J Nanopart Res (2015)17:401 DOI 10.
1007/s11051-015-3205-0
RESEARCH PAPER
Intensification of the separation of CuO nanoparticles
from their highly diluted suspension using a foam flotation
column with S type internal
Nan Hu . Rui Li . Zhao-liang Wu .
Di Huang . Hong Zhen Li
Received: 6 August 2015 / Accepted: 29 September 2015
© Springer Science+Business Media Dordrecht 2015
Abstract Foam flotation is a promising technique
for recovering nanoparticles from their highly diluted
suspensions. In this work, a novel S type internal was
developed to intensify the foam flotation of CuO
nanoparticles (357.6 nm in average particle size)
from their suspension of 6.2 9 10-2 mmol/L. By
enhanc- ing foam drainage, the S type internal
increased the enrichment ratio of CuO nanoparticles
by
139.3 ± 12.5 % without significantly affecting their
recovery percentage. Under the optimal conditions of
Cetyl trimethyl ammonium bromide (CTAB) concen-
tration 0.45 mmol/L, superficial airflow rate 2.6 mm/
s, and volumetric feed rate 1.0 mL/min, the enrich-
ment ratio and recovery percentage of CuO nanopar-
ticles reached 81.6 ± 4.1 and 95.4 ± 4.9 %,
respectively, using the foam flotation column with
the S type internal. Furthermore, about 95 % CTAB
could be recycled by recovering CTAB from the
foamate and the residual solution. The recovered
CuO nanoparticles were associated with CTAB
molecules, so they had better dispersity and
dispersion stability than the starting CuO
nanoparticles. Therefore, they would have good
reusability.
Nan Hu and Rui Li have contributed equally to the work.
N. Hu · R. Li · Z. Wu (&) ·D. Huang H. Z. Li
·
School of Chemical Engineering and Technology, Hebei
University of Technology, No.8 Guangrong Road, Dingzi
Gu, Hongqiao District, Tianjin 300130, China
e-mail: zhaoliangwu_hebut@163.com
Keywords Foam flotation · S type internal · CuO
nanoparticles · Enrichment ratio · Colloids
Introduction
Nanoparticles, which are defined as particles between
1 and 100 nm in size, are a bridge between bulk
materials and atomic or molecular structures (Rao
and Cheetham 2011). Due to their extremely high
specific surface areas, nanoparticles possess
unexpected optical, elec- tric, thermal, magnetic, or
chemical properties, so they have wide applications
in biomedical, optical, food, and electronic fields
(Qiang et al. 2006; Rehman et al. 2011; Aresta et al.
2013; Lyubutin et al. 2013). However, nanoparticles
also result in serious environmental pollution and
harm to human health (Donaldson et al. 2006),
because they readily diffuse to air and water and
become suspended in them (Stone et al. 2007; Valca
´rcel 2011). As the applications of nanoparticles are
increas- ingly wide in daily life, their pollution to the
environ- ment becomes more serious. Therefore, the
effective removal of nanoparticles from air or water
has been a greatly important issue in the fields of
nanotechnology and environmental protection.
The removal or recovery of nanoparticles from
water faces two major challenges: one is that they
cannot freely precipitate due to their high dispersity
in water and the other is that their concentrations in
water are extremely low (Westerhoff et al. 2011; Liu
et al. 2010). Thus, centrifugation and membrane
1
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separations

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401 Page 2 of 11
are not suitable options due to their high separation
costs. Activated sludge process, as an industrial
method for wastewater treatment, has high perfor-
mances in removing nanoparticles (Westerhoff et al.
2011; Limbach et al. 2008). However, it needs long
processing time and it also results in the large loss of
useful nanoparticles. For flocculation and cloud point
extraction, the subsequent separation of low-concen-
tration precipitates by centrifugation or membrane
separation needs high costs, despite the high removal
percentages (Liu et al. 2010; Zhang et al. 2008).
Similar to cloud point extraction, foam flotation also
uses surfactants to capture fine particles. However,
foam flotation is able to highly enrich the targeted
fine particles into a very small volume by using rising
foam as the separation medium (Shen 1998). Thus,
the costs for the subsequent separation will be largely
reduced. Furthermore, this technique has low cost
and high efficiency, so it is widely used in mining
industry to separate fine metallic mineral particles of
which the sizes are ranged from 1 lm to 10 mm
(Awatey et al. 2013). Therefore, foam flotation has
great potentials in effectively recovering
nanoparticles from their highly diluted suspensions.
The key to successful foam flotation of nanoparti-
cles is to obtain a high enrichment of them by
enhancing foam drainage. The effective enhancement
of foam drainage is achieved mainly by developing
new foam flotation columns (Dickinson et al. 2010).
At present, there are two major principles on which
the development of new columns is based. One is
increasing the contacting area between foams and
walls to allow the entrained liquid between bubbles
to quickly drain onto the walls and then return to the
bulk solution along them (Dickinson et al. 2010;
Yang et al. 2011; Lu et al. 2013) and the other is
successively expanding and contracting foam flows
to break the drainage balance and then continuously
decrease the liquid holdups in the foams (Saint-
Jalmes et al. 2000; Linke et al. 2005; Li et al. 2011).
Comparing the two principles, the latter is more
suitable to enhance the nanoparticle-containing foam,
because the nanoparti- cles will be more readily
adsorbed at various walls so that their recovery
percentage will be largely decreased (Guzman et al.
2005). However, the reported columns based on the
latter principle are not suitable for large-scale foam
flotation of nanopar- ticles. Specifically, the scale-up
of the Eiffel Tower- shaped, bowl-shaped, or
ellipsoid-shaped column will
J Nanopart Res (2015)17:401
result in a large loss of useful space (Saint-Jalmes et
al. 2000; Linke et al. 2005; Li et al. 2012). So
inserting an internal into a conventional foam
flotation column to achieve the successive expansion
and contraction of foam flows is more practical. A
foam riser was once used, but it readily trapped
nanoparticles in the dead zones of foam flow, thus
decreasing their recovery percentage (Li et al. 2011).
Therefore, it is necessary to develop new internals to
achieve the successive expansion and contraction of
foam flows to intensify the foam flotation of
nanoparticles from their highly diluted suspensions.
The objective of this work is to develop a new S
type internal to intensify the foam flotation of CuO
nanoparticles from their highly diluted suspension by
achieving the successive expansion and contraction
of foam flows. The selection of CuO nanoparticles as
a model is because of its wide applications in
catalysis and semiconductor manufacturing and its
toxicity to human bodies (Jing et al. 2015). Firstly,
the role of the S type internal in intensifying the foam
flotation of CuO nanoparticles from their highly
diluted suspen- sion will be studied. Then, the
recovery of the collector will be investigated. Finally,
the reusability of the recovered CuO nanoparticles
will be evaluated.
Materials and methods
Materials and reagents
CuO nanoparticles (99.5 % metals basis, 357.6 nm in
average particle size) were purchased from Aladdin
Industrial Co. Ltd., China. They were dispersed in
distilled water and then treated by an ultrasonic
cleaner (SK3200H, Shanghai Kudos Ultrasonic
Instru- ment Co. Ltd., China) for 1 h to obtain a
highly dispersed suspension of 5 mg/L at pH 6.5.
Cetyl trimethyl ammonium bromide (CTAB), sodium
dode- cyl sulfate (SDS), and tween 80 with analytical
grade were purchased from Tianjin Chemical
Reagent Co. Ltd., China.
Equipment
Figure 1 shows the schematic diagram of the
experi- mental setup for the continuous foam
flotation of CuO nanoparticles from their
J Nanopart Res (2015)17:401 Page 3 of 11 401
-2
suspension of 6.2 9 10 mmol/L. The foam
flotation column constructed by
Fig. 1 Schematic diagram
of the experimental setup
for continuous foam
flotation of CuO
nanoparticles from their
suspension of
6.2 9 10-2 mmol/L

transparent plexiglass had 1000 mm in height and (725N, Shang- hai Precision & Science Instrument
80 9 80 mm in cross-sectional area. The S type Co. Ltd., China) at a wavelength of 600 nm. The linear
internal made of transparent polypropylene plastic fitting equation is
had 600 mm in height, 80 mm in width, and 0.5 mm
in thickness. It was installed at the height of 400 mm
from the bottom of the column. In the experiments,
the foam flotation column with S type internal was
used as the experimental column, while the column
without the internal was used as the contrasted
column. At the foam- suspension interface, the feed
suspension, a mixture of CuO nanoparticles and their
collector, was pumped into the column by a
peristaltic pump (BT100-2J, Baoding Longer
Precision Pump Co. Ltd., China). At the bottom of
the column, the air was bubbled through a gas
distributor of sintered glass with a pore diameter of
380 ± 20 lm into the column by an air compressor
(AC0-318, Guangdong Hailea Group Co. Ltd.,
China) and its flow rate was controlled by a
rotameter (LZB-6T, 0.4–5.0 L/min, Wuhuan
Instrument Factory, China). All the foam
fractionation experiments were carried out at room
temperature 25 ± 2 °C.

Measurement of concentration of CuO

nanoparticles

The concentration of CuO nanoparticles was

measured by using a UV–Vis spectrophotometer

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A = 0.60CCuO-0.00157, R2 = 0.99998, where A is
the absorbance; CCuO (mmol/L) is the concentration
of CuO nanoparticles; and R is the linear correlation
coefficient.

Measurement of CTAB concentration

The concentration of CTAB was measured as the

method of Gerakis and Koupparis (1994) by using a
pBr-1-01 bromide selective electrode with a double-
junction saturated calomel reference electrode
(Yueci Electronic Technology Co. Ltd, Shanghai,
China), which was attached at a pHS-3C pH/mV
meter (Precision Scientific Instruments Co. Ltd.,
Shanghai, China). The standard curve for calculating
the CTAB concentration is E =
-48.90logCCTAB ? 20.13, R2 = 0.99906, where E
(mV) and CCTAB (mmol/L) are the conductivity value
and the CTAB concentra- tion, respectively.

Measurement of bubble diameters

The bubble diameters were measured by the

software Scion Image 4.03 (Scion Crop., USA) from
digital photographs (Nikon CooLPIX P6000) taken
through the transparent column wall. The
photographs were taken at five positions which had
distances of 100, 200, 300, 400, and 500 mm from
the foam-suspension interface, respectively. In each
photograph, at least

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300 bubbles were measured. The mean bubble diam- washed with distilled water. After 6 repeats of the
eter, d32, was calculated by Eq. (1) (Rakoczy and above procedures, the precipitate was dried by FD-
Masiuk 2009). 1A-50 vacuum freeze dryer (Beijing Boyikang
Pk 3 Laboratory Instruments Co., Ltd). Finally, the pure
d i
d ¼ d black powder of
i
P32 ;
i 2 CuO nanoparticles
nanoparticles werewas obtained. The
characterized recovered
by using CuO
a Fourier
ð1Þ
ki¼1
where di is the ith bubble diameter and n is the transform
number Co., USA)infrared spectrophotometer
and scanning (Nexus, Nicolet
electron microscope (SEM,
of bubbles. Nova Nano SEM450, FEI Co., USA). The average
Measurement of the liquid holdup of the foam particle sizes of CuO nanoparticles in SEM images
out of the column were determined using the software (Scion Image).
The size distributions of the CuO nanoparticles
When the continuous foam fractionation reached a before and after foam flotation were also analyzed by
steady state, the liquid holdup of the foam out of the Zetasizer Nano ZS (Nano-ZS90, Malvern Instruments
column was calculated by Eq. (2). Ltd., UK). Further- more, their dispersion stability
was also evaluated by measuring their concentration
variation with
suspension time
of an in the
initial CuO-nanoparticle
eout Qf concentration
¼ × 100 %; ð2Þ of 1.3 mmol/L.
Qf þ Qg
where Qf (mL/min) and Qg (mL/min) are the volu-
metric liquid velocity at the outlet of the foam Statistical analysis
fractionation column and the volumetric gas velocity,
respectively. Qf was calculated as Eq. (3). Each of the experiments was at least triply repeated.
Qf ¼ Qo — Qr; ð3Þ An analysis of variance of the data was performed by
using Microsoft Excel. The t test with p B 0.05 was
where Qo (mL/min) and Qr (mL/min) are the volu-
used to determine the difference between mean
metric velocities of the feed solution and residual
values. The standard deviation was provided for the
solution, respectively.
measured values.
Determination of foam flotation performances
Results and discussion
The performances of foam flotation were evaluated
by enrichment ratio (E) and recovery percentage (R)
Effects of surfactant type on enrichment ratio
defined as Eqs. (4) and (5).
and recovery percentage of CuO nanoparticles
Cf C0Q0 —
C
E rQ ð4Þ For foam flotation, the primary work is to select
¼r
C0 C0Qf by a TDZ-WZ centrifuge (Changsha Xiangyi Labora-
C0Q0 — CrQr tory Instrument Co., Ltd) at 4320 g for 5 min and then
R¼ 100
× %; ð5
Þ C0Q0
where C0, Cf, and Cr are the concentration of CuO
nanoparticles or CTAB in the feeding solution,
foamate, and residual solution (mmol/L),
respectively.

Characterization of the recovered CuO

nanoparticles

The CuO nanoparticles in the foamate were separated

suitable collectors which are able to capture the
targeted particles and then make them stably
adsorbed at the gas–liquid interface. Thus in this
section, the effects of surfactant type on the
enrichment ratio (ECuO) and recovery percentage
(RCuO) of CuO nanoparticles were investigated to
determine the suitable collector. The experiments
were carried out at superficial airflow rate 5.2 mm/s,
volumetric feed rate 2.0 mL/min, and
surfactant concentration
0.30 mmol/L using the contrasted column. The used
surfactants were CTAB, SDS, and Tween 80, as the
representatives of cationic surfactant, anionic surfac-
tant, and nonionic surfactant, respectively. The
results are presented in Table 1.
 From Table 1, ECuO and RCuO with CTAB were
much higher than those with SDS and Tween 80. It is
indicated that the cationic surfactant is the most
suitable to serve as the collector of CuO
nanoparticles at pH 6.5. Liu et al. (2010) observed
that the zeta potential of CuO nanoparticles was zero
at pH 6.0 and decreased to a negative value as pH
increased over this point. At pH 6.5, the surface of
CuO nanoparticles was negatively charged, so CTAB
was able to more effectively capture CuO
nanoparticles onto the gas– liquid interface than the
other two surfactants accord- ing to the charge
theory. So the surface excess of CuO nanoparticles
was much higher in the presence of CTAB, and then
ECuO and RCuO had much higher values than those with
the other two surfactants. Therefore, CTAB was
chosen as the suitable collector for the foam flotation
of CuO nanoparticles.
Process intensification of foam flotation of CuO
nanoparticles using S type internal
Role of S type internal in enhancing foam drainage
Before using the S type internal to intensify the foam
flotation of CuO nanoparticles, its role in enhancing
foam drainage was investigated in this section. Under
the same conditions as the above section, the effects
of S type internal on the variation of bubble diameter
(d32) with foam height and the liquid holdup of the
foam out of the column (eout) were investigated. The
results are shown in Fig. 2.
From Fig. 2, d32 with the S type internal (on the
left or on the right) was larger than that without the S
type internal at each foam height. It is indicated that
the S type internal intensified bubble coalescence. As
a result, eout without the S type internal was 1.5 times
higher than that with the S type internal. So the S
type internal enhanced foam drainage. The S type
internal divided the rising foam into two parts and
each of them underwent successive expansion and
contraction to gradually decrease its liquid holdup.
Therefore, the S
Table 1 Effects of surfactant type on enrichment ratio and recovery percentage of CuO nanoparticles
Surfactants CTAB
Enrichment ratio, ECuO 11.4 ± 1.5a
Recovery percentage, RCuO (%) 75.5 ± 3.3d
type internal had good ability to enhance foam
drainage.
Specifically, the foam flow on the left of the S
type internal suffered expansion and then contraction
and the tendency was just opposite on the right,
according to Fig. 1. So the two foam flows would
different drainage processes. The conjecture was
confirmed by the different variations of bubble
diameter with foam height in the presence of the S
type internal in Fig. 2. When the foam suffered
expansion, its flowrate became slow so that bubble
coalescence more readily occurred. Resultantly, a
higher level in foam drainage would be obtained (Li
et al. 2011), resulting in enhancing bubble
coalescence. As the foam suffered contraction, its
flow rate increased and thus bubble coalescence did
not readily occur. So the bubble diameter on the left
of the S type internal was larger and then smaller
than that on the right as foam height increased,
although the difference was not significant.
Effects of S type internal on ECuO and RCuO at different
CTAB concentrations
Due to the good ability of S type internal to enhance
foam drainage, it was used to intensify foam flotation
Fig. 2 Effects of S type internal on the variation of bubble
diameter with foam height and the liquid holdup of the foam
out of the column (eout)
SDS Tween 80
5.9 ± 0.7a 4.4 ± 0.5c
36.0 ± 1.5e 45.4 ± 2.3f
The superscripts ‘‘a, b, c, d, e, and f’’ indicate different significance levels with p B 0.05
of CuO nanoparticles from their highly diluted
suspension. CTAB was used as the collector of CuO
nanoparticles and also the foaming agent. Its concen-
tration certainly affected the foam flotation perfor-
mances. Thus in this section, the effects of S type
internal on ECuO and RCuO at different CTAB
concentrations were investigated. The experiments
were carried out at superficial airflow rate 5.2 mm/s,
volumetric feed rate 4.0 mL/min, and CTAB concen-
trations from 0.15 to 0.75 mmol/L. The results are
presented in Fig. 3.
From Fig. 3, ECuO with the S type internal was
higher than that without the S type internal at each
CCTAB and the difference decreased with increasing
CCTAB from 0.15 to 0.75 mmol/L. At CCTAB
0.15 mmol/L, ECuO had the highest relative increase
of 150 ± 15 %. For RCuO, its value with the S type
internal was slightly lower than that without the S
type internal at each CCTAB and the difference was
decreased as CCTAB increased. Furthermore, the
increase of RCuO became very slow as CCTAB increased
over 0.45 mmol/L. The results indicate that the S type
internal was able to effectively intensify the foam
flotation of CuO nanoparticles from their highly
diluted suspension.
The S type internal could effectively enhance foam
drainage, so it increased ECuO. The increased CCTAB
improved the adsorption of CTAB at the gas–liquid
interface so that bubble size decreased and foam
stability increased. In addition, the adsorption of CuO
nanoparticles was also improved to enhance the foam
stability (Binks and Horozov 2005). Resultantly, the
Fig. 3 Effects of S type internal on enrichment ratio and
recovery percentage of CuO nanoparticles at different CTAB
concentrations
ability of the S type internal to enhance foam
drainage was weakened. So the difference between
ECuO with the S type internal and that without the S
type internal gradually reduced as CCTAB increased. In
the rising foam, most CuO nanoparticles were
adsorbed at the gas–liquid interface rather than in the
entrained liquid between bubbles, so the enhanced
foam drainage did not largely decrease RCuO.
Furthermore, though the S type internal intensified
bubble coalescence, the desorbed CuO nanoparticles
could be re-adsorbed at the gas–liquid interface by
interacting with the adsorbed free CTAB molecules.
Therefore, the S type internal could not significantly
decrease the adsorption of CuO nanoparticles at the
gas–liquid interface so that it just slightly decreased
RCuO. As CCTAB increased over 0.45 mmol/L, most
CuO nanoparticles were associated with CTAB
molecules, so RCuO approached an asymptotic value.
Thus, 0.45 mmol/L was selected as the best CTAB
concentration. Because the amount of CuO
nanoparticles in the feed solution was much larger
than that adsorbed at the gas–liquid interface, the
asymptotic value of RCuO was much lower than 100
%.
Effects of S type internal on ECuO and RCuO at different
superficial airflow rates
In this section, the effects of S type internal on ECuO
and RCuO were investigated at different superficial
airflow rates, because this parameter had significant
effects on the foam flotation performances (Shen
1998). The experiments were carried out at
volumetric feed rate
4.0 mL/min, CTAB concentration 0.45 mmol/L, and
superficial airflow rates (jg) from 1.3 to 6.5 mm/s.
The results are presented in Fig. 4.
From Fig. 4, the S type internal significantly
improved ECuO but insignificantly decreased RCuO, of
which the reasons had been clearly explained in the
above section. Furthermore, the increase in ECuO
decreased from 55.1 ± 5.5 to 2.9 ± 0.3 as jg
increased from 1.3 to 6.5 mm/s. The increased jg
reduced the time of the rising foam in the column and
thus the time for foam drainage (Yang et al. 2011). In
addition, the level in bubble coalescence was also
decreased. Thus, the ability of the S type internal to
improve ECuO decreased. With increasing jg, ECuO with
or without the S type internal decreased, while RCuO
increased because the increased jg improved the
liquid holdup in the foam and the amount of
CuO
Fig. 4 Effects of S type internal on enrichment ratio and Fig. 5 Effects of S type internal on enrichment ratio and
recovery percentage of CuO nanoparticles at different superfi- recovery percentage of CuO nanoparticles at different volumet-
cial airflow rates ric feed rates

nanoparticles adsorbed at the gas–liquid interface. did not significantly

The results were consistent with the previous work of
Yan et al. (2011). For obtaining a high ECuO, 2.6 mm/s
was selected as the optimal superficial airflow rate,
where ECuO with the S type internal was 71.2 ± 3.6
with a RCuO of 24.5 ± 1.2 %.

Effects of S type internal on E CuO and RCuO at different

volumetric feed rates

Volumetric feed rate is an important parameter

closely related to recovery percentage in a continuous
foam flotation system (Merz et al. 2011). For
effectively improving RCuO, the effects of S type
internal on ECuO and RCuO at different volumetric feed
rates were investigated at CTAB concentration 0.45
mmol/L, superficial airflow rate 2.6 mm/s, and
volumetric feed rates from 1.0 to 5.0 mL/min. The
results are presented in Fig. 5.
From Fig. 5, the S type internal effectively
improved ECuO but did not significantly affect RCuO.
The results were consistent with those in the above
sections. More importantly, ECuO had no significant
changes, while RCuO sharply decreased with increas-
ing Q0 from 1.0 to 5.0 mL/min in the presence or
absence of the S type internal. For a given rising
foam, there existed a maximal superficial liquid
velocity at a fixed airflow rate (Stevenson 2007),
corresponding to the maximum separation capacity of
the foam. When it was lower than the feeding rate,
some of the targeted molecules had to flow out of the
column with the residual solution. As a result, the
increased Q0 sharply decreased RCuO. In addition, it
affect the adsorption of CuO nanoparticles, so it just
slightly affected ECuO. For obtaining a high RCuO,
1.0 mL/min was selected as the optimal volumetric
feed rate.
Under the optimized conditions of CTAB
concen- tration 0.45 mmol/L, superficial airflow rate
2.6 mm/ s, and volumetric feed rate 1.0 mL/min,
ECuO and RCuO with the S type internal reached 81.6
± 4.1 and
95.4 ± 4.9 %, respectively. ECuO increased by
139.3 ± 12.5 %, compared to that without the S type
internal. Therefore, the S type internal effectively
intensified the foam flotation of CuO nanoparticles
from their highly diluted suspension. Shen (1998)
used foam flotation to separate submicron TiO2
particles from their aqueous solution and obtained
the recovery percentage of nearly 100 % under the
optimum operating conditions. However, the
enrichment ratio of submicron TiO2 particles was
not mentioned in his work. Compared to the work of
Shen (1998), the current work achieved both high
recovery percentage and enrichment ratio of the
CuO nanoparticles. Particularly, the high enrichment
ratio would largely decrease the cost for the
subsequent treatment of the CuO nanoparticles.
Thus, the current work was very important for the
separation of nanoparticles from their aqueous
solutions.

Recycling CTAB in recovery of CuO

nanoparticles from their highly diluted
suspension

After the foam flotation, CuO nanoparticles were

highly enriched in the foamate, so it could be further
separated by centrifugation. In the supernate, CTAB Fig. 6 Effects of superficial airflow rate on enrichment ratio and
had a high concentration of 35.1 ± 3.2 mmol/L and recovery percentage of CTAB
thus could be reused to separate CuO nanoparticles.
For the residual solution, it had a relatively high
CTAB concentration of 0.10 mmol/L so that it could
not be directly discharged to the environment. Thus
in this section, the efforts were made to recover
CTAB from the residual solution as much as possible
using the column without the S type internal in Fig. 1.
Furthermore, a gas distributor of 100 ± 20 lm in
pore diameter instead of that in Fig. 1 was installed at
the bottom of the column. With the volumetric feed
rate fixed at 2.0 mL/min, the effects of superficial
airflow rate on enrichment ratio and recovery
percentage of CTAB (ECTAB and RCTAB) were
investigated. The results are presented in Fig. 6.
From Fig. 6, ECTAB decreased from 25.1 ± 2.0 to
12.1 ± 1.3, while RCTAB increased from 48.4 ± 2.4
to
80.2 ± 3.9 % with increasing jg from 6.5 to 11.7
mm/
s. The results agreed with the previous work of Yan
et al. (2011). Increasing jg improved the total amount
of CTAB adsorbed at the gas–liquid interface and
also the liquid holdup of the rising foam, so it
decreased ECTAB but increased RCTAB. At jg = 11.7
mm/s, RCTAB reached 80.2 ± 3.9 %, corresponding to
CCTAB in the residual solution of 2.1 ± 0.1 9 10-
2
mmol/L (7.7 ± 0.4 mg/L). Thus, the residual
solution could be readily further treated by
biochemical process and then discharged. For the
foamate, it had a CTAB concentration of 1.21
mmol/L and thus could be reused in the recovery of
CuO nanoparticles. By recovering CTAB from the
foamate and the residual solution, about 95 % CTAB
could be recycled.
Characterizations of the recovered CuO
nanoparticles

FT-IR spectra analysis

Figure 7 shows the FT-IR spectra of the starting

CuO nanoparticles and the recovered CuO
nanoparticles in the foamate. By comparing the two
spectra, both of them had the peaks at 3448, 2343,
1637, 518, and 600 cm-1. Specifically, the peaks
at 3448 and 1637 cm-1 indicate the presence
of water in the samples. The peak at 1637 cm-1
was attributed to CO2 in the air. The last two peaks
corresponded to the vibration of Cu–O bands
(Jayaprakash et al. 2014). More importantly, the
spectrum of the recovered CuO nanoparticles had
the peaks at 2912, 2850, and 1038 cm-1, but that of
the starting CuO nanoparticles did not have them.
The former two peaks corre- sponded to the
vibration of CH3–, while the latter one corresponded
to the vibration of C–N. It is indicated that CTAB
was absorbed at the recovered CuO nanoparticles.
However, the adsorption of CTAB was not strong
because the three characteristic peaks of CTAB were
small.

Size distribution analysis

Figure 8 shows the size distributions of the CuO

nanoparticles in the aqueous solutions before and
after foam floatation. The results present that after
foam floatation, the size distribution of the CuO

Fig. 7 FT-IR spectra of the starting CuO nanoparticles and the

recovered CuO nanoparticles by foam flotation
nanoparticles suffered a ‘‘red’’ shift with their
average size increasing from 357.6 to 431.0 nm. The
increase in the size of the CuO nanoparticles was due
to their association with CTAB molecules.
Morphology analysis
The SEM images of the starting CuO nanoparticles
and the recovered CuO nanoparticles are shown in
Fig. 9. It is presented that the recovered CuO
nanoparticles had a higher dispersity than the starting
ones. Owing to their surface atoms had very high
activity, nanoparticles were prone to agglomeration
(Ren et al. 2001). When the nanoparticles were
associated with surfactant molecules, their energy
could be effectively reduced and thus could not
readily aggregate (Esumi et al. 1998). Thus, the high
dispersity of the recovered CuO nanoparticles was
because of their association with CTAB molecules.
Fig. 8 Size distributions of the starting CuO nanoparticles and
the recovered CuO nanoparticles in aqueous solutions
Fig. 9 SEM images of the starting CuO nanoparticles (a) and the recovered CuO nanoparticles by foam flotation (b)
Furthermore, the average sizes of the starting CuO
nanoparticles and the recovered CuO nanoparticles in
the SEM images were 322.4 and 411.8 nm, respec-
tively. The results indicate that the association of the
CuO nanoparticles with CTAB did increase their
sizes, and thus, they were consistent with those in
Fig. 8. The average sizes of the CuO nanoparticles
obtained in Fig. 9 were slightly smaller than those
obtained in Fig. 8. The results are because the CuO
nanoparticles suffered a slight expansion.
Dispersion stability analysis
The variations in the relative contents of the starting
CuO nanoparticles and the recovered ones in their
individual suspensions with time are presented in
Fig. 10. From Fig. 10, the decrease in relative content
of the recovered CuO nanoparticles was gradually
Fig. 10 Variations in the relative contents of the starting CuO
nanoparticles and the recovered ones in their individual
suspensions with time
higher than that of the starting CuO nanoparticles.
Thus, the recovered CuO nanoparticles had better
dispersion stability in their suspension due to their
association with CTAB. Thus, the recovered CuO
nanoparticles would have good reusability.
Conclusions
The S type internal effectively enhanced foam
drainage and also intensified bubble coalescence, so
it considerably improved the enrichment ratio of CuO
nanoparticles. Using the S type internal, the enrich-
ment ratio and recovery percentage of CuO nanopar-
ticles reached 81.6 ± 4.1 and 95.4 ± 4.9 %,
respectively, under the optimized conditions of
CTAB concentration 0.45 mmol/L, superficial
airflow rate
2.6 mm/s, and volumetric feed rate 1.0 mL/min. The
enrichment ratio with the S type internal was 2.4
times of that without the S type internal. By
recovering CTAB from the foamate and the residual
solution, about 95 % CTAB could be recycled. The
recovered CuO nanoparticles were associated with
CTAB molecules to increase the particle sizes. They
had better dispersity and dispersion stability than the
starting CuO nanoparticles. Thus, they would have
good reusability. The current results had significant
implications to the recovery of nanoparticles from
their highly diluted suspensions.
Acknowledgments This work was financially supported by
the Natural Science Foundation of China (21346008).
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