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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
44
Hydrolysis yield
=
45
Fig. 2. The schematic diagram of the apparatus for esterification and rectification (a) and for hydrolysis (b).
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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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.
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