Colloids and Surfaces A: Physicochem. Eng.

Aspects 520 (2017) 361–368

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Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Repeating recovery and reuse of SDS micelles from MEUF retentate

containing Cd2+ by acidification UF
Jinhui Huang a,b,∗ , Fei Qi a,b , Guangming Zeng a,b,∗ , Lixiu Shi a,b , Xue Li c , Yanling Gu a,b ,
Yahui Shi a,b
a
College of Environmental Science and Engineering, Hunan University, Changsha, Hunan, 410082, China
b
Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha, Hunan, 410082, China
c
Department of Bioengineering and Environmental Science, Changsha University, Changsha, Hunan, 410003, China

g r a p h i c a l a b s t r a c t

h i g h l i g h t s

• Many factors influence the recovery efficiency of sodium dodecyl sulfate (SDS) and the efficiency of the removal of metal ions by reused SDS.
• Surfactant recovery and reuse was largely affected by the volume of the concentrated solution.
• SDS can be acidified, recovered, and reused many times when its concentration achieves twice the critical micellar concentration (CMC).

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

Article history: The SDS is investigated as a surfactant for heavy metal ion removal via micellar enhanced ultrafiltration
Received 2 November 2016 (MEUF). It is important to recover and reuse surfactant from the retentate stream due to the high cost
Received in revised form 18 January 2017 of surfactant. Repeated acidification is a new way to recover and reuse surfactant. The effects of pH, the
Accepted 2 February 2017
initial surfactant concentration of simulated retentate solution, the volume of concentrated solution, and
Available online 4 February 2017
acidification times on SDS recovery and reuse were studied. At pH 1.0, the Cd2+ was effectively separated
from the surfactant micelles, and the SDS had the highest recovery rate. Additionally, the rate of the
Keywords:
removal by reused SDS of metal ions was higher than 85% at pH 1.0. When the initial SDS concentration
Micellar-enhanced ultrafiltration (MEUF)
Sodium dodecyl sulfate (SDS)
of the simulated retentate solution was 2.0 CMC, the efficiency of SDS recovery and reuse was better than
Acidification of that at 1.0 CMC. The smaller the concentrated solution volume was, the higher the rates of separation
Recovery and removal by reused SDS of metal ions were. SDS can be repeatedly used when the concentration
Reuse achieves its CMC.
© 2017 Elsevier B.V. All rights reserved.

∗ Corresponding authors at: College of Environmental Science and Engineering, Hunan University, Changsha, Hunan, 410082, China.
E-mail addresses: huangjinhui 59@163.com (J. Huang), zgming@hnu.edu.cn (G. Zeng).
http://dx.doi.org/10.1016/j.colsurfa.2017.02.001
0927-7757/© 2017 Elsevier B.V. All rights reserved.
362 J. Huang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 520 (2017) 361–368
1. Introduction
Heavy metals such as zinc, lead, cadmium, copper, mercury and
nickel are on the Environmental Protection Agency (EPA) list of pri-
ority pollutants and they are thought to cause serious harm [1]. The
conventional treatment method for heavy metal ions was precipita-
tion, but the concentration of metal ions in treated water cannot be
reduced below the solubility of precipitation [2]. Heavy metal ions
can also be removed effectively and selectively by ion-exchange,
but the cost of resin is very high [3]. The removal of heavy metal ions
by membrane processes such as nanofiltration (NF) [4] or reverse
osmosis (RO) [5] was efficient, but high energy consumption and
low permeate solution flux were main obstacles.
To solve these problems, the combination of surfactant and
ultrafiltration (UF) called micellar-enhanced ultrafiltration (MEUF)
has been suggested [6]. MEUF is a process for heavy metal ion
separation, especially for the low concentrations of heavy met-
als in wastewater, and it ultimately produces retentate solution.
Surfactant consists of a hydrophilic head and hydrophobic tail [7].
When the concentration of surfactant was higher than the critical
micelle concentration (CMC), a spherical or cylindrical aggregate
was formed by the surfactant monomers called micelle [8]. The
cationic surfactants adsorb anions while the anionic surfactant
adsorbs polyvalent metal cations [9]. Heavy metal ions on the sur-
face of the micelle, which are bound with negative charge, can then
be intercepted by the UF membrane, which has higher flux and
less energy consumption than NF or RO [10]. The anionic surfac-
tant sodium dodecyl sulfate (SDS) is often selected for the effective
removal of heavy metal ions such as chromium [11], zinc [12],
cadmium [13–17], nickel [18], plumbum [19] and copper [20,21]
in MEUF. It is essential to recover and reuse the surfactant from
the retentate stream economically, due to the surfactant making
up a large portion of costs [22]. Furthermore, timely recovery of
surfactant can avoid secondary pollution to the environment.
There are many methods to recover surfactant [23–25]. Adding
multivalent counterions such as Ca2+ in slight excess of the stoichio-
metric value can cause a high proportion (45–55%) of precipitation
for the surfactants [26]. Lowering the temperature of the SDS solu-
tion in a temperature-controlled room using an ice-water bath to
4 ◦ C, which is below the reported Kriff point of SDS (16 ◦ C) [27–29].
The foam fractionation can recover SDS and Cd2+ from the permeate
solution [30]. Regardless, surfactant Tween 80 can be recovered by
electrochemical treatment [31]. However, the metal ions and sur-
factant mix and precipitate, which generated using these methods
are difficult to separate. Besides the surfactant having a low recov-
ery rate, micelle molecules are subject to a certain damage, and the
result of the reuse of recovered micelles is far less than that of the
first use [32–34]. Consequently, the separation of heavy metal ions
from micelles is very important for the recovery and reuse of SDS
[26]. Three methods can be used for the separation of Cd2+ from the
SDS micelles solution [35]. The first is acidification followed by UF.
The second is the use of a chelating agent followed by UF. The last
one is precipitation by ferric- and ferrocyanide followed by cen-
trifugation. The simplest and most efficient process for surfactant
recovery is acidification [35].
According to previous research, the optimal condition for the
recovery and reuse of SDS was at pH 1.0 acidified with sulfuric acid
[36,37]. Under these conditions, the recovery ratio of SDS from SDS
micelles combined with Cd2+ is 58.1%. The reused micelles came
from a concentrated solution that was obtained by micellar acid-
ified regeneration (MAR). The removal efficiency of heavy metal
ions for Cd2+ is 88.1% with the reclaimed SDS [38,39]. We can find
that the SDS reuse’s rate of removal of Cd2+ is higher than 80%, so it
is necessary to recover SDS from the MEUF-concentrated solution.
In this study, sulfuric acid was selected for separating Cd2+ from
SDS micelles, and the separated metal ions that passed through the
ultrafiltration membrane and the surfactant micelles stayed in the
feed tank [40,41]. Then the SDS was recovered by ultrafiltration.
The recovered SDS was reused to remove heavy metal ions based
on MEUF separation processes [41,42]. Many factors influence the
separation of metal ions from micelles and the recovery of SDS.
The factors include the value of pH, the SDS initial concentration
of simulated retentate solution, the concentrated solution volume,
and the acidification times [43]. In order to obtain the optimal
conditions during the recovery and reuse of SDS, the efficiency of
separating metal ions from SDS, the recovery rate of surfactant, and
the recovered SDS’s rate of removing metal ions were investigated.
2. Materials and methods
2.1. Materials
Cd(NO3 )2 ·4H2 O (analysis purity) was selected as the heavy
metal ions and sodium dodecyl sulfate (chemistry purity) as the
anionic surfactant. Both were obtained from Sinopharm Chemi-
cal Reagent Co., Ltd, in China. Sulfuric acid (guaranteed reagent)
was obtained from Zhuzhou Chemical Industry Research Insti-
tute, Hunan, China. Sodium hydroxide (guaranteed reagent) was
purchased from Tianjin Sailboats Chemicals Co., Ltd., in China.
Ultra-pure water was prepared for all the solutions. The CMC of SDS
(7.8 mmol/L) was obtained from conductivity measurement [39].
Sulfuric acid and sodium hydroxide solutions of different densities
were prepared in advance for adjusting pH.
2.2. MEUF system
The Millipore Labscale TFF System was used for UF experimen-
tation in a cross-flow membrane module. The pore size of the
polyethersulfone membrane (Pellicon XL Device, Millipore Corpo-
ration, USA) is 8 kDa, and the filtration area of the membrane is
50 cm2 . The membrane can be used under the condition of a tem-
perature at 4–45 ◦ C and a pH of 1–14. Furthermore, the operating
pressure of the module is at maximum 5.5 bar. The maximum mem-
brane permeability pressure is 2.8 bar. The retention volume is
3.2 mL. The flow velocity is 10–100 mL/min at 4.0 bar. The filtra-
tion process was intermittent. All the UF experiments were carried
on at room temperature 25 ◦ C and a fixed transmembrane pressure
(TMP) 1.5 bar. The permeate solution flowed into the infiltration
tank and the concentrated liquid was sent back to the feed tank.
After each UF experiment, the membrane was washed for 30 min
without pressure with ultra-pure water, and then ultra-pure water
was used to rinse the membrane at a low pressure for 30 min for the
surfactants remaining. After that, the membrane was washed with
HNO3 for 30 min to remove metal ions from the membrane, and
NaOH was used to neutralize the HNO3 until the pH was neutral.
The HNO3 and NaOH concentration are all 1 mol/L. Next, the ultra-
pure water was filtered through the membrane to ensure that the
permeate solution flux recovered up to 90% of the original water
flux, and finally, ultra-pure water was injected and filled into the
membrane cell to protect the membrane [44].
2.3. Experiment methods
In each experiment the quality of Cd(NO3 )2 ·4H2 O and sur-
factant SDS (1.0 CMC, 2.0 CMC) was calculated and dissolved in
ultra-pure water, and then the volume was set to 1000 mL for the
simulation-concentrated waste solution. The simulated retentate
solution was stirred thoroughly and settled for 1 h to make sure
that the surfactant monomers formed micelles and that the solutes
were solubilized. The pH (0.5, 1.0, and 2.0) of the solution was
adjusted with sulfuric acid. The acidification-concentrated liquid
 J. Huang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 520 (2017) 361–368
Fig. 1. The schematic of MEUF and MAR.
was sent back to the feed tank, and then it underwent ultrafiltra-
tion by the ultrafiltration membrane, which is called acidification
ultrafiltration (AUF). When the volume (0.1 L, 0.2 L, and 0.3 L) of the
solution in the feed tank achieved the demand, the acidification
experiment was ended. After acidification, the SDS was reused for
the first time. The solution volume was set to be 1000 mL by adding
heavy metal ions Cd2+ into the retentate solution. The newly added
Cd2+ was 30 mg/L in the 1000 mL solution without considering the
Cd2+ remaining in the retentate solution, and the pH was adjusted
to be the same as that of the initial solution, pH 6.4. The solution
was stirred to make it adequately mixed and left standing for 1 h to
make sure the reaction was complete. The MEUF-concentrated liq-
uid was sent back to the feed tank. When the volume of the solution
in the feed tank was the same as in the acidification experiment,
the MEUF experiment was ended. Then acidification of the reten-
tate solution continued by adjusting the pH with sulfuric acid and
adding ultra-pure water to make the solution 1000 mL. The above
operation was repeated for a total of three times for the SDS to be
recovered and reused. When adjusting the pH (0.5, 1.0, and 2.0)
the initial SDS concentration of the simulated retentate solution
2.0 CMC and the volume of the concentrated solution at 0.2 L were
kept constant. The initial SDS (1.0 CMC, 2.0 CMC) concentration of
simulated retentate solution was changed at the condition of pH
1.0, and the volume of the concentrated solution at 0.2 L. Finally,
363
MEUF: micellar enhanced ultrafiltration; MAR: micellar acidified regeneration.
the different volumes of the concentrated solution (0.1 L, 0.2 L, and
0.3 L) were adjusted at the condition of pH 1.0, and the SDS ini-
tial concentration of simulated retentate solution at 2.0 CMC. The
full experiment process and diagram are shown in Fig. 1. In the
whole course of the experiment, after every UF experiment, the
concentration of SDS and of the metal ions Cd2+ from the permeate
solution and the retentate solution were measured. The concentra-
tion of surfactant SDS was measured by the Shimadzu total organic
carbon analyzer from Japan, and the concentration of heavy metal
ions was analyzed by flame atomic absorption.
3. Calculations
The experimental results can be expressed by the metal ion
separation efficiency R, the recovery rate of SDS R0 , and Rr which
represents the removal rate of metal ions Cd2+ by reused SDS. The
calculated formulas are as follows:
R(%) = Cp Vp /Cf Vf × 100% (1)
R0 (%) = Cs Vs /Ci Vi × 100% (2)
Rr (%) = (Cr − Ct )/Cr × 100% (3)
where Cp (mg/L) is the heavy metal ions of Cd2+
concentration in
the acidification permeate solution, Vp (L) is the volume of the
364 J. Huang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 520 (2017) 361–368

Fig. 2. Separation rates (R) of metal ions Cd2+ with different pH values. The initial Fig. 3. The recovery efficiency (R0 ) of SDS with different pH. The initial SDS con-
SDS concentration in the simulated retentate solution was 2.0 CMC, and the volume centration in the simulated retentate solution was 2.0 CMC, and the volume of the
of the concentrated solution was 0.2 L. concentrated solution was 0.2 L.

acidification permeate solution, Cf (mg/L) is the heavy metal ion

1.0), the reaction of hydrolysis is faster than the re-formation of
concentration in the acidification feed solution, and Vf (L) is the ini-
SDS micelles, and therefore, in spite of at pH 0.5 the solution sep-
tial acidification feed solution volume. The SDS (g/L) concentration
aration efficiency of heavy metal ions being highest, the negative
in the acidification retentate solution is Cs , and Vs (L) is the volume
impact was very serious, such as the hydrolysis of SDS by H+ , which
of the acidification retentate solution. The SDS concentration in the
consumes more sulfuric acid and makes the solution more sticky.
retentate solution after each MEUF is Ci (g/L), and Vi (L)is the vol-
According to what has mentioned above, 800 mL of 37.5 mg/L
ume of the retentate solution after each MEUF. The concentration of
of heavy metal ions Cd2+ was added into 200 mL of reclaimed SDS
Cd2+ in the MEUF retentate solution is Cr (mg/L). The concentration
solution. The solution was obtained with sulfuric acid at pH 1.0
of Cd2+ in the MEUF permeate solution is Ct (mg/L).
by acidification UF, which are good conditions for SDS recovered
from an acidification retentate solution. The pH of the solution was
4. Results and discussion
adjusted to 6.4 (uncontrolled), and then followed by ultrafiltration.
The efficiency of removing heavy metal ions with reclaimed SDS
4.1. Effect of pH on surfactant recovery and reuse
is shown in Fig. 4. Taking the metal ions still in the reclaimed SDS
solution into consideration, the efficiency of removing Cd2+ with
Under the condition of strong acid, the H+ take the place of the
the recycled SDS is 63.57%, 86.13%, and 94.38% at the different pH
heavy metal ions and then bind with the SDS micelles. The free
(0.5, 1.0, and 2.0). It is obvious that under the conditions of pH
heavy metal ions replaced by H+ can pass through the membrane
1.0 and 2.0, the rate of removing metal ions with recovered SDS is
by ultrafiltration, but the SDS micelles are retained. Fig. 2 shows
lower than that in the results of fresh SDS. The rate of removing
the effect of pH on the separation efficiency of Cd2+ from micelles.
metal ions with recovered SDS has much to do with SDS and Cd2+
The results point out how the separation efficiency declined rapidly
concentration. By comprehensive consideration, adjusting pH to
when the pH value increased to above 1.0, which is similar to in
the other papers [39]. When sulfuric acid was added, the pH was
adjusted to 0.5, and the separation efficiency of Cd2+ from SDS
micelles was more than 70.0%. The highest separation efficiency
was presented at pH 0.5. This is because under the condition of
low pH the H+ has more opportunities to displace heavy metal ions
from surfactant micelles. It can be found in Fig. 3 that the SDS recov-
ery rate results differed with different pH; the recovery rate of SDS
increased at first and then decreased with the pH increasing. The
highest point is 92.7% when the pH value is 1.0, and at pH 0.5 the
recovery rate of SDS is 66.79%. From the above discussion, when pH
increases, the electrostatic repulsive force increases. Meanwhile,
under strong acidic conditions, SDS hydrolysis is accelerated, which
is expressed as below [45]:

2 C12 OSO3 Na + H2 SO4 → 2 CH12 OSO3 H + Na2 SO4 (4)

CH12 OSO3 H + H2 O → CH12 OH + H2 SO4 (5)

After all reactions were finished, the SDS recovery rate

decreased due to the continuously formed dodecanol. Besides,
under the strong acidic conditions the pore size of the ultrafiltration
membrane was expanded, and as a result, some of the SDS micelles
Fig. 4. The removal efficiency (Rr ) of metal ions Cd2+ by recovered SDS with different
passed through it and got into the acidification permeate solution. pH values. The initial SDS concentration in the simulated retentate solution was 2.0
The results show that in the strong acidic region (below about pH CMC, and the volume of the concentrated solution was 0.2 L.
 J. Huang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 520 (2017) 361–368
1.0 with sulfuric acid is the best way to recover and reuse SDS by
acidification.
4.2. Effect of surfactant concentration on surfactant recovery and
reuse
Two different SDS (1.0 CMC, 2.0 CMC) concentrations of
simulated retentate solution were selected for the acidification
experiment. From Table 1, we can see that SDS concentration has
little influence on Cd2+ separation from SDS micelles. Table 1 shows
that the SDS recovery rate at concentration 2.0 CMC of the simu-
lated retentate solution was higher than at 1.0 CMC. The quality
of recovered SDS decreased after the acidification UF experiment,
because some SDS were adsorbed on the membrane surface and
then formed a concentration polarization layer. Apart from this,
a number of surfactant monomers passed through the membrane
and got into the acidification permeate solution. The concentration
2.0 CMC of simulated retentate solution can form more micelles
than the 1.0 CMC solution, and fewer surfactants flow into the
acidification permeate solution. In Table 1, the reused SDS’s effi-
ciency of removing Cd2+ is 76.00% and 86.13% at different SDS
concentrations (1.0 CMC, 2.0 CMC). At each calculation of the rate
of removal of metal ions with reused SDS, the metal ions still in
the reclaimed SDS solution were taken into consideration. The SDS
concentration of 1.0 CMC was below its CMC after the acidifica-
tion experiment. As a result, the efficiency of removing metal ions
with reused SDS declined rapidly. During the MEUF experiment,
on the surface of the UF membrane, the SDS molecules gradually
accumulated and formed an accumulation layer on it. Therefore the
SDS concentration may exceed its CMC value and form micelles,
which can bind heavy metal ions on it. This is the reason why
the initial SDS concentration 1.0 CMC of the simulated retentate
solution still has a certain degree of efficiency. On the contrary,
in spite of the decline of the SDS concentration, after the acidi-
fication experiment the initial SDS concentration 2.0 CMC of the
simulated retentate solution was still higher than SDS’s CMC. When
the concentration of SDS was higher than 2.0 CMC, the removal
efficiency of Cd2+ decreased gradually. In addition, the SDS concen-
tration increases significantly in the acidification permeate solution
under these conditions. A similar conclusion has been reported in
other literature [30,46–51]. This could account for the phenomenon
of the micelles being deformed and changing their shape near the
membrane surface due to the high SDS concentration. The Cd2+
concentration in the permeate solution increased because some
micelles passed through the membrane. It is speculated that when
surfactant concentration exceeds the second CMC (about 7.0 CMC)
the spherical micelles combine to create so-called rod-like aggre-
gates that can pass through the membrane with heavy metal ions
[52–54]. Consequently, the experiment will no longer consider SDS
initial concentration of simulated retentate solution more than 2.0
CMC.
Table 1
The effect of SDS concentration regarding the metal ions separation rate, SDS (2.0
CMC) recovery, and reuse efficiency. The pH was 1.0 and the concentrated solution
0.2 L.
SDS Separation of Recovery of Removal rate of
concentration Cd2+ (%) SDS (%) metal ions by
reused SDS (%)
1.0 CMC 60.70 82.45 76.00
2.0 CMC 61.69 92.27 86.13
365
Fig. 5. The separation efficiency (R) of metal ions Cd2+ with different concentrated
solution volumes. The pH value was 1.0, and the SDS concentration was 2.0 CMC.
4.3. Effect of concentrated solution volume on surfactant
recovery and reuse
In the AUF experiment, the metal ions increase in acidification
penetrants with the increase of acidification penetrant volume. As
a result, the separation efficiency of metal ions from surfactant
SDS increases. But with the increase of acidification permeate solu-
tion volume, the loss of surfactant increases, and the acidification
retentate solution concentration becomes larger, which leads to a
membrane-flux decline. In practical applications, we need to sepa-
rate Cd2+ from SDS micelles as much as possible and recover more
SDS. For that reason, it was important to choose a suitable con-
centrated solution volume in the UF experiment. The solution was
acidified by adding sulfuric acid to adjust the pH to 1.0, which is
a good condition for SDS recovered from the simulated retentate
solution. When the solution volume in the feed tank achieved the
demand condense volume (0.1 L, 0.2 L, 0.3 L), the acidification UF
experiment was ended. Heavy metal ions Cd2+ were added into the
reclaimed SDS solution (0.1 L, 0.2 L, and 0.3 L). Then the solution pH
was adjusted to 6.4 for reuse of the recovered SDS to remove metal
ions.
From Fig. 5 we can see that the efficiency of separating Cd2+
from SDS micelles decreases with the increase of concentrate solu-
tion volume, because the larger the acidification permeate solution
volume is, the higher the quality of metal ions is. The maximum effi-
ciency of separating metal ions from surfactant micelles is 69.12% at
concentrate volume 0.1 L, and the minimum efficiency is 51.23% at
concentrate volume 0.3 L. In Fig. 6 the SDS recovery rates at three
different volumes are all higher than 85% and have little differ-
ence. The reason is that most of the surfactant SDS was formed
of micelles, and the micelles’ diameter was bigger than the mem-
brane pores and could not flow into the acidification permeate
solution. The concentration of SDS increased with the decrease
of acidification retentate volume. It is easier to form a concen-
tration polarization layer and then lead the SDS to pass through
the membrane more difficult. The solution that passed through the
membrane and entered into the osmotic solution was mostly water
and metal ions. Fig. 7 explains the efficiency of removing metal ions
with recovered SDS. Taking the metal ions still in the reclaimed SDS
solution into consideration, the metal ions concentration increased
with the decrease of acidification retentate solution volume. As a
result, the rate of removal of metal ions increased. When the acid-
ification concentrated solution volume was 0.1 L, the efficiency of
removing metal ions exceeded 90%, which is similar to that of fresh
366 J. Huang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 520 (2017) 361–368
Fig. 6. The recovery efficiency (R0 ) of SDS with different concentrated solution
volumes. The pH value was 1.0, and the SDS concentration was 2.0 CMC.
Fig. 7. The removal efficiency (Rr ) of metal ions Cd2+ by recovered SDS with con-
centrated solution volume. The pH value was 1.0, and the SDS concentration was
2.0 CMC.
SDS. The other volumes of the acidification concentrated solution
were also high in their efficiency of removing metal ions, which
was greater than 80%. Due to the filtration time influenced by
the acidification concentrated solution volume, the surfactant con-
centration increased with the decrease of acidification retentate
volume, therefore the smaller the concentrated solution volume,
the more time we needed to complete the UF experiment. As is
discussed above, the concentrated solution volume influences the
metal ions separation rate, SDS recovery rate, and the reused SDS
rate of removing metal ions. Consequently, a suitable concentrated
solution volume should be selected in practical applications.
4.4. Effect of acidification times on surfactant recovery and reuse
The acidification experiment is the simplest and most efficient
method to recover surfactant, and it has good results. Many people
have done the experiment of recovering surfactant SDS through
the acidification experiment, but they recovered and reused SDS
just one time. Few people have repeatedly recovered and reused
SDS [55]. Consequently, the surfactant SDS can be not used as
much as possible. In order to use the SDS more effectively and
economically, we recovered the SDS many times with the acidi-
Table 2
The effect of acidification times regarding the rate of separating metal ions. SDS (2.0
CMC) recovery and reuse efficiency. The pH was 1.0, and the concentrated solution
was 0.2 L.
Acidification Separation of Recovery of Removal rate of
times Cd2+ (%) SDS(%) metal ions by
reused SDS(%)
1 61.69 92.27 86.13
2 66.23 89.37 82.38
3 75.81 83.56 81.41
Table 3
The effect of acidification times on the rate of separating metal ions, SDS (1.0 CMC)
recovery, and reuse efficiency. The pH was 1.0, and the concentrated solution was
0.2 L.
Acidification Separation of Recovery of Removal rate of
times Cd2+ (%) SDS (%) metal ions by
reused SDS (%)
1 60.70 82.45 76.00
2 64.94 79.02 64.46
3 71.14 76.97 54.79
fication experiment until the surfactant concentration was below
its CMC. The experiment was in a good condition of pH 1.0, initial
SDS concentration of 2.0 CMC of the simulated retentate solu-
tion, and concentrated solution volume 0.2 L, and acidification was
done three times. The results for the efficiency of separating metal
ions, the SDS recovery rate, and the rate of removal of metal ions
by recycled SDS are shown in Table 2. For a better comparison
of the three acidification experiments, take account of the total
metal ions, which includes the metal ions combined with the SDS
micelles remaining in the acidification retentate solution. In each
MEUF experiment, the metal ions in the solution were less than the
last time. The efficiency of separating metal ions from surfactant
micelles increases with the increase of acidification times, which
shows that the acidification times cannot influence the separation
of metal ions from SDS micelles. The SDS recovery rate gets smaller
and smaller, because it cannot avoid losing SDS in the UF process.
In each UF experiment, part of the SDS monomers passed through
the membrane and entered into the permeate solution. Some of the
surfactant adsorbed on the surface of the film, forming a gel group,
and in the process of acidification some of the surfactants were
hydrolyzed by the strong acid. But the SDS was little reduced at
each time of recovery. Most important is the ability of recycled SDS
to be used to remove metal ions. From Table 3, taking the metal ions
still in the reclaimed SDS solution into consideration, compared
with at 1.0 CMC, the rate of removing metal ions at a simulated
retentate solution of 2.0 CMC declined slowly by recycling used
SDS each acidification experiment. That is because after the first
acidification experiment the initial SDS concentration 1.0 CMC of
the simulated retentate solution was far below its CMC. In the three
reuses of the SDS, the rates of removing metal ions were all higher
than 80% when the SDS initial concentration of the simulated reten-
tate solution was 2.0 CMC. It can be concluded that the initial SDS
concentration at 2.0 CMC of the simulated retentate solution can be
acidified and reused four times, but the concentration at 1.0 CMC
cannot. As long as the solution concentration of SDS is higher than
or slightly below its CMC, the SDS can be reused to remove heavy
metal ions. The surfactant SDS can be recovered and reused with
the acidification experiment repeatedly.
4.5. Removal efficiency of Cd2+ in MEUF by fresh SDS and reused
SDS
The removal efficiency of Cd2+ of reused SDS compared with
the fresh SDS is very important to MEUF. In previous studies, the
 J. Huang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 520 (2017) 361–368
Table 4
The cost of MEUF when using fresh SDS and recovered SDS treatment 3 L wastewater.
Reagents H2 SO4
Price 38 RMB/L
Dosage Reuse SDS 50.00 mL
Fresh SDS / /
Cost Reuse SDS 1.9 RMB
Fresh SDS / /
Notes: 1. SDS (chemistry purity), H2 SO4 (guaranteed reagent), NaOH (guaranteed reagent); 2. The total cost in MEUF of use recovered SDS was 4.60 RMB and use fresh SDS
was 1.00 RMB.
Table 5
The removal efficiency of Cd2+ of different SDS concentration in MEUF.
Different SDS concentration 1.0 CMC 2.0 CMC
Fresh SDS About 95.00% About 98.00%
First reuse SDS 76.00% 86.13%
Second reuse SDS 64.46% 82.38%
Third reuse SDS 54.79% 81.41%
removal efficiency of Cd2+ with fresh SDS has been done [13,56].
We compared the fresh SDS with reused SDS removal efficiency of
Cd2+ in MEUF at different SDS concentration. The Cd2+ in simulated
concentration wastewater was 30 mg/L–70 mg/L. The comparison
of removal efficiency of Cd2+ is in Table 4. According to the results,
we can find that the SDS micelles can be reused by acidification
recovery.
4.6. The cost estimation of the whole process in MEUF
The expenses of the whole process including surfactant recovery
are really important. We made a price list containing primary mate-
rials and power in our experiments. The dosage of HNO3 and NaOH
is small in the process of membrane cleaning, so their cost did not
include. Moreover, In Table 5 we compared two types cost of MEUF
in 3 L wastewater, one is using fresh SDS and another is using recov-
ered SDS. In conclusion, the cost of MEUF when using fresh SDS is
less than to that acidification and reuse SDS three times. Although
all of these can’t save money in our experimental method but we
resolve the issue of SDS in concentrating and reduce the secondary
pollution.
5. Conclusions
The experimental results illustrate that SDS that is obtained
from the MEUF retentate solution can be recovered and reused
by acidification. The optimal condition for recovery and reuse of
SDS was at pH 1.0 adjusted with sulfuric acid and at initial SDS
concentration 2.0 CMC of the simulated retentate solution and an
acidification concentrated solution volume of 0.2 L. The SDS can be
recovered and reused by acidification only if the surfactant concen-
tration exceeded its CMC. So when the initial SDS concentration of
the simulated retentate solution is 2.0 CMC, it can be recovered
and reused three times. It can be inferred that the SDS charac-
ter is essentially unchanged after acidification. Although repeated
recovery and reuse of SDS by acidification can’t save money but we
resolve the issue of SDS in concentrated solution and reduce the
secondary pollution effectively.
Acknowledgments
This study was financially supported by the National Natu-
ral Science Foundation of China (51178172, 51578222, 51521006,
51308076 and 51378190), the Project of Chinese Ministry of Educa-
tion (113049A), the Research Fund for the Program for Changjiang
Scholars and Innovative Research Team in University (IRT-13R17),
367
NaOH SDS Power
32 RMB/kg 72 RMB/kg 0.5 RMB/kw h
70.00 g 4.31 g 0.29 kw h
12.93 g 0.14 kw h
2.24 RMB 0.31 RMB 0.15 RMB
0.93 RMB 0.07 RMB
and the Hunan Provincial Innovation Foundation for Postgradu-
ate(Grant No.CX2015B092).
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