Research Article

Received: 4 January 2012 Revised: 14 March 2012 Accepted: 16 April 2012 Published online in Wiley Online Library:

(wileyonlinelibrary.com) DOI 10.1002/jctb.3847

Investigation of liquid–liquid phase equilibria

for reactive extraction of lactic acid with
organophosphorus solvents
Susanne Lux∗ and Matthäus Siebenhofer

Abstract
BACKGROUND: Lactic acid is a versatile commodity chemical with a variety of applications. Synthesis of lactic acid either through
fermentation of carbohydrates or through chemical synthesis is state of the art. Separation from dilute aqueous solution is
complex and accounts for the major part of production costs. Reactive extraction based on reversible adduct formation is a
promising alternative for the separation of lactic acid.

RESULTS: Extraction was carried out with the organophosphorus solvents tri-n-butyl phosphate, tri-n-octylphosphine oxide
and Cyanex 923. Shellsol T was used as diluent. Partition coefficients increase with increasing extractant content and decreasing
temperature. Cyanex 923 has several advantages compared with tri-n-butyl phosphate and tri-n-octylphosphine oxide with
respect to lactic acid distribution and hydrodynamic properties. Liquid-liquid phase equilibria for lactic acid extraction with
Cyanex 923 were modeled. Selectivity of lactic acid extraction with respect to glycolic acid and formic acid was discussed.

CONCLUSION: The organophosphorus extractant Cyanex 923 was found to be an appropriate solvent for lactic acid extraction
from aqueous solutions. Experimental data and model data based on the Law of Mass Action showed good agreement. Lactic
acid extraction from multi-acid solution showed good selectivity compared with glycolic acid. Lactic acid selectivity is low with
respect to formic acid.

c 2012 Society of Chemical Industry

Keywords: reactive extraction; lactic acid; Cyanex 923; liquid–liquid equilibrium

SYMBOLS AND NOTATION Synthesis of lactic acid either through fermentation

a acitivity of carbohydrates or through chemical synthesis from 2-
aqu aqueous phase hydroxypropanenitrile (lactonitrile) are state-of-the-art routes.2
α degree of dissociation Glycerol based synthesis of lactic acid is a new approach in pro-
c concentration cessing fats and oils.3 Enantiopure lactic acid can be produced
γ activity coefficient via fermentation. Consequently, 90% of lactic acid is produced
HA carboxylic acid through this route.2
KD partition coefficient The quality grade of lactic acid depends on the usage.
Kdiss dissociation constant Purification requirements for polylactic acid production are
Kst stoichiometric equilibrium constant considerable. The conventional route for lactic acid recovery is
Kth thermodynamic equilibrium constant based on precipitation of poorly soluble calcium lactate with
n association coefficient Ca(OH)2 or CaCO3 . The precipitated calcium lactate cake is filtered
org organic phase off, washed and reacidified with strong mineral acids, leading to
RPO phosphorus-bonded oxygen donor extractant free lactic acid and CaSO4 .4 This conventional downstream process
nondiss non-dissociated needs huge amounts of chemicals and generates large quantities
V volume of gypsum sludge. The sludge is difficult to dispose of due to
retained organic impurities. There is loss of calcium lactate along
INTRODUCTION with the washing (5% at 20 ◦ C in the mother liquor) and additional
2-Hydroxypropionic acid (lactic acid, LA) is a versatile commodity
chemical with a variety of applications in food, beverages,
chemical, pharmaceutical, and cosmetics industries. The food ∗
Correspondence to: Susanne Lux, Institute of Chemical Engineering and
industry used to be the main consumer of lactic acid and lactates.
Environmental Technology, Graz University of Technology, Inffeldgasse 25C,
In the last ten years consumption of lactic acid for industrial use has 8010 Graz, Austria. E-mail: susanne.lux@tugraz.at
become the leading market. Future growth in demand is expected
to be driven mainly by lactic acid-based polymers and, to a lesser Institute of Chemical Engineering and Environmental Technology, Graz
degree, lactate solvents.1 University of Technology, Inffeldgasse 25C, 8010 Graz, Austria

J Chem Technol Biotechnol (2012) www.soci.org

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purification steps are required to produce commercial grade lactic
acid.5
Formation of calcium sulfate waste can be avoided by extractive
separation of lactic acid. Due to high polarity and the hydrophilic
character of lactic acid, it is poorly extracted with conventional
organic extractants. High consumption of solvent is inevitable.
Jenemann6 used iso-propyl ether as solvent. For one volume of
aqueous lactic acid solution 50 volumes of iso-propyl ether were
applied due to unfavorable distribution.
Addition of reactive components to the organic solvent may
increase lactic acid distribution. The organic extractant reacts
with the solute at the water/solvent interface. The hydrophobic
reaction adduct formed is then solubilized into the organic phase.
Reactive extraction of carboxylic acids may be based on solvation
with carbon-bonded or phosphorus-bonded oxygen-bearing
extractants and on ion-pairing formation with high-molecular
weight aliphatic amines.7 High partition coefficients are achieved
with secondary and tertiary amines. But re-extraction is often
carried out with bases because of high thermal stability due to the
ionic character of amine salts.8 With increasing concentration of
bases the tendency for emulsification increases.
Extraction with phosphorus-bonded oxygen-bearing extrac-
tants is promising. Selectivity is affected by strength of
donor–acceptor interaction and solvation. Due to their higher
Lewis basicity phosphorus-bonded oxygen donor extractants pro-
vide better distribution of carboxylic acids than carbon-bonded
oxygen donor extractants. Basicity of the phosphoryl group is
determined by its substituents. Alkoxy groups suppress basicity
whereas alkyl substituents increase it. Generally, extraction ca-
pability of carboxylic acid uptake increases in the order: trialkyl
phosphate ((RO)3 P=O) < alkyl dialkylphosphinate ((RO)2 P=O) <
trialkylphosphine oxide (R3 P=O). With tributyl- and trioctylphos-
phine oxides, higher partition coefficients are achieved than with
triphenylphosphine oxides.9,10
According to Wang et al.11 the degree of extraction is controlled
by two effects. One is the strength of the acid. The stronger the
acid, the stronger the interaction with the organophosphorus
extractant will be. Second, hydrophobicity of the acid will affect
extraction. Hano et al.12 concluded that the extraction equilibrium
is only controlled by the hydrophobicity of the acid, not by the
pKa value. As the extractant forms adducts with the carboxylic
acid, the pH-value of the aqueous solution should be below the
pKa value of the acid.13 Partition coefficients of reactive extraction
with organophosphorus extractants increase with decreasing acid
concentration and decreasing temperature.5,11
Typically, reactive extractants are highly viscous. Tri-n-butyl
phosphate (TBP) is highly viscous at room temperature (3.8 mPas
at 20 ◦ C) and density is close to one. Tri-n-octylphosphine oxide
(TOPO) is in solid state at ambient temperature. Improvement
of hydrodynamics is obtained with diluents.14 According to
Yabannavar and Wang13 tri-n-octylphosphine oxide can only
be applied after dissolving in nonpolar diluents. Polar diluents
interfere with the extraction step by disintegrating the laden
solvent phase. A liquid phosphine oxide (Cyanex 923) was
developed by Watson et al.15 It consists of a mixture of four
trialkylphoshine oxides with n-hexyl-and n-octyl substituents.
Use of tri-n-butyl phosphate for the extraction of carboxylic acids
was already reported by Pagel and McLafferty16 in 1948. Decrease
of extraction behavior with increasing acid concentration was
observed. But due to minor change of partition coefficients it was
concluded that TBP does not associate with the acid.
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S Lux, M Siebenhofer
Morales et al.17 investigated extraction equilibria of different
monocarboxylic acids, including lactic acid, with tri-n-butyl
phosphate in dodecane. Extractant concentration was varied
between 10 and 80 vol%. Matsumoto et al.18 investigated the
synergistic effect of alkylamine and tri-n-butyl phosphate on lactic
acid extraction.
Yabannavar and Wang13 used tri-n-octylphosphine oxide
dissolved in dodecane and Isopar-M for lactic acid extraction
from model solutions and fermentation broths. Feed lactic acid
concentration was varied between 1 and 6 g L−1 and TOPO content
between 5 and 15%. Diluents dodecane and Isopar-M showed a
similar behavior.
Extraction equilibria of lactic acid and other monocarboxylic
acids with trialkylphosphine oxide CH3 (CH2 )7 – 9 )3 =O in kerosene
were studied by Wang et al.11 Extraction equilibrium constant was
found to be 1.0 mol L−1 .
Frieling and Schügerl5 investigated lactic extraction with Cyanex
923 in kerosene. Extraction equilibrium studies were carried out
for Cyanex 923 concentration ranging from 0.11 to 0.85 mol L−1 .
Lactic acid production through fermentation could benefit
from integrated recovery by extraction.19 Biocompatibility of
extractants is often unsatisfactory though. Alex et al.20 suggested
the use of hollow fibre liquid–liquid contactors. This membrane
process technology could broaden the use of liquid–liquid
extraction.
Main objective of this work was an extensive study on lactic
acid extraction with different organophosphorus extractants. Tri-
n-butyl phosphate, tri-n-octylphosphine oxide and Cyanex 923
diluted with Shellsol T were used as extactants. Equilibrium
data were given for highly concentrated and also undiluted
extractant, which had been scarce in the literature so far. The
effect of extractant content, temperature, and initial lactic acid
concentration on lactic acid distribution and water co-extraction
was investigated. Phase equilibrium data were compared with a
model based on the Law of Mass Action.
MODELING LACTIC ACID EXTRACTION WITH
ORGANOPHOSPHORUS SOLVENTS
The extraction equilibrium of lactic acid with organophosphorus
compounds can be represented by the general reaction equation
nHAaqu + RPOorg ↔ (RPO(HA)n )org (1)
with n representing the number of reacting molecules of lactic
acid (HA) per molecule of organophosphorus extractant (RPO).
The overall partition coefficient KD of the extracted acid represents
the ratio of the total acid concentration in the solvent phase to the
total acid concentration in the aqueous phase.
cHA,org
KD = (2)
cHA,aqu
Deviation from ideal (Nernst) partition has to be assumed in acid
extraction with organophosphorus based solvents. This includes
dissociation of the acid in the aqueous phase and association
in the solvent phase. Distribution equilibria of carboxylic acids
with organophosphorus extractants are therefore analytically best
described by an algorithm according to the Law of Mass Action
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with the thermodynamic equilibrium constant Kth : 0.14

aRPO(HA)n ,org 0.12

Kth =
anHA,aqu · aRPO,org

Degree of dissociation a
cRPO(HA)n ,org · γRPO(HA)n ,org 0.1
= n (3)
cHA,aqu · γHA,aqu
n
· cRPO,org · γRPO,org
0.08
Whereas the thermodynamic equilibrium constant Kth is inde-
pendent of acid concentration, the stoichiometric equilibrium 0.06
constant Kst may change with increasing acid concentration, since
the activity coefficients are likely to change as well. 0.04

cRPO(HA)n ,org 0.02

Kst = (4)
n
cHA,aqu · cRPO,org
0
0 20 40 60 80
The thermodynamic equilibrium constant Kth and the stoichio-
clactic acid (g/L)
metric equilibrium constant Kst are correlated by the product of
activity coefficients. With the assumption of γ = 1 under relatively Figure 1. Degree of lactic acid dissociation for different lactic acid
high dilution conditions for the substances involved, Kth equals concentrations (T = 20 ◦ C).
Kst .
It has to be taken into account that non-dissociated carboxylic
acid is extracted into the organic phase due to adduct formation plotting the inverse equilibrium concentration c 1 against
HA,org
c 1
with the extractant.21 Substitution of cRPO(HA)n ,org through HA,org
n n . This results in the linear equation shown in
c cHA,aqu,nondiss
and cRPO,org = cRPO,0,org − HA,org
n then results in a simplified version Equation (10).
of Equation (3)
1 1 1
cHA,org = + (10)
Kst = (5) cHA,org n · Kst · cHA,aqu,nondiss
n
· cRPO,0,org cRPO,0,org · n
n · cHA,aqu,nondiss
n
· (cRPO,0,org − cHA,org /n)
With specified initial concentration of the extractant cRPO,0,org and
Dissociation of monobasic acids is expressed by the dissociation by altering the degree of association the stoichiometric equilibrium
constant KDiss constant Kst is calculated from the slope.
cH+ · cA− cHA,0 2 · α 2
KDiss = = (6)
cHA cHA,0 · (1 − α) MATERIALS AND METHODS
Chemicals
The non-dissociated fraction of the carboxylic acid is expressed Lactic acid (pur., Riedel-de Haën) was provided in aqueous
through solution with a concentration of 1 mol L−1 . Glycolic acid (2-
cHA,aqu,nondiss = cHA,aqu · (1 − α) (7) hydroxyethanoic acid, 98%, p.a.) and formic acid (methanoic acid,
with the dissociation degree α 99%, p.a.) were purchased from Merck.
The extractants tri-n-octylphosphine oxide (TOPO) and Cyanex

923, a mixture of tertiary n-octyl- and n-hexylphosphine oxides,
−KDiss ± KDiss 2 + 4 · cHA,0 · KDiss were supplied by Cytec Industries Inc. The content of trialkylphos-
α= (8)
2 · cHA,0 phine oxides was 93% in both extractants. Tri-n-butylphosphate
(TBP, 99%, pur.) was purchased from Merck. All extractants were
Degree of dissociation is low at high acid concentration but, as used without further purification. The diluent Shellsol T (SST), an
shown in Fig. 1, it cannot be neglected at low acid concentration. isoparaffinic hydrocarbon solvent with a hydrocarbon range of
Consequently, Equation (9) represents the analytical expression C11 to C13 and a distillation range of 187–213 ◦ C, was supplied by
of liquid–liquid phase equilibria for extraction with chemical re- Shell Chemicals.
action. The equilibrium concentration of the species extracted Tri-n-butyl phosphate, tri-n-octylphosphine oxide, and in some
into the solvent phase cHA,org is given as a function of feed experiments Cyanex 923 were diluted with Shellsol T. Cyanex
concentration of reactive extractant cRPO,0,org and the correspond- 923 and tri-n-butyl phosphate were also applied without dilution.
ing concentration of non-dissociated acid in the aqueous phase Aqueous solutions of lactic acid were prepared by dissolving
(cHA,aqu,nondiss ). different quantities of the acid in deionized water without pH
adjustment.
n · Kst · cHA,aqu,nondiss
n
· cRPO,0,org
cHA,org = (9)
1 + Kst · cHA,aqu,nondiss
n
Extraction experiments
Extraction experiments were carried out in temperature controlled
Determination of equilibrium acid concentration in the organic mixing funnels. A solvent to water ratio of 1 : 2 was applied,
phase, degree of association n, stoichiometric equilibrium constant yielding in 25 mL of organic and 50 mL of aqueous phase. The
Kst and maximum concentration n · cRPO,0,org is achieved by solvent phase and the aqueous phase were equilibrated for

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30 min on a mechanical shaker (Janke&Kunkel HS-500) with a
frequency of 150–160 rpm. In previous experiments it was proven
that equilibrium is achieved within 30 min. After equilibration the
mixture was allowed to settle in the temperature controlled flasks
for 20 h. In most experiments time was sufficient for complete
phase separation. In some cases, when TBP was used as extractant
at 25 ◦ C, further centrifugation was required for separation of the
two emulsified phases. Emulsification tendency of Cyanex 923 is
low, even when it is applied without dilution.
After phase separation the concentration of lactic acid in the
aqueous phase and the water content in the solvent phase were
determined. Equilibrium concentration of lactic acid in the solvent
phase was calculated via mass balance. Mass and density of the
aqueous and the solvent phase were measured before and after
extraction. The pH of the aqueous feed lactic acid solution was
determined. Concentration of trialkylphosphine oxides cRPO,0 in
TOPO and Cyanex 923 were used as specified by the supplier.
Extractant solubility in water was specified by the supplier too. As
Cyanex 923 solubility in water is 0.001 wt%, losses of extractant
with the aqueous phase are of minor relevance.
Sample analysis
Lactic acid was analyzed by high-performance liquid chromatogra-
phy (HPLC). The HPLC system Ultimate 3000 (Dionex) was equipped
with the column Acclaim OA (Dionex). Detection was carried out
with a UV/VIS detector (Dionex) at 210 nm. Elution of substances
from the column was carried out with 0.1 mol L−1 Na2 SO4 in ul-
trapure water at 30 ◦ C. The pH-value of 2.65 was adjusted with
methanesulfonic acid.
For Karl Fischer titration the titration manager Radiometer
Copenhagen equipped with VIT 90 video titrator, ABU 93 triburette
and SAM 90 sample station was used. Mean deviation of lactic acid
concentration and water content was determined to be 3%. Mean
error for KD values was 0.05.
RESULTS AND DISCUSSION
Screening of extractants TBP, TOPO and Cyanex 923
Extractability of the extractants TBP, TOPO and Cyanex 923 for
lactic acid extraction was compared at different temperatures
(25 ◦ C, 40 ◦ C and 60 ◦ C) and feed extractant contents (Fig. 2). TBP
and Cyanex 923 were used in the concentration range 30 to 70
wt% in Shellsol T, and without dilution. Mass fraction of TOPO in
Shellsol T was varied between 5 and 20% due to limited solubility
of TOPO at ambient temperature. Feed lactic acid concentration
was 2 g L−1 .
Partition coefficients for reactive extraction of carboxylic acids
with organophosphorus compounds increase from phosphate
via phosphonate to phosphine oxide.9,10 Increasing temperature
results in a decrease of partition coefficients.5,11 Both trends
are confirmed for lactic acid extraction with TBP, TOPO and
Cyanex 923.
Extraction capacity of TOPO based solvents is low due to its
poor solubility in Shellsol T resulting in low TOPO concentration
in the solvent phase. At 25 ◦ C partition coefficients increase from
0.20 to 0.86 with increasing TOPO content from 5 wt% to 20 wt%.
Increasing temperature results in decrease of partition coefficients
to 0.10 and 0.64, respectively. Partition coefficients derived in this
work are comparable to those given by Yabannavar and Wang13
for lactic acid extraction with TOPO in dodecane. For a feed lactic
acid concentration of 1 g L−1 partition coefficients were reported
to be 0.35 and 0.95 with 5 wt% and 15 wt% TOPO extractant.
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5
Partition coefficient KD,lactic acid
Cyanex 923
4
TBP
TOPO
3
2
1
0
0 20 40 60 80 100
Extractant content (%)
Figure 2. Partition coefficients of lactic acid extraction with Cyanex 923,
TBP and TOPO for different extractant contents at 25 ◦ C (black), 40 ◦ C (grey)
and 60 ◦ C (white) (clactic acid,0 = 2 g L−1 ; Vorg : Vaqu = 1 : 2).
Partition coefficients of lactic acid extraction with TBP are low
with KD = 0.30 for 50 wt% TBP and KD = 0.85 for undiluted TBP
at 25 ◦ C. Further decrease of partition coefficients to 0.16 and 0.63
is observed with increasing temperature to 60 ◦ C. Similar results
were obtained by Matsumoto et al.18 for lactic acid extraction
(0.1 mol L−1 ) with TBP in hexane. Partition coefficients were 0.4
with 50 wt% TBP (2 mol L−1 ) and 0.7 when using 80 wt% TBP
(3 mol L−1 ) at 25 ◦ C.
Highest partition coefficients are achieved with Cyanex 923. At
25 ◦ C partition coefficients increase from 2.14 (50 wt% Cyanex 923)
to 4.46 (undiluted Cyanex 923). Partition coefficients decrease to
1.69 (50 wt% Cyanex 923) and 3.27 (undiluted Cyanex 923) with
increasing temperature to 60 ◦ C.
Partition coefficients as a function of extractant content are
comparable for TOPO and Cyanex 923, expected due to the similar
hydrocarbon substituents of both extractants. All extractants show
linear correlation of partition coefficients and extractant content,
confirming that the diluent Shellsol T has no impact on lactic acid
distribution.
The amount of water dissolved and co-extracted into the organic
phase is shown in Fig. 3 for various extractant contents at 25 ◦ C,
40 ◦ C and 60 ◦ C. Maximum water content is 8.7 wt% when using
undiluted Cyanex 923 at 25 ◦ C.
Extraction with Cyanex 923
For lactic acid extraction from dilute aqueous solution Cyanex
923 shows several advantages over TBP and TOPO. Apart from
achieving higher partition coefficients compared with TBP, Cyanex
923 does not tend to form emulsions. In contrast to TOPO
the liquid phosphine oxide Cyanex 923 can be used at high
concentration and even without dilution. Cyanex 923 can be used
at elevated temperature as well as ambient temperature. All further
investigation of extraction equilibria was carried out with Cyanex
923 at 20 ◦ C.
As may be concluded from Equation (9) partition coefficients
for acid extraction with organophosphorus compounds are
influenced by the initial acid concentration. The higher the
initial acid concentration in the aqueous phase, the smaller is
the partition coefficient.
Liquid–liquid phase equilibria for different concentrations of
Cyanex 923 in the solvent phase are given in Table 1. As may be
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9 120
Water content of the organic phase (%)

8
Cyanex 923 100
7 TBP
TOPO
6 80

corg-1 (kg/mol)
5
60
4

3 40
30%
2 50%
70%
20
1 100%

0
0 20 40 60 80 100 0
0 100 200 300 400
Extractant content (%) (caqun·(1-α)n)-1 (kg/mol)
Figure 3. Equilibrium water contents of solvent phases for lactic acid
extraction with Cyanex 923, TBP and TOPO for different extractant contents Figure 4. Determination of the association factor n, representing the
at 25 ◦ C (black), 40 ◦ C (grey) and 60 ◦ C (white) (clactic acid,0 = 2 g L−1 , number of molecules of lactic acid reacting per molecule of phosphine
Vorg : Vaqu = 1 : 2). oxide, and the stoichiometric equilibrium constant Kst according to
Equation (10).

deduced from Table 1, partition of lactic acid depends both on

the initial acid concentration and the Cyanex 923 content in the Table 2. Association factor n and stoichiometric equilibrium constant
solvent phase. Kst for different extractant contents at 20 ◦ C

Determination of the association factor n wCyanex 923 (%) n Kst (kg mol−1 )
The association factor n represents the number of reacting 30 0.93 1.51
molecules of lactic acid per molecule of organophosphorus 50 0.96 1.49
compound. For determination of the association factor n the 70 0.94 1.58
inverse concentration of lactic acid in the organic phase is plotted 100 0.95 1.51
over the inverse concentration of non-dissociated lactic acid in the
mean: 0.95 ± 0.01 1.52 ± 0.04
aqueous phase according to Equation (10) (Fig. 4). The assumption
γ = 1 for all substances involved was taken as a basis, and proven
as valid.
Association factors n for different extractant contents were The total water content of the organic phase arises both from
derived from best fit data. The association factors are given in water dissolution in the organic phase and water co-extraction
Table 2, indicating that 1 : 1 adducts of lactic acid and Cyanex with the lactic acid extraction. The amount of water co-extracted
923 are formed. The stoichiometric equilibrium constant is then into the organic phase is given by subtraction of the amount
obtained from the slope with Kst = 1.52 ± 0.04 kg mol−1 . of water dissolved in the organic phase from the total water
content. 1 mole of water is co-extracted per mole of lactic acid
Investigation of water co-extraction when using 30 wt% of Cyanex 923 in Shellsol T. With increasing
Water co-extraction into the organic phase was investigated for Cyanex 923 content the amount of lactic acid extracted into the
Cyanex 923 at 25 ◦ C. Feed lactic acid concentration was 2 g L−1 . organic phase increases. Higher concentration of lactic acid in the

Table 1. Liquid–liquid phase equilibria for lactic acid (LA) extraction with Cyanex 923 at 20 ◦ C (Vorg : Vaqu = 1 : 2; mean deviation 3%)

c (mol kg−1 ) 30% Cyanex 923

cLA,aqu 0.007 0.014 0.069 0.102 0.161 0.199 0.290 0.378 0.608
cLA,org 0.010 0.019 0.090 0.119 0.133 0.188 0.239 0.280 0.350
50% Cyanex 923
cLA,aqu 0.006 0.011 0.056 0.081 0.124 0.169 0.264 0.315 0.525
cLA,org 0.013 0.025 0.119 0.166 0.219 0.255 0.308 0.427 0.545
70% Cyanex 923
cLA,aqu 0.004 0.009 0.044 0.067 0.102 0.157 0.131 0.200 0.266 0.358
cLA,org 0.012 0.030 0.130 0.193 0.270 0.290 0.392 0.440 0.526 0.603
100% Cyanex 923
cLA,aqu 0.004 0.007 0.036 0.054 0.079 0.104 0.099 0.159 0.214 0.374
cLA,org 0.016 0.031 0.149 0.212 0.302 0.374 0.433 0.549 0.597 0.931

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Table 3. Partition coefficients KD for carboxylic acid extraction with
Cyanex 923 from aqueous solution containing lactic acid (LA), glycolic
acid (GA) and formic acid (FA) (Vorg : Vaqu = 1 : 2, cLA,0 = 0.06 mol L−1 ,
molar feed ratio (LA : GA : FA) = 1 : 1 : 2, diluent: Shellsol T, 20 ◦ C)
Cyanex Lactic Glycolic Formic
923 (wt%) acid acid acid
100% 3.55 1.87 10.75
70% 2.53 1.08 8.50
organic phase provides higher hydrophilic behavior, which makes
water co-extraction favorable. The amount of water co-extracted
increases to 6 and 8 moles of water per mole of extracted lactic acid
for 70 wt% of Cyanex 923 and undiluted Cyanex 923, respectively.
Lactic acid extraction from aqueous multi-acid mixtures
The performance of lactic acid extraction with Cyanex 923
from aqueous solution containing various carboxylic acids was
investigated with respect to glycolic acid and formic acid. Feed
molar ratio of lactic acid, glycolic acid, and formic acid was
1 : 1 : 2. Feed lactic acid concentration was 5.3 g L−1 . Extraction
temperature was 20 ◦ C. Overall lactic acid extractability decreases
significantly through the presence of glycolic acid and formic
acid in the feed. Lactic acid partition coefficients decrease from
3.17 to 2.53 for 70 wt% Cyanex 923 and from 4.24 to 3.53 for
undiluted Cyanex 923 with glycolic acid and formic acid in the
feed. Selectivity for carboxylic acid extraction with Cyanex 923
increases in the order glycolic acid < lactic acid < formic acid.
Partition coefficients for lactic acid, glycolic acid and formic acid
extraction from the multi-acid mixture are given in Table 3. Lactic
acid shows good selectivity compared with glycolic acid. Partition
coefficients are of a factor of 2 higher for lactic acid extraction than
for glycolic acid extraction. Compared with formic acid, selectivity
for lactic acid is low. Even though feed formic acid concentration
is twofold feed lactic acid concentration, partition coefficients for
formic acid are 3 times higher than lactic acid partition coefficients.
CONCLUSIONS
The organophosphorus extractant Cyanex 923 was found to
be an appropriate solvent for lactic acid extraction from dilute
aqueous solution. Compared with TBP and TOPO, Cyanex 923
shows several advantages regarding hydrodynamic properties
and partition coefficients. Liquid–liquid phase equilibria for lactic
acid extraction were modeled and effects of acid concentration
and extractant content on the stoichiometric equilibrium constant
were investigated. It was shown that both initial lactic acid
concentration and extractant content have a significant effect
on lactic acid distribution. The algorithm gives access to complete
data interpretation.
Lactic acid extraction from multi-acid solution containing
glycolic acid and formic acid shows good selectivity compared
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S Lux, M Siebenhofer
with glycolic acid. Lactic acid selectivity is low with respect to
formic acid.
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