Separation and Purification Technology 185 (2017) 186–195

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Separation and Purification Technology

journal homepage: www.elsevier.com/locate/seppur

Reactive extraction and recovery of levulinic acid, formic acid and

furfural from aqueous solutions containing sulphuric acid
Thomas Brouwer a, Marek Blahusiak a, Katarina Babic b, Boelo Schuur a,⇑
a
University of Twente, Faculty of Science and Technology, Sustainable Process Technology Group, PO Box 217, 7500AE Enschede, The Netherlands
b
DSM ACES Ahead R&D, P.O. Box 1066, 6160 BB Geleen, The Netherlands

a r t i c l e i n f o a b s t r a c t

Article history: Levulinic acid (LA) can be produced from lignocellulosic materials via hydroxylation followed by an
Received 11 November 2016 acid-catalyzed conversion of hexoses. Inorganic homogeneous catalysts are mostly used, in particular
Received in revised form 17 May 2017 sulphuric acid, yielding a mixture of LA with sulphuric acid, formic acid (FA) and furfural. Significant
Accepted 20 May 2017
attention has been paid to optimization of the yield, but purification of the LA is a challenge too. This
Available online 23 May 2017
work focuses on the separation of LA from the complex aqueous mixtures by liquid-liquid extraction.
Two aqueous product feeds were considered, reflecting two different processes. One aqueous product
Keywords:
stream contains sulphuric acid and LA, while the second product stream also contains formic FA and
Levulinic acid
Sulphuric acid
furfural. Furfural could be removed selectively via liquid-liquid extraction with toluene. For selective
Furfural extraction of LA and FA without co-extracting sulphuric acid, 30 wt.% of trioctylphosphine oxide
Formic acid (TOPO) in methylisobutylketone (MIBK) was found most suitable, showing a high selectivity over
Solvent screening sulphuric acid, and a high equilibrium partitioning of LA. When instead of MIBK, 1-octanol was applied
Liquid-liquid extraction as diluent, the co-extraction of FA was enhanced, while hexanoic acid suppressed the acid extraction. To
Temperature swing back extraction obtain the LA pure, eventually a distillation is required, and the potential of temperature swing back
extraction (TSBE) at 90 °C to pre-concentrate the acid solutions was evaluated for 30 wt.% TOPO in
MIBK. This pre-concentration step increased the concentrations of LA and FA by a factor of 2.45 and
2.45 respectively, reducing the distillation reboiler duty from roughly 31.5 to 11.3 GJ per ton LA, at a cost
of roughly 4.5 GJ heating duty per ton produced LA.
Ó 2017 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://
creativecommons.org/licenses/by/4.0/).

1. Introduction
Levulinic acid (LA) is widely described as one of the high poten-
tial platform chemicals which can be derived from lignocellulosic
materials [1]. The predominant conversion route in production of
LA starts with hydrolysis of the polymeric lignocellulosic materials
into the hexose- and pentose monomers under acidic conditions.
LA is formed via an acid-catalyzed reaction of the hexoses via the
intermediate 5-hydroxymethylfurfural (5-HMF). Formic acid (FA)
is obtained as an unavoidable side product. In parallel, the pen-
toses are converted into a second side product, furfural. The total
yield of useful products is reduced by the formation of black insol-
uble particles, called humins, via a polymerization reaction [2].
Abbreviations: 5-HMF, 5-hydroxymethylfurfural; HPLC, High Pressure Liquid
Chromatography; KF, Karl Fischer; DIPE, diisopropylether; TOA, trioctylamine;
TOPO, trioctylphosphine oxide; TB, 4-tert-butylbenzenediol; TSBE, temperature
swing back extraction; GJ, gigajoule.
⇑ Corresponding author.
E-mail address: b.schuur@utwente.nl (B. Schuur).
This unwanted by-product can be removed together with the unre-
acted lignocellulosic materials by in situ filtration of the reaction
mixture [3]. Various acidic materials have been reported to facili-
tate the reaction to LA. Usually homogeneous acid catalysts, such
as inorganic acids [4–7], enzymes [8], acidic functionalized ionic
liquids [9], organic acids [5] and metal salts of such acids [8] are
considered. Besides those, heterogeneous acid catalysts i.e. ion
exchange resins, were mentioned too [8,10]. Despite purification
complications, inorganic acids are most often used in the conver-
sion to LA, because very long reaction times are required to obtain
similar yield when using a heterogeneous catalyst [11].
The homogeneous mineral acids hydrochloric acid and sul-
phuric acid can be used both, with sulphuric acid as preferred acid
[12], due to the potential risk of releasing chlorine in the biosphere
when using hydrochloric acid [11].
Research papers and patents focus mainly on the description of
the pre-fractionation [4,5,13–15] or conversion [6,7,16–22] of var-
ious types of feedstocks to LA. In acid-catalyzed reactions of ligno-
cellulosic materials to LA, two approaches are commonly applied

http://dx.doi.org/10.1016/j.seppur.2017.05.036
1383-5866/Ó 2017 The Authors. Published by Elsevier B.V.
This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
 T. Brouwer et al. / Separation and Purification Technology 185 (2017) 186–195
using strong inorganic acids, i.e. using high acid concentrations at
mild temperatures (55–60 wt.% hydrochloric acid or 31–70 wt.%
sulphuric acid at 20–50 °C), or diluted acids (<10 wt.%) at high tem-
peratures of 170–240 °C [3,12,16,20,23–32]. The high reaction
temperature and diluted catalyst option is most often applied
[6,7,12,16,20,22,29,32]. This prevents the use of expensive equip-
ment which can withstand the high acid concentration, which is
considered beneficial over the advantage of high acid concentra-
tions that according to Mullen et al. [6] Reunanen et al. [12] and
Cuzens et al. [24] result in less char formation, a higher LA yield
and fewer by-products at lower temperatures. .
After the conversion step, producing the LA, a complex aqueous
product mixture is obtained, which needs further fractionation.
Although the LA concentration in the mixture is strongly depen-
dent on the type of lignocellulosic material used and the reaction
conditions applied, often 3–8 wt.% has been found, for both FA
and furfural a concentration of 1–5 wt.% was found
[7,20,22,24,31,32].
For dilute high boilers such as LA, due to the low concentration
of products in the aqueous stream, direct distillation is economi-
cally less favorable, and liquid-liquid extraction has been men-
tioned as potential technique for fractionating the product
mixture [7,32].
Traditionally high molecular weight aliphatic amines [21,33–
36] and organophosphorus extractants [12,37] have been used to
extract carboxylic acids from diluted aqueous streams. In addition
a large variety of physical solvents have been suggested such as
alkylphenols [6,17], ketones [6], alcohols [6], fatty acids [6,12],
esters [12], ethers [6,20], and halogenated hydrocarbons [6]. Very
recently, a study has been reported using octanol, MIBK and fur-
fural as physical solvents, and the heat duty to recover the LA from
these solvents was compared [38]. Recently new extractants have
been designed to further improve the extraction of carboxylic
acids, such as aromatic amines [39] and ionic liquids [40–43]. Rey-
hanitash et al. [44] recently showed that both aliphatic amines and
ionic liquids cause significant co-extraction of sulphuric acid, mak-
ing them less suited for selective extraction of LA due to the pres-
ence of sulphuric acid as catalyst. Since the raffinate of the acid
extraction is recycled back to the reaction step, and the product
should not contain sulphuric acid, any sulphuric acid co-
extraction results in the necessity of an additional catalyst recov-
ery step.
It is thus important to find a solvent that shows a high selectiv-
ity for LA over sulphuric acid, and here, we report a solvent screen-
ing study focusing on the acid fractionation, which is a key step in
the process allowing product isolation without loss of catalyst. Pos-
sibly, the acid fractionation is preceded by a furfural extraction sec-
tion (but this might also be done afterwards). In the complete
fractionation scheme, as shown in Fig. 1, these are the second
and third sections. After the physical solvent screening for furfural
removal, the composite solvent screening study was performed in
two stages, in the first stage only sulphuric acid and LA were pre-
sent in the mixtures, while in the second stage the more complex
mixtures were applied that also contain FA and furfural.
Next to selectivity and distribution in the extraction process,
any economically feasible process should exhibit good recyclability
of the solvent. Next to the solvent screening, also recyclability by
back-extraction at elevated temperature was investigated.
2. Experimental
2.1. Chemicals
All chemicals were purchased by Sigma Aldrich and used as
received without further treatment, i.e. levulinic acid (98%),
187
1-octanol (
99%), formic acid (
95%), heptane (99%), 4-tert-
butylcatechol (
98.0%), 4-methyl-2-pentanone (
98.5%), dode-
cane (
99%), sulphuric acid (95.0–98.0%), toluene (
99.9%),
diisopropyl ether (
98.5%), furfural (99%), 1-pentanol (
99%),
1-butanol (
99.7%), 1-hexanol (
99%), hexanoic acid (
98.0%),
trioctylamine (99.6%) and trioctylphosphine oxide (99%).
2.2. Liquid – liquid extraction experiments
Liquid-liquid extraction experiments were conducted in 10 mL
glass vials. An analytical balance was used to weigh all compounds
in both phases with an accuracy of 0.5 mg. The biphasic systems in
the vials was shaken rigorously using a mechanical mixer and con-
secutively shaken in a shaking bath for at least 20 h at a constant
temperature. All the experiments have been performed at
25 ± 0.02 °C, with the exception of experiments where the temper-
ature is indicated otherwise. The mass of the aqueous phase was
kept constant at 4 g with a solvent to feed ratio of 1 (mass based).
The aqueous phase contained 8 wt.% LA and 10 wt.% sulphuric acid,
and in case the more complicated feed was used, also 5 wt.% FA and
5 wt.% furfural was added to the aqueous phase. These concentra-
tions reflect achievable concentrations for the acid catalyzed con-
version in various processes with various lignocellulosic
feedstocks.
2.3. Analytical procedures
2.3.1. High Pressure Liquid Chromatography (HPLC)
The aqueous phase concentrations of LA, FA, furfural and sul-
phuric acid were determined with HPLC using an Agilent 1200 ser-
ies apparatus, equipped with a Hi-Plex-H column (300  7.7 mm)
and a refractive index detector (RID). 5 mM aqueous sulphuric acid
solution was applied as eluent at a flow rate of 0.6 mL/min. The
injection volume was 10 lL and the column oven was isothermally
operated at 65 °C.
2.3.2. Karl Fischer Titration (KFT)
The water content of all the organic phases was analyzed with
Karl Fischer Titration using a 787 KF Titrino 730 TiStand of Metrohm,
each sample was analyzed in duplo. A methanol/dichloromethane
(volumetric ratio of 3:1) solution and HYDRANALÒ were used as
titrant. A standard deviation over all measurements was deter-
mined to be 0.19 vol.%.
2.4. Definitions
The reported distribution coefficients are defined on molar
basis:
 
½io mole=L
K D;i ¼ ð1Þ
½iaq mole=L
where i represents LA, FA, sulphuric acid or furfural. The organic
phase concentrations were determined using the mass balance,
and taking into account the mass of water leached to the organic
phase and the mass of solvent leached to the aqueous phase.
3. Results and discussion
Eight physical solvents were evaluated, both as monomolecular
solvent, and as diluent when in a composite solvent with an extrac-
tant. In addition the process side product, furfural, was evaluated
as described by Nhien et al. [38]. Though in presence of sulphuric
acid, furfural was found to be unstable and formed humins.
188 T. Brouwer et al. / Separation and Purification Technology 185 (2017) 186–195

Fig. 1. The conceptual design of the process which separates LA, FA and furfural from an acidic aqueous solution. In the acid section, LA and FA are extracted, and sulphuric
acid (the catalyst), is fully recovered and recycled to the reaction section.

3.1. Physical solvent evaluation
A series of 8 different physical solvents was evaluated for
extracting the complex mixture containing all four components
LA, FA, furfural and sulphuric acid. The obtained distribution coef-
ficients for LA, FA, furfural and sulphuric acid are presented in
Fig. 2, whereas the mutual solubility’s of these physical solvents
and water are given in Fig. 3.
As can be seen from Fig. 2, dodecane and toluene show only
affinity towards furfural, although the distribution in dodecane is
low. In addition furfural has the highest distribution coefficient
with respect to the other compounds in all physical solvents. This

Fig. 2. The distribution coefficient of LA, FA, furfural and sulphuric acid at 25 °C for
8 different physical solvents. Fig. 3. Mutual solubility of water and organic solvents at 25 °C.
 T. Brouwer et al. / Separation and Purification Technology 185 (2017) 186–195
can be attributed to the high activity coefficient of furfural in water
[45], making the extraction of furfural from the aqueous phase into
an apolar phase highly energetically favorable. For the alcohols, it
was found that the extraction of LA and FA increases as the molec-
ular size of the alcohol decreases. This trend can be assigned to the
increasing relative amount of functional hydroxyl groups in
the organic phase with decreasing molecular size of the alcohols.
The alcohols are thus less suitable for selective removal of furfural
from the mixture. Sulphuric acid extraction is negligible in all
investigated physical solvents, which is due to the unfavorable
solvation of the dissociated sulphuric acid in the hydrophobic
environments.
Next to toluene, also MIBK showed good furfural extraction
capacity, however, as follows from Fig. 3, MIBK leaches signifi-
cantly. Therefore the toluene may be considered most suitable
for the furfural removal prior to acid fractionation. Toluene was
also described in the patent by De Jong et al. for furfural removal
[46].
3.2. Composite solvent evaluation
The extraction capacity of composite solvents can benefit from
complexation interactions between the solute and the extractant.
In order to investigate whether a beneficial interaction for LA is
possible, without too strong co-extraction of sulphuric acid, three
different extractants, trioctylamine (TOA), trioctylphosphine oxide
(TOPO) and 4-tert-butylbenzenediol (TB), have been evaluated in
combination with several diluents. TOA and TOPO are well known
extractants for acid extractions [12,33,37], while also alkylphenols
are known to extract LA [17]. The LA distribution into TB is
expected to benefit from TB’s two hydroxyl groups.
3.2.1. Simple mixtures with only LA and sulphuric acid
The experimental results concerning the extraction of LA and
sulphuric acid with TOA, TOPO and TB in various diluents are pre-
sented in Fig. 4.
As can be seen in Fig. 4a and b, the extraction of LA and sul-
phuric acid increases as function of the TOA concentration, except
when hexanoic acid or 1-octanol are used as diluents. At 30 wt.% of
TOA, the molar distribution coefficient of TOA for sulphuric acid
was observed to be 0.77–0.84 for all diluents, except for hexanoic
acid, for which the capacity at 30 wt.% was only 0.47, indicating
hexanoic acid is counteracting the complexation of TOA with sul-
phuric acid. 1-Octanol as diluent also causes a slight decrease in
the distribution coefficient of LA as function of the TOA concentra-
tion, though the molar capacity is not decreased relative to the
other diluents.
Due to the low pH of the aqueous phase, LA is present in its
undissociated form. Therefore it is likely that the extraction is done
via H-bonding and solvation [47]. Senol et al. [47] also explain the
high distribution coefficient of LA when using toluene as diluent by
p-system–carboxylic group stabilization interaction during the
complexation stage. In the case of hexanoic acid as diluent, adducts
are potentially formed between the hexanoic acid and TOA, which
can decrease the capability for interactions with the sulphuric acid,
as is supported by the experimental observations.
The significant extraction of dissociated sulphuric acid can be
explained by ion pair formation with TOA. The highest selectivity
of 4.4 was obtained with hexanoic acid and 10 wt.% of TOA. At
30 wt.% of TOA independent of the diluent used, the selectivity
drops to approximately 0.5.
A negligible amount of sulphuric acid was observed in the
extract when using TOPO as an extractant, as can be seen in Fig. 4d.
This was also observed by Shuyun et al. [48] when using TOPO
diluted in heptane. The lack of sulphuric acid extraction may be
explained by the fact that TOPO is a solvatizing carrier [49], instead
189
of an anion-active carrier such as high aliphatic amines. Solvatizing
carriers form non-stoichiometric complexes with neutral solutes,
thereby making sulphuric acid extraction unlikely. The solvation
mechanism, extraction without the formation of complexes, will
also be present.
In Fig. 4f, it can be seen that also a negligible amount of sul-
phuric acid was found in the extract when TB was used as an
extractant, which is comparable to the extraction with TOPO in
Fig. 4d. In contrary to the results for TOPO and TOA, hexanoic acid
as diluent results in the highest distribution coefficient for LA, as
can be seen in Fig. 4e. This may be explained by the absence of a
complexation interaction and solely the solvation mechanism
was predominant. The dimer formation between hexanoic acid,
LA and TB were not disrupting complexation interactions, but were
possibly enhancing the solvation mechanism.
Due to the low selectivity arising from the preferential extrac-
tion of sulphuric acid. TOA was considered an unsuitable extrac-
tant to isolate LA from an acidic aqueous mixture. For this
reason, TOA was not evaluated in the following experiments where
additionally FA and furfural was added to the complex acidic aque-
ous mixture.
3.2.2. Complex mixtures containing LA, FA, furfural and sulphuric acid
3.2.2.1. Trioctylphosphine oxide (TOPO). The experimental results
concerning the extraction of LA, FA, furfural and sulphuric acid
with TOPO in various diluents are presented in Fig. 5.
In Fig. 5a an increasing distribution coefficient of LA with
increasing TOPO concentration can be observed for MIBK and
toluene, whereas for hexanoic acid the LA distribution coefficient
drops with increasing TOPO concentration, and for 1-octanol as
diluent the distribution coefficient is constant. In Fig. 5b, it can
be seen that with 1-octanol as a diluent also the formic acid distri-
bution coefficient is more or less stable, at values just over 2. With
hexanoic acid as diluent, FA extraction was not very significant,
while for toluene and MIBK an increasing distribution with
increasing TOPO concentration was measured, similar to LA. In
Fig. 5c significant distribution coefficients for furfural can be
observed, which coincides with statements made during the phys-
ical solvent screening. It was however observed that the selectivity
between FA and LA can be significantly influenced through selec-
tion of the appropriate diluent. Sulfuric acid extraction is negligible
for all diluents with TOPO.
3.2.2.2. 4-tert-butylbenzenediol (TB). The experimental results con-
cerning the extraction of LA, FA, furfural and sulphuric acid with
TB in various diluents are presented in Fig. 6. There were no exper-
iments done using toluene as diluent, because the solubility of TB
in toluene was found to be very low.
It follows from Fig. 6a that the distribution coefficient of LA
increases with hexanoic acid as diluent up to a value of about
1.2, i.e. higher than the highest value observed with TOPO. How-
ever, FA is not extracted very well using hexanoic acid as diluent,
as follows from Fig. 6b. In all cases, just as with TOPO, the furfural
has a higher distribution coefficient than the acids, and will be co-
extracted when it is not removed prior. Based on the extraction
results at 25 °C, TOPO with toluene and with MIBK, as well as TB
in hexanoic acid were selected for studies on temperature swing
back extraction.
3.3. Temperature swing back extraction equilibrium
The solvent screening in the previous sections confirmed the
possibility of selectively removing furfural from an aqueous mix-
ture containing LA, FA and sulphuric acid with toluene, followed
by selective extraction of the carboxylic acids FA and LA with com-
190 T. Brouwer et al. / Separation and Purification Technology 185 (2017) 186–195

Fig. 4. The distribution coefficient of LA and sulphuric acid at 25 °C for 7 different diluents containing TOA (A & B), TOPO (C & D) and TB (E & F).

posite solvents containing TB and TOPO as extractant without the
co-extraction of sulphuric acid.
In order to obtain a pure LA product, the carboxylic acids need
to be recovered from the solvent, and fractionated. For this solvent
regeneration and acid fractionation, either a direct distillation from
the solvent could be applied, or a back-extraction followed with a
distillation from an aqueous stream. For the last option, tempera-
ture swing back extraction (TSBE) was attempted. Back extraction
experiments at 50 °C, 75 °C and 90 °C, seen in Fig. 7, showed a
decreasing distribution coefficient of LA with increasing tempera-
 T. Brouwer et al. / Separation and Purification Technology 185 (2017) 186–195 191

Fig. 5. The distribution coefficient of LA (A), FA (B), furfural (C) and sulphuric acid (D) at 25 °C for 4 different diluents containing TOPO.

Fig. 6. The distribution coefficient of LA, FA, furfural and sulphuric acid at 25 °C for 3 different diluents containing TB.
192 T. Brouwer et al. / Separation and Purification Technology 185 (2017) 186–195
ture for 30 wt.% of TOPO in MIBK and toluene, however no signifi-
cant temperature dependency was observed using 30 wt.% of TB in
hexanoic acid.
The absence of a temperature dependency in the mixture con-
taining TB limits the applicability of TSBE to zero, and this solvent
can thus not be used for this application. The composite solvent
30 wt.% TOPO in MIBK was found to obtain the highest distribution
coefficient for LA and in addition showed a strong temperature
dependency, it was therefore chosen as most appropriate solvent
for this recovery strategy, and the TSBE was studied in more detail
for this solvent.
The molar concentrations of LA and FA are related to the molar
ratio units which are used in the McCabe-Thiele method [50];
½LAaq ½FAaq ½LAo
X LA ¼ ; X FA ¼ Y LA ¼ ; assumed that all furfural is already removed via extraction with
1  ½LAaq 1  ½FAaq 1  ½LAo
½FAo
Y FA ¼
1  ½FAo
where X is the molar ratio in the aqueous phase, Y is the molar ratio
in the organic phase and the concentrations of the acids are in
weight fractions. Because the acid concentrations are relatively
low, in Eq. (2) only the acids themselves and the solvent are consid-
ered. The equilibrium isotherms of LA and FA have been determined
at 25 °C and 90 °C and are shown in Fig. 8. Three regions of LA
extraction behavior were observed, as can be seen in Fig. 8a. Region
I is at low concentrations of LA, where a significant fraction of LA is
likely in the dissociated form, and at increasing acid concentration,
more of the weak acid will be in the undissociated form. This buffer-
ing equilibrium causes the line to flatten off in the region II, where
the undissociated LA becomes predominant. In region III an over-
load of LA in the organic phase is seen. The shape of the LA iso-
therms are consistent with a type II adsorption isotherm
described by Brunauer [51] and is associated with multimolecular
BET adsorption. [52] Due to the complex nature of the BET
isotherms and the relative small amount of data points. The
isotherms are fitted via a 5th degree polynomial function (see
Tables 1 and 2):
Y LA ¼ a5 X 5LA þ a4 X 4LA þ a3 X 3LA þ a2 X 2LA þ a1 X LA þ b
Tamada et al. [53] also observed Type II isotherms of carboxylic
acids in amine extractants and assigned the overload to higher
order stoichiometric complexations between the carboxylic
acid and amine extractant. TOPO most likely forms neutral
Fig. 7. The temperature dependency of three composite solvents; TOPO (30 wt.%) in
MIBK, TOPO (30 wt.%) in toluene and TB (30 wt.%) in hexanoic acid. The deviation in
the distribution coefficient is ± 10%.
non-stoichiometric complexes with LA. Hence, a specific stoi-
chiometry could not be coupled to these isotherms. The FA behav-
ior could be described by a Freundlich isotherm [54], as can be seen
in Fig. 8b:
1
Y FA ¼ K  X nFA ð4Þ
3.4. Process design
A schematic overview of a Temperature Swing Bach Extraction
(TSBE) is given in Fig. 9. Two Counter-Current Extraction column
are used, where a solvent is circulated between both columns.
The feed of the process was defined to contain; 8.4 wt.% LA,
5.3 wt.% FA and 10.5 wt.% sulphuric acid in water. It has been
toluene, see Fig. 1. As can be seen in Fig. 9, there are four operation
points that can be distinguished, A1, A2, B1 and B2.
ð2Þ
Under the condition of minimal solvent to feed ratio, point A1
describes the equilibrium of the aqueous feed stream with the exit-
ing organic stream, the extract. To really reflect a minimum solvent
to feed ratio, A2 for the exiting aqueous stream (the raffinate) is
also drawn on the equilibrium line. The raffinate is in equilibrium
with the organic stream coming from the back extraction column.
Both equilibria are in the forward extraction column at 25 °C. The
Point B1 represents the point where the loaded organic stream
enters the back-extraction. The organic phase composition is thus
equal to that of A1, and the aqueous phase composition is selected
such that the operating line of the back extractor does not cross the
equilibrium line at 90 °C. At minimal Wash to Extract ratio, point
B1 indicates equilibrium between the water wash stream leaving
the back extraction column and the organic stream entering. The
organic phase composition of point B2 in the back-extractor is
linked to the composition of the raffinate in the extractor, since
the solvent is cycled back to the extraction with that composition.
The maximum driving force for washing the acids out of the sol-
vents is obtained when clean wash liquor is entering the back-
extractor, hence, X(B1) = 0.
The following procedure is applied to design the TSBE opera-
ð3Þ tion, see Fig. 10;
(1) Point A1 is set on the 25 °C equilibrium line, at the known
acid feed concentration.
(2) A2 is an operator choice which is on the 25 °C equilibrium
line. The choice of A2 may be limited by the 90 °C back
extraction equilibrium. By choosing A2, also the B2 operation
point will be defined. Any acids left in the raffinate will not
be lost, but may be recycled back in the process, see Fig. 1,
thus depending on the back-extraction considerations, the
choice for a relatively high raffinate concentration that
may be necessary for technical feasibility is not necessarily
detrimental for the process feasibility.
(3) Point B1 is again an operator choice. An aqueous concentra-
tion as high as possible was chosen here, so the highest
obtainable acid concentration in the product stream was
obtained.
(4) From point B1 to B2 the operation line of the back extraction
will hit the equilibrium line of 90 °C at a minimum wash to
extract ratio, (W/E)min.
The solvent to feed ratio, (S/F), and the wash to extract ratio,
(W/E), can be determined from operational lines resp. A1-A2 and
B1-B2 by the following equation [50];
     
F F
Y out ¼ X out þ Y in X in ð5Þ
S S
 T. Brouwer et al. / Separation and Purification Technology 185 (2017) 186–195 193

Fig. 8. The isotherm extraction profiles of LA and FA at 25 °C and 90 °C between water and the composite solvent TOPO (30 wt.%) in MIBK.

Table 1
The fitting parameters of the LA isotherms at 25 °C and 90 °C for a 5th degree polynomial function. The error in Y LA is given as twice the standard deviation, e.g. a 95% confidence
interval.

a5 a4 a3 a2 a1 b error
3
25 °C 389.6 365.3 134.8 24.00 2.297 7.992  10 3.001  103
90 °C 207.1 174.5 60.43 11.14 1.382 4.181  103 3.292  104

Table 2 coupling both McCabe-Thiele approaches seen in Fig. 10a and b.

The fitting parameters of the FA Freundlich isotherms at 25 °C and 90 °C. The error in
Y FA is given as twice the standard deviation, e.g. a 95% confidence interval.
K n error
25 °C 0.1329 3.202 5.997  103
90 °C 0.1105 2.775 3.425  103
From the operating equation, see Eq. (4), the solvent to feed
ratio, or wash to extract ratio, can be determined by taking the
inverse of the slope. If the operating line simulate a limited case,
than the minimum solvent to feed ratio, (S/F)min, or minimum
wash to extract ratio, (W/E)min, can be obtained.
Fig. 10 simulated a TSBE operation wherein a minimum solvent
to feed ratio, (S/F)min = 0.78, and a minimum wash to extract ratio,
(W/E)min = 0.39, is used. Though each isotherm has been measured
independently, the co-extraction of both acids is simulated by
The coupling is done by keeping the slopes of the operation lines
between A1 and A2, and B1 and B2, equal for both acids. By keeping
the slopes equal in both approaches, the same extraction operation
is simulated simultaneously, thereby reflecting the co-extraction of
LA and FA. Resulting from the TSBE operation, two aqueous raffi-
nate streams are obtained starting with the feed concentration, F.
R1 is the recycle stream which is lean on LA and FA, while R2 is
the aqueous stream where LA and FA are concentrated. The extrac-
tion of LA was observed to be the limiting factor, due to the fact
that during the forward extraction FA cannot achieve equilibrium
at 25 °C due to the equilibrium line of the back extraction at
90 °C. The result of the TSBE operation is that LA and FA are con-
centrated with a factor of resp. 1.69 and 1.58.
An increase in solvent to feed ratio or wash to extract ratio,
causes the operational lines to become less steep. If the acid feed
concentration is set and both operational lines become less steep,

Fig. 9. A temperature swing back extraction (TSBE) Operation where the forward extraction is performed with 30 wt.% TOPO in MIBK at 25 °C and the back extraction is
performed with water at 90 °C.
194 T. Brouwer et al. / Separation and Purification Technology 185 (2017) 186–195
Fig. 10. McCable-Thiele graphic approach to simulate a temperature swing back extraction between 25 °C and 90 °C of (a) LA and (b) FA. From the operational lines follow a
(S/F)min and (W/E)min of resp. 0.78 and 0.39.
Fig. 11. McCable-Thiele graphic approach to simulate a second temperature swing back extraction between 25 °C and 90 °C of (a) LA and (b) FA. From the operational lines
follow a (S/F)min and (W/E)min of resp. 0.48 and 0.28.
the raffinate, A1, must be become richer in acid. Also the product,
B1, must become leaner in acid in order to keep the operational
lines within the border of the equilibrium lines. For this reason it
would be most beneficial to operate the TSBE operation as to the
(S/F)min and (W/E)min as possible.
Until now, a single TSBE operation was simulated. This method
can be repeated to concentrate the acid to a further extent, hence a
double TSBE is obtained in Fig. 11. The aqueous concentration of R2
from the initial TSBE operation is equal to the aqueous feed con-
centration of the second TSBE operation.
By applying a second TSBE operation, LA and FA are additionally
concentrated with a factor of resp. 1.45 and 1.55. Combining both
TSBE operations the LA and FA concentration are concentrated
with a factor of resp. 2.45 and 2.45. During both TSBE operations
an aqueous raffinate stream was obtained lean on LA and FA.
Though, both raffinate streams decreases the total amount of LA
and FA in the product stream, these raffinate streams may be recy-
cled to the reaction section, see Fig. 1, preventing any loss of LA and
FA.
A rough estimation of the heater duty for pre-dehydrating the
product stream via a double TSBE is made in AspenPlus. Heating
the organic phase and the water wash stream to 90 °C will be the
sources of the heater duty. In addition a heat exchanger is present
to minimize the energy requirement. A minimum temperature dif-
ference of 10 °C over the heat exchanger over the cold outlet and
hot inlet stream was assumed. Roughly a heater duty of 4.5 GJ
per produced tons of LA was necessary to concentrate LA and FA
with a factor of resp. 2.45 and 2.45. Still, distillation has to be done
to isolate LA from the aqueous FA mixture. Via the heat of vapor-
ization of FA and water, this evaporation operation was estimated
to require roughly 11.3 GJ per tons of produced LA on heater duty.
Without the double TSBE operation, this evaporation would have
required roughly 31.5 GJ per tons of produced LA on heater duty.
4. Conclusions
From an exploratory solvent study selective extraction of LA
from an aqueous solution containing solely sulphuric acid was
observed using polar solvents. In addition TOA was deemed unsuit-
able due to the significant extraction of sulphuric acid. The possi-
bility of selective removal of furfural using apolar solvents, in
particular toluene was likewise observed. MIBK may also be used
to extract furfural, though a lower selectivity to furfural is
observed. Both TB as TOPO were suitable extractants for the selec-
tive extraction of both LA and FA. It was observed that 1-octanol
can enhance the FA extraction, while hexanoic acid suppresses this
extraction. A double TSBE was performed to concentrate LA and FA
with a factor of resp. 2.45 and 2.45 using a heater duty of 4.5 GJ per
produced tons of LA. The heater duty of the final distillation col-
umn drops due to the TSBE operations from approximately 31.5
 T. Brouwer et al. / Separation and Purification Technology 185 (2017) 186–195 195

to 11.3 GJ per produced tons of LA. These rough calculations show [23] W.W. Moyer, Preparation of levulinic acid, 1942, US2270328 A.
[24] J.E. Cuzens, W.A. Farone, A method for the production of levulinic acid and its
the potential energy savings by pre-dehydrating an aqueous feed
derivatives, 1998, EP0937024 A1.
via TSBE operations. [25] J.Y. Cha, M.A. Hanna, Levulinic acid production based on extrusion and
Raising the environmental and toxicity issue of using toluene pressurized batch reaction, Ind. Crops Prod. 16 (2002) 109–118.
for the extraction of furfural. An alternative multistage fractional [26] J. Dumesic, J. Bond, D. Alonso, T. Root, Method to produce and recover levulinic
acid and/or gamma-valerolactone from aqueous solutions using alkylphenols,
extraction column could also be designed to fractionate LA, FA 2013, WO2012162028 A1.
and furfural from an aqueous solution containing sulphuric acid [27] E. Ramos-Rodriguez, Process for jointly producing furfural and levulinic acid
by the same composite solvent as in the LA and FA extraction, from bagasse and other lignocellulosic materials, 1972, US3701789 A.
[28] C.P. Sassenrath, W.L. Shilling, Preparation of levulinic acid from hexose-
30 wt.% TOPO in MIBK. containing material, 1966, US3258481 A.
[29] W.A. Frey, J.W. Brown, J.P. Kelly, M.E. Carroll, P.C. Guion, Method for producing
Acknowledgements levulinic acid from lignocellulosis biomass, 2013, US20150052806 A1.
[30] C. Chang, P. Cen, X. Ma, Levulinic acid production from wheat straw, Biores.
Technol. 98 (2007) 1448–1453.
This has been an ISPT project. ISPT is Institute for Sustainable [31] L.J. Carlson, Process for the manufacture of levulinic acid, 1962, US3065263 A.
Process Technology, headquartered in Amersfoort, the [32] A.P. Dunlop, J.P.A. Wells, Process for producing levulinic acid, 1957,
US2813900 A.
Netherlands. [33] H. Uslu, S.I. Kırbaslar, Equilibrium studies of extraction of levulinic acid by
(trioctylamine (TOA)+ ester) solvents, J. Chem. Eng. Data 53 (2008) 1557–
References 1563.
[34] R. Canari, A.M. Eyal, Selectivity in monocarboxylic acids extraction from their
mixture solutions using an amine-based extractant: effect of pH, Ind. Eng.
[1] T. Werpy, G. Petersen, Top Value Added Chemicals from Biomass: Results of
Chem. Res. 42 (2003) 1301–1307.
Screening for Potential Candidates from Sugars and Synthesis Gas, U.S.,
[35] Y.K. Hong, W.H. Hong, Removal of acetic acid from aqueous solutions
Department of Energy, 2004.
containing succinic acid and acetic acid by tri-n-octylamine, Separat.
[2] S. Bertarione, F. Bonino, F. Cesano, S. Jain, M. Zanetti, D. Scarano, A. Zecchina,
Purificat. Technol. 42 (2005) 151–157.
Micro-FTIR and micro-Raman studies of a carbon film prepared from furfuryl
[36] M.E. Marti, T. Gurkan, Selective recovery of pyruvic acid from two and three
alcohol polymerization, J. Phys. Chem. B 113 (2009) 10571–10574.
acid aqueous solutions by reactive extraction, Sep. Purif. Technol. 156 (2015)
[3] B. Girisuta, L.P.B.M. Janssen, H.J. Heeres, Kinetic study on the acid-catalyzed
148–157.
hydrolysis of cellulose to levulinic acid, Ind. Eng. Chem. Res. 46 (2007) 1696–
[37] M. Wisniewski, M. Pierzchalska, Recovery of carboxylic acids C1–C3 with
1708.
organophosphine oxide solvating extractants, J. Chem. Technol. Biotechnol. 80
[4] J.G. De Vries, J.A. Kroon, R.F.M.J. Parton, P.L. Woestenborghs, A. De Rijke,
(2005) 1425–1430.
Process for the production of furfural and levulinic acid from lignocellulosic
[38] L.C. Nhien, N.V.D. Long, S. Kim, M. Lee, Design and assessment of hybrid
biomass, 2013, EP2872495 A1.
purification processes through a systematic solvent screening for the
[5] T. Retsina, V. Pylkkanen, K. Nelson, R. O’connor, Processes and apparatus for
production of levulinic acid from lignocellulosic biomass, Ind. Eng. Chem.
producing furfural, levulinic acid, and other sugar-derived products from
Res. 55 (2016) 5180–5189.
biomass, 2014, WO2014105289 A1.
[39] A. Krzyzaniak, B. Schuur, A.B. de Haan, Equilibrium studies on lactic acid
[6] B.D. Mullen, D.J. Yontz, C.M. Leibig, Process to prepare levulinic acid, 2013,
extraction with N,N-didodecylpyridin-4-amine (DDAP) extractant, Chem. Eng.
US9073841 B2.
Sci. 109 (2014) 236–243.
[7] S.W. Fitzpatrick, Production of levulinic acid from carbohydrate-containing
[40] F.S. Oliveira, J.M.M. Araujo, R. Ferreira, L.P.N. Rebelo, I.M. Marrucho, Extraction
materials, 1997, US5608105 A.
of L-lactic, L-malic, and succinic acids using phosphonium-based ionic liquids,
[8] M.A. Lake, S.W. Burton, W.C. Fuller, R. Sasser, M.E. Lindstrom, J.T. Wheless,
Sep. Purif. Technol. 85 (2012) 137–146.
Production of levulinic acid and levulinate esters from biomass, 2010,
[41] M. Blahusiak, S. Schlosser, J. Martak, Extraction of butyric acid with a solvent
US20100312006 A1.
containing ammonium ionic liquid, Sep. Purif. Technol. 119 (2013) 102–111.
[9] N.A.S. Ramli, N.A.S. Amin, A new functionalized ionic liquid for efficient
[42] A.I. Pratiwi, T. Yokouchi, M. Matsumoto, K. Kondo, Extraction of succinic acid
glucose conversion to 5-hydroxymethyl furfural and levulinic acid, J. Mol.
by aqueous two-phase system using alcohols/salts and ionic liquids/salts, Sep.
Catal. A: Chem. 407 (2015) 113–121.
Purif. Technol. 155 (2015) 127–132.
[10] B.C. Redmon, Process for the production of levulinic acid, 1956, US2738367 A.
[43] K. Tonova, I. Svinyarov, M.G. Bogdanov, Biocompatible Ionic Liquids in Liquid-
[11] J. Ahlkvist, S. Ajaikumar, W. Larsson, J.-P. Mikkola, One-pot catalytic
Liquid Extraction of Lactic Acid: A Comparative Study, Int. J. Chem. Mol. Nucl.
conversion of Nordic pulp media into green platform chemicals, Appl. Catal.
Mat. Metallurg. Eng. 9 (2015) 558–562.
A 454 (2013) 21–29.
[44] E. Reyhanitash, B. Zaalberg, S. Kersten, B. Schuur, Extraction of volatile fatty
[12] J. Reunanen, P. Oinas, T. Nissinen, A process for recovery of formic acid, 2009,
acids from fermented wastewater, Sep. Purif. Technol. 161 (2016) 61–68.
WO2009130386A1.
[45] M.O. Hertel, K. Sommer, Limiting separation factors and limiting activity
[13] R. Jansen, J.A. Lawson, N. Lapidot, B. Hallac, R. Perry, Methods for preparing
coefficients for 2-furfural, c-nonalactone, benzaldehyde, and linalool in water
thermally stable lignin fractions using various biomass types, 2014,
at 100 °C, J. Chem. Eng. Data 51 (2006) 1283–1285.
WO2014179777A1.
[46] W. De Jong, G. Marcotullio, Overview of biorefineries based on co-production
[14] C.G. Yoo, C.-W. Lee, T.H. Kim, Two-stage fractionation of corn stover using
of furfural, existing concepts and novel developments, Int. J. Chem. React. Eng.
aqueous ammonia and hot water, Appl. Biochem. Biotechnol. 164 (2011) 729–
8 (2010).
740.
[47] A. Senol, Influence of conventional diluents on amine extraction of picolinic
[15] M.S. Tunc, J. Chheda, E. van der Heide, J. Morris, A. van Heiningen, Two-stage
acid, Sep. Purif. Technol. 43 (2005) 49–57.
fractionation and fiber production of lignocellulosic biomass for liquid fuels
[48] X. Shuyun, Y. Yonghui, Y. Yanzhao, S. Sixiu, B. Borong, Extraction of sulfuric
and chemicals, Ind. Eng. Chem. Res. 52 (2013) 13209–13216.
acid with TOPO, J. Radioanal. Nucl. Chem. 229 (1998) 161–163.
[16] V.M. Ghorpade, M.A. Hanna, Method and apparatus for production of levulinic
[49] M. Siebold, P.V. Frieling, R. Joppien, D. Rindfleisch, K. Schügerl, H. Röper,
acid via reactive extrusion, 1999, US5859263A.
Comparison of the production of lactic acid by three different lactobacilli and
[17] V. Badarinarayana, M.D. Rodwogin, B.D. Mullen, I. Purtle, E.J. Molitor, Processes
its recovery by extraction and electrodialysis, Process Biochem. 30 (1995) 81–
to prepare levulinic acid, formic acid and/or hydroxymethyl furfural from
95.
various biomass materials, 2014, WO2014189991A1.
[50] A.B. De Haan, H. Bosch, Liquid-liquid extraction, in: Industrial Separation
[18] S.W. Fitzpatrick, Lignocellulose degradation to furfural and levulinic acid,
Processes: Fundamentals, Walter de Gruyter, 2013.
1990, US4897497 A.
[51] S. Brunauer, L.S. Deming, W.E. Deming, E. Teller, On a theory of the van der
[19] D. Hayes, Report on optimal use of DIBANET feedstocks and technologies, EU’s
Waals adsorption of gases, J. Am. Chem. Soc. 62 (1940) 1723–1732.
Seventh Framework Programme, 2013.
[52] J.D. Seader, E.J. Henley, D.K. Roper, Adsorption, ion exchange, chromatography,
[20] A. De Rijke, G.W.A. Hangx, R.F.M.J. Parton, B. Engendahl, Process for the
and electrophoresis, in: Separation Process Principles, 3rd ed., John Wiley &
isolation of levulinic acid, 2014, WO2014087013 A1.
Sons, 2010, p. 821.
[21] G.-T. Jeong, S.-K. Kim, D.-H. Park, Detoxification of hydrolysate by reactive-
[53] J.A. Tamada, A.S. Kertes, C.J. King, Extraction of carboxylic acids with amine
extraction for generating biofuels, Biotechnol. Bioprocess Eng. 18 (2013) 88–
extractants. 1. Equilibria and law of mass action modeling, Ind. Eng. Chem. Res.
93.
29 (1990) 1319–1326.
[22] J.A. Dumesic, D.M. Alonso, E.I. Gürbüz, S.G. Wettstein, Production of levulinic
[54] H. Freundlich, The impact of the adsorption in the precipitation of suspension
acid, furfural, and gamma valerolactone from C5 and C6 carbohydrates in
colloid, Zeitschrift für Physikalische Chemie 73 (1910) 385–423.
mono- and biphasic systems using gamma-valerolactone as a solvent, 2013,
US8399688 B2.