Separation and Purification Technology 191 (2018) 328–339

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Separation and Purification Technology

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

Bio-butanol separation by adsorption on various materials: Assessment of T

isotherms and effects of other ABE-fermentation compounds
⁎
Francesca Raganatia, , Alessandra Procenteseb, Giuseppe Olivieria, Maria Elena Russob,
Piero Salatinoa, Antonio Marzocchellaa
a
Dipartimento di Ingegneria Chimica, dei Materiali e della Produzione Industriale – Università degli Studi di Napoli Federico II, P.le V. Tecchio 80, 80125 Napoli, Italy
b
Istituto di Ricerche sulla Combustione – Consiglio Nazionale delle Ricerche, P.le V. Tecchio 80, 80125 Napoli, Italy

A R T I C L E I N F O A B S T R A C T

Keywords: In the general effort to produce chemicals and fuels from renewable resources there is new interest in the
Adsorption biotechnological route to produce butanol. Acetone-Butanol-Ethanol (ABE) fermentation leads to low product
Fermentation broth yield because butanol is toxic to microorganisms. Selecting an efficient technology to recover butanol from low
Butanol concentration butanol (about 2%) solutions is key to a successful implementation of this butanol production
Selectivity
process on an industrial scale. Adsorption has been suggested as a potential technology for butanol recovery.
Amberlites
This paper reports a systematic investigation of the adsorption of the metabolites that are typically present in
the ABE fermentation broth: acetone, butanol, ethanol, acetic acid, butyric acid, yeast extract. The effect of
glucose as a carbon source for the ABE fermentation was also investigated. Three adsorbents were characterized:
Amberlite XAD-4, Amberlite XAD-7 and Zeolite Y. Batch tests under a wide interval of operating conditions were
carried out for the assessment of the adsorption capacities of the three adsorbents. The selectivity of the three
adsorbent materials towards the main components of ABE broths was also investigated. These tests were carried
out using both dilute model solutions and real fermentation broths.
The tests show that Amberlite XAD-7 has the highest affinity for butanol adsorption. The co-presence of all the
metabolites in the solution - synthetic broth and real broth - changes the distribution in the adsorbed phase
remarkably. The distribution of the concentration of the adsorbed components can be affected by pH. The
presence of glucose does not affect butanol adsorption. Amberlite XAD-7 has a great potential as an adsorbent in
ABE fermentation coupled with in situ recovery product removal techniques.

1. Introduction
The production of butanol via the biotechnological route is a pro-
mising process. The typical biotechnological route is based on Acetone-
Butanol-Ethanol ABE) fermentation, a quite old process that is still of
interest [22]. The industrial success of this route is hindered by several
significant engineering challenges because the inhibiting effect of bu-
tanol on microorganisms limits its final concentration: about 2% w/w
[24,25,11]. This limited concentration has two consequences: the need
for a product recovery process that is very efficient even at low butanol
concentrations; the partial conversion of the substrate during fermen-
tation because cells stop converting substrate under harsh conditions
[28].
An efficient technique to recover butanol from the ABE fermenta-
tion broth is key to the success of butanol production on an industrial
scale. The recovery unit can be off-line – downstream the fermentation
unit – or integrated with the fermentation unit. Having the two units
integrated leads to less toxic broth and longer fermentation and can
reduce plant/operation costs improving the overall process efficiency.
The fermentation and recovery operations can be integrated in many
ways. However, a pre-requisite of recovery is that the energy require-
ment for butanol separation is lower than the butanol energy content
(36 MJ/kg).
Table 1 reports the energy demand for butanol recovery from the
fermentation broth – or synthetic mixtures – with the separation pro-
cesses that are known nowadays.
According to previous investigations [10,5,12,18,1,26,8,31] the
energy required to recover butanol recovery may be as large as the
butanol energy content. Therefore, the energy gain of the butanol
production process can be close to zero – or negative – when the energy
required by the other process steps – e.g. feedstock pre-treatments,
fermentation, auxiliary operations - is included in the overall balance.

⁎
Corresponding author.
E-mail address: francesca.raganati@unina.it (F. Raganati).

http://dx.doi.org/10.1016/j.seppur.2017.09.059
Received 29 June 2017; Received in revised form 11 September 2017; Accepted 26 September 2017
Available online 28 September 2017
1383-5866/ © 2017 Elsevier B.V. All rights reserved.
F. Raganati et al. Separation and Purification Technology 191 (2018) 328–339

Table 1
Energy requirement to separate ABE from fermentation broth using different recovery techniques.

Recovery process Butanol concentration jump MJ/kgButanol Ref.

Hybrid process gas-stripping/distillation (GSD) from 0.78 wt% to pure 21 [10]

Gas-stripping/pervaporation/distillation (GSPD) hybrid process from 1 wt% to > 99.5 wt% 23 [5]
Extraction/distillation (ED) from 2.2 wt% ABE to 92 wt% ABE 4 [12]
Pervaporation/distillation (PD) from 1 wt% to pure 4 [18]
Adsorption/drying/desorption (ADD) From 2 wt% to 98 wt% 3.4 [1]
Liquid-liquid extraction (LLE) From 1.8 wt% to 99.5 wt% 9.9 [31]
Gas stripping/absorption/distillation (GSAD) From 1.8 wt% to 99.5 wt% 10 [32]

The analysis of the data reported in Table 1 suggests that the energy
requirement for adsorption is the lowest when compared to other
techniques. This process consists in using solid materials – named ad-
sorbents – that chemically-physically bind to the adsorbate, i.e. the
species adsorbed. Under properly selected operating conditions it is
possible to recover a target compound from a solution.
Adsorbents are generally more biocompatible than solvents as well
as fully immiscible and unsusceptible to emulsification. Thanks to these
features they can be easily separated from cultures and potentially re-
generated and reutilised. The butanol stream recovered after the ad-
sorbent regeneration is a rich solution of the compounds adsorbed and a
further concentration operation is required to produce a pure butanol
stream [3].
A spectrum of factors must be taken into account during the selec-
tion of suitable adsorbents: adsorption rate, adsorption capacity, com-
plexity of the desorption operation, selectivity for the desired product,
and cost of the adsorbent and of the regeneration operation. The ad-
sorption kinetics directly affects the contact time required between the
solution containing the adsorbate and the adsorbent [38]. The ad-
sorption capacity, selectivity and complexity of the regeneration op-
eration depend on the type of solid adsorbent used.
The selectivity of the adsorbent towards butanol significantly affects
the performance of the recovery process because the ABE fermentation
broth contains numerous species: substrates, nutrients and metabolites
[6]. Apart from solvents, the main components of the ABE fermentation
broth are sugars, butyric acid and acetic acid. The adsorption of these
components would subtract them from their further fermentation with
an increase in the cost of fermentation. Nielsen et al. [19] tuned the pH
value of the solutions miming the ABE fermentation broth to control the
adsorption of butyric acid. However, it is not clear whether this ap-
proach is applicable to all the adsorbents and also to acetic acid. In this
framework, the highly efficient recovery of butanol is still an open issue
with adsorption.
There is a great deal of literature on separation and recovery of
butanol from model solutions. A wide range of materials such as
polymeric resins, activated carbon, zeolites have been used as butanol
adsorbents from model solutions and fermentation broths
[15,19,37,20,21,33,34,36,29,30] . Zeolites and activated carbons are
characterized by high adsorption capacity for butanol [35,21,33,34].
Despite all these studies on butanol adsorption, only few investigations
have been carried out using various adsorbents to assess the adsorption
rate, the effect of temperature, pH and of the other components that are
typically present in fermentation broths [19]. The majority of the works
reported in literature are mainly concerned with the assessment of the
adsorption capacity of the adsorbent selected.
This work reports a systematic investigation of the adsorption of the
metabolites that are typically present in the ABE fermentation broth:
acetone, butanol, ethanol, acetic acid, butyric acid, sugar, yeast extract.
Three adsorbents – Amberlite XAD-4, Amberlite XAD-7 and Zeolite Y –
were investigated. Batch tests – under a wide interval of operating
conditions – were carried out for the assessment of the adsorption ca-
pacity of the three adsorbents. The selectivity of the three adsorbent
materials towards the main components of ABE broths was also in-
vestigated to find the most suitable adsorbent material for butanol re-
covery. Tests were also carried out using model ABE solutions and the
real ABE fermentation broth.
2. Materials and methods
2.1. Materials
Three adsorbent materials were investigated: Amberlite XAD-4,
Amberlite XAD-7 and Zeolite Y. The chemicals used in this study were
of high-purity analytical grade from Sigma-Aldrich.
The Amberlites were used after washing with water. Zeolite Y was
used after calcination at 500 °C for 4 h.
Table 2 reports some relevant features of the adsorbents in-
vestigated.
1-Butanol (Sigma, purity 99.5%), acetone (Sigma, purity 99.9%)
and ethanol (Sigma, purity 99.9%), acetic acid (Sigma, purity 99.9%),
butyric acid (Sigma, purity 99.9%) and glucose (Sigma) were used.
2.2. Test procedure
Batch adsorption equilibrium tests were carried out in 50 mL closed
vials filled with 25 mL liquid solution. The vials contained a pre-set

Table 2
Adsorbent features (Sigma-Aldrich Product Information Sheet).

Materials Chemical nature Dry density Specific superficial Pore diameter Specific pore
(g/mL) area (m2/g) (Angstrom) volume. (mL/g)

Amberlite XAD- Hydrophobic polyaromatic (dipol moment 0.3). Used to remove small 1.08 725 50 0.98
4 hydrophobic compounds, surfactants; used to remove chlorinated
organics, pesticides, etc.

Amberlite XAD- Acrylic ester (dipol moment 1.8). Used to adsorb molecules up to MW 1.24 450 90 1.14
7 60000; insulin recovery, metal ions, dry waste, organic compounds
removal and recovery, antibiotic recovery)

Zeolite Y SiO2/Al2O3 Mole Ratio: 80 – 700 – 0.5

Nominal Cation Form: Hydrogen
Na2O Weight %: 0.03
Unit Cell Size, A: 24.24

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F. Raganati et al.
amount of butanol, acetone, ethanol, acetic acid, butyric acid, glucose,
water and adsorbent. Typically, 0.5 g of adsorbent were used. The vials
were placed in a thermostatic shaker for 24/48 h with agitation at
120 rpm. All the adsorption tests were carried out in duplicate.
Prefixed masses of sorbent (ma,0) and volumes of solution (V0) were
mixed and kept in a thermostatic shaker (rotation rate 120 rpm) for 24/
48 h. The solution was periodically sampled. Each sample was cen-
trifuged for 10 min at 10000 rpm and the concentration of the in-
vestigated component (ci) in the recovered supernatant was measured.
Equilibrium conditions was assumed when the concentration of the
components were constant with the time. The component uptake per
unit mass of adsorbent at equilibrium (qi,e) was determined by pro-
cessing the mass balance of the investigated component extended to the
volume of liquid. In particular, Eq. (1) was used.
(ci,0−ci,e )·V0
qi,e =
ma,0 (1)
where Ci,0 is the initial concentration of adsorbate in the solution, Ci,e
the concentration of the adsorbate in the solution at the equilibrium.
2.3. Theoretical framework
The adsorption isotherm for single component was described ac-
cording to the Langmuir-type model for single site adsorption (Eq. (2))
under the assumption of water adsorption negligible:
qmax ,i ·KL,i·Ci,e
qi,e =
1 + KL,i·Ci,e (2)
where qi,e is the i-component uptake per unit mass of adsorbent at
equilibrium, qmax,i the maximum uptake of i-component per unit mass
of adsorbent, KL,i an adsorption constant for the i-component and Ci,e
the concentration of the i-component in the solution at the equilibrium.
The data of adsorption at constant temperature of the i-component
in a multi-component mixture – containing j components – were de-
scribed according to the Langmuir model for adsorption of component
(i) as reported in Eq. (3)) [23,9]:
qmax ·KL,i·Ci,e
qi,e = n used for the analysis of acids acetic acid, butyric acid) and alcohol
1+ ∑ KL,j·Cj,e
j=1 (3)
where qmax is the monolayer capacity (the amount of adsorbate per unit
mass of adsorbent required to occupy all adsorption sites on the solid
surface) and KL,j an adsorption constant for the i-component.
The Langmuir model parameters were estimated using nonlinear
least squares regression via the lsqcurvefit function in MATLAB.
2.4. Adsorption test typologies and operating conditions
Adsorption tests may be grouped as follows:
SCA – single component adsorption isotherm. The liquid phase con-
tained just one solvent (butanol, ethanol, acetone). The initial con-
centration of the solvent was set up to a value larger than the maximum
concentration typically reached at the end of the ABE fermentation
(acetone and ethanol 0.1–30 g/L for both; butanol: 0.1–50 g/L). Tests
were carried out at pre-set temperatures (25, 30, 37, and 45 °C) to as-
sess the adsorption isotherms for acetone, butanol, and ethanol.
MCA – multi component adsorption isotherm. The isotherms were as-
sessed at 37 °C. Five classes of mixtures were tested.
TM: Ternary mixture of acetone, butanol and ethanol. The operating
conditions were: ABE molar ratio set at 3:6:1; total ABE initial
concentration set at 5, 10, 20, 30, and 60 g/L. The A:B:E ratio was
measured during the adsorption tests and solvents were supple-
mented to keep the ratio constant at 3:6:1.
TM-G: ABE ternary mixture supplemented with glucose. The operating
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Separation and Purification Technology 191 (2018) 328–339
conditions were: ABE molar ratio set at 3:6:1; total ABE initial
concentration set at 20 g/L; initial glucose concentration set at 0.5,
1, 10, and 30 g/L.
TM-A: ABE ternary mixture supplemented with acetic and butyric acids.
The operating conditions were: ABE molar ratio set at 3:6:1; total
ABE initial concentration set at 20 g/L; total initial concentration of
acids set at 0.5, 1, 10, and 15 g/L. Two test campaigns were carried
out: the first campaign was based on tests carried out without any
control of the initial pH of the mixture; the second campaign was
based on tests carried out setting the initial pH at 5. The second
campaign was carried out with the best adsorbent candidate for the
butanol recovery based on SCA and MCA-TM tests.
TM-AG: ABE ternary mixture supplemented with acids and glucose. The
operating conditions were: ABE molar ratio set at 3:6:1; total ABE
initial concentration set at 20 g/L; the initial concentration of glu-
cose set at 30 g/L; total initial concentration of acids was set at 0.5,
1, 10, and 15 g/L. The initial pH of the mixture was not controlled.
SB and RB: Synthetic broth and real broth. SB tests were carried out
with a solution of ABE, yeast extract, acetic acid, butyric acid, and
sugar. The concentration of the components was set to mime the
composition of a real fermentation broth. The initial pH was not
controlled. RB tests were carried out with the cell-free fermentation
broth from the biofilm reactor system described in Raganati et al.
[28]. The composition of the ABE synthetic solution and of the broth
is reported in Table 3.
2.5. Analytical methods
Sugar concentration. Sugar concentration was measured by means of
high performance liquid chromatography (HPLC) using an Agilent 1100
system (Palo Alto, CA). Sugars were separated on a 8 µm Hi-Plex H,
30 cm 7.7 mm column at room temperature and detected by means of a
refractive index detector. Deionized water was used as mobile phase at
a flow rate of 0.6 mL/min. 20 µL of sample were injected in the column.
Typically, sugar resolution was carried out in 10–13 min [27].
Acid and alcohol concentration. A GC apparatus equipped with a FID,
and outfitted with a capillary column Poraplot Q 25 m × 0.32 mm) was
ethanol, butanol) concentration. An internal standard hexanoic acid)
was used to assess acids and alcohols and their concentrations [28].
3. Results and discussion
There is a reasonable amount of literature on butanol recovery from
ABE fermentation broths using adsorbents (Ezeji et al., 2007; Milestone
and Bibby, 1983); [7,26,17,16], but very few investigations report
quantitative information – e.g. Langmuir adsorption parameters - to
support the modelling of adsorption columns [21,33]. In this work,
results from batch adsorption tests using Amberlite XAD-4, Amberlite
XAD-7 and Zeolite Y as adsorbent are reported. Binary component
Table 3
Concentration of the main components of a synthetic broth and ABE fermentation broth
after [28].
Component Concentration – g/L
SB* RB**
Glucose 50 55
Yeast Extract 5 Not measured
Acetic Acid 3.7 4
Butyric Acid 5.3 5.8
Acetone 2.3 2.7
Butanol 13 13.5
Ethanol 1.7 2
* pH = 2.9.
** pH = 4.7.
F. Raganati et al.
adsorption tests – e.g. adsorption in aqueous solutions of one solvent –
and multicomponent adsorption tests – e.g. adsorption in aqueous so-
lutions of solvents and sugar and/or acids - were carried out.
The Langmuir adsorption isotherms were assessed processing binary
and/or multicomponent data. The adsorption tests were carried out
with a model ABE fermentation solution and with a cell-free ABE fer-
mentation broth to assess the adsorption selectivity in multicomponent
adsorption tests.
3.1. SCA - single component adsorption isotherm
Figs. 1–3 report the adsorption isotherms of butanol, acetone, and
ethanol adsorbed from binary hydrocarbon/water solutions in the three
selected adsorbent materials at different temperatures (25 °C, 30 °C, 37,
45 °C). The qe vs. ce behaviour observed for the binary couples solvent-
adsorbent was typical for adsorption on microporous materials. Butanol
has the highest affinity for all the materials tested; this trend is in
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Separation and Purification Technology 191 (2018) 328–339
Fig. 1. Amberlite XAD-4 adsorption isotherms.
agreement with many works reported in the literature [13,14,4,20].
Acetone and ethanol have a progressively lower affinity. The scale of
affinity observed was as expected: it may be rationalized in terms of the
relative hydrophobicity of the solvents and the hydrophobic character
of the adsorbent.
The adsorbed concentration vs. liquid phase concentration under
equilibrium conditions suggests that the Langmuir model may be used
for all the solvents and adsorbents investigated. The experimental data
were processed in agreement with the Langmuir model Eq. (2): the
saturation loading (qmax) and the Langmuir adsorption constant (KL)
assessed for the couple solvent-adsorbent investigated are reported in
Table 4 for the four temperatures investigated. The plots of the Lang-
muir model – setting the model parameters as reported in Table 4 – are
reported in Figs. 1–3. The fitting was successful for the three solvents
whatever the adsorbent material and the temperature.
Table 4 shows that the butanol adsorption capacity of Amberlite
XAD-4, Amberlite XAD-7, and Zeolite Y increases with the temperature
F. Raganati et al.
while that of acetone and ethanol decreases. This opposite behaviour of
the three solvents is mainly due to the different effect of temperature on
the solvent solubility in water. Actually temperature affects the ad-
sorption process – e.g. the adsorption rate and the repartition among
the phases – and also the solubility of the adsorbate in the solution. The
solubility of a substance affects its chemical potential, which in turn
controls adsorption: the solubility factor cannot be neglected when
investigating the adsorption of components from solutions. The re-
lationship between solubility and chemical potential was expressed as
[23]: ‘The greater the solubility of a substance in any solvent, the less
the potential for any given concentration.’ According to these ob-
servations, if the solubility of the adsorbate increases with temperature,
both effects – repartition and solubility - work in the same direction and
the adsorption decreases with temperature. On the contrary, if the so-
lubility of the adsorbate decreases with temperature, the global effect of
temperature on adsorption depends on the dominant factor. For a large
number of chemicals in aqueous solutions solubility is characterized by
a positive temperature coefficient: the general idea that the adsorption
from aqueous solutions always decreases with increasing temperature is
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Separation and Purification Technology 191 (2018) 328–339
Fig. 2. Amberlite XAD-7 adsorption isotherms.
acceptable. The positive effect of the temperature increase on butanol
adsorption for all the investigated adsorbents was caused by the de-
crease in the solubility of butanol whatever the adsorbent material, in
agreement with the data reported by Lin et al. [13]. It should be pointed
out that at a temperature higher than the investigated range the butanol
solubility increases with the temperature and a negative effect of the
temperature on the adsorption is expected.
The analysis of the adsorption isotherms and of the Langmuir
parameters reported in Figs. 1–3 and Table 4 suggests that Amberlite
XAD-7 is characterized by the best results in terms of butanol adsorp-
tion capacity. Indeed, the qmax for Amberlite XAD-7 was almost three
times that of Amberlite XAD-4 and Zeolite Y.
3.2. MCA – Multi component adsorption isotherm
The results reported in this section refer to tests carried out at 37 °C
with aqueous solutions of Acetone-Butanol-Ethanol (molar ratio 3:6:1).
The temperature and the molar ratio of the solvents were typical of a
fermentation broth.
F. Raganati et al. Separation and Purification Technology 191 (2018) 328–339

Fig. 3. Zeolite Y adsorption isotherms.

Table 4
Langmuir parameters for Amberlite XAD-4, Amberlite XAD-7 and Zeolite Y at the investigated temperature.

Solvent Langmuir parameters R2

qmax – mg/gads KL – L/g

25 °C 30 °C 37 °C 45 °C 25 °C 30 °C 37 °C 45 °C 25 °C 30 °C 37 °C 45 °C

Amberlite XAD-4 Acetone 70.9 63.2 56.0 48.5 1.42 2.90 1.56 0.94 0.98 0.98 0.99 0.98
Butanol 118 162 187 272 0.23 0.17 0.25 0.21 0.99 0.99 0.99 0.99
Ethanol 52.3 34.8 11.8 9.40 0.83 2.15 1.39 1.13 0.98 0.99 0.93 0.96

Amberlite XAD-7 Acetone 293 251.3 225 223 1.40 0.73 0.80 0.44 0.93 0.98 0.99 0.98
Butanol 400 438 538 761 0.20 0.21 0.21 0.20 0.99 0.99 0.99 0.99
Ethanol 127 120 115 109 1.60 0.93 0.57 0.43 0.92 0.97 0.99 0.99

Zeolite Y Acetone 71.0 61.0 48.9 39.5 2.32 1.20 0.92 0.69 0.98 0.97 0.99 0.98
Butanol 154 182 222 244 0.14 0.24 0.19 0.18 0.99 0.99 0.99 0.99
Ethanol 43.3 25.4 22.3 9.76 1.26 0.86 0.40 1.00 0.98 0.95 0.99 0.96

333
F. Raganati et al. Separation and Purification Technology 191 (2018) 328–339

Fig. 4. Acetone-Butanol-Ethanol competitive adsorption on

(A) Amberlite XAD-4, (B) Amberlite XAD-7 and (C) Zeolite
Y. Initial ABE molar ratio 3:6:1. Temperature 37 °C. Solid
lines: plots of Eq. (3) (parameters in Table 5). Dashed lines:
plots of Eq. (2) (parameters in Table 4).

Table 5 Langmuir isotherm setting the model parameters as reported in Table 5.

Competitive Langmuir parameters for Amberlite XAD-4, Amberlite XAD-7 and Zeolite Y at The plot of the Langmuir model (Eq. (2)) for the three solvents - setting
37 °C.
the model parameters as reported in Table 4 – is also reported.
Solvent Langmuir parameters R2
An expected result comes from the comparison of the adsorption
capacity of the investigated materials with respect to the solvents
qmax – mg/gads KL – L/g measured for single solvent solutions and for ABE solutions.
Competitive adsorption leads to a lower adsorption capacity of a sol-
Amberlite XAD-4 Acetone 232 0.041 0.95
Butanol 0.058
vent when it is mixed in the ABE system, as pointed out by Lin et al.
Ethanol 0.022 [14] and Abdehagh et al. [4]. As a consequence, the Langumir constants
referred to a solvent (acetone, butanol or ethanol) and assessed based
Amberlite XAD-7 Acetone 737 0.043 0.96
Butanol 0.069 on tests carried out on solutions of that single solvent cannot be ex-
Ethanol 0.018 tended to describe the recovery of the same solvent when mixed with
Zeolite Y Acetone 336 0.025 0.96 other solvents.
Butanol 0.039 The analysis of data in Fig. 4 points out that butanol was the most
Ethanol 0.017 adsorbed solvent under the operating conditions tested. The adsorbed
concentrations of acetone and ethanol were lower than that of butanol
and – as expected – the concentration of acetone was higher than that of
3.2.1. MCA TM
ethanol (see result section “SC isotherm”). The preference towards the
Fig. 4 reports the adsorption capacities of the three solvents (qi,e) vs.
butanol over the other solvents proves that all the adsorbent materials
the liquid phase concentration under equilibrium conditions. The initial
tested were quite selective towards butanol.
ABE concentration was set at 5, 10, 20, 30, and 60 g/L. Data regression
according to the competitive multicomponent Langmuir isotherm (Eq.
(3)) was carried out and the calculated competitive isotherm model
3.2.2. MCA TM-G
parameters for the three tested materials are reported in Table 5. Fig. 4
Tests were carried out at total ABE initial concentration set at 20 g/
reports the plots (solid line) of the competitive multicomponent
L. The initial glucose concentration was set at 0.5, 1, 10, and 30 g/L to

334
F. Raganati et al.
mime the possible sugar residue present in the fermentation broth.
Fig. 5 reports equilibrium data assessed from the adsorption tests.
The analysis of the figure points that:
• glucose was not adsorbed on the investigated solids whatever the
initial glucose concentration;
• the presence of glucose in the solution did not affect the solvent
adsorption. The concentration of the adsorbed solvents was almost
unchanged even at the highest concentration of the sugar. Line et al.
[14] also reported a negligible adsorption of glucose on KA-resin.
On the contrary, Abdehagh et al. [2] reported a significant adsorp-
tion of glucose on activated carbon F-400. Therefore, the adsorbent
features play a key role in the sugar adsorption.
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Separation and Purification Technology 191 (2018) 328–339
Fig. 5. Acetone-Butanol-Ethanol and glucose competitive
adsorption on (A) Amberlite XAD-4, (B) Amberlite XAD-7
and (C) Zeolite Y. Initial ABE molar ratio 3:6:1. Initial ABE
concentration 20 g/L. Glucose concentration 0–30 g/L.
Temperature 37 °C.
The results reported are very interesting as regards the ABE fer-
mentation performance. Glucose is one of the principal sources of
carbon for microorganisms and its low (absent) adsorption makes the
broth utilisable after the adsorption process without any loss of feed-
stock.
3.2.3. MCA TM-A
Tests were carried out at total ABE initial concentration set at 20 g/
L. The ratio acetic/butyric acids (AA/AB) was set at 0.7 g/g according
to the experimental observation reported by Raganati et al. [28]. Two
test campaigns were carried out: the first campaign was based on tests
carried out without any control of the initial pH of the mixture; the
second campaign was based on tests carried out setting the initial pH at
F. Raganati et al.
5.
Fig. 6 reports the adsorption capacities of the three adsorbents for
the three solvents and the two investigated (acetic and butyric) acids at
different total initial concentration of acids under equilibrium condi-
tions. The data refer to tests carried out without any control of the
initial pH.
The main results of the analysis of Fig. 6 are as follows:
• The total amount of adsorbed matter (solvents plus acids) did not
change with the mass of supplemented acids. The total adsorbed
mass was: about 120 mg/g for Amberlite XAD-4, about 300 mg/g for
Amberlite XAD-7, about 140 mg/g for Zeolite Y. It can be inferred
that adsorbent materials were saturated under the operating con-
ditions investigated.
• As the concentrations of total acids increased, butanol/solvent ad-
sorption decreased and that of acids increased, whatever the
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Separation and Purification Technology 191 (2018) 328–339
Fig. 6. Acetone-Butanol-Ethanol and acids competitive ad-
sorption on (A) Amberlite XAD-4, (B) Amberlite XAD-7 and
(C) Zeolite Y. Initial ABE molar ratio 3:6:1. Initial ABE
concentration 20 g/L. AA/AB mass ratio set at 0.7 g/g.
Temperature 37 °C. No pH control.
adsorbent material. The adsorption sites for acids and solvents were
the same. Any supplementation of acids caused the redistribution of
solvent-acids for the same adsorption sites. The observed behaviour
was more pronounced for Amberlite XAD-4 and Zeolite Y than
Amberlite XAD-7.
• For Amberlite XAD-4 and Zeolite Y, the equilibrium loading (qe) of
butyric acid was higher than that of butanol as the total con-
centration of the acids was higher than 10 g/L. The strong compe-
tition between butanol and butyric acid may be due to their similar
chemical structure, the acid being more hydrophilic.
The adsorption of the acetic and butyric acids has a double dis-
advantage for the fermentation/recovery process. These acids are used
during the solventogenic phase to achieve high butanol and ABE yields
and production. Therefore, the acid capture subtracts potential feed-
stock for the ABE fermentation. Furthermore, acids adsorption may
F. Raganati et al.
Fig. 7. Acetone-Butanol-Ethanol and acids competitive adsorption on Amberlite XAD-7.
Initial ABE molar ratio 3:6:1. Initial ABE concentration 20 g/L. AA/AB mass ratio set at
0.7 g/g. Temperature 37 °C. pH 5.
introduce additional problems during the further butanol concentration
and purification. As a result of these observations, Amberlite XAD-7
seems to be a good candidate for butanol recovery because it was
characterized by high selectivity towards butanol.
Amberlite XAD-7 was used in the test campaign aimed at assessing
the effect of pH on adsorption. Tests were carried out setting the initial
pH of the solutions at 5.0, above the pKa of both acids: 4.76 for acetic
acid, 4.82 for butyric acid. The equilibrium solid phase concentration of
the individual components (acetone, butanol, ethanol, acetic and bu-
tyric acid) in the experiments is reported in Fig. 7.
The analysis of the results reported in Fig. 7 confirms the observa-
tions reported for Fig. 6B except for the extent of the acid adsorption.
The total amount of adsorbed matter was about 300 mg/g under both
operating conditions: uncontrolled and controlled pH. When pH in-
creased, the adsorbed acids decreased and the adsorbed solvents in-
creased. The comparison of data in Figs. 6B and 7 suggests that there is
a clear difference in the adsorption behaviour of the protonated and
deprotonated form of the acids: the protonated form was characterized
by higher affinity for Amberlite XAD-7 than the deprotonated one. The
different affinity may be due to the hydrophobicity of molecules: de-
protonated molecules being more polar than the protonated molecules.
As a result, it is possible to control the affinity of the butyric and acetic
acids for the Amberlite XAD-7 by adjusting the pH of the solution. The
same effect of the solution pH on the adsorption selectivity may be
expected for Amberlite XAD-4 and Zeolite Y.
3.2.4. MCA TM-AG
Tests were carried out supplementing acids and glucose to an ABE
solution. The solutions were characterized by total ABE concentration
20 g/L, glucose concentration 30 g/L, AA/AB mass ratio at 0.7 g/g
[28]. The total acid concentration was increased up to 15 g/L based on
experimental data reported by Raganati et al. [28]. No pH control.
The results of the tests confirm the absence of glucose adsorption.
Moreover, the distribution of solvents and acids in the adsorbent phase
was not affected by the presence of glucose. Results of the MCA-TM-AG
tests were not reported.
3.2.5. MCA SB & RB
SB tests were carried out with a synthetic fermentation broth
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Separation and Purification Technology 191 (2018) 328–339
characterized by the concentration reported in Table 3. The con-
centration of the components in the solid phase (qe,i) and in the liquid
phase under equilibrium conditions for the three investigated ad-
sorbents are reported in Fig. 8A–C. The analysis of Fig. 8A–C points out
that:
• butanol was characterized by the highest affinity whatever the in-
vestigated adsorbent materials. In particular, the concentration on
Amberlite XAD-7 was 4 times higher than on Amberlite XAD-4 and
Zeolite Y;
• glucose was not adsorbed whatever the adsorbent material;
• butyric acid was characterized by higher affinity for the tested ad-
sorbent materials than did acetic acid.
• both butanol and butyric acid were preferentially adsorbed when
compared to the other main components that may be found in the
ABE fermentation broth.
RB tests were carried out with the fermentation broth produced
from the biofilm reactor system described in Raganati et al. [28] and
fed with a 100 g/L glucose solution. The composition of the fermenta-
tion broth is reported in Table 3. The concentration of the components
in the solid phase (qi,e) and in the liquid phase under equilibrium
conditions for the three investigated adsorbents are reported in Fig. 8 D,
E and F. The analysis of Fig. 8 D, E and F points out that:
• butanol was characterized by the highest affinity among the three
solvents whatever the investigated adsorbent materials. In parti-
cular, the concentration on Amberlite XAD-7 was 3 times higher
than on Amberlite XAD-4 and Zeolite Y;
• glucose was not adsorbed whatever the adsorbent material;
• acetic acid and butyric were poorly adsorbed whatever the tested
adsorbent materials;
• butanol was preferentially adsorbed when compared to the other
main components present in the ABE fermentation broth.
The comparison of the results of SB and RB adsorption tests confirms
the effect of pH on the adsorption process. The total amount of ad-
sorbed matter did not change remarkably for SB (pH=2.9) and RB
(pH=4.7) tests but the distribution of the adsorbed components
changed. The comparison of data in Fig. 8A–C and D–F suggests that
there is a clear difference in the adsorption behaviour of the protonated
and deprotonated form of the acids: the protonated form was char-
acterized by higher affinity than the deprotonated one whatever ad-
sorbent material.
4. Conclusions
Batch adsorption tests were successfully carried out to characterize
and select the best adsorption material for butanol recovery from ABE
fermentation broth. Three adsorbents were investigated: Amberlite
XAD-4, Amberlite XAD-7 and Zeolite Y.
The tests carried out with aqueous solutions of a single solvent
proved that Amberlite XAD-7 was characterized by the highest ad-
sorption capacity for butanol. The results suggest that the adsorption
capacity increased with increasing temperature for T < 45 °C. The
equilibrium data were successfully modelled according to the Langmuir
model.
The selectivity of the three investigated adsorbents towards butanol
in model solutions and real fermentation broths was also investigated.
Amberlite XAD-7 confirmed to be characterized by high affinity for
butanol and to a lesser extent for butyric acid: the adsorption capacity
for other fermentation broth components was very low. Tests carried
out under controlled pH pointed out that the adsorption of the acids
was strongly pH dependent: high/low adsorption at pH smaller/higher
than the acid pKa. This effect opens up for controlled adsorption of
selected products.
F. Raganati et al.
Fig. 8. Initial and equilibrium liquid composition and adsorption capacity for Acetone-Butanol-Ethanol, acids and glucose from synthetic broth (A, B and C) and real fermentation broth
(D, E and F) on Amberlite XAD-4, Amberlite XAD-7 and Zeolite Y. Initial ABE, acids and glucose concentration are also reported in Table 3. Temperature 37 °C.
The Langumir constants of a solvent (acetone, butanol or ethanol)
and assessed based on tests carried out with solutions of the single
solvent cannot be extended to describe the recovery of the same solvent
when mixed with other solvents. The characterization of the solvent
mixture distribution between the liquid phase and the solids phase is
required.
Glucose presence did not have any effect on butanol adsorption
whatever the adsorbent tested. Therefore, the broth stream could fur-
ther fermented after recovering the solvent.
Acknowledgements
The authors are grateful to Mrs. Stella Romanucci for her precious
assistance in the experimental work. The authors thank the European
Union’s Horizon 2020 research and innovation program for the fi-
nancial support to the project Waste2Fuels (grant agreement No.
654623).
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