Journal of Environmental Management 247 (2019) 1–8

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Journal of Environmental Management

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Research article

Removal of sodium oleate from synthetic manganese leaching solution by T

coagulation-dissolved air flotation
Jianrong Xuea,b, Hong Zhongb, Shuai Wangb,∗
a
College of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, 411201, China
b
College of Chemistry and Chemical Engineering, Hunan Provincial Key Laboratory of Efficient and Clean Utilization of Manganese Resources, Central South University,
Changsha, 410083, China

A R T I C LE I N FO A B S T R A C T

Keywords:
Coagulation-dissolved air flotation
Sodium oleate
Solution chemistry calculation
Partially hydrolyzed polyacrylamide
The coagulation-dissolved air flotation for removal of sodium oleate (NaOL) from synthetic manganese leaching
solution was focused in this study. It indicates that partially hydrolyzed polyacrylamide (HPAM), NaOL dosage
and pH have a multiple effect on the removal efficiency of NaOL. The results represents a significant removal
efficiency of 97.6% NaOL was achieved under the optimal conditions of coagulation-dissolved air flotation by
dosage of 20 mg/L HPAM and 30 mg/L NaOL, pH 8.0. Solution pH has a significant effect on the distribution of
oleate species and Mn2+ species. The addition of HPAM facilitates the formation of OL− micelle and the de-
crease of critical micelle concentration (CMC). Oleate species primarily exist, containing Mn(OL)2(s), OL− and
HOL(aq). HPAM could cause the Zeta potential of NaOL to shift negatively. HPAM could decrease CMC of NaOL
and lead to a transition from three dimensional network structure to lamellar structure. NaOL can be removed by
coagulation-dissolved air flotation through the adsorption and bridge effect of HPAM chains on the floating
bubble surface.

1. Introduction floated mineral surface. In the downstream leaching process, NaOL

Manganese carbonate ores (rhodochrosite) are the most common
manganese ores. High grade manganese carbonate ores can be leached
directly by sulphuric acid. However, the grade of manganese carbonate
ores has decreased from 18%-20% to 13%–15% in several manganese
mine, due to the flourishing demand for manganese metal (Liu et al.,
2014). Low grade rhodochrosite can be used economically when they
are enriched by flotation process (Luo et al., 2018).
The collectors used in the flotation process of low grade ores are
commonly fatty acids or their salts. Among these, sodium oleate (NaOL)
is widely used as the collector for enrichment of numerous minerals,
such as scheelite, pyrochlore, hematite, due to its active carboxyl
functional groups (Wang et al., 2019; Liu et al., 2019; Hao et al., 2019).
Sodium oleate is also widely used for manganese ore flotation (Zhou
et al., 2015). Electrokinetic analyses were used to interpret the flotation
and interfacial behavior of manganese dioxide with NaOL as collector
(Fuerstenau and Shibata, 1999). However, a large dosage of NaOL is
required when it is employed in the flotation of manganese ores be-
cause carboxylate of NaOL is the least selective of all collectors used in
mineral flotation, which might lead to a certain amount of NaOL being
remained in the manganese concentrate, due to its adsorption on the
stranded on the mineral surface were entered into the leaching solution.
This may have some potential effects on subsequent processes. The
reason is that manganese electrodeposition can be affected by any
amount of impurity (Lu et al., 2014). In the process of manganese
electrodeposition, NaOL of low concentration has no adverse effect on
the manganese electrodeposition, and a certain amount of NaOL can
facilitate manganese electrodeposition. However, with the electro-
deposition process, the concentration of Mn2+ ions gradually decreases
while OL− ions are accumulated in the electrolyte solution, which leads
to the increase of OL− concentration. However, NaOL of high con-
centration may have detrimental effects of manganese electrodeposi-
tion, which can decrease the cathode current efficiency and even lead to
the “burning board” (Xue et al., 2016). The main purification methods
for organic impurities from aqueous solutions include activated carbon
adsorption (Loressnc-Grabowska et al., 2016), coagulation (Zhao et al.,
2014), chemical oxidation (Liao et al., 2019), dissolved air flotation and
so on (Pereira et al., 2018). These methods, however, are not ideal, and
each has its own advantages and disadvantages. For example, the oil
removal rate of coagulation method can be up to 80–90%, but there are
many waste residue and sludge and more problem difficult to handle
(Almojjly et al., 2018). Therefore, it is of great significance to find an

∗
Corresponding author. College of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, 411201, China.
E-mail address: wangshuai@csu.edu.cn (S. Wang).

https://doi.org/10.1016/j.jenvman.2019.06.026
Received 22 February 2019; Received in revised form 22 May 2019; Accepted 8 June 2019
Available online 20 June 2019
0301-4797/ © 2019 Elsevier Ltd. All rights reserved.
J. Xue, et al.
efficient and environmentally friendly method for organic impurities
removal.
To conduct dissolved air flotation efficiently, a coagulation process
can be generally introduced to facilitate the destabilization of colloidal
particles or emulsions. In addition, some coagulants, such as partially
hydrolyzed polyacrylamide (HPAM), aluminum potassium sulfate,
ferric chloride and ferric sulfate, are added into the system to enhance
the flotation efficiency. Therefore, coagulation-dissolved air flotation is
widely employed to remove various contaminants from aqueous solu-
tions, such as microalgal strains, oils (Zhang et al., 2016; Younker and
Walsh, 2014), microalgae biomass (Naghdi and Schenk, 2016) and
animal by-products (Nardi et al., 2008). Coagulation-dissolved air flo-
tation is generally accomplished using four different mechanisms, in-
cluding double layer compression, charge neutralization, entrapment in
a precipitate and inter-particle bridging (Zouboulis and Avranas, 2000).
There is no literature on the NaOL removal from synthetic manganese
leaching solution by the coagulation-dissolved air flotation.
In this study, the coagulatio-dissolved air flotation processes for
removal of NaOL from synthetic manganese leaching solution were
investigated. The effects of coagulant dosage, NaOL dosage and pH on
the removal efficiency of NaOL were optimized. The mechanisms of
removal of NaOL by the coagulation-dissolved air flotation from syn-
thetic manganese leaching solution were further explored by analysis of
the solution chemistry, the colloid chemistry and Zeta potential mea-
surements.
2. Materials and methods
2.1. Reagents and solutions
Synthetic leaching solution was prepared by dissolving with ana-
lytic reagents manganese sulfate and sodium oleate in deionized water.
The composition of synthetic leaching solution is as follows: 30 g/L
Mn2+ and different dosages (0 mg/L-60 mg/L) of NaOL. HPAM with a
viscosity-averaged molecular weight of 1.7 × 107 and a hydrolysis
degree of 23%–25% was provided by China's SINOPEC Shengli Oilfield.
Sodium oleate (C17H33COONa, NaOL), aluminum potassium sulfate,
ferric chloride and ferric sulfate were purchased from Tianjin Chemical
Agents Company (China) and used without further purification. Sulfuric
acid or sodium hydroxide solution was employed to adjust solution pH
when needed. The water used was distilled three times.
2.2. Experiment procedure
The experiments of coagulation-dissolved air flotation were carried
out in a flotation column system, consisting of a Φ630 mm × 200 mm
flotation column, rotor flowmeter and a high pressure pump, as in-
dicated in Fig. 1. Prior to the experiments of coagulation-dissolved air
flotation, synthetic manganese leaching solution containing each
chosen coagulant was stirred by 200 r/min for 30 s firstly, and then
stirred by 50 r/min for 8 h slowly so that the coagulation was fully
dissolved.
Subsequently, the experiments of coagulation-dissolved air flotation
were performed in the flotation column. In the process of coagulation-
dissolved air flotation, pressured air is released under desired super-
ficial velocity to form micro bubbles (about 0.01 mm–0.1 mm).
Synthetic leaching solution flows into flotation column through the
feeding mouth located in the upper part of the flotation column. The
micro bubble regions are formed by the reverse collision between the
declining synthetic leaching solution and the rising bubble. The micro
bubbles adhesion of NaOL overflow through the collecting groove on
the top of the flotation column. Meanwhile, leaching solutions after
purification are discharged from the liquid outlet at the bottom of the
flotation column. For each test condition, three experiments were re-
peatedly conducted and the mean value of the data was reported with
the deviation less than 1%.
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Journal of Environmental Management 247 (2019) 1–8
2.3. Analysis methods
2.3.1. Manganese concentration measurements
The purified leaching solutions are diluted. Manganese concentra-
tion during the leaching process was estimated using a Shimadzu UV-
Vis spectroscopy at 525 nm (Zhou et al., 2013). On the basis of formula
(1), the retention efficiency of manganese ions was calculated by re-
ferring the amount of preserved manganese in the purified leaching
solutions to its original input quantity. All measurements in this study
were performed at 25 °C.
Co − Ct
X= × 100%
Co (1)
where X is the retention (or removal) efficiency, C0 is the initial dosage,
Ct is the dosage (in mg/L) at a predetermined time t (min).
2.3.2. Zeta potential measurements
The zeta potential value of the respecting solutions was measured
by using a Zeta Plus zeta potential analyzer (Brookhaven corporation,
USA). The sample solution was stirred for 5 min, and the pH was con-
ditioned with dilute NaOH or H2SO4 solution to the desired value. The
zeta potential measurement was conducted in the agitated solutions.
The results presented were the average of five independent measure-
ments with a typical variation of ± 5 mV. All measurements were per-
formed at 25 °C.
2.3.3. Turbidity measurement for dosage of NaOL
Turbidity is the measurement of scattered light that results from the
interaction between a beam of light and particulate material in a liquid
sample (Li et al., 2019). In this study, the concentration of NaOL was
determined by turbidity measurement method. A series of manganese
leaching solutions containing different dosage NaOL were prepared.
The purified leaching solutions were diluted. The turbidity measure-
ments were performed using a WGZ-3 astigmatism turbidity instru-
ment. The turbidity changing with NaOL concentration is concluded,
where is the good linear relationship between the turbidity of synthetic
manganese leaching solution and the dosage of NaOL in the range of 0
mg/L-60 mg/L, which indicates that NaOL dosage in this range can be
characterized by turbidity. Therefore, the turbidity of the synthetic
leaching solution was first measured, and the dosage of NaOL was de-
termined by the interpolation. Thus, the removal efficiency of NaOL
was calculated using the above-mentioned formula (1).
2.3.4. Conductometry measurement for critical micelle concentration
(CMC) of NaOL
The measurement of electrical conductivity was performed at dif-
ferent concentration in a thermostat water bath, by using a digital
conductivity meter DDS-307A based conductivity cell with platinized
platinum electrodes purchased from Rex Electric Chemical Ltd., China.
Conductivity cell was calibrated with the aqueous KCl solution (0.74 g/
L-74 g/L) prior to measurements. As for CMC of each concentration, the
mean values of five measurements were taken into account. The un-
certainty of measurements is below ± 4%. The conductivity was mea-
sured in different concentration (0 g/L-1.6 g/L) of NaOL solutions at
298.15 K. All data analysis was performed using Microsoft Excel and
Origin 8.0 software.
2.3.5. Polarized optical microscopy
Polarized optical microscopy is usually used to detect certain or-
dered structures, anisotropic structures and optical refraction property
of the samples. It can also be used to detect chemical components in
certain samples (Chiccolia et al., 2018; Polowsky et al., 2018). Polar-
ized microscopy analysis was conducted on an AXIOSKOP 40 Pol (Zeiss,
Germany) microscope.
J. Xue, et al.
Fig. 1. Simplified schematic diagram of the experimental coagulation-dissolved air flotation system.
3. Results and discussion
3.1. Effects of coagulant dosage on the removal efficiency of NaOL
Prior to the experiments of coagulation and dissolved air flotation,
four coagulants (HPAM, aluminum potassium sulfate, ferric chloride
and ferric sulfate) with different dosages were added into manganese
leaching solution, and the leaching solution was rapidly stirred by 200
r/min for 30 s firstly, and then stirred by 50 r/min for 60 min slowly.
Subsequently, the experiments of coagulation-dissolved air flotation
were performed in the leaching solution with different dosage of the
chosen coagulant under the conditions of 30 mg/L NaOL, pH 8.0, su-
perficial gas velocity of 0.5 mL/min, foam layer height of 1.0 cm,
temperature and time of 30 °C and 5 min. The results are represented in
Fig. 2.
Ferric sulfate has little effect on the removal process of NaOL, as is
shown in Fig. 2(a). However, other three coagulants have a great in-
fluence on the removal process of NaOL, in which the impact of HPAM
is the most significant. The removal efficiency of NaOL increases when
the dosages of three coagulants are in the range of about 0 mg/L-
40 mg/L, but the removal efficiency of NaOL increases sharply as the
dosage of HPAM is less than 20 mg/L. The removal efficiency of NaOL
reaches 85.6% when the dosage of HPAM increases 20 mg/L. It is ob-
served that the leaching solution changes from relative clarification to
very turbid with dosage increase of ferric sulfate, and there is without
Fig. 2. Effects of different coagulant dosage on the removal efficiency of NaOL (a) and retention efficiency of Mn2+ ions (b).
3
Journal of Environmental Management 247 (2019) 1–8
obvious bubble layer during the flotation process. The filaments of clear
and small size form when the dosage of ferric chloride coagulant
reaches 40 mg/L. Massive clusters occur obviously when the dosage of
HPAM is less than 20 mg/L, and sodium oleate is difficult to be sepa-
rated by the dissolved air flotation when NaOL dosage is over 60 mg/L,
for the flocculation sizes are close to each other and foams are in the
steady state of upper and lower fluctuations in flotation column.
Compared to the effect of three flocculants on removal efficiency of
NaOL, the removal efficiency of HPAM is the highest relatively, prob-
ably due to the formation of good flocculation flotation by combined
agglomeration effect between HPAM and NaOL. Therefore, HPAM is
selected to remove NaOL.
Meanwhile, Fig. 2(b) indicates the retention efficiency of manga-
nese ions by four coagulants gradually decreases as the dosages of four
coagulants increase from 0 mg/L to 80 mg/L. It was observed that there
was no beneficial effect of increasing coagulant dosage over 80 mg/L.
Among them, the retention efficiency of manganese ions of ferric sulfate
and ferric chloride at each coagulant dosage is relatively higher than
that of aluminum potassium sulfate. The amide (-CONH2) and carboxyl
group (-COO-) of HPAM could coordinate with Mn2+ ions, which re-
sults in the decrease of Mn2+ retention slightly. Aluminium hydroxide
colloids form through hydrolysis of aluminum potassium sulfate in
aqueous solution. Ion adsorption in solution and colloidal particles are
charged. The ions are negatively charged when negatively charged
colloidal particles are adsorbed. Fayence rule indicates that ions of the
J. Xue, et al. Journal of Environmental Management 247 (2019) 1–8

Fig. 3. Effect of NaOL dosage on the removal efficiency of NaOL (a) and retention efficiency of manganese ions (b) under different pH values.

same chemical elements are adsorbed preferentially with the colloidal each NaOL dosage as compared to that of pH 5.0. This has been possibly
particles. Therefore, ferric hydroxide colloid can only be combined with attributed to that manganese ions are hydrolyzed and OL− concentra-
H+ ions, which results from the hydrolysis of ferric sulfate and ferric tion increases as pH increases. And the retention efficiency of manga-
chloride in aqueous solution. On the other hand, aluminum hydroxide nese ions is different for different products of interaction among man-
is an amphoteric compound, that is aluminum hydroxide can be Al ganese ions, HPAM and OL− ions. The removal efficiency of NaOL is
(OH)3 and aluminum hydroxide colloid being positive as combined primarily focused in this study. Therefore, the parameters of 30 mg/L
with H+ to attract negative charge; aluminum hydroxide also can exist NaOL and pH 8.0 are optimized.
in form of H3AlO3, which can lose H+ ions when the solution is alka-
line, with a negative charge adsorbing Mn2+ ions. Hence, Mn2+ ions 3.3. Existing form of oleate species in the leaching solution
are weakly adsorbed by ferric sulfate and ferric chloride. In conclusion,
HPAM is used as flocculant in subsequent experiment. 3.3.1. Effect of pH on existence form of Mn2+ species
Based on the information (Rudnik, 2015), the chemical reactions
3.2. Effect of NaOL dosage and pH value on the removal efficiency of NaOL and equilibrium constants of the leaching solution of manganese ore are
obtained, as listed in Table 1.
To investigate the effect of NaOL dosage and pH value on the re- Table 1 indicate that the existence form of Mn2+ species is influ-
moval efficiency of NaOL, experiments were performed by varying pH enced by the solution pH and exists in the form of Mn2+, Mn(OH)+, Mn
(5.0–8.0) and NaOL dosage (0 mg/L-60 mg/L) under the conditions of (OH)2, Mn(OH)3-, Mn(OH)42- species. Therefore, total concentration of
15 mg/L HPAM, superficial gas velocity of 0.5 mL/min, foam layer Mn2+ species ([Mn2+]T) in aqueous manganese sulfate solution was
height of 1.0 cm. The results were plotted in Fig. 3. Fig. 3(a) represents calculated by the mass balance according to Eqs (2)–(5), as follows.
that the removal efficiency of NaOL obviously increases with increase [Mn2 +]T = [Mn2 +] + [Mn (OH )+] + [Mn (OH )2(aq) ] + [Mn (OH )−3 ]
of NaOL dosage and pH values, and the rising amplitude of removal
efficiency of NaOL at pH 8.0 is the biggest in the leaching solution. The + [Mn (OH )24−] (6)
removal efficiency of NaOL at each pH is the highest as 30 mg/L NaOL Eq. (6) can be transformed into the following equation by introdu-
dosage in the leaching solution. The removal efficiency of NaOL reaches cing a side reaction coefficient α(Mn2+
) .
97.6% when the dosage of NaOL reaches 30 mg/L at pH 9.0. The me-
chanisms of chemical coagulants destabilizing colloidal particles or [Mn2 +][Mn2 +]T
α (Mn2 +) = = 1 + K1 [OH−] + K2 [OH−]2 + K3 [OH−]3 + K 4
emulsions include: double layer compression, charge neutralization, [Mn2 +]
entrapment in a precipitate and intraparticle bridging. Sodium oleate [OH−]4
colloid and HPAM are anionic surfactants with a negatively charged (7)
surface. The primary goal of HPAM is to overcome the negative elec-
trical double layer surrounding colloids in aqueous solution and “sta- Hence, the concentration of free Mn2+ ions are listed.
bilizes” the colloids, hindering them from adhering to each other and [Mn2 +][Mn2 +]T
[Mn2 + ]=
forming larger particles. If the solution pH is below the Zero potential α (Mn2 +) (8)
(around Zero7.6) of manganese hydroxide, then positively charged
2+
polymers will prevail and the adsorption of these can destabilize the According to formulas (2)–(8), various Mn species can be ex-
negatively charged colloids or emulsion droplets of NaOL by the me- pressed, as follows:
chanism of charge neutralization. Above Zero potential, anionic poly-
mers will predominate and particle destabilization may take place Table 1
through adsorption and bridge formation. Meanwhile, the tertiary Equilibrium reactions and relevant constants (25 °C).
amine group of HPAM is protonated as pH is lower, and oleate ions and Reaction Equilibrium coefficient Constant No.
the grafted chain will be adsorption effect, so that the adsorption ca-
Mn2 + + OH− ⇋Mn (OH )+ [Mn (OH )+] (2)
pacity is higher (Zhu et al., 2012). These possible effects can be at- K1 = K1=103.54
[Mn2 +][OH −]
tributed improving the removal efficiency of NaOL. Mn2 + + 2OH− ⇋Mn (OH )2(aq) [Mn (OH )2 ] K2=105.8 (3)
K2 =
Moreover, Fig. 3(b) shows the retention efficiency of Mn2+ ions of [Mn2 +] [OH −]2
Mn2 + + 3OH− ⇋ Mn (OH )− [Mn (OH )−
3] (4)
each pH gradually decreases as NaOL dosage increases in the range of 3 K3 = K3=107.2
[Mn2 +][OH −]3
0 mg/L to 40 mg/L. The retention efficiency of manganese ions keeps (5)
Mn2 + + 4OH− ⇋ Mn (OH )24− [Mn (OH )24 −] K4=107.3
constant at 79.67% (pH 8.0) when NaOL dosage is over 40 mg/L. The K4 =
[Mn2 +][OH −]4
retention efficiency of manganese ions of pH 8.0 is relatively higher at

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J. Xue, et al. Journal of Environmental Management 247 (2019) 1–8

Fig. 4. Distribution percentage of Mn2+ species with pH in aqueous manganese Fig. 5. Relationship between logCT and pH of aqueous sodium oleate solution
sulfate solution (0.55 mol/L MnSO4, 25 °C). (CT = 3.5 × 10−5 mol/L). The following is the supposed reaction between free
Mn2+ ([Mn2+]) and free OL− ([OL−]) ions in aqueous manganese sulfate so-
lution (Xue et al., 2016).
⎞
log[Mn2 +] = log[Mn]T − log(1 + K1 [OH−] + K2 [OH−]2 + K3 [OH−]3 ⎟ Mn2 + + 2OL−⇋Mn(OL)2 Ksp = [Mn2 +][OL−] Ksp = 1.0 × 10−15.3 (14)
⎟
+ K 4 [OH−]4 ⎠ [HOL]
OL− + H+⇋HOLKH = K H = 1.0 × 10 4.95
(9) [H+][OL−] (15)

log[Mn(OH)+ ]= logK1 + log[Mn2 + ]+ log[OH−] (10) α (OL−) = 1+ KH[H+] (16)

log[Mn (OH )2(aq) ] = log K2 + log[Mn2 +] + 2 log[OH−] (11)

log[Mn (OH )−3 ] = log K3 + log[Mn2 +] + 3 log[OH−] (12)

log[Mn (OH )24−] = log K 4 + log[Mn2 +] + 4 log[OH−] (13)

2+
Based on Eqs (2)-(13), Mn species-pH diagram was shown in
Fig. 4. Fig. 4 demonstrates that Mn2+ species are dominantly in the
form of free Mn2+ ions in aqueous manganese sulfate solution (pH
1.0–8.0). Other Mn2+ species have a minor share in total Mn2+ ions.
Mn2+ distribution decreases gradually as pH increases from 8.0 to 14.0,
but distributions of Mn(OH)+, Mn(OH)2, Mn(OH)3- and Mn(OH)42-
start to varying.

3.3.2. Thermodynamic analysis of reaction between OL− and Mn2+ ions

Oleate species exist in multiple forms in aqueous sodium oleate
solution, and a species-pH diagram for sodium oleate (3.5 × 10−5 mol/
L) may be used to interpret the mechanism of dissolved air flotation,
given in Fig. 5 (Xue et al., 2016). Fig. 5 indicates that the insoluble HOL
is the only significant species in solution as pH less than 8.4. And OL−
and (OL)22- anions will be the dominant forms in the system (pH Fig. 6. ΔGθ curves of Mn2+ and OL− reaction for different pH.
8.4–14.0). This means that there is the interaction possibility of Mn2+
coordination with OL− ions in aqueous manganese sulfate solution. complex reaction of Mn2+ and OL− can occur. Thus, OL− ions exist in
In the complex system (Mn2+, Mn(OH)-, OL− and so on), the the form of Mn2+-OL- complex. On the other hand, the hydrophobic
standard Gibbs free energy (ΔGθ) were further estimated to determine groups of NaOL are arranged closely as the concentration of manganese
whether the probability reaction between OL− and Mn2+ ions occurs in sulfate increases, which is conducive to the adsorption of carboxylic
aqueous manganese sulfate solution. ΔGθ can be calculated by sub- group (-COO-) on the foam surface. Moreover, CMC may decrease due
stituting K ’sp into formula (17). to the increase of manganese sulfate concentration. Meantime, the
ΔGθ = RTlnK ’sp = RTln(K spα Mn2 +)α 2(OL−)) maximum adsorption capacity of NaOL reaches when the equilibrium
(17)
concentration of NaOL is lower in aqueous manganese sulfate solution.
where K ’sp is
the conditional solubility product constant; R is the uni- And the concentration of manganese sulfate is the larger, the maximum
versal gas constant (8.314 J/(mol·K)); T is absolute temperature (K). adsorption capacity of NaOL reaches easily. This may facilitate the re-
According to Eq. (7) and Eqs. (14)-(17), the relationship between ΔGθ moval efficiency of NaOL by coagulation-dissolved air flotation.
and pH is presented in Fig. 6.
Fig. 6 indicates ΔGθ decreases as pH increases in the range from 1.0
to 6.0. Afterward, it remains constant until pH 10.0. ΔGθ increases as 3.3.3. Relationship between Mn(OL)2(s) and remained (OL−)R
pH successively increases to pH 14.0. It is concluded from Fig. 6 that Based on the abovementioned discussions, the relationships

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J. Xue, et al. Journal of Environmental Management 247 (2019) 1–8

between Mn(OL)2 and the remained OL− ions ([OL−]R) are calculated.
Eq. (18) can be deduced from Eq. (14).
[Mn2 +][OL−]2
Ksp = [Mn2 +][OL−]2 =
αMn2 + αOL−2 (18)

Eq. (19) can be further derived, as follows.

Ksp αMn2 + αOL−2
[Mn2 +] =
[OL−]R 2 (19)

The following formulas are also obtained from mass conservation.

[Mn2 +]T = [Mn (OL)2] + [Mn2 +] (20)

[OL−]T = 2[Mn(OL)2 ]+ [OL−]R (21)

2+ − 2+
where [Mn ]T and [OL ]T are initial concentrations of Mn and
OL− ions in aqueous manganese sulfate solution. And [Mn2+] and
[OL−]R are concentrations of Mn2+ and (OL−)R in aqueous manganese
sulfate solution. Based on above formulas, [Mn2+] can be concluded, as
follows. Fig. 8. Zeta potential of NaOL as a function of pH before and after HPAM ad-
OL−] OL−] L−]R [OL−] T dition.
[Mn2 +] = [Mn2 +]T − ≈ [Mn2 +]T −
2 2 (22)
− In summary, most of the oleate ions in this study exist in the form of
So [OL ]R and [Mn(OL)2] can be expressed as the following for-
Mn(OL)2(s). Other residual OL− ions primarily exist in the form of OL−
mula.
and HOL(aq).
Ksp αMn2 + αOL−2
[OL−]R = OL−]T
[Mn2 +]T − 3.4. Interaction between HPAM and NaOL
2 (23)
3.4.1. Zeta-potential analysis between HPAM and NaOL
2 − ⎞
1 Ksp αMn2 + αOL Influence of HPAM on electric charge of NaOL surface was char-
[Mn (OL)2⎤ = ⎛⎜ ⎡OL−⎤ − [OL−]T ⎟⎟
⎥ 2 ⎝⎢ ⎥ [Mn2 +]T − acterized by Zeta potential. The zeta potential values of NaOL (with or
⎦ ⎣ ⎦T 2 ⎠ (24)
without HPAM) as a function of pH are displayed in Fig. 8. As can be
−
The relationships between Mn(OL)2(s) and (OL )R concentration seen from Fig. 8, the Zero point of NaOL occurs at pH about 4.0. The
were discussed on the base of formula (2)-(24). The obtained results are Zeta potential of NaOL under the same pH value shifted negatively with
indicated in Fig. 7. Fig. 7 represents that most of NaOL added is con- the addition of HPAM; the Zero electric point decreased from 4.0 to
verted to Mn(OL)2(s) in aqueous manganese sulfate solution. about 2.0, and when pH < 2.0, the potential was positive and shifted
In Mn2+-OL system of this study, the concentration of manganese negatively relative to the original. The adsorption of HPAM on NaOL
ions exceeds that of oleate ions. Therefore, the chemical reaction of Mn surface may be electrostatic adsorption or chemical adsorption; when
(OL)2(s) formation reaches equilibrium. Under optimal conditions, the pH > 2.0, HPAM is added to make the Zeta potential of NaOL at the
[OL−]R is calculated from Eqs.(2)-(24), as follows. same pH value shifted negatively, especially in the pH region with the
relatively high removal efficiency of NaOL. The amplitude of the po-
[OL−]R = 3.037 × 10−8mol/ L (25)
tential decrease is more obvious in this pH region, inferring that HPAM
−
The calculated result infers that the (OL )R ions exist in liquid form, was adsorbed on NaOL surface. With anionic HPAM with the same
for that [OL−]R (3.037 × 10−8 mol/L) is less than solubility of oleic charge of anionic NaOL can be well adsorbed on HPAM surface, in-
acid (10−7.6 mol/L). dicating that the interaction between HPAM and NaOL is not dominated
by electrostatic force, but should be related to the chemical action (Xiao
et al., 2017), which is consistent with the aforementioned results.

3.4.2. Effect of HPAM on CMC of NaOL

To investigate effect of HPAM on CMC of NaOL, conductivity
measurement were carried out in 7.0 g/L NaOL solution containing
different addition of HPAM (0 mg/L-1.2 mg/L). The uncertainty of CMC
has been found to be ± 0.03. The obtained result is shown in Fig. 9.
Fig. 9 indicates that CMC of NaOL decreases with the increase of HPAM
addition. The reason is that Na+ concentration increases as HPAM
dosage increases, which results in the slow spread of NaOL, the de-
crease of double electric layer thickness of micelle and the decrease of
CMC of NaOL. On the other hand, negative charge (RCOO−) increases
with the increase of HPAM concentration, making electrostatic repul-
sion between RCOO− and OL− ions increase, which facilitates OL−
ions to form micelles and CMC value to lower. Therefore, the formation
of micelle favors the removal efficiency of NaOL by coagulation-dis-
solved air flotation system.

3.4.3. Effect of HPAM on distribution structure of NaOL

Fig. 7. Relationship between pH and logC of Mn(OL)2(s) and (OL−)R. In order to investigate effect of HPAM on distribution structure of

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J. Xue, et al. Journal of Environmental Management 247 (2019) 1–8

NaOL, polarized microscopy observations were conducted. The results

were shown in Fig. 10. Fig. 10 demonstrates there is full of “empty”
background indicating no polarized property in 10 mg HPAM+5 mg
NaOL (Fig. 10(a)), and some Malta crosses are clearly observed in
15 mg HPAM + 30 mg NaOL (Fig. 10(b)), inferring the formation of
two-dimensional lamellar structure. Meantime, it may be concluded
that the three-dimensional network is the majority structure of NaOL
still although two-dimensional lamellar structure starts emerging in
these samples.

3.4.4. Schematic illustration on interaction mechanism among NaOL,

Fig. 9. Variation between CMC of NaOL and HPAM dosage.
Fig. 10. Polarized micrograph of 10 mg HPAM+5 mg NaOL (a) and 15 mg
HPAM + 30 mg NaOL (b).
HPAM and bubble
The interaction mechanism among NaOL, HPAM and bubble be-
tween HPAM and NaOL may also be explained by CMC of NaOL and
adsorption state. There is a little NaOL molecule around HPAM chain as
NaOL concentration is lower (Fig. 11(a)) in the bulk solution. Hence,
Fig. 11(a) illustrated that NaOL molecules act as bridges and form
network structures through HPAM chains, due to interpolymer cross-
linking through hydrogen-bonding interaction between the carboxyl
group of NaOL and the amide group of HPAM molecules.
Accordingly, polarized phenomena wasn't observed in these systems
through polarized microscopy observations (Fig. 10(a)). The hydrogen
bonding could result in the adsorption of HPAM chains to the surfactant
monolayer at the air-water surface. It also caused some surfactant
molecules to adsorb onto the polymer chains, which decreased the
surface adsorption density of the surfactant. The degree of cross-links
increases with NaOL concentration increasing as shown in Fig. 11(b),
which resulted in turbidity increasing gradually. Meanwhile, Fig. 11(b)
illustrates that the micelle of NaOL are formed, which eventually re-
sulted in most of HPAM chains wrapping around the surface of NaOL
micelle. This could lead to the formation of the two-dimensional la-
mellar structure (Fig. 10(b)). The HPAM flocculant has the absorption
and bridge effect for the NaOL removal. Therefore, Fig. 11 illustrates
that the adsorption of NaOL to HPAM chains on the floating bubble
surface efficiently promotes NaOL removal by coagulation-dissolved air
flotation.

Fig. 11. Schematic illustration of interaction among NaOL, HPAM and bubble in coagulation-dissolved air flotation process, low NaOL concentration (a) and high
NaOL concentration (b).

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4. Conclusions
Partially hydrolyzed polyacrylamide is efficient to remove sodium
oleate from synthetic manganese leaching solution by coagulation-dis-
solved air flotation. 97.6% NaOL could be removed and 79.67% man-
ganese ions are effectively retained under the optimal conditions of
20 mg/L HPAM, 30 mg/L NaOL and pH 8.0. Most of oleate species
primarily exist in the form of Mn(OL)2(s), OL− and HOL(aq). The addi-
tion of HPAM could make the Zeta potential of NaOL shift negatively
and CMC of NaOL decrease. Polarized microscopy observation indicates
that three-dimensional network becomes weak and two-dimensional
lamellar structures. NaOL can be removed by coagulation-dissolved air
flotation through the adsorption and bridge effect of HPAM chains on
the floating bubble surface.
Declaration of interest statement
The Authors declared that they had no conflicts of interests in their
authorship and publication of this contribution.
Acknowledgments
The authors would acknowledge with gratitude for the National
Science and Technology Support Program of China (No.
2015BAB17B01) and the Hunan Provincial Science and Technology
Plan Project, China (No. 2016TP1007).
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