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Applied Surface Science

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Full Length Article

Fabrication and adsorption properties of hybrid fly ash composites

Mengfan Gao a , Qingliang Ma b,∗ , Qingwen Lin a , Jiali Chang a , Hongzhu Ma a,∗
a
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal
University, Xi’an710119, Shaanxi, PR China
b
Key Laboratory of Coal Science and Technology, Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan, 030024, China

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

Article history: In order to realize the utilization of fly ash (FA) as industrial solid waste better, high-efficient inor-
Received 23 August 2016 ganic/organic hybrid composite adsorbents derived from (Ca(OH)2 /Na2 FeO4 ) modified FA (MF) was
Received in revised form 19 October 2016 fabricated. The hydrophilic cationic polymer (P(DMDAAC-co-AAM) or hydrophobic modifier (KH-570)
Accepted 25 October 2016
were used. The prepared composites were characterized by X-ray fluorescence spectroscopy, energy
Available online xxx
dispersive spectroscopy, scanning electron microscopy, Brunauer-Emmett-Teller, Fourier transform
infrared spectroscopy, thermogravimetry, and contact angle test. The adsorption of cationic compos-
Keywords:
ites MF/P(DMDAAC-co-AAM) towards Orange II in wastewater was investigated. The results show that:
Fly ash
Adsorption
adsorption amount of 24.8 mg/g with 2000 mg/L of composites, 50 mg/L Orange II, original pH (6–8), at
Hydrophilic 40 min and room temperature, was obtained. Meanwhile, oil adsorption ratio Q(g/g) of hydrophobic com-
Hydrophobic posites MF/KH-570 was also evaluated. The maximum Q of 17.2 g/g to kerosene was obtained at 40 min.
Orange II The isotherm and kinetics of these two adsorption processes were also studied. The results showed that
Kerosene the fabricated MF composites modified with hydrophilic or hydrophobic group can be used to adsorb dye
in wastewater or oil effectively.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction modification of purified FA and its application in polymer, the result

As an industrial solid waste and most common silicate material,
the principle components of fly ash (FA) consisted of silica, alumina,
ferrous oxide, calcium oxide and various of carbon, so many active
sites exhibit on its surface [1].
Reusing FA as adsorbents in removal of different kinds of pol-
lutants in wastewater has aroused broad attention. For its hollow
sphere and activated surface area, FA has been used to the removal
of heavy metals, dyes from water, as a non-conventional suitable
efficient sorbent [2]. But adsorption capacity of raw FA is limited for
large closed holes. All kinds of traditional modified fly ash, such as
acid/FA [3], alkali/FA [4] and mixed modified FA have been widely
used to the adsorption of pollution from wastewater. However,
these modifications cannot make it fully activated, which limit the
application. Moreover, the disposal of alkaline or acidic wastewater
presents an additional difficulty in practical application.
To improve the adsorption properties of FA and the resource
utilization as solid waste, most of surface modification techniques
have been investigated [5,6]. Yang etc. [7] has studied the surface
∗ Corresponding authors.
E-mail addresses: maqingliang@tyut.edu.cn (Q. Ma), hzmachem@snnu.edu.cn
(H. Ma).
showed that the treated FA can be filled well in polymer as filler.
Karakasi and Moutsatsou have discussed the sorption of three types
of oil (heating oil, light cycle oil and Iranian light crude oil) on two
high calcium FAs (HCFA). and the results showed that the addition
of HCFA to an oil spill form a semi-solid oil-HCFA phase, allowing
the quite total removal of oil from the water surface [8]. How-
ever, these single modifications by a monomer or polymer mainly
focused on increasing the specific surface area and roughness to
improve adsorption capacity.
Extensive use of the industrial material in various parts of the
world always generate harmful pollutants, such as coloured efflu-
ents, which containing various dyes and pigments, large amounts of
these dyes from textile industries often are very toxic even at a very
low concentration when they are discharged to natural water bod-
ies [9]. Azo dyes are important synthetic colorants that represent
the largest class of dyes generally characterized by the presence of
one or more azo bonds ( N N ) [10].
In addition, one of the most visible and important source of
marine pollutions is the oil pollution caused oil spills and chemi-
cal leakage. And approximately tens of thousands of tones of oil are
spilled annually worldwide in the past [11]. Oil pollution is harmful
to both environment and biology immediately and chronically.

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Scheme 1. Flow diagram of the composite adsorbents preparation.

Table 1
The chemical composition of all FA samples.

Samples Weight(%)

SiO2 Al2 O3 Fe2 O3 CaO K2 O MgO TiO2 SrO

FA 50.95 36.10 3.91 2.94 2.23 0.70 1.06 0.09

MF 29.61 22.10 11.53 33.17 1.45 0.00 0.94 0.07
MF/P(DMDAAC-co-AAM) 34.16 24.63 10.13 26.60 1.67 0.56 0.84 0.07
MF/KH-570 37.47 20.44 9.05 30.38 0.00 0.59 0.85 0.09

Many different treatment techniques such as biological treat-
ment, coagulation, oxidation, and adsorption have been used in
the removal of coloured dyes [12–14]. And some oil spill clean-
up techniques have been developed, such as the use of booms and
skimmers, the oil pumping [15], the use of chemical agents, such as
sorbents [16]. However, it has been reported that adsorption is one
of the effective methods with the advantages of high treatment
efficiency and no harmful by-product to treated water including
dyes and oil [17]. Nowadays, there are more and more lots of non-
conventional, low cost adsorbents such as activated carbon [18],
clay including bentonite and kaolinite [19,20] and so on, have been
used for removal dyes and oil. However, these adsorption materi-
als all have high costs and problems in regeneration [21]. And the
adsorption capacity of these adsorbents is also limited.
In our previous paper [22], Na2 FeO4 and Ca(OH)2 mixed
modified FA (Na2 FeO4 /Ca(OH)2 /FA, MF) was fabricated with bet-
ter mechanical strength, higher porosity and higher efficient
in dye removal. Here MF from FA was further modified by
the hydrophilic cationic polymer, dimethyl diallyl ammonium
chloride-co-acrylamide (P(DMDAAC-co-AAM)) or hydrophobic ␥-
methyl propenyl acyloxy propyl trimethoxy silane (KH-570), to
construct two types of hybrid composites with hydrophily or
hydrophobicity, respectively, which then were used as adsorbents
for dye removal from wastewater or oil adsorption. The surface of
MF can be regulated by hydrophilic/hydrophobic groups instead
of single modification to active surface fully, which can make full
use of FA and realize resource utilization. Moreover, the adsorption
behaviors for Orange II (O-II) (removal efficiency, R%) in wastewater
by MF/P(DMDAAC-co-AAM) composite and kerosene (oil adsorp-
tion ratio, Q(g/g)) by MF/KH-570 were studied. The effects of
various experimental parameters such as pH, concentration, con-
tact time, and adsorbent dosage on the adsorption properties were
evaluated. The hydrophobicity of MF/KH-570 was studied by con-
tact angle test. In addition, the adsorption thermodynamics and
kinetics of the composites were also investigated. Here, the pur-
pose is to construct high-efficient adsorbents by modified MF
with hydrophilic or hydrophobic group, the modification of MF or
FA with two different organic polymer or group has rarely been
reported, and it would further expand the utilization of solid waste
FA.
2. Experimental
2.1. Materials and regents
The raw FA, was collected from the electro-filters from a power
plant in Shaanxi Province. Dimethyl diallyl ammonium chloride
(DMDAAC, analytical grade, and acrylamide (AAM, analytical grade
were, purchased from Shanghai Chemical Co., China. ␥-methyl
propenyl acyloxy propyl trimethoxy silane (KH-570) was provided
by Chengdu Chenguang Silane Co., Ltd, China. Other reagents were
analytical grade and used without any further purification. Distilled
water was used throughout.
O-II as a typical anionic dye, was chosen as the substrate in the
hydrophilic adsorption test. Benzene, methylbenzene, kerosene,
abies oil, and olive oil were chosen as the substrates in oil adsorp-
tion experiment.
2.2. Synthesis of composite adsorbents
FA/Ca(OH)2 /Na2 FeO4 (MF) was prepared as the previous paper
reported [22]. 4 g organic hydrophilic (P(DMDAAC-co-AAM)
(DMDAAC:AAM = 1:1) or hydrophobic modifier (KH-570) was dis-
persed into 25 mL distilled water with stirring evenly using SZCL-3A
stirrer, 1 g MF was then introduced into the suspension at 343 K
for 2 h. After the sample cooling, separated, and the precipitate
was washed with distilled water 2–3 times, then dried at 373 K for

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Fig 1. EDX of (a) FA; (b) MF; (c) MF/P(DMDAAC-co-AAM); (d) MF/KH-570.

Table 2
Porosity parameters of MF samples.
b
Specific pore volume.
c
Average pore diameter calculated by BJH method.

Adsorbents SBET a (m2 /g) Vp b (cm3 /g) dBJH c (nm) Pore volume distribution

MF 1.43 0.0044 13.6 2–50 nm

MF/P(DMDAAC-co-AAM) 3.27 0.0208 1.9 <2 nm
MF/KH-570 14.28 0.0569 1.7 <2 nm
a
BET specific surface area.
b
Specific pore volume.
c
Average pore diameter calculated by BJH method.

2 h to obtain the modified samples MF/P(DMDAAC-co-AAM) and FT-IR spectra of MF, MF/P(DMDAAC-co-AAM) and MF/KH-570
MF/KH-570, as Scheme 1 shown. composites were undertaken on a Tensor 27 FTIR spectrometer
(Bruker, Germany) over 4000–500 cm−1 with KBr pellets.
Thermal analysis were performed on a thermogravimetric ana-
lyzer (TA corporation, USA) to evaluate the amount of the organic
2.3. Analysis and characterization of the samples
contents in the hybrid composites at a rate of 10 K min−1 under N2 .
Zeta potential measurements were performed by using a Laser
The chemical and elemental compositions of FA samples were
particle size zeta potentiometer (Nano Zetasizer Delsa Nano C, Kurt
determined by means of X-ray fluorescence spectroscopy (XRF
beckman company) injecting a small portion of the pure dispersion
1800, Shimadzu corporation, Japan) and energy dispersive spec-
of hydrogel and detergent at room temperature.
troscopy (EDX, high vacuum, Quanta 200, FEI corporation).
Contact angle measurements were performed on an OCA-20
The surface morphology of all FA samples were analyzed on a
Contact Angle-meter (Data Physics Instruments, Germany) to test
Scanning Electron Microscopy (SEM) (TM3030, Hitachi).
the hydrophobicity of MF/KH-570, using the sessile drop method
The Brunauer-Emmett-Teller (BET) specific surface areas of
with water as wetting liquid.
samples were determined by N2 adsorption (Physical Adsorption
meter, Mike, USA). All samples were degassed at 373 K.

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Fig. 2. SEM images of (a) FA; (b) MF; (c) MF/P(DMDAAC-co-AAM); (d) MF/KH-570.

2.4. O-II adsorption onto MF/P(DMDAAC-co-AAM) was introduced and immersed into the pure oily substrate. At the
predetermined time intervals, the oily substrate was adsorbed and
A series of adsorption experiments were studied at different its weight (St, g) was then recorded. The oil adsorption ratio (Qt ) at
conditions. Typically, a certain amount of hydrophilic composites time t was calculated by Eq. (4):
MF/P(DMDAAC-co-AAM) was added into O-II solution with stirring
St − S0
(100 rpm). At the predetermined time intervals, MF/P(DMDAAC- Qt (g/g) = (4)
S0
co-AAM) was filtered from the solution and the concentrations of
O-II were then determined by UV–vis spectrophotometer (UVT6,
2.6. The adsorption isotherms models
Beijing Purkinje General Instrument Co. Ltd, China) at ␭max of
484 nm. And all the adsorption experiments were repeated for 3
Batch experiments were conducted at different temperatures
cycles to decrease error.
and Langmuir and Freundlich isotherm models were employed. The
The removal efficiency of O-II was calculated by Eq. (1) [23]:
Langmuir isotherm model can be expressed as Eq. (5) [25]:
A0 − At
R(%) = × 100% (1) Ce
= 1
+ Ce
A0 qe kL qL qL (5)
Where A0 and At represent O-II concentration at the initial time and
time t (min), respectively. Where qL (mg/g) represents the maximum monolayer adsorption
The equilibrium adsorption amount (qe ) and the adsorption capacity, kL is a constant related to the adsorption free energy, qe is
amount at time t (min) (qt ) were calculated by Eqs. (2)–(3): the amount of O-II adsorbed from the solution with the equilibrium
concentration, Ce .
(C0 − Ce)V The Freundlich isotherm model can be expressed as Eq. (6) [26]:
qe = (2)
W
1
ln qe = ln kF + ln Ce (6)
(C0 − Ct)V n
qt = (3)
W Where kF is the Freundlich constant, an indicator of the adsorption
where C0 (mg L−1 ), Ce (mg L−1 ) and Ct (mg L−1 ) are O-II concentra- capacity, and the dimensionless parameter 1/n is a measure of the
tion at the initial, equilibrium time and time t (min), V (L) is the adsorption density.
volume of the solution, and W (g) is the weight of MF/P(DMDAAC-
co-AAM) composites. All the experimental data were averages of 2.7. Thermodynamic studies
duplicate or triplicate determinations.
The thermodynamic parameter, such as the change of Gibbs free
2.5. Oil adsorption onto MF/KH-570 energy (G), was calculated by Eq. (7):

G = −RT ln K (7)
Batch oil adsorption experiments were conducted with various
substrates. Gravimetric method [24] was used to test oil adsorption K is the equilibrium constant, R is the gas constant (8.314 J/(mol. K)),
ratio Q. Typically, a certain amount of MF/KH-570 adsorbent (S0, g) and T is absolute temperature (K).

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Fig. 4. FTIR spectra of (a) MF(I); MF/P(DMDAAC-co-AAM) (II); MF/P(DMDAAC-co-

AAM)-O-II(III) and (b) MF(I); MF/KH-570(II); MF/KH-570 −Kerosene(III).

2.8. Adsorption kinetics [28,29]

The Lagergren pseudo-first-order kinetic equation:

ln(qe − qt ) = ln qe − k1 t (9)

k1 is the Lagergren constant, qe is the equilibrium uptake value and

qt is the uptake value at time t (min).
The Ho and McKay pseudo-second-order kinetics equation:
t 1
qt = + qte (10)
k2 qe 2

Where k2 is the pseudo-second-order rate constant of adsorption

(g−1 min−1 ).

3. Results and discussion

Fig. 3. Nitrogen adsorption-desorption isotherms and pore size distributions of (a)
MF, (b) MF/P(DMDAAC-co-AAM) and (c) MF/KH-570.
3.1. Compositions and characterization of the composite
adsorbents
The apparent enthalpy (H) and entropy (S) of adsorption
were calculated using Eq. (8) [27]: The chemical compositions of FA samples were determined
S H by XRF and the results were listed in Table 1. It showed that
ln K = − (8) four FA samples are mainly composed of four metal oxides, SiO2 ,
R RT
Al2 O3 , Fe2 O3 and CaO. After modification by the organic silane
Lnk was obtained from the intercept of the plot of ln(Qe /Ce ) versus coupling agent KH-570, the content of CaO increased significantly
Qe [29]. than that of MF. Also elemental analysis of all samples was deter-

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Fig. 5. TGA curves of (a) MF/P(DMDAAC-co-AAM) and (b) MF/KH-570 composites.

mined by EDX (Fig. 1). The contents of C, N and Cl elements of
MF/P(DMDAAC-co-AAM) composites increased compared to those
of MF, and the contents of C, Si of MF/KH-570 increased apparently
after the introduction of KH-570, confirmed that MF was modified
by P(DMDAAC-co-AAM) or KH-570 successfully.
To gain the real morphology of samples, SEM was used to
determine the qualitative and morphological characteristics [30].
A large amount of cotton-like materials were produced on the sur-
face of spherical MF, after the introduction of cationic polymer
P(DMDAAC-co-AAM) and the surface tended to be more rough and
uneven, which was beneficial for adsorption [31]. The flocculent
structure with surface roughness and the dispersion of fine parti-
cles was obtained for MF/KH-570, it is likely that the hydrophobic
group, organic silane coupling agent KH-570, loaded to the surface
of the of MF (Fig. 2).

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Fig. 6. Contact angle of (a) MF and (b) MF/KH-570.

Fig. 3 showed the adsorption–desorption isotherms of N2 and

size distribution of three MF samples at 100 K. The type IV appar-
ent hysteresis loops in the relative pressure P/P0 range of 0.1–0.8
were observed [32]. The quantity of nitrogen adsorption increased
significantly at a P/P0 of 0.8, suggesting the capillary condensation
of nitrogen within the primary mesopores. The pore size distribu-
tions were calculated from the nitrogen desorption isotherm using
the Barrett-Joyner-Halenda (BJH) model. The BET specific surface
area, specific pore volume, and average pore diameter, were sum-
marized in Table 2. The results showed that MF was principally
mesoporous (average pore diameter 2–50 nm), and the hybrid com-
posites were principally microporous (<2 nm), centered at 13.6 nm,
1.9 nm and 1.7 nm, respectively [33]. The largest specific surface
area of 14.28 m2 /g was observed for MF/KH-570 composites. It can
also be seen that with the pore diameter increased, the pore volume
decreased sharply, indicating that well developed pores led to the
large surface area. Hence it was beneficial for the adsorption effi-
ciency improvement for MF/P(DMDAAC-co-AAM) and MF/KH-570
composites. Fig. 7. Effect of various parameters O-II removal (a) initial concentration and contact
The FTIR spectra of MF, MF/P(DMDAAC-co-AAM) and MF/KH- time; (b) adsorbent dosage; (c) initial pH.
570 before and after adsorption of O-II or kerosene were shown in
Fig. 4. A broad band at 3450 cm−1 , in the FT-IR spectra of MF (Fig. 4a
(I) and b (I)), due to O H stretching vibration band in Si O H The weak band at 550 cm−1 was assigned to Al O stretching vibra-
groups and H2 O, the peak at 1640 cm−1 , attributed to the H O H tion band [35]. After modification by P(DMDAAC-co-AAM) (Fig. 4a
bending vibration in H2 O, and the peak at 1447 cm−1 , attributed (II)), the characteristic absorption bands of amide group −CONH
to the OH stretching vibration, all these bands suggested that the at 3420 cm−1 and 1665 cm−1 were overlapped. A weak band at
presence of adsorbed water and/or water of crystallization in the 2360 cm−1 was attributed to the stretching vibration of two five-
material [34]. Two peaks at 1010 cm−1 and 970 cm−1 were assigned membered rings of DMDAAC [36]. Therefore, it can be deduced that
to Si-O asymmetric and symmetric stretching vibration bands, and the P(DMDAAC-co-AAM) has been introduced into MF framework.
the peak at 460 cm−1 was attributed to the Si-O bending vibration. After the adsorption of O-II (Fig. 4a (III)), no new band appeared,

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Table 3
Adsorption isotherm parameters for O-II adsorption onto MF/P(DMDAAC-co-AAM).

T (K) Langmuir Freundlich

qL (mg/g) kL (L/(mg)) R2 kf n R2

298 67.90 0.0110 0.999 1.075 1.239 0.961

308 105.8 0.00999 0.987 2.576 1.171 0.983
318 140.1 0.00750 0.989 1.302 1.146 0.978

Table 4
Thermodynamic parameters for O-II adsorption onto MF/P(DMDAAC-co-AAM).

T (K) lnK G (kJ/mol) H (kJ/mol) S (kJ/(mol K))

298 1.93 −4.76 −8.12 −0.36

308 0.27 −0.68
318 −0.14 0.36

the band at 3440 cm−1 strengthened significantly, which can also

be attributed to the intermolecular hydrogen bond, maybe indi-
cating that the physical adsorption was the main pattern in O-II
adsorption onto MF/P(DMDAAC-co-AAM).
For MF/KH-570 (Fig. 4b(II)), the significant increase in the
intensity of the hydroxyl stretching vibration peaks at 3450 cm−1
compared to MF, suggested that Si OH groups in the sample
increased significantly. The band at 1635 cm−1 can be assigned to
C C vibrations. The band at 1245 cm−1 can be attributed to C O
stretching vibrations. The bands at 870 cm−1 can be assigned to
the vibrations of C C C O group. All of these bands indicated that
KH-570 was successfully developed in MF skeleton. After kerosene
adsorption (Fig. 4b (III)), some new bands, 713, 875, 1720 and
3642 cm−1 can be attributed the groups of saturated or unsaturated
hydrocarbon in kerosene, indicating the adsorption of kerosene
occured [37].
The percentage of organic component in hybrid composites
MF/P(DMDAAC-co-AAM) and MF/KH-570 were calculated by the
TGA curves (Fig. 5) [38]. Three stages of weight loss at different
temperature ranges were observed, and all the organic compo-
nents decomposed completely upon about 700 K, the percentage
of organic component in the hybrid composites were calculated as
the ratio of the weight loss during 400–700 K to the residuals at
700 K [39]. A weight loss of about 88.1% for MF/KH-570, 91% for
MF/P(DMDAAC-co-AAM) were obtained, which was closed to the
theoretical value. It was the high percentage of organic component
in the hybrid composites that promote the adsorption of the organic
anionic dye and oily substrates.
The hydrophobicity of MF/KH-570 was measured by contact
angle test as Fig. 6 shown. The contact angles were about 47◦ and
104◦ for MF and MF/KH-570, respectively, indicating that MF mod-
ified by organic KH-570 with lipophilic long carbon chain could
improve the hydrophobicity significantly, that was essential for the
adsorption of oily substrate [40].
3.2. Hydrophilic adsorption properties of
MF/P(DMDAAC-co-AAM)
3.1.1. Effect of operating parameters on O-II removal
Fig. 8. Comparison of various oily substrates adsorption onto MF/KH-570.
3.1.1.1. Effect of O-II initial concentration and contact time. The
adsorption of O-II onto MF/P(DMDAAC-co-AAM) at different
concentrations (30 mg/L, 50 mg/L, 100 mg/L, 200 mg/L) at room
temperature was studied as a function of time (Fig. 7a). O-II
removal increased sharply at the initial 15 min, and then increased
slowly until to the adsorption equilibrium at 40 min. Moreover, the
removal efficiency at various concentrations followed the order:
50 mg/L >100 mg/L > 200 mg/L > 30 mg/L, indicating that moderate
concentration (50 ∼ 100 mg/L) of dye was suitable for higher O-
II removal, it is probably due to that the initial concentration of
O-II molecules might provide the necessary driving force to over-
come the resistances of mass transfer between the aqueous and
solid phases. Meanwhile, there are redundant dye molecules in
reaction system cannot contact with adsorbents fully at too high
concentration of dye [41,42]. So the optimal contact time and initial
concentration were chosen as 40 min and 50 mg/L for the subse-
quent adsorption experimental study.
3.1.1.2. Effect of adsorbent dosage. Since the adsorption of O-II
occurs at the surface of MF/P(DMDAAC-co-AAM) mainly, the sur-
face properties and dosage of adsorbent are key factor on O-II
removal (R%). Fig. 7b clearly showed that O-II removal increased
with dosage increasing, and then stabilized after dosage 2000 mg/L
(R% = 99.2%, qe = 24.8 mg/g). After adsorption, the Zeta potential
of MF/P(DMDAAC-co-AAM) composites decreased from +11.2 mV
to +8.3 mV, indicating that neutralization effect happened on the
composites surface. So 2000 mg/L adsorbent was considered as an
optimum dosage.
3.1.1.3. Effect of initial pH. As shown in Fig. 7c, high R% was obtained
at strongly acidic condition (pH = 2), after a slightly decrease in
the pH range of 2–4, the adsorption capacity then increased with
pH higher than 4, and the maximum O-II removal was obtained
at pH 6. This was probably due to that more H+ facilitated the
neutralization function [43]. Furthermore, higher cationic degree
(positive charged) of P(DMDAAC-co-AAM) was not favorable to the

Table 5
The kinetic parameters for O-II adsorption onto MF/P(DMDAAC-co-AAM).

C0 (mg/L) Pseudo-first-order Pseudo-second-order

k1 (min−1 ) qe,1 (mg/g) R2 k2 ((mg/L)−1 min−1 ) qe,2 (mg/g) R2

100 0.08 25.25 0.987 0.072 11.25 0.999

200 0.09 12.38 0.919 0.036 20.38 0.997
300 0.12 24.74 0.954 0.032 35.37 0.998

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Fig. 9. The photo image for kerosene adsorption onto MF/KH-570 (a) dyeing kerosene by SudanII; (b) MF/KH-570 after adsorbed kerosene.

Table 6
Adsorption isotherm parameters for kerosene adsorption onto KH-570.

T (K) Langmuir Freundlich

qL (mg/g) kL (L/(mg)) R2 kf n R2

298 68.90 0.0110 0.949 1.075 1.249 0.999

308 103.8 0.00999 0.947 2.576 1.173 0.996
318 142.1 0.00750 0.981 1.302 1.147 0.998

Fig. 10. The kinetics of kerosene adsorption onto MF/KH-570 using (a) pseudo-first-
order and (b) pseudo-second-order model.
Scheme 2. Fabrication of MF/P(DMDAAC-co-AAM) composites (a) and its possible
interaction with O-II (b).

Please cite this article in press as: M. Gao, et al., Fabrication and adsorption properties of hybrid fly ash composites, Appl. Surf. Sci.
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adsorption of anionic dye due to the electrostatic repulsion. O-II
removal decreased gradually at pH higher than 6, maybe due to the
increased repulsion between the negative charged surface of adsor-
bent and more electronegative OH− , −SO3 − and −O− in anionic dye
[44,45]. In addition, the intermolecular hydrogen bonding could
also play an important role in the adsorption process [46,47].
3.1.2. The isotherms of O-II adsorption onto
MF/P(DMDAAC-co-AAM)
The model parameters from Langmuir and Freundlich isotherms
obtained from linear regression are presented in Table 3. As can
be seen that the Langmuir isotherm model described better than
the Freundlich model (at 298 K) from correlation coefficients (RL 2
(0.999) > RF 2 (0.961)) suggesting that the monolayer adsorption or
pores on the surface of MF/P(DMDAAC-co-AAM) play a main role
in O-II adsorption [48,49].
The removal efficiency of O-II adsorbed by MF/P(DMDAAC-co-
AAM) decreased from 99.2% to 70.6% when temperature increased
from 25 to 45 ◦ C, indicating that the adsorption process was
exothermic [50]. Higher temperature might break the intermolec-
ular forces between O-II and composites adsorbents, which was
consistent with the thermodynamic characteristic of the negative
H (Table 4). Moreover, G values increased with temperature
increasing, suggesting that the sorption process was favorable at
lower temperature.
3.1.3. The kinetics of O-II adsorption onto
MF/P(DMDAAC-co-AAM)
The change of concentration over time on the adsorption of O-II
at higher concentration range of 100–300 mg/L was examined The
kinetic parameters of the pseudo-first-order and pseudo-second-
order kinetic models are shown in Table 5. It can be seen that
the adsorption perfectly fitted the pseudo-second-order model
rather than pseudo-first-order with higher R2 value, indicated that
hydrophilic cationic MF/P(DMDAAC-co-AAM) exhibited excellent
adsorption performance towards anionic dye with neutralization
and intermolecular forces [51].
3.2. Hydrophobic oil adsorption properties of MF/KH-570
3.2.1. The oil adsorption ratios of MF/KH-570 towards various
oily substrates
Oil adsorption ratios Q (g/g) of hydrophobic MF/KH-570 towards
various oily substrates (kerosene, benzene, methylbenzene, olive
oil and abies oil) were investigated and the results were shown in
Fig. 8. All Q values increased in different degree with the contact
time prolonging, eventually reached adsorption equlibrium and
the maximum Q value at 40 min. And Q values followed the order:
kerosene > methylbenzene > benzene > olive oil > abies oil, but the
maximum Q value of 17.2 g/g was obtained for kerosene at 40 min.
This probably related with the components and the mobility of the
oily substrates, and kerosene was composed of more complex com-
ponents and worse mobility than abies oil to be desorbed from
MF/KH-570 well [52]. More precise reason would be further stud-
ied. The photo image for kerosene adsorption onto MF/KH-570 was
provided in Fig. 9. And kerosene was chosen as the oily substrate
in the further study, and the optimal contact time was chosen as
40 min.
3.2.2. The isotherms of kerosene adsorption onto MF/KH-570
The model parameters for kerosene adsorption onto MF/KH-
570 for Langmuir and Freundlich isotherms obtained from linear
regression are presented in Table 6.
It can be found that the Freundlich isotherm model described
the oil adsorption process better than the Langmuir model (as evi-
dent from correlation coefficients RF 2 > RL 2 ), and n > 1 in Freundlich
Please cite this article in press as: M. Gao, et al., Fabrication and adsorption properties of hybrid fly ash composites, Appl. Surf. Sci.
(2016), http://dx.doi.org/10.1016/j.apsusc.2016.10.167
Scheme 3. Fabrication of MF/KH-570 composites and its possible interaction with
kerosene.
parameters. This suggested that some heterogeneity and uneven
adsorption dominated in oil adsorption.
3.2.3. The kinetics of kerosene adsorption onto MF/KH-570
Oil adsorption kinetics were investigated in the pure kerosene
phase at room temperature. Fitting the data by pseudo-first-order
and pseudo-second-order kinetic equations, respectively (Fig. 10).
It can be seen that the kerosene adsorption process fitted better
with the pseudo-second-order model, which was consistent with
some researches reported [53].
3.4. Possible mechanism of fabrication the high-efficient FA
composite adsorbents and adsorption process
The inorganic composites MF exhibited good adsorption capac-
ity to the anionic dye with more active sites and strong basicity [22].
Hydrophilic or hydrophobic groupintroduced into MF expected
to further modulate and fabricate the high adsorption efficient
inorganic-organic hybrid composites, which then used to adsorb
water-soluble dye molecular or oily substrates [54]. In this study,
in order to enhance the hydrophilic of MF surface and improve
the adsorption capacity towards the anionic dye (O-II), hydrophilic
polymer P(DMDAAC-co-AAM) was in-situ polymerized from the
water-soluble cationic monomer diallyl dimethyl ammonium chlo-
ride (DMDAAC), which was widely used in wastewater treatment
and dye industry, and further modified MF with positive-charged
adsorption active site (-CONH2 -N+ -), which was confirmed by
Zeta potential test. Generally, some interactions play important
role during the adsorption process: one is electrostatic interaction
between the positive charged adsorbent and the negative charged
dye, the other is the hydrogen bonding between the −OH of O-II
and the amine groups −NH2 of polymer chain as Scheme 2 shown.
Since AAM is a non-ionic polymer, DMDAAC can increase ioniz-
able groups on the polymer [55], which can increase the reaction
between the anionic dye molecular and adsorbents. Similarly, MF
was modified by hydrophobic KH-570 with long carbon chain to
build the high hydrophobic surface composites, which enhanced
its hydrophobicity, which confirmed by contact angle test and inter
solubility to the oily molecular, as Scheme 3 shown.
4. Conclusion
In summary, the high-efficient hybrid MF composite adsor-
bents were fabricated with hydrophilic MF/P(DMDAAC-co-AAM)
or hydrophobic MF/KH-570 modifiers in our study, and their
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adsorption properties to O-II or oily substrates were investigated.
The results showed that the physical and intermolecular forces
between adsorbents and anionic dye maybe both existed. The
higher organic contents in P(DMDAAC-co-AAM) and KH-570 were
beneficial for the adsorption process. The highest O-II removal
(99.2%) was obtained with 2000 mg/L dosage in a 50 mg/L O-II solu-
tion in 40 min with MF/P(DMDAAC-co-AAM) as the adsorbent. The
Langmuir isotherm and the pseudo-second-order kinetic model
fit better with the experimental results. Additionally, MF/KH-570
showed better hydrophobic property (contact angle 104◦ ), and
exhibited encouraging oil sorption behavior towards kerosene, the
Freundlich isotherm and pseudo-second-order kinetic model fit
better with kerosene adsorption. The experimental results indi-
cated the potential application of modified FA in dye and oil
adsorption, and more importantly, it also could realize the waste
resource reutilization better.
Acknowledgment
The authors are grateful to be supported by the Fundamental
Research Funds for the Central Universities (GK201302013).
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