata c
a

Department of Environmental Science and Engineering, Harbin Institute of Technology, 202 Haihe Road, Nangang District, Harbin 150090, China
b Department of Environmental Engineering, University of Science and Technology Beijing, Beijing 100083, China
c Department of Applied Chemistry, Faculty of Engineering, Kyushu Institute of Technology, 1-1 Sensui-cho, Tobata-ku, Kitakyushu 804-8550, Japan
Received 17 April 2005; received in revised form 23 August 2005; accepted 23 August 2005

Abstract
Lactic acid (LA) is easily produced in bacterial fermentations, but a substantial processing and cost are involved in extraction and purification
of LA in the fermentation broth. Conversion of LA or ammonium lactate (NH4 LA) into esters and subsequent hydrolysis of the purified ester into
LA is a widely accepted way to extract and purify because using this method can obtain high pure LA. In this study, using two reactors with a
rectifying column carried out recovery of LA from the fermentation broth. NH4 LA obtained by fermentation was used directly to produce butyl
lactate by reacting with butanol for 6 h, and the esterification yield of NH4 LA was 87.7%. In this procedure, a cation exchange resin which was
modified by SnCl2 replaced sulphuric acid as a catalyst, and neutral NH4 LA replaced former LA as a starting material, which not only eliminated
corrosion of a reactor, but also avoid generating calcium salts as a by-product. Then butyl lactate was rectified, and the purified butyl lactate was
sequentially hydrolyzed into LA in presence of the cation exchange resin in the H+ form as a catalyst for 4 h, and the hydrolysis yield was 89.7%
and the purity of recovered LA was 90%. In the present recovery process, the liberated butanol in hydrolysis procedure and unreacted butanol in
esterification procedure can be recycled to the above esterification, and the recovery ratio of butanol was 85.6%.
2005 Elsevier B.V. All rights reserved.
Keywords: Lactic acid recovery; Esterification; Hydrolysis; Butyl lactate; Ammonium lactate

1. Introduction
Lactic acid (LA) is an important chemical that can be used
to synthesize biodegradable polymers, such as polylactic acid
(PLA) and its copolymers. For their production, highly purified
monomer LA is needed.
LA can currently be produced either by chemical synthesis
or by fermentation from biomass, and the latter one is prevailing. The conventional fermentation produces calcium lactate
salts. When they are acidified in LA extraction process, the calcium sulphate will be produced as a by-product, causing high
chemical cost and waste generation. For purification of LA the
solvent extraction [16], adsorption [612], direct distillation
[13], and electrodialysis [1420] are conventionally adopted.
However, such purification procedures are difficult because of
the low volatility of LA (122 C at 1661.73 Pa), with its affin-

Corresponding author. Tel.: +86 451 86283030; fax: +86 451 86418414.
E-mail address: wangqh59@hit.edu.cn (Q. Wang).

1383-5866/$ see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2005.08.005

ity to water, and its tendency to self-polymerize. Considering


favorable selectivity and reactivity of NH4 LA with alcohol, the
esterification of NH4 LA with a suitable alcohol into some of its
esters, much more volatile than LA itself, once purification of
the ester, and subsequent hydrolysis of the purified ester back
into LA is a feasible way to extract and purify LA from fermentation broth without generating calcium sulphate as a by-product
[2124].
In this research, in a reactor with a rectifying column, NH4 LA
reacted with butanol to produce butyl lactate, and then produced
butyl lactate was rectified. Further purified butyl lactate was
hydrolyzed into LA in another reactor with a rectifying column.
To recover LA from a fermentation broth with a high yield, the
effects of operating variables, such as the rectifying column, and
the reactant molar ratio, on the esterification yield of NH4 LA
and hydrolysis yield of butyl lactate were investigated. Besides
thinking over the recovery of LA with a high yield, we also
need to consider eliminating catalytic corrosion of a reactor.
Therefore, to replace a traditional sulphuric acid catalyst, the
cation exchange resin modified by SnCl2 was used as a catalyst

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X. Sun et al. / Separation and Purication Technology 49 (2006) 4348

Hydrolysis yield
=

Fig. 1. The diagram of lactic acid extraction from fermentation broth.

for esterification reaction [25,26] and the cation exchange resin


in the H+ form was employed for hydrolysis reaction. The effect
of catalysts was examined. In addition, to reduce expenditure
on extraction and purification of LA, the butanol recovery and
reuse were also evaluated. The whole recovery process of LA is
shown in Fig. 1.
2. Materials and methods
2.1. Materials
Butanol of 99.9% purity (Bodi Chemical Plant, Tientsin, PR
China) was used without further treatment. Water for hydrolysis
was distilled twice. The cation exchange resin in the H+ form
(732#, Nankai Chemical Plant, Tientsin, PR China. The ionexchange capacity of the resin is larger than 4.2 mmol g1 dry
resin) was washed several times with distilled water and dried at
99 C before use for modification and hydrolysis. The modified
resin for esterification was prepared by reacting of SnCl2 with
the resin in the H+ form in butanol for 5 h under 100 C. The
mass ratio of the resin to SnCl2 was 1:3, and the content of SnCl2
in butanol was 45%.
2.2. Apparatus and procedure
Two reactions are involved in recovering LA by esterification
and hydrolysis method. They are as follows:
Ammonium lactate + butanol  butyl lactate + water
+ ammonia (esterification reaction)
Butyl lactate + water
 lactic acid + butanol (hydrolysis reaction)
From two reaction formulas it can be observed that recycle of
butanol is possible.
Three technical terms concerning with above two reactions
are defined as follows:
Esterification yield
=

actual yield of butyl lactate in esterification


100%
theoretical yield of butyl lactate in esterification

actual yield of LA in hydrolysis


100%
theoretical yield of LA in hydrolysis

Purity of LA means a percentage of LA to total hydrolysis products.


NH4 LA used in the following experiment was produced
from glucose by LA bacteria anaerobic fermentation for 3
days at 35 C in a medium contained (in g/l): glucose, 150;
peptone, 10; yeast extract, 5; K2 HPO4 , 2; sodium acetate, 5;
MgSO4 7H2 O, 0.58; MnSO4 H2 O, 0.2; pH 6.2. During the fermentation, pH of the cultures was adjusted to 67 by ammonia
water (2528 wt.%). Then the cultures were separated by a centrifuge and a membrane filter. The obtained fermentation broth
mainly contained water, residual glucose and organic acids such
as lactic acid, formic acid, and acetic acid. LA yield in the fermentation broth was 93 g/l. Further the fermentation broth was
concentrated by evaporation of water.
The concentrated fermentation broth and butanol were placed
into a 500 ml reactor equipped with a rectifying column, a polytetrafluoroethylene stirrer with a sealing rubber ring, a condenser
and a water separator where water was added before reaction and
the water level approached a control valve 8. The apparatus for
esterification and rectification is schematically shown in Fig. 2a.
NH4 LA and butanol reacted to form the butyl lactate in the presence of the cation exchange resin modified by SnCl2 . The stirred
reactor with a 350 rpm stirrer speed was heated to a boiling point
by a numerical control heater, and a butanol-water azeotrope (the
azeotropic point is 92.7 C, the 42.5% of the azeotrope is water
and the other 57.5% is butanol [27]) was removed overhead
through the rectifying column to the water separator. Owing to
low solubility of butanol in water, the condensed overhead phase
separated into a light butanol phase and a heavy water phase, and
only the light butanol phase was returned through the control
valve 8 to the rectifying column, another heavy water phase was
removed through the sampling valve 7. Ammonia stripped in
the esterification procedure was vented through a vent-pipe 11,
collected and reused to adjust the culture pH at the fermentation
step.
The reaction liquid obtained in the esterification procedure
was subjected to rectification by closing control valves 8 and
15, reducing a pressure to 200 mmHg, controlling a reflux ratio
1:1 with a reflux ratio control system and keeping a temperature
80 C at a column top to recover unreacted butanol. Next, on the
conditions of temperature 72 C at a column top and a reflux ratio
1:1, a pressure was continuously reduced to 20 mmHg to obtain
butyl lactate of 95.3% purity. The reflux ratio control system
consists of an external reflux head, a reflux ratio controller and
control power.
Then, the purified butyl lactate was hydrolyzed with water to
LA in the presence of the cation exchange resin in the H+ form in
another apparatus. The apparatus for hydrolysis is schematically
shown in Fig. 2b. The heavy water phase was returned to the
rectifying column through the control valve 6* , and light butanol
phase was removed through the control valve 7* . The purity of
recovered LA was 90%.

X. Sun et al. / Separation and Purication Technology 49 (2006) 4348

45

Fig. 2. The schematic diagram of the apparatus for esterification and rectification (a) and for hydrolysis (b).

The rectifying column was a glass column with a packing


height of 300 mm and a diameter of 40 mm.The height of the column with the reactor, the water separator and the condenser was
approximately 1200 mm. The column was filled with Rasching
ceramic rings with an average diameter and length of 8 mm.
2.3. Analytical methods
LA and lactate salt were measured by high-performance liquid chromatography (HPLC) (a Waters company in US). The C18
column (4.6 mm 250 mm) and ultraviolet absorption detector were installed. The mobile phase was H2 SO4 liquor of
0.01 mol l1 . The current velocity was 0.7 ml min1 . The detection wavelength was 210 nm. The injection volume was 10 l.
The column temperature was all room temperature. Butanol and
butyl lactate were analyzed using a gas chromatograph (Agilent, 4890D). The GC column was a capillary HP-5 column
(crosslinked 5% Ph Me Silicone, 25 m 0.25 mm 0.25 m).
The oven was operated at variable-programmed temperature,
from 343 to 463 K at a rate of 30 K min1 . The injector and
detectors were at 473 and 513 K, respectively.
3. Results and discussion
3.1. The effect of rectifying column on esterication yield
and hydrolysis yield
The effect of the rectifying column on the esterification yield
from NH4 LA converting into butyl lactate and hydrolysis yield
from butyl lactate converting into LA are shown in Fig. 3a and
3b, respectively.
Fig. 3a indicates that the esterification yield of NH4 LA was
higher in the reactor with a rectifying column than that in the

Fig. 3. (a) The time profiles of the esterification yield (initial concentration of
NH4 LA was 30 wt.%, catalytic concentration for esterification was 1.5 wt.%, and
the molar ratio of butanol to ammonium lactate was 3:1): () with rectifying
column; () without rectifying column. (b) The time profiles of the hydrolysis
yield (catalytic concentration for hydrolysis was 2.5 wt.%, and the molar ratio
of water to butyl lactate was 15:1): () with rectifying column; () without
rectifying column.

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X. Sun et al. / Separation and Purication Technology 49 (2006) 4348

reactor without a rectifying column, and the esterification yield


after 6 h increased to 87.7%. However, in the reactor without a
rectifying column, within 8 h the esterification yield was only
72%.
Changes in a hydrolysis yield of butyl lactate (shown in
Fig. 3b) indicated a similar trend, and the maximal value was
89.7% (after 4 h) in the reactor with a rectifying column and
75% (after 6 h) in the reactor without a rectifying column, respectively. It could be explained that through the use of the rectifying
column, the content of water in the overhead phase was increased
and the separation of water from the reaction system became
faster, which resulted in increase of esterification and hydrolysis efficiency.
3.2. The effect of initial concentration of NH4 LA on
esterication yield
Fig. 4 depicted the effect of different initial concentration
of NH4 LA on the esterification yield of NH4 LA in the esterification reaction. When the initial concentration was lower than
30 wt.%, the esterification yield enhanced markedly with the
enhancement of the initial concentration. However, the initial
concentration was more than 30 wt.%, the esterification yield
was not significantly increased. Therefore, in order to reduce the
expenditure on the concentrating fermentation broth, the initial
concentration can be determined to be 30 wt.%.
3.3. The effect of catalyst on esterication yield and
hydrolysis yield
In order to eliminate that a traditional catalyst, such as sulphuric acid, corrodes a reactor, the cation exchange resin that
was modified by SnCl2 was used as a catalyst for the esterification reaction. The effect of catalysts on the esterification yield
is shown in Fig. 5a. It can be observed that the catalytic activity
of the modified cation exchange resin is better than that of the
unmodified cation exchange resin. The esterification yield was
lowest, when there was no catalyst in the reactor. It might be
considered that SnCl2 has been reacted with a sulphonate structure of the resin to form a new acidic-catalytic center, which can

Fig. 4. The effects of initial concentrations of NH4 LA on the esterification yield


(esterification time 6 h, catalytic concentration for esterification was 1.5 wt.%,
and the molar ratio of butyl to ammonium lactate was 3:1).

Fig. 5. (a) The effects of catalyst varieties on esterification yield (esterification


time 6 h, initial concentration of NH4 LA was 30 wt.%, catalytic concentration for
esterification was 1.5 wt.%, and the molar ratio of butyl to ammonium lactate was
3:1): () modified cation resin with Sn; () unmodified cation resin; () without
catalyst. (b) The effects of catalyst varieties on hydrolysis yield (hydrolysis time
4 h, catalytic concentration for hydrolysis was 2.5 wt.%, and the molar ratio of
water to butyl lactate was 15:1): () cation resin in the H+ form; () without
catalyst.

obviously reduce the apparent activation energy of the esterification reaction.


For this hydrolysis reaction, the cation exchange resin in the
H+ form was used as a catalyst, and the effect of a catalyst on
hydrolysis yield is shown in Fig. 5b. Comparing two hydrolysistime curves could find that the cation exchange resin in the H+
form has higher catalytic activity for hydrolyzing butyl lactate,
and can markedly increase the hydrolysis reaction rate. When
the hydrolysis time was over 4 h, the hydrolysis yield did not
change much. That is to say 4 h may regard as an ideal time for
the reaction.
The effect of catalytic concentration (w/w; weight of catalyst/total weight of reactants) on the esterification yield of
NH4 LA and the hydrolysis yield of butyl lactate are depicted
in Fig. 6. In the esterification reaction (shown in Fig. 6a), as the
catalytic concentration increased, the esterification yield became
high and the esterification yield was highest at the concentration
around 1.5 wt.%. However, the esterification yield decreased
when the concentration was above 1.5 wt.%. The hydrolysis
yieldcatalyst concentration curve (shown in Fig. 6b) indicated
a similar trend. When the catalytic concentration was increased
to 2.5 wt.%, the hydrolysis yield was highest.
The reason may be as follows. In the reaction system as the
catalytic concentration increases, the number of active species

X. Sun et al. / Separation and Purication Technology 49 (2006) 4348

47

Fig. 7. The effect of the molar ratio of W/B on the hydrolysis yield (hydrolysis
time 4 h, catalytic concentration for hydrolysis was 2.5 wt.%, and the molar ratio
of water to butyl lactate was 15:1).
Table 1
Summary of butanol recovery

Recovered total
amount (g)
Butanol
concentration (%)
Recovered butanol
(g)
Fig. 6. (a) The effect of catalytic concentration on esterification yield (esterification time 6 h, initial concentration of NH4 LA was 30 wt.%, and the molar ratio
of butyl to ammonium lactate was 3:1). (b) The effect of catalytic concentration
on hydrolysis yield (hydrolysis time 4 h and the molar ratio of water to butyl
lactate was 15:1).

increases and the reaction velocity makes more quickly, and further, the quicker reaction velocity also leads to markedly increase
of the reactant molar ratio. The quicker reaction velocity and
more reactant molar ratio result in quicker approach of esterification and hydrolysis equilibriums. However, as the catalytic
concentration gradually increases, some side-reactions are catalyzed, which causes decrease of the esterification yield and the
hydrolysis yield, and appearance of maximum in the two profiles.
3.4. Effect of reactant molar ratio on esterication yield
and hydrolysis yield
In our previous study [28] we discussed the effect of the molar
ratio of butanol to ammonium lactate (B/A) on the esterification
yield of NH4 LA in the esterification reaction, and the result
was that the optimum molar ratio of B/A was 3:1. The effect of
the molar ratio of water to butyl lactate (W/B) on the hydrolysis
yield is shown in Fig. 7. The hydrolysis yield was increased with
increment of the molar ratio, and the hydrolysis yield was 89.7%
at the ratio about 15:1. When the molar ratio was more than 15:1,
the yield did not significantly increase for the following reason.
As the ratio of W/B continuously increases, the concentration of
butyl lactate becomes lower, which results in reduction of the
hydrolysis rate.

Esterification
Water fraction

Rectification
Butanol fraction

Hydrolysis
Butanol fraction

84.0

58.5

28.0

7.8

88.2

80.7

6.6

51.6

22.6

The initial amount of NH4 LA was 0.425 mol and total butanol added in esterification was 94.4 g.

3.5. The recovery of butanol


The experiment of the butanol recovery is reported in Table 1.
On the basis of experimental data, the butanol recovery
ratio can be calculated to be 85.6% (6.6 g + 51.6 g + 22.6 g/
94.4 g 100%). Owing to the fact that the content of butanol in
water fraction is lower (approximately 8%), recovering butanol
is uneconomical, and the water fraction can be reused to
hydrolyze or ferment. However, the butanol fraction can be recycled to esterification.
Under the aforementioned and optimized conditions for esterification, the butanol fraction was reused to react with NH4 LA
to produce butyl lactate, and the esterification yield of NH4 LA
was 86%. It showed that a recycling butanol in the esterification
procedure is feasible.
4. Conclusions
(1) In this paper, the extraction and purification of LA from a
fermentation broth by esterification and hydrolysis method
was studied. Through the use of the rectifying column, the
esterification and hydrolysis efficiency could be enhanced.
(2) In the esterification procedure, the neutral NH4 LA obtained
by fermentation was employed as a starting material, and
the modified cation exchange resin with SnCl2 was used
as a catalyst, which not only eliminated corrosion of the
reactor, but also avoided generating calcium salts as a byproduct. In the range of conditions studied in esterification,

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X. Sun et al. / Separation and Purication Technology 49 (2006) 4348

the optimum conditions for esterification were as followed:


the initial concentration of NH4 LA was 30%, the catalytic
concentration was 1.5 wt.%, the esterification time was 6 h,
and the molar ratio of butanol to NH4 LA was 3:1. Under
above conditions, the esterification yield of NH4 LA was
87.7%.
(3) In the hydrolysis procedure, the cation exchange resin in
the H+ form was used as a catalyst. In the range of conditions studied in hydrolysis, the optimum conditions for
hydrolysis were as followed: the catalytic concentration was
2.5 wt.%, the hydrolysis time was 4 h, and the molar ratio of
water to butyl lactate was 15:1. Under above conditions, the
hydrolysis yield of butyl lactate was 89.7%, and the purity
of recovered LA was 90%.
(4) In the present process, the recovery of butanol was also
discussed and the result showed that 85.6% of total butanol
could be recovered and recycled in this technology.
Acknowledgements
This research was supported by National Natural Science
Foundation of China (50278024) and the Scientific Research
Foundation for the Returned Overseas Chinese Scholars, Hei
Longjiang Province (LC02C03).
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